CN115197573B - Composition, low-cost high-dielectric-constant low-modulus high-breakdown-voltage-strength silicone rubber dielectric elastomer and application thereof - Google Patents

Composition, low-cost high-dielectric-constant low-modulus high-breakdown-voltage-strength silicone rubber dielectric elastomer and application thereof Download PDF

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CN115197573B
CN115197573B CN202210845412.XA CN202210845412A CN115197573B CN 115197573 B CN115197573 B CN 115197573B CN 202210845412 A CN202210845412 A CN 202210845412A CN 115197573 B CN115197573 B CN 115197573B
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silicone rubber
dielectric
dielectric elastomer
composition
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CN115197573A (en
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张志杰
喻研
费华峰
黄彬
赵云峰
高希银
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Institute of Chemistry CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

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Abstract

The application provides a composition, a low-cost high-dielectric-constant low-modulus high-breakdown-voltage-strength silicone rubber dielectric elastomer and application thereof. The composition of the application comprises the following components: (a) at least one organopolysiloxane; (b) a dielectric filler; (c) an auxiliary agent; the auxiliary agent is at least one selected from a cross-linking agent, a polymerization inhibitor and a catalyst; the dielectric filler is an oxide filler. The application can prepare the silicon rubber dielectric elastomer with high dielectric constant, low modulus and high breakdown voltage strength by adding the oxide into the silicon rubber matrix. The method has simple process and low cost, can effectively control the performance of the silicone rubber according to the needs, and can promote the practical application of the dielectric elastomer of the silicone rubber.

Description

Composition, low-cost high-dielectric-constant low-modulus high-breakdown-voltage-strength silicone rubber dielectric elastomer and application thereof
Technical Field
The application belongs to the field of dielectric elastomer materials, and particularly relates to a composition for a silicon rubber dielectric elastomer, which is prepared by filling silicon rubber with inorganic oxide filler and has the advantages of high dielectric constant, low Young modulus, high breakdown voltage strength and low production cost, and application thereof.
Background
The dielectric elastomer is an electroactive polymer, and can change shape under the stimulation of an external electric field, so as to realize the mutual conversion of electric energy and mechanical energy. Compared with other electroactive polymers, the dielectric elastomer has the advantages of large electro-deformation, high energy density, high conversion efficiency, high response speed and the like, and can be used in the fields of drivers, generators, inductors and the like.
Silicone rubber is an ideal matrix material for dielectric elastomers due to its excellent high and low temperature resistance, chemical stability, and insensitivity to humidity. However, the dielectric constant of the silicone rubber material itself is low<3，10 3 Hz), which does not meet the practical requirements, fillers are added to increase the dielectric constant of the silicone rubber composite.
Common additional fillers are inorganic ceramic fillers and conductive fillers. The inorganic ceramic filler is barium titanate, titanium dioxide, lead magnesium niobate and the like, but more inorganic ceramic filler is required to be added for preparing the silicon rubber with high dielectric constant, so that the mechanical property of the silicon rubber can be damaged, and the elastic modulus and breakdown voltage strength of the silicon rubber can be reduced; chinese patent application 201110351670.4 discloses a high dielectric silicone rubber and a method for preparing the same, in which ceramic filler, conductive filler and semiconductor filler are added into the silicone rubber, the dielectric constant is effectively improved, but the addition of the filler causes deterioration of mechanical properties of the material. The conductive filler comprises carbon nano tubes, graphene and the like, and the dielectric constant of the silicon rubber can be effectively improved by adding a trace amount of conductive filler, but the dielectric loss of the conductive filler is also increased, and the breakdown voltage strength is obviously reduced.
Disclosure of Invention
In order to solve the problems in the prior art, the application aims to provide a silicone rubber dielectric elastomer material with high dielectric constant, low modulus and high breakdown voltage strength, which can be produced in a large scale at low cost, and a preparation method and application thereof.
The application aims at realizing the following technical scheme:
a composition comprising the following components:
(a) At least one organopolysiloxane;
(b) A dielectric filler;
(c) An auxiliary agent; the auxiliary agent is at least one selected from a cross-linking agent, a polymerization inhibitor and a catalyst;
the dielectric filler is an oxide filler.
According to the present application, the oxide filler is at least one selected from zinc oxide, ferric oxide, copper oxide, titanium oxide, cerium oxide, niobium pentoxide, aluminum oxide, and silicon dioxide.
According to the application, the oxide filler may also be chosen from mixtures of the above-mentioned fillers, for example mica powder (in which the silica content is about 43.13 to 49.04% and the alumina content is about 27.93 to 37.44%).
According to the application, the composition comprises the following components in parts by weight:
(a) 100 parts of at least one organopolysiloxane;
(b) An oxide filler of more than 0 and less than or equal to 100 parts;
(c) 0.01 to 5 portions of auxiliary agent.
According to the application, the composition comprises the following components in parts by weight:
(a) 100 parts of at least one organopolysiloxane;
(b) 10-80 parts of oxide filler;
(c) 0.05 to 3 portions of auxiliary agent.
Illustratively, the oxide filler is added in parts of 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts.
According to the application, the composition further comprises the following components in parts by weight: silica filler, 0-60 parts.
Preferably, the silica filler is derived, for example, from white carbon black.
According to the present application, the organopolysiloxane is at least one selected from the group consisting of a hydroxyl group-containing organopolysiloxane, an alkenyl group-containing organopolysiloxane, an alkyl group-containing organopolysiloxane, and an aryl group-containing organopolysiloxane.
Illustratively, the organopolysiloxane is selected from one or more of methyl polysiloxane, methyl ethyl polysiloxane, diphenyl polysiloxane, dimethyl polysiloxane, methyl phenyl polysiloxane, methyl vinyl polysiloxane, dimethyl vinyl polysiloxane, methyl phenyl vinyl polysiloxane, methyl diphenyl vinyl polysiloxane.
According to the application, the organopolysiloxane has a number average molecular weight of 1 to 70, for example 5, 10, 15, 20, 30, 40, 50, 60, 70.
According to the present application, the terminal group of the organopolysiloxane is selected from at least one of a terminal hydroxyl group, a terminal alkenyl group (e.g., vinyl group), a terminal alkyl group (e.g., methyl group, ethyl group), or a terminal aryl group (e.g., phenyl group).
According to the present application, the crosslinking agent is at least one selected from the group consisting of a condensation type crosslinking agent, an addition type crosslinking agent, and a radical type crosslinking agent.
Preferably, the condensation type crosslinking agent may be at least one of a dealcoholization type crosslinking agent, a dehydroxylamine type crosslinking agent, a dehydrogenation type crosslinking agent, or a dehydration type crosslinking agent. Specifically, the dealcoholization crosslinking agent may be Si (OR) 4 Or a partial hydrolysate thereof, wherein R is Et, pr, bu, e.g. Si (OEt) 4 . In particular, the dehydroxylamine-type crosslinking agent may be a polymer containing 2 or more aminooxy groups (R 2 NO) cyclic or linear oligosiloxanes, e.g. Et 2 NO(Me 2 SiO) n Net 2 ，Me 3 SiO(Me 2 SiO) n [Me(Et 2 NO)SiO] m SiMe 3 [n＝0、1、2、…；m＝2、3、4、…]Etc. In particular, the dehydrogenative crosslinking agent may be a silicon-hydrogen bond-containing oligosiloxane, e.g. RMe 2 SiO(Me 2 SiO) n (MeHSiO) m SiMe 2 R < R > is Me, OH; n=0, 1, 2 …; m is greater than or equal to 3]. In particular, the dehydrated crosslinker may be a polyhydroxy siloxane, such as an MQ-type Si-OH containing siloxane prepared by cohydrolytic condensation of trimethylchlorosilane with tetrachlorosilane or tetraethoxysilane.
Preferably, the addition-type crosslinking agent may be a small molecule containing SiH functional groups or a polysiloxane containing multiple sihs. In particular, the small molecule containing SiH functionality may be Ph 2 SiH、PhSiH 3 、D 4 H 、PhMeSiH 2 One or more of them. Specifically, the SiH containing polysiloxanes are hydrogen containing silicone oils, and the hydrogen content may be 0.5% to 1.6%, specifically 0.7% to 1.4%, for example 0.7%, 0.824%, 1%, 1.2% or 1.4%.
Preferably, the radical crosslinking agent may be one or more of dibenzoyl peroxide, dicumyl peroxide, 2, 4-dichlorobenzoyl peroxide, t-butyl benzoyl peroxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-di-t-butyl hexane peroxide.
According to the present application, the catalyst is at least one selected from the group consisting of a condensation catalyst and an addition catalyst.
Preferably, the condensation catalyst may be at least one of organotin, organotitanium, amine or platinum compounds.
Preferably, the addition catalyst may be a noble metal complex containing Pt, rh, ru, pd, etc., and a transition metal complex containing Ni, co, etc. Specifically, the noble metal complex may be H 2 PtCl 6 、K 2 PtCl 4 Platinum (0) -1, 3-diethylene-1, 3-tetramethyldisiloxane (Karstedt catalyst), pt (C) 2 H 4 )(PPh 3 ) 2 、Rh(PPh 3 ) 3 Cl、Ru 3 (CO) 12 And PdCl 2 Any one of them. Specifically, the transition metal complex may be Ni (Cp) 2 、Ni(PPh 3 ) Cl and Co (H) (CO) 4 Any one of them.
According to the application, the polymerization inhibitor may be one or more of N, P, S-containing organic compounds, alkynyl-and/or polyvinyl-containing compounds. In particular, the N, P, S-containing organic compound may be one or more of ammonium oxide, triphenylphosphine, dimethylsulfoxide, and methylhydrazine. Specifically, the alkynyl-and/or multi-vinyl-containing compound may be one or more of tetramethyl tetra-vinyl cyclotetrasiloxane, 3-methyl-1-butyn-3-ol, 3-phenyl-1-butyn-3-ol, 3-propyl-1-butyn-3-ol, 3-octyl-1-butyn-3-ol, 1-ethynyl cyclohexyl alcohol, and 1-dimethylsiloxy-1-ethynyl-cyclohexane.
According to an exemplary embodiment of the present application, when the end group of the organopolysiloxane is a hydroxyl-terminated group, the composition comprises the following components:
(a) At least one organopolysiloxane;
(b) A dielectric filler;
(c) An auxiliary agent; the auxiliary agent is selected from a condensation type cross-linking agent and a condensation type catalyst.
Preferably, the mass ratio of the organopolysiloxane, the condensation type cross-linking agent and the condensation type catalyst is 100: (0.01-5): (0.01-0.1), and the curing temperature is 20-65 ℃.
According to an exemplary embodiment of the present application, when the terminal group of the organopolysiloxane is an alkenyl terminal group, the composition comprises the following components:
(a) At least one organopolysiloxane;
(b) A dielectric filler;
(c) An auxiliary agent; the auxiliary agent is selected from an addition type cross-linking agent, a polymerization inhibitor and an addition type catalyst.
Preferably, the mass ratio of the organopolysiloxane, the addition-type cross-linking agent, the polymerization inhibitor and the catalyst is 100: (0.01-5): (0.01-0.5): (0.01-0.1), and the curing temperature is 80-150 ℃.
According to an exemplary embodiment of the present application, when the organopolysiloxane has a terminal group that is a terminal alkyl group or a terminal aryl group, the composition comprises the following components:
(a) At least one organopolysiloxane;
(b) A dielectric filler;
(c) An auxiliary agent; the auxiliary agent is a free radical type cross-linking agent.
Preferably, the mass ratio of the organopolysiloxane to the radical crosslinking agent is 100: (0.01-5), and the curing temperature is 150-250 ℃.
The application also provides a silicone rubber dielectric elastomer which is prepared from the composition.
According to the application, the dielectric constant of the silicone rubber dielectric elastomer is 2-15.
According to the application, the dielectric loss of the silicone rubber dielectric elastomer is 1 multiplied by 10 -4 ～1×10 -1 。
According to the application, the tensile strength of the silicone rubber dielectric elastomer is 2.0-10.0 MPa.
According to the application, the Young's modulus of the silicone rubber dielectric elastomer is 1.0-3.5 MPa.
According to the application, the elongation at break of the silicone rubber dielectric elastomer is 500-1400%.
According to the present application, the method of preparing the silicone rubber dielectric elastomer may employ conventional methods known in the art, for example, the method of preparing the silicone rubber dielectric elastomer includes: the silicon rubber dielectric elastomer is prepared by mixing and vulcanizing the raw materials comprising the composition.
According to the application, the mixing is carried out on a three-roll mill or a two-roll mill, the purpose of which is to disperse the raw materials uniformly. Preferably, the temperature of the mixing is 20-45 ℃, and the mixing time is 0.2-1 h.
Illustratively, when the organopolysiloxane terminal groups are hydroxyl-terminated, the temperature of the vulcanization is 20 to 65 ℃ and the time of the vulcanization is 5 to 48 hours.
Illustratively, when the organopolysiloxane is terminated with a terminal alkyl or aryl group, the vulcanization treatment comprises a one-stage vulcanization and a two-stage vulcanization.
Preferably, the temperature of the one-stage vulcanization is 150-250 ℃, and the time of the one-stage vulcanization is 3-15 minutes.
Preferably, the temperature of the secondary vulcanization is 180-250 ℃, and the time of the secondary vulcanization is 1-4 hours.
Illustratively, when the organopolysiloxane terminal groups are terminal alkenyl groups, the temperature of the vulcanization treatment is 80 ℃ to 150 ℃, and the time of the vulcanization treatment is 1 hour to 3 hours.
The application also provides application of the dielectric elastomer, which is applied to the fields of artificial muscles, tactile feedback devices, sensors, power generation and the like.
Advantageous effects
Compared with the prior art, the silicon rubber dielectric elastomer has the advantages of high dielectric constant, low Young's modulus and high breakdown voltage strength; the preparation method is simple, low in cost and easy for industrial production.
The application can prepare the silicon rubber dielectric elastomer with high dielectric constant, low modulus and high breakdown voltage strength by adding the oxide into the silicon rubber matrix. The method has simple process and low cost, can effectively control the performance of the silicone rubber according to the needs, and can promote the practical application of the dielectric elastomer of the silicone rubber.
Detailed Description
The technical scheme of the application will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the application. All techniques implemented based on the above description of the application are intended to be included within the scope of the application.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
The physical and mechanical properties of the rubber were tested in the examples described below using GB/T528-1998 and GB/T531-1999.
German Novocontrol Technologies GmbH is used in the examples below&Concept-49/50 type dielectric relaxation spectrometer manufactured by Co.KG company, referring to national standard GB/T1693-2007, testing at room temperature, 10 -2 ～10 6 Dielectric constants and dielectric losses in the Hz frequency range.
EXAMPLE 1 preparation of Zinc oxide/free radical Silicone rubber dielectric elastomer Material
100 parts of methyl vinyl silicone rubber raw rubber (Mn=28ten thousand raw rubber is VMQ, wherein, in the molecular structure of the raw rubber, a terminal group is methyl, a lateral group is dimethyl, and meanwhile, the lateral group contains 0.05-0.5% of vinyl), 20 parts of white carbon black, 60 parts of zinc oxide and 0.8 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are added into a mixing mill, mixed for 5 times, and the silicone rubber dielectric elastomer material is obtained after one-stage vulcanization (170 ℃ for 10 min) and two-stage vulcanization (200 ℃ for 2 h) on the vulcanizing mill.
The dielectric property test data of the dielectric elastomer material prepared in this example are shown in table 1, and the mechanical property data are shown in table 2.
EXAMPLE 2 preparation of Zinc oxide/addition-type Silicone rubber dielectric elastomer Material
100 parts of double-end vinyl polydimethylsiloxane raw rubber (Mn=5ten thousand), 20 parts of white carbon black, 60 parts of zinc oxide, 1 part of hydrogen-containing silicone oil (the hydrogen content is 0.824 wt%), 0.5 part of Karsted catalyst and 1 part of tetramethyl tetravinyl cyclotetrasiloxane are added into a mixing mill, mixed for 5 times, and vulcanized at 120 ℃ for 2.5 hours after mixing is finished, so that the silicon rubber dielectric elastomer material is obtained.
The dielectric property test data of the dielectric elastomer material prepared in this example are shown in table 1, and the mechanical property data are shown in table 2.
EXAMPLE 3 preparation of ferroferric oxide/free radical Silicone rubber dielectric elastomer Material
100 parts of methyl vinyl silicone rubber raw rubber (Mn=28 ten thousand, the same as in example 1), 20 parts of white carbon black, 60 parts of ferroferric oxide and 0.8 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are added into a mixing mill, mixed for 5 times, and vulcanized for two times (200 ℃ C. For 2 hours) on a vulcanizing mill to obtain the silicone rubber dielectric elastomer material.
The dielectric property test data of the dielectric elastomer material prepared in this example are shown in table 1, and the mechanical property data are shown in table 2.
EXAMPLE 4 preparation of ferroferric oxide/addition type Silicone rubber dielectric elastomer Material
100 parts of double-end vinyl polydimethylsiloxane raw rubber (Mn=5ten thousand), 20 parts of white carbon black, 60 parts of ferroferric oxide, 1 part of hydrogen-containing silicone oil (the hydrogen content is 0.824 wt%), 0.5 part of Karsted catalyst and 1 part of tetramethyl tetravinyl cyclotetrasiloxane are added into a mixing mill, mixed for 5 times, and vulcanized at 120 ℃ for 2.5 hours after mixing is finished, so that the silicon rubber dielectric elastomer material is obtained.
The dielectric property test data of the dielectric elastomer material prepared in this example are shown in table 1, and the mechanical property data are shown in table 2.
EXAMPLE 5 preparation of ferric oxide/free radical Silicone rubber dielectric elastomer Material
100 parts of methyl vinyl silicone rubber raw rubber (Mn=28 ten thousand, the same as in example 1), 20 parts of white carbon black, 60 parts of ferric oxide and 0.8 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are added into a mixing mill, mixed for 5 times, and vulcanized for two times (200 ℃ C. For 2 hours) on a vulcanizing mill to obtain the silicone rubber dielectric elastomer material.
The dielectric property test data of the dielectric elastomer material prepared in this example are shown in table 1, and the mechanical property data are shown in table 2.
EXAMPLE 6 preparation of ferric oxide/addition type Silicone rubber dielectric elastomer Material
100 parts of double-end vinyl polydimethylsiloxane raw rubber (Mn=5ten thousand), 20 parts of white carbon black, 60 parts of ferric oxide, 1 part of hydrogen-containing silicone oil (the hydrogen content is 0.824 wt%), 0.5 part of Karsted catalyst and 1 part of tetramethyl tetravinyl cyclotetrasiloxane are added into a mixing mill, mixed for 5 times, and vulcanized at 120 ℃ for 2.5 hours after mixing is finished, so that the silicon rubber dielectric elastomer material is obtained.
The dielectric property test data of the dielectric elastomer material prepared in this example are shown in table 1, and the mechanical property data are shown in table 2.
EXAMPLE 7 preparation of cerium oxide/free radical Silicone rubber dielectric elastomer Material
100 parts of methyl vinyl silicone rubber raw rubber (Mn=28ten thousand, the same as in example 1), 20 parts of white carbon black, 60 parts of cerium oxide and 0.8 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are added into a mixing mill, mixed for 5 times, and the silicone rubber dielectric elastomer material is obtained after one-stage vulcanization (170 ℃ for 10 min) and two-stage vulcanization (200 ℃ for 2 h) on the mixing mill.
The dielectric property test data of the dielectric elastomer material prepared in this example are shown in table 1, and the mechanical property data are shown in table 2.
EXAMPLE 8 preparation of ferric oxide/addition-type Silicone rubber dielectric elastomer Material
100 parts of double-end vinyl polydimethylsiloxane raw rubber (Mn=5ten thousand), 20 parts of white carbon black, 60 parts of cerium oxide, 1 part of hydrogen-containing silicone oil (the hydrogen content is 0.824 wt%), 0.5 part of Karsted catalyst and 1 part of tetramethyl tetravinyl cyclotetrasiloxane are added into a mixing mill, mixed for 5 times, and vulcanized at 120 ℃ for 2.5 hours after mixing is finished, so that the silicon rubber dielectric elastomer material is obtained.
The dielectric property test data of the dielectric elastomer material prepared in this example are shown in table 1, and the mechanical property data are shown in table 2.
EXAMPLE 9 preparation of niobium pentoxide/free radical Silicone rubber dielectric elastomer Material
100 parts of methyl vinyl silicone rubber raw rubber (Mn=28 ten thousand, the same as in example 1), 20 parts of white carbon black, 60 parts of niobium pentoxide and 0.8 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are added into a mixing mill, mixed for 5 times, and subjected to primary vulcanization (170 ℃ for 10 min) and secondary vulcanization (200 ℃ for 2 h) on the vulcanizing mill to obtain the silicone rubber dielectric elastomer material.
The dielectric property test data of the dielectric elastomer material prepared in this example are shown in table 1, and the mechanical property data are shown in table 2.
EXAMPLE 10 preparation of ferric oxide/addition-type Silicone rubber dielectric elastomer Material
100 parts of double-end vinyl polydimethylsiloxane raw rubber (Mn=5ten thousand), 20 parts of white carbon black, 60 parts of niobium pentoxide, 1 part of hydrogen-containing silicone oil (the hydrogen content is 0.824 wt%), 0.5 part of Karsted catalyst and 1 part of tetramethyl tetravinyl cyclotetrasiloxane are added into a mixing mill, mixed for 5 times, and vulcanized at 120 ℃ for 2.5 hours after mixing is finished, so that the silicone rubber dielectric elastomer material is obtained.
The dielectric property test data of the dielectric elastomer material prepared in this example are shown in table 1, and the mechanical property data are shown in table 2.
EXAMPLE 11 preparation of mica powder/free radical Silicone rubber dielectric elastomer Material
100 parts of methyl vinyl silicone rubber raw rubber (Mn=28 ten thousand, the same as in example 1), 20 parts of white carbon black, 60 parts of niobium pentoxide and 0.8 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are added into a mixing mill, mixed for 5 times, and subjected to primary vulcanization (170 ℃ for 10 min) and secondary vulcanization (200 ℃ for 2 h) on the vulcanizing mill to obtain the silicone rubber dielectric elastomer material.
The dielectric property test data of the dielectric elastomer material prepared in this example are shown in table 1, and the mechanical property data are shown in table 2.
EXAMPLE 12 preparation of Zinc oxide/free radical Silicone rubber dielectric elastomer Material
100 parts of methyl vinyl silicone rubber raw rubber (Mn=28ten thousand, the same as in example 1), 20 parts of white carbon black, 20 parts of zinc oxide and 0.8 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are added into a mixing mill, mixed for 5 times, and the silicone rubber dielectric elastomer material is obtained after one-stage vulcanization (170 ℃ for 10 min) and two-stage vulcanization (200 ℃ for 2 h) on the mixing mill.
The dielectric property test data of the dielectric elastomer material prepared in this example are shown in table 1, and the mechanical property data are shown in table 2.
EXAMPLE 13 preparation of Zinc oxide/free radical Silicone rubber dielectric elastomer Material
100 parts of methyl vinyl silicone rubber raw rubber (Mn=28ten thousand, the same as in example 1), 20 parts of white carbon black, 40 parts of zinc oxide and 0.8 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are added into a mixing mill, mixed for 5 times, and the silicone rubber dielectric elastomer material is obtained after one-stage vulcanization (170 ℃ for 10 min) and two-stage vulcanization (200 ℃ for 2 h) on the mixing mill.
The dielectric property test data of the dielectric elastomer material prepared in this example are shown in table 1, and the mechanical property data are shown in table 2.
Comparative example 1 preparation of radical type Silicone rubber dielectric elastomer Material
100 parts of methyl vinyl silicone rubber raw rubber (Mn=28ten thousand, the same as in example 1), 20 parts of white carbon black and 0.8 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are added into a mixing mill, mixed for 5 times, and vulcanized for one period (170 ℃ for 10 min) and vulcanized for two periods (200 ℃ for 2 h) on the vulcanizing mill to obtain the silicone rubber dielectric elastomer material.
The dielectric property test data of the dielectric elastomer material prepared in this comparative example are shown in Table 1, and the mechanical property data are shown in Table 2.
Comparative example 2 preparation of an addition type Silicone rubber dielectric elastomer Material
100 parts of double-end vinyl polydimethylsiloxane raw rubber (Mn=5ten thousand), 20 parts of white carbon black, 1 part of hydrogen-containing silicone oil (hydrogen content is 0.824 wt%), 0.5 part of Karsted catalyst and 1 part of tetramethyl tetravinyl cyclotetrasiloxane are added into a mixing roll, mixed for 5 times, and vulcanized at 120 ℃ for 2.5 hours after mixing is finished, so that the silicone rubber dielectric elastomer material is obtained.
The dielectric property test data of the dielectric elastomer material prepared in this comparative example are shown in Table 1, and the mechanical property data are shown in Table 2.
Comparative example 3 preparation of highly filled ferric oxide/free radical type silicon rubber dielectric elastomer Material
100 parts of methyl vinyl silicone rubber raw rubber (Mn=28 ten thousand, the same as in example 1), 20 parts of white carbon black, 110 parts of ferric oxide and 0.8 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are added into a mixing mill, mixed for 5 times, and vulcanized for two times (200 ℃ C. For 2 hours) on a vulcanizing mill to obtain the silicone rubber dielectric elastomer material.
The dielectric property test data of the dielectric elastomer material prepared in this comparative example are shown in Table 1, and the mechanical property data are shown in Table 2.
TABLE 1 dielectric Property test data for Silicone rubber dielectric elastomer
TABLE 2 mechanical test data for dielectric elastomers of silicone rubber
Sample preparation Tensile Strength (MPa) Elongation at break (%) Young's modulus (MPa)
Example 1 9.21 1143 3.30
Example 2 8.57 1050 3.43
Example 3 5.23 800 3.71
Example 4 4.89 750 3.98
Example 5 3.93 1013 1.62
Example 6 3.54 954 1.84
Example 7 8.64 1114 3.22
Example 8 7.86 1030 3.65
Example 9 7.89 1163 3.35
Example 10 7.54 1030 3.65
Example 11 2.46 878 1.21
Example 12 9.02 1040 2.85
Example 13 9.15 1100 3.14
Comparative example 1 8.99 938 2.70
Comparative example 2 8.43 858 2.93
Comparative example 3 10.54 540 5.67
As can be seen from tables 1 and 2: compared with the prior art, the dielectric constant of the silicon rubber dielectric elastomer prepared by the application is obviously improved, the Young modulus is not greatly improved, even is reduced, the breakdown voltage strength is obviously improved, the dielectric constant is improved to 4.24 from 3.06, the Young modulus is reduced to 1.62MPa from 2.70MPa, and the breakdown voltage strength is improved to 10.76kV/mm from 6.78kV/mm in comparison with comparative example 1 in example 5. The result shows that the silicon rubber dielectric elastomer with high dielectric constant, low modulus and high breakdown voltage strength can be obtained by adding the oxide into the silicon rubber according to a certain proportion.
The above description of exemplary embodiments of the application has been provided. However, the scope of the present application is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, or the like, which are within the spirit and principles of the present application, should be made by those skilled in the art, and are intended to be included within the scope of the present application.

Claims (15)

1. A composition, characterized in that it comprises the following components:
(a) Alkenyl-terminated organopolysiloxanes;
(b) A dielectric filler; the dielectric filler is selected from zinc oxide, ferroferric oxide, ferric oxide, cerium oxide and niobium pentoxide;
(c) An auxiliary agent; the auxiliary agent comprises an addition type cross-linking agent, a polymerization inhibitor and an addition type catalyst;
the mass ratio of the alkenyl-terminated organopolysiloxane to the dielectric filler to the addition-type cross-linking agent to the polymerization inhibitor to the catalyst is 100:60: (0.01 to 5): (0.01 to 0.5): (0.01 to 0.1).
2. The composition according to claim 1, further comprising, per 100 parts by mass of the terminal alkenyl organopolysiloxane: silica filler, 0-60 parts by mass and not 0.
3. The composition of claim 1, wherein the alkenyl-terminated organopolysiloxane has a number average molecular weight of 1 to 70 tens of thousands.
4. The composition of claim 1, wherein the composition has a cure temperature of 80 to 150 ℃.
5. The composition of any of claims 1-4, wherein the addition-type crosslinking agent is a SiH functional group-containing small molecule or a multiple SiH containing polysiloxane;
and/or the polymerization inhibitor is one or more of N, P, S-containing organic compounds, alkynyl-and/or polyvinyl-containing compounds.
6. A composition, characterized in that it comprises the following components:
(a) A terminal alkyl organopolysiloxane;
(b) A dielectric filler; the dielectric filler is selected from zinc oxide, ferroferric oxide, ferric oxide, cerium oxide and niobium pentoxide;
(c) An auxiliary agent; the auxiliary agent is a free radical type cross-linking agent;
the mass ratio of the terminal alkyl organopolysiloxane to the dielectric filler to the auxiliary agent is 100: (20-60): (0.01 to 5).
7. The composition according to claim 6, further comprising, per 100 parts by mass of the terminal alkyl organopolysiloxane: silica filler, 0-60 parts by weight and not 0.
8. The composition of claim 6 wherein the alkyl-terminated organopolysiloxane has a number average molecular weight of 1 to 70 tens of thousands.
9. The composition of claim 6, wherein the composition has a cure temperature of 150 to 250 ℃.
10. The composition according to any one of claims 6 to 9, wherein the free radical crosslinking agent is one or more of dibenzoyl peroxide, dicumyl peroxide, 2, 4-dichlorobenzoyl peroxide, t-butyl benzoyl peroxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-di-t-butyl hexane peroxide.
11. A silicone rubber dielectric elastomer prepared from the composition of any one of claims 1-10.
12. The silicone rubber dielectric elastomer of claim 11, wherein the dielectric constant of the silicone rubber dielectric elastomer is 2-15;
and/or the dielectric loss of the silicone rubber dielectric elastomer is 1×10 -4 ~1×10 -1 ；
And/or the tensile strength of the silicone rubber dielectric elastomer is 2.0-10.0 MPa;
and/or the Young's modulus of the silicone rubber dielectric elastomer is 1.0-3.5 MPa;
and/or the elongation at break of the silicone rubber dielectric elastomer is 500-1400%.
13. The silicone rubber dielectric elastomer of claim 11, wherein the method of preparing the silicone rubber dielectric elastomer comprises: the silicone rubber dielectric elastomer is prepared by mixing and vulcanizing the raw materials comprising the composition of any one of claims 1 to 10.
14. The silicone rubber dielectric elastomer of claim 13, wherein the temperature of the mixing is 20 ℃ to 45 ℃ and the time of the mixing is 0.2h to 1h.
15. Use of the silicone rubber dielectric elastomer of any of claims 11-14 in the field of artificial muscles, haptic feedback, sensors, power generation.
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