WO2013113846A1 - Convertisseur électromécanique comprenant un polymère de polyuréthane à motifs polyester et/ou polycarbonate - Google Patents

Convertisseur électromécanique comprenant un polymère de polyuréthane à motifs polyester et/ou polycarbonate Download PDF

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Publication number
WO2013113846A1
WO2013113846A1 PCT/EP2013/051956 EP2013051956W WO2013113846A1 WO 2013113846 A1 WO2013113846 A1 WO 2013113846A1 EP 2013051956 W EP2013051956 W EP 2013051956W WO 2013113846 A1 WO2013113846 A1 WO 2013113846A1
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groups
isocyanate
polyurethane polymer
reaction
polycarbonate
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PCT/EP2013/051956
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German (de)
English (en)
Inventor
Joachim Wagner
Sebastian Dörr
Werner Jenninger
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Bayer Intellectual Property Gmbh
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Publication of WO2013113846A1 publication Critical patent/WO2013113846A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B06—GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS IN GENERAL
    • B06B—METHODS OR APPARATUS FOR GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS OF INFRASONIC, SONIC, OR ULTRASONIC FREQUENCY, e.g. FOR PERFORMING MECHANICAL WORK IN GENERAL
    • B06B1/00—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency
    • B06B1/02—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy
    • B06B1/06—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/098—Forming organic materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/857—Macromolecular compositions

Definitions

  • Electromechanical transducer comprising a polyurethane polymer with polyester and / or
  • the present invention relates to an electromechanical transducer comprising a dielectric elastomer contacted by a first electrode and a second electrode, the dielectric elastomer comprising a polyurethane polymer.
  • the polyurethane polymer here comprises at least one polyester and / or polycarbonate unit.
  • the invention further relates to a method for producing such an electromechanical transducer, the use of the dielectric elastomer used and an electrical and / or electronic device comprising an electromechanical transducer according to the invention.
  • Electromechanical transducers play an important role in converting electrical energy into mechanical energy and vice versa. Electromechanical converters can therefore be used as sensors, actuators and / or generators. As an example of this, the systems mentioned in WO-A 2001/006575 are presented, which use prestressed polymers.
  • One class of such transducers is based on electroactive polymers. It is a constant goal to increase the properties of the electroactive polymers, in particular the electrical resistance and the breakdown strength. At the same time, however, the mechanics of the polymers make them suitable for use in electromechanical transducers.
  • WO-A 2008/095621 describes soot-filled polyurethane compositions which at least consist of polyetherurethanes incorporated with polyol components containing from 50 to 100% by weight of polyalkylene oxides prepared by DMC catalysis, in particular polypropylene oxides, and 0-50% by weight. % of catalyst-free polyols, in particular those which are purified by distillation or by recrystallization, or those which have not been prepared by ring-opening polymerization of oxygen heterocycles constructed. Furthermore, the polyurethane compositions contain 0.1-30 wt .-% carbon black.
  • the invention therefore proposes an electromechanical transducer comprising a dielectric elastomer contacted by a first electrode and a second electrode, wherein the dielectric elastomer comprises a polyurethane polymer.
  • the converter according to the invention is characterized in that the polyurethane polymer is obtainable from the reaction of
  • the polyurethane polymers provided in the electromechanical converter according to the invention have particularly high tear propagation strengths with simultaneously small remaining elongations.
  • the polyurethanes are present as soft elastomers. The combination of these properties results in an advantageous use in electromechanical transducers.
  • the transducer When a mechanical stress is applied to such a transducer, the transducer deforms along its thickness and area, for example, and a strong electrical signal can be detected at the electrodes. This converts mechanical energy into electrical energy.
  • the converter according to the invention can consequently be used both as a generator and as a sensor.
  • the converter according to the invention can equally serve as an actuator.
  • the electrodes basically all materials are suitable which have a sufficiently high electrical conductivity and can advantageously follow the expansion of the dielectric elastomer.
  • the electrodes can be constructed from an electrically conductive polymer, from lead ink or from carbon black.
  • Dielectric elastomers for the purposes of the present invention are elastomers that can change their shape by the application of an electric field.
  • the thickness may decrease while at the same time extending the film lengthwise in the planar direction.
  • the thickness of the dielectric elastomer layer is preferably> 1 ⁇ to ⁇ 500 ⁇ and more preferably> 10 ⁇ to ⁇ 150 ⁇ . It can be constructed in one piece or in several pieces. For example, a multi-piece layer can be obtained by laminating individual layers.
  • the dielectric elastomer may have other ingredients in addition to the inventively provided polyurethane polymer. Such ingredients include, for example, crosslinkers, thickeners, cosolvents, thixotropic agents, stabilizers, antioxidants, light stabilizers, emulsifiers, surfactants, adhesives, plasticizers, water repellents, pigments, fillers and leveling agents.
  • fillers in the elastomer can regulate the dielectric constant of the polymer.
  • ceramic fillers in particular barium titanate, titanium dioxide and piezoelectric ceramics such as quartz or lead zirconium titanate, as well as organic fillers, in particular those having a high electrical polarizability, for example phthalocyanines.
  • a high dielectric constant can also be achieved by introducing electrically conductive fillers below their percolation threshold.
  • electrically conductive fillers below their percolation threshold.
  • these are carbon black, graphite, single-walled or multi-walled carbon nanotubes, electrically conductive polymers such as polythiophenes, polyanilines or polypyrroles, or mixtures thereof.
  • electrically conductive polymers such as polythiophenes, polyanilines or polypyrroles, or mixtures thereof.
  • those types of carbon black which have a surface passivation and therefore at higher concentrations below the percolation threshold increase the dielectric constant and nevertheless do not lead to an increase in the conductivity of the polymer.
  • the polyurethane polymer provided in the electromechanical converter according to the invention is obtainable from the reaction of a polyisocyanate A) and / or a polyisocyanate prepolymer B) with a compound C) which comprises at least two isocyanate-reactive groups, with no further isocyanate-reactive for the preparation of the polyurethane polymer Compounds in addition to component C) are used and wherein the molar ratios of isocyanate groups in A) and / or B) to isocyanate-reactive groups in C) of 0.8: 1.0 to 1.3: 1.0, preferably 0, 9: 1.0 to 1.2: 1.0.
  • B) and / or C) have polycarbonate and / or polyester units, wherein the polycarbonate units contain hydroxyl-containing polycarbonate polyols which have an even number of CH 2 groups between the hydroxyl groups, and / or the polyester units the reaction of adipic acid and / or adipic anhydride with diols having an even number of CH 2 groups between the hydroxy groups.
  • the polycarbonate and / or polyester units according to the invention can be obtained by known methods, for example from the reaction of polyisocyanates A) and / or polyisocyanate prepolymers B) with the corresponding polycarbonate polyols and / or polyester polyols. These polycarbonate polyols and / or polyester polyols can also be used to form the prepolymers.
  • suitable polyisocyanates A) are 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4 and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4, 4'-isocyanatocyclohexyl) methanes or mixtures thereof of any isomer content, 1,4-cyclohexylene diisocyanate, 4-isocyanatomethyl-1,8-octane diisocyanate (nonane triisocyanate), 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 1,5-naphthylene diisocyanate, 2,2'- and / or 2,4'- and / or 4,4'-diphenylmethane diisocyanate, 1,3- and / or l,
  • uretdione, isocyanurate, biuret, iminooxadiazinedione or oxadiazinetrione-containing compounds based on the diisocyanates mentioned are suitable building blocks of component A).
  • HDI 1,6-hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • bis (4,4'-isocyanatocyclohexyl) methane tolylene diisocyanate and / or diphenylmethane diisocyanate
  • HDI 1,6-hexamethylene di
  • the polyisocyanate prepolymers which can be used as component B) can be obtained by reacting one or more of the abovementioned diisocyanates with one or more hydroxy-functional, in particular polymeric, polyols, if appropriate with addition of catalysts and auxiliaries and additives.
  • components for chain extension for the formation of the polyisocyanate prepolymer can be used in addition, such as components having primary and / or secondary amino groups.
  • Hydroxy-functional, polymeric polyols for the conversion to the polyisocyanate prepolymer B) according to the invention include, for example, polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols and / or polyurethane polycarbonate polyols and / or polyester polycarbonate polyols. These can be used to prepare the polyisocyanate prepolymer individually or in any mixtures with each other.
  • diisocyanates with the polycarbonate polyols containing an even number of CH 2 groups and / or polyester polyols based on the reaction of adipic acid and / or adipic anhydride with diols having an even number of CH 2 - Groups, to be implemented.
  • diisocyanates may be reacted with the polyols at a ratio of the isocyanate groups to hydroxyl groups (NCO / OH ratio) of 2: 1 to 20: 1, preferably of 8: 1 to 15: 1.
  • NCO / OH ratio a ratio of the isocyanate groups to hydroxyl groups
  • urethane and / or allophanate structures can be formed.
  • the proportion of unreacted polyisocyanates can then be separated off.
  • a thin-film distillation can be used, with residual monomer low products with residual monomer contents of, for example, ⁇ 1 weight percent, preferably ⁇ 0.5 weight percent, more preferably ⁇ 0.1 weight percent, are obtained.
  • the reaction temperature may be from 20 ° C to 120 ° C, preferably from 60 ° C to 100 ° C, amount.
  • stabilizers such as benzoyl chloride, isophthaloyl chloride, dibutyl phosphate, 3-chloropropionic acid or methyl tosylate may be added during the preparation.
  • Components suitable for chain extension in the polyisocyanate prepolymers B) according to the invention are organic di- or polyamines.
  • organic di- or polyamines For example, ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, isophoronediamine, isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylene - Diamine, diethylenetriamine, diaminodicyclohexylmethane or dimethylethylenediamine or mixtures thereof are used.
  • compounds which, in addition to a primary amino group, also have secondary amino groups or, in addition to an amino group (primary or secondary), OH groups for the preparation of the polyisocyanate prepolymers B).
  • primary / secondary amines such as diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, alkanolamines such as N-aminoethylethanolamine, ethanolamine , 3-aminopropanol, neopentanolamine.
  • amines with an isocyanate-reactive group such as methylamine, ethylamine, propylamine, Butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine,
  • the polyisocyanate prepolymers or mixtures thereof used according to the invention as component B) preferably have an average NCO functionality of> 1.8 to ⁇ 5, more preferably> 2 to ⁇ 3.5 and very particularly preferably> 2 to ⁇ 2.5 ,
  • component C) may in principle be a compound having at least two isocyanate-reactive groups, preferably amino and / or hydroxyl groups, particularly preferably hydroxy groups.
  • component C) may be a polyol having at least two isocyanate-reactive hydroxyl groups, such as, for example, trimethylolpropane (TMP).
  • TMP trimethylolpropane
  • Polyester components which can be used as component C) and / or for the preparation of component B) are the known polycondensates of di- and optionally tri- and tetraols and di- and optionally tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones , Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols for the preparation of the polyesters. Polyester polyols having number-average molecular weights M n of from 1000 to 10000 g / mol, preferably from 1500 to 4000 g / mol, particularly preferably from 1800 to 2300 g / mol, may be used.
  • M n is determined by gel permeation chromatography (GPC) at 23 ° C in THF using as calibration relationship polystyrene standards in the relevant molecular weight range.
  • suitable diols for the preparation of the polyester polyols are those which have an even number of CH 2 groups between the hydroxyl groups, for example ethylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, butanediol (1,3), butanediol (1 , 4), hexanediol (1,6).
  • the polyester polyols are preferably obtainable as component C) and / or for the preparation of component B) by reacting adipic acid and / or adipic anhydride with Diols which have an even number of CH 2 groups between the hydroxyl groups, particularly preferably with hexanediol (1,6), butanediol (1,4) and ethylene glycol and very particularly preferably with hexanediol (1,6) and ethylene glycol.
  • Polycarbonate components which can be used as component C) and / or for the preparation of component B) are hydroxyl-containing polycarbonate polyols, preferably polycarbonate diols having an even number of CH 2 groups between the hydroxyl groups, with number-average molecular weights M n of 1000 to 10000 g / mol, preferably from 1500 to 4000 g / mol, particularly preferably from 1800 to 3000 g / mol.
  • M n number-average molecular weights
  • M n number-average molecular weights
  • These are obtainable by reaction of carbon dioxide, carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene, with polyols, preferably diols, which have an even number of CH 2 groups between the hydroxyl groups.
  • diols examples include ethylene glycol, 1,3- and 1, 4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1, 4-bishydroxymethylcyclohexane, dibutylene glycol and polybutylene glycols.
  • the diol component contains 40 to 100 wt .-% of hexanediol, preferably 1,6-hexanediol and / or hexanediol derivatives.
  • Such hexanediol derivatives are based on hexanediol and have ester or ether groups in addition to terminal OH groups. Such derivatives are obtainable by reaction of hexanediol with excess caprolactone or by etherification of hexanediol with itself to di- or trihexylenglykol. Particularly preferred is 1,6-hexanediol as the diol component.
  • the equivalent ratio of the isocyanate groups from A) to the isocyanate groups from B) is advantageously between> 1:10 to ⁇ 10: 1, more preferably> 1: 5 ⁇ 5: 1, and most preferably> 1: 3 to ⁇ 3: 1.
  • the terms "a” and “an” in connection with the components A), B) and C) are not used as number words but as an indefinite article.
  • the polyurethane polymer is obtainable from the reaction of a polyisocyanate prepolymer B) with a compound having at least two NCO-reactive groups C).
  • the polyurethane prepolymer B) is obtainable from the reaction of a diisocyanate A) with a polycarbonate polyol containing an even number of CH 2 groups, and / or a polyesterpolyol, based on the reaction of adipic acid and / or adipic anhydride with diols having an even number of CH 2 groups, particularly preferably used as diisocyanate A) hexamethylene diisocyanate.
  • the polyurethane polymer is obtainable from the reaction of a polyisocyanate prepolymer B) with C) a polycarbonate polyol containing an even number of CH 2 groups and / or a polyester polyol based on the reaction of adipic acid and / or adipic anhydride with diols having an even number of CH 2 groups and the polyisocyanate prepolymer B) is obtainable from the reaction of an at least difunctional polyisocyanate with a polycarbonate polyol containing an even number of CH 2 groups, and / or a polyester polyol based on the reaction of adipic acid and / or adipic anhydride with diols having an even number of CH 2 groups, particularly preferably the diisocyanate A) used is the monomer and / or trimerizate (biuret or isocyanurate) of hexamethylene diisocyanate.
  • the polyisocyanate A) used is the monomer and / or trim
  • the proportion of polyester and / or polycarbonate units is> 20% by weight to ⁇ 90% by weight. This proportion is preferably between> 25% by weight and ⁇ 80% by weight and more preferably between> 30% by weight and ⁇ 50% by weight.
  • the polyurethane polymer has a modulus of elasticity at an elongation of 50%>from> 0.1 MPa to ⁇ 15 MPa.
  • the module is determined according to DIN EN 150 672 1-1 and can also be> 0.2 MPa to ⁇ 5 MPa.
  • the polyurethane polymer may have a maximum stress of> 0.2 MPa, in particular of> 0.4 MPa to ⁇ 50 MPa and a maximum elongation of>200%>, in particular of>350%>.
  • the polyurethane polymer contained in the electromechanical transducer according to the invention has a tensile strength of> 1, 5kN / m, preferably of> 1.6 kN / m. The tear strength was determined according to ASTM D 624-00 on films of thickness from 30 ⁇ to 200 ⁇ .
  • a further subject of the present invention is a method for producing an electromechanical transducer, comprising the steps:
  • dielectric elastomer comprises a polyurethane polymer
  • polyurethane polymer is obtainable from the reaction of
  • the provision of the dielectric elastomer is preferably carried out by applying the reaction mixture leading to the polyurethane polymer to the first and / or second electrode.
  • the advantage of this procedure is in particular that the curing elastomer can build a good adhesion to the electrodes.
  • the application of the reaction mixture can be carried out, for example, by knife coating, brushing, pouring, spinning, spraying or extrusion.
  • drying and / or tempering is carried out after application of the reaction mixture.
  • the drying / tempering can take place in a temperature range from 0 ° C to 200 ° C, for example for 0.1 min to 48 h, in particular for 6 h to 18 h; drying / heat treatment for a period of 15 minutes to 30 minutes in the temperature range from 60 ° C. to 120 ° C. is particularly preferred.
  • the present invention further relates to the use of a dielectric elastomer as an actuator, sensor and / or generator in an electromechanical transducer, wherein the dielectric elastomer comprises a polyurethane polymer, and the polyurethane polymer is obtainable from the reaction of
  • the present invention further relates to the use of a dielectric elastomer as an actuator, sensor and / or generator in an electromechanical transducer, wherein the dielectric elastomer comprises a polyurethane polymer, and the polyurethane polymer is obtainable from the reaction of
  • Uses can be found in a variety of different applications in the electro-mechanical and electro-acoustic field, in particular in the field of energy production from mechanical vibrations (energy harvesting), acoustics, ultrasound, medical diagnostics, acoustic microscopy, mechanical sensors, in particular pressure force and / or strain sensors, robotics and / or communication technology.
  • Typical examples include pressure sensors, electroacoustic transducers, microphones, loudspeakers, vibration transducers, light deflectors, diaphragms, Modulators for optical fiber optics, pyroelectric detectors, capacitors and control systems; and 'intelligent' floors, and systems for converting water wave energy, in particular sea-wave energy, into electrical energy.
  • Another object of the invention is an electrical and / or electronic device comprising an electromechanical transducer according to the invention.
  • the tensile tests were carried out by means of a tractor from Zwick, model number 1455, equipped with a load cell of the total measuring range 1 kN according to DIN 53 504 with a pulling speed of 50 mm / min. S2 specimens were used as specimens. Each measurement was carried out on three identically prepared test specimens and the mean of the data obtained was used for the evaluation. The elongation at break in [%] and the modulus of elasticity in [MPa] at 50% elongation were determined.
  • the stress relaxation (creep) of the elastomer films was determined on rectangular bars of dimensions 15 mm ⁇ 100 mm according to DIN 53 441 at 10% elongation after a time of 30 minutes.
  • the propagation energy was determined according to ASTM D 624-00 at a strain rate of 100 mm / min on rectangular bars of dimensions 15 mm ⁇ 100 mm.
  • the electrical resistance was determined by means of a Keithley Instruments Model No. 6517 A and 8009 laboratory setup in accordance with ASTM D 257 (a method for determining the insulation resistance of materials). Substances used and abbreviations:
  • Desmodur® N 100 trifunctional biuret based on hexamethylene diisocyanate (HDI biuret), NCO content 21.95 ⁇ 0.3% (according to DIN EN ISO 1 909), viscosity at 23 ° C. 9630 ⁇ 750 mPa ⁇ s, Bayer MaterialScience AG, Leverkusen, DE. Desmodur® 44M 4,4'-methylene diphenyl diisocyanate, Bayer MaterialScience AG,
  • Desmodur® XP 2599 Aliphatic, ether group-containing prepolymer based on
  • Example 1 Preparation of a di-isocyanate-functional polyisocyanate prepolymer
  • Example 3 (comparative): Preparation of a polymer not to be used according to the invention
  • the raw materials used were not degassed separately. 55.2 g of a prepolymer from Example 2 and 33.33 g of PolyTHF® 2000 were mixed with an amount of 0.00083 g of DBTDL in a polypropylene beaker in the Speedmixer at 3000 revolutions per minute for 1 minute. From the still liquid reaction mixture, films of a wet layer thickness of 1 mm were laced by hand on glass plates. All films were dried after production at 80 ° C in a drying oven overnight and then post-annealed at 120 ° C for 5 min. The films could be easily released from the glass plate after tempering by hand.
  • Example 4 Preparation of a polymer not to be used according to the invention The raw materials used were not degassed separately. 50.0 g of Acclaim® 4220 and 0.05 g of Irganox® 1076 were weighed into a polypropylene beaker and mixed in the Speedmixer at 3000 rpm for 1 minute with 0.4 g DBTDL and 5.75 g Desmodur® N 100 mixed. From the still liquid reaction mixture, films of a wet layer thickness of 1 mm were laced by hand on glass plates. All films were dried after production at 80 ° C in a drying oven overnight and then post-annealed at 120 ° C for 5 min. The films could be easily released from the glass plate after tempering by hand.
  • Example 5 Preparation of a polymer not to be used according to the invention The raw materials used were not degassed separately. 29, ll g of Desmodur® XP 2599 and 50.0 g of Desmophen® C 2200 were loaded with 0.045 g of Desmorapid® SO and 0.05 g of Irganox® 1076 in a polypropylene beaker in the Speedmixer at 3000 revolutions per minute for the duration mixed for 1 minute. From the still liquid reaction mixture, films of a wet layer thickness of 1 mm were laced by hand on glass plates. All films were dried after production at 80 ° C in a drying oven overnight and then post-annealed at 120 ° C for 5 min. The films could be easily released from the glass plate after tempering by hand.
  • Example 6 Preparation of a Polymer Not According to the Invention
  • the raw materials used were not degassed separately.
  • 50.0 g Desmophen® C 1200 was mixed with 0.05 g Irganox® 1076, 9.188 g Desmodur® N100 and 0.013 g DBTDL in a polypropylene beaker in the Speedmixer at 3000 rpm for 1 minute.
  • films of a wet layer thickness of 1 mm were laced by hand on glass plates. All films were dried after production at 80 ° C in a drying oven overnight and then post-annealed at 120 ° C for 5 min. The films could be easily released from the glass plate after tempering by hand.
  • Example 7 Preparation of a polymer to be used according to the invention
  • films of a wet layer thickness of 1 mm were laced by hand on glass plates. All films were cured after production at 100 ° C in the oven for a period of 1 h. The films could be easily released from the glass plate after curing by hand.
  • Elongation at break and modulus of elasticity in tension (DIN EN 150 672 1-1), tension relaxation in tension (Creep; DIN 53 441), tensile elongation at break (ASTM D 412), tear strength (ASTM D 624 -00) and the electrical resistance (ASTM D 257) determined.
  • the results for the examples not according to the invention and the examples of polymer elements according to the invention are shown in Table 1 below. Numerical values the volume resistances are given in exponential notation. For example, the numerical value 3 means a volume resistance of 1.88 ⁇ 10 12 ohm cm.
  • Particularly advantageous when using the film according to the invention is the combination of high elongation at break, low creep, high electrical resistance and high tear propagation resistance.
  • Particularly advantageous electromechanical transducers can be produced with this polymer according to the invention.

Abstract

La présente invention concerne un convertisseur électromécanique comprenant un élastomère diélectrique dans lequel un contact est établi au moyen d'une première et d'une deuxième électrode, l'élastomère diélectrique comprenant un polymère de polyuréthane. Ici, le polymère de polyuréthane comprend au moins un motif polyester et/ou polycarbonate. L'invention concerne en outre un procédé de fabrication d'un tel convertisseur électromécanique, l'utilisation de l'élastomère diélectrique, ainsi qu'un dispositif électrique et/ou électronique comprenant un convertisseur électromécanique selon l'invention.
PCT/EP2013/051956 2012-02-01 2013-01-31 Convertisseur électromécanique comprenant un polymère de polyuréthane à motifs polyester et/ou polycarbonate WO2013113846A1 (fr)

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WO2014006005A1 (fr) * 2012-07-03 2014-01-09 Bayer Materialscience Ag Procédé de fabrication d'un système de films de polyuréthane diélectriques multicouches
CN108912661A (zh) * 2018-08-14 2018-11-30 南京大学射阳高新技术研究院 一种介电薄膜及其制备方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014006005A1 (fr) * 2012-07-03 2014-01-09 Bayer Materialscience Ag Procédé de fabrication d'un système de films de polyuréthane diélectriques multicouches
JP2015533671A (ja) * 2012-07-03 2015-11-26 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトＢａｙｅｒ ＭａｔｅｒｉａｌＳｃｉｅｎｃｅ ＡＧ 多層誘電性ポリウレタンフィルム系を製造するための方法
CN108912661A (zh) * 2018-08-14 2018-11-30 南京大学射阳高新技术研究院 一种介电薄膜及其制备方法
CN108912661B (zh) * 2018-08-14 2021-04-20 南京大学射阳高新技术研究院 一种介电薄膜及其制备方法

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