EP3143061A1 - Films diélectriques eap à bas point de transition vitreuse et à base de polyester-polyols - Google Patents

Films diélectriques eap à bas point de transition vitreuse et à base de polyester-polyols

Info

Publication number
EP3143061A1
EP3143061A1 EP15719757.5A EP15719757A EP3143061A1 EP 3143061 A1 EP3143061 A1 EP 3143061A1 EP 15719757 A EP15719757 A EP 15719757A EP 3143061 A1 EP3143061 A1 EP 3143061A1
Authority
EP
European Patent Office
Prior art keywords
component
weight
acid
dielectric
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15719757.5A
Other languages
German (de)
English (en)
Inventor
Jens Krause
Joachim Wagner
Hartmut Nefzger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP3143061A1 publication Critical patent/EP3143061A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
    • C08G18/4233—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups derived from polymerised higher fatty acids or alcohols
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters

Definitions

  • Dielectric EAP films with a low glass point based on polyester polyols Dielectric EAP films with a low glass point based on polyester polyols
  • the present invention relates to a process for producing a polyurethane dielectric film from a mixture comprising A) an isocyanate group-containing compound with B) a specific polyester polyol. Furthermore, the invention relates to the obtainable by this method dielectric polyurethane film. Further objects of the invention are a method for producing an electrochemical transducer and an electrochemical transducer obtainable by this method.
  • Transducers - also called electromechanical transducers - convert electrical energy into mechanical energy and vice versa. They can be used as part of sensors, actuators and / or generators.
  • EAP electroactive polymers
  • the basic structure of such a transducer consists of electroactive polymers (EAP).
  • EAP electroactive polymers
  • EAPs are a ductile dielectric that deforms in the electric field.
  • dielectric elastomers are mostly in film form (DEAP, dielectric electroactive polymer) which have a high electrical resistance and are coated on both sides with stretchable electrodes with high conductivity (electrode), as described, for example, in WO-A 01/06575.
  • This basic structure can be used in a variety of configurations for the production of sensors, actuators or generators. In addition to single-layered structures, multi-layered structures are also known.
  • Electroactive polymers as elastic dielectric in transducer systems must - depending on the application in different components: actuators / sensors or generators - have different properties. Common mechanical properties are sufficiently high elongation at break, low residual strains and sufficiently high compressive / tensile strengths. These properties provide a sufficiently large elastic deformability without mechanical damage to the energy converter. For energy converters operated in Switzerland, it is particularly important that these elastomers have no permanent elongation, otherwise no electroactive effect will occur after a certain number of cycles of strains and, moreover, no stress relaxation under mechanical load.
  • the voltage is in turn dependent on the breakdown field strength, d. H. if the breakdown rupture field strength is very low, no high voltage can be applied. Since this value is squared in the equation for calculating the strain caused by the electromechanical attraction of the electrodes, the breakdown field strength must be correspondingly high.
  • a typical equation can be found in: Federico Carpi, Dielectric Elastomers as Electromechanical Transducers, Elsevier, page 314, Equation 30.1, as well as similarly in R. Pelrine, Science 287, 5454, 2000, page 837, Equation 2. Actors Heretofore Known are too low in either the dielectric constant and / or the breakdown field strength or too high in the module.
  • a disadvantage of known solutions is also the low electrical resistance, which leads to high leakage currents in actuators and in the worst case to an electrical breakdown.
  • WO-A 2014/001272 WO-A 2012/019979 and WO-A 2014/006005 describe electrochemical converters containing polyurethanes as electroactive polymers.
  • dielectric polyurethane films it is possible, inter alia, to use various OH-functional polymeric compounds, for example polyetherpolyols, polyesterpolyols or polycarbonatepolyols.
  • the transducers have too low an electrical resistance and an insufficient breakdown field strength.
  • thermoplastic polyurethanes are generally linear in construction, i. the overall functionality of the components used is ⁇ 2, 1. However, such linear, uncrosslinked systems show a high stress relaxation (Creep).
  • the dielectric polyurethane films should have one or more of the following properties: a) a tensile modulus (modulus of elasticity) of ⁇ 5 MPa, preferably ⁇ 4 MPa and more preferably ⁇ 3 MPa at 25% elongation determined according to DIN 53 504, b) Elongation at break of> 20%, preferably> 50%> and especially> 70%> according to DIN 53 504, c) a glass point according to DIN 53 513 ⁇ - 10 ° C d) a stress relaxation (creep) at 10%> deformation after 30 min according to DIN 53 441 of
  • the object according to the invention has been achieved by a method for producing a dielectric polyurethane film from a mixture comprising
  • an isocyanate group-containing compound having a content of isocyanate groups of> 10 and ⁇ 50 wt .-% and a number average functionality of isocyanate groups of> 2.6 and ⁇ 4 and
  • the inventive method is particularly suitable for the production of dielectric polyurethane films, which are suitable for the production of electrochemical transducers, which in particular have a good electrical resistance and a high breakdown field strength and due to their low glass transition temperatures to that also at typical ambient temperatures, especially in winter , can be used.
  • the polyurethane films have good mechanical strength and high elasticity.
  • the ester group content (dimension: mol ester groups / kg ester) is understood to mean the amount of ester groups of a polyester polyol relative to 1 kg of substance. This is calculated directly from the recipe by determining the molar amount of carboxylic acid groups or carboxylic acid group equivalents required to produce 1 kg of ester.
  • Carboxylic acid equivalent are, for example, low molecular weight carboxylic acid esters and / or carboxylic anhydrides and / or lactones.
  • Aromatic components are likewise calculated directly from the formulation by determining the amount of aromatic carboxylic acids and / or aromatic carboxylic acid group equivalents required for preparing 100 g of the polyesterpolyol, and optionally aromatic diols , aromatic Carboxylic acid group equivalents are, for example, low molecular weight aromatic carboxylic acid esters and / or aromatic carboxylic anhydrides.
  • Number-average functionalities of the polyester polyols are calculated by first determining the number of molecules present before starting the reaction starting from the respective polyester polyol formulation. Furthermore, the number of moles of hydroxyl groups of all polyols before starting the reaction is determined as well as the number of moles of carboxyl groups. When carboxylic acid anhydrides and / or low molecular weight carboxylic acid esters and / or lactones are used as carboxylic acid equivalents, this number of carboxyl groups results from the fact that the anhydrides and / or esters are theoretically hydrolyzed to form carboxylic acid groups. The functionality of the reacted polyester polyol can now be determined from these data by dividing the number of moles of hydroxyl groups remaining by the number of molecules after the reaction.
  • the number of moles of hydroxyl groups remaining after the reaction is calculated from the number of moles of hydroxyl groups used before the reaction, minus the hydroxyl groups reacted by reaction with carboxyl groups. The latter corresponds to the number of moles of the carboxylic acid groups present before the reaction.
  • the ester group content of the polyester polyol is> 1 and ⁇ 6.5 mol / kg, more preferably> 2 and ⁇ 6.5 mol / kg.
  • the aromatic content of the polyester polyol is ⁇ 45% by weight, particularly preferably ⁇ 35% by weight.
  • the OH number of the polyester polyol is> 35 and ⁇ 90 mg KOH / g.
  • the number-average functionality of the polyester polyols is advantageously> 1.6 and ⁇ 2.8, preferably> 1.8 and ⁇ 2.4.
  • the polyester polyol has an OH number> 27 and ⁇ 120 mg KOH / g, determined according to DIN 53240, an ester group content of> 1 and ⁇ 6.5 mol / kg and a content of aromatic structures of ⁇ 45 % By weight.
  • the polyester polyol has an OH number> 35 and ⁇ 90 mg KOH / g, determined according to DIN 53240, an ester group content of> 2 and ⁇ 6.5 mol / kg and a proportion of aromatic structures of ⁇ 35% by weight.
  • polyester polyols are prepared in a conventional manner by polycondensation.
  • the polyesterpolyol is preferably obtainable from at least a) one or more aromatic and / or aliphatic dicarboxylic acids and / or dicarboxylic acid equivalents and b) one or more linear and / or branched aliphatic diols which have> 6 C atoms, c) optionally one or more Alcohols which are different from the alcohols b) and d) optionally at least one further constituent components which is selected from monocarboxylic acids, polycarboxylic acids having a functionality> 2 and / or hydroxycarboxylic acids and / or the carboxylic acid equivalents of the abovementioned and / or lactones.
  • component a) it is possible in principle to use all aliphatic and / or aromatic dicarboxylic acids having> 4 and ⁇ 50 carbon atoms, and also their anhydrides or low molecular weight esters as carboxylic acid equivalents and / or carbonic acid and their equivalents.
  • phthalic acid isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, suberic acid, nonanedicarboxylic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid are suitable , and dimer fatty acids and / or 2,2- Dimethylsuccinic.
  • the acid source used may also be the corresponding analogous anhydrides and / or low molecular weight esters, which are referred to as carboxylic acid equivalents in the context of this invention.
  • carbonic acid in the context of this invention is likewise a dicarboxylic acid, which can preferably be used as dicarboxylic acid equivalent in the form of dialkyl esters, for example as dimethyl carbonate, or as diaryl esters, for example as diphenyl carbonate.
  • component a) are in particular linear, unbranched dicarboxylic acids having> 8 and ⁇ 18 C atoms and / or dimer fatty acids and / or phthalic acid, isophthalic acid and / or terephthalic acid and the carboxylic acid equivalents of the aforementioned.
  • component a) preferably contains> 5% by weight, more preferably> 10% by weight and very preferably> 15% by weight, based on the total weight of component a), of at least one aliphatic dicarboxylic acid having> 30 and ⁇ 44 C atoms (component al) and / or their carboxylic acid equivalents.
  • Component a) can in one embodiment consist entirely of al).
  • Component a) preferably contains> 5% by weight and ⁇ 90% by weight, more preferably> 10% by weight and ⁇ 80% by weight of component a1), based on the total weight of component a).
  • the aliphatic dicarboxylic acid of component al) is branched.
  • component al) is one or more dimer fatty acids and / or their carboxylic acid equivalents.
  • dimer fatty acids dicarboxylic acids which can be prepared by dimerization of unsaturated monocarboxylic acids, such as oleic acid. Suitable dimer fatty acids are, for example, Pripol 1006, Pripol 1009, Pripol 1012, Pripol 1013, Pripol 1017, Pripol 1022, Pripol 1025 and Pripol 1027 from Croda.
  • component a) preferably comprises at least one further aromatic and / or aliphatic dicarboxylic acid a2) and / or its dicarboxylic acid equivalent, which is different from al). The sum of the proportions of al) and a2) adds up to 100% by weight, based on the entire component a).
  • Suitable as component a2) are, in principle, all abovementioned dicarboxylic acids and / or their carboxylic acid equivalents, which do not correspond to component a1).
  • the further dicarboxylic acid a2) is preferably selected from linear, unbranched dicarboxylic acids having> 8 and ⁇ 18 C atoms and / or phthalic acid, isophthalic acid and / or terephthalic acid, and the carboxylic acid equivalents of the abovementioned.
  • Suitable as component b) are in principle all linear and / or branched aliphatic diols which have> 6 C atoms.
  • suitable components (b) are 1,8-octanediol, 1,10-decanediol, 1,1,1-undecanediol, 1,6-hexanediol, 3-methylpentanediol-1,1,5,9-nonanediol and / or 1,12 -Dodecanediol, as well as dimer fatty acid diols from Croda, such as Pripol 2030 and 2033.
  • component b) is selected from 1,8-octanediol, 1, 10-decanediol, 1,1,1-undecanediol, 1,6-hexanediol, methylpentanediol, 1,9-nonanediol and / or 1,12-dodecanediol.
  • Component c) of the polyester polyols according to the invention is preferably selected from difunctional or polyhydric aromatic alcohols having> 8 C atoms and / or aliphatic diols having> 2 and ⁇ 5 C atoms and / or trihydric or polyhydric aliphatic alcohols, more preferably from aliphatic diols with> 2 and ⁇ C atoms and / or trihydric or more aliphatic alcohols, very particularly preferably from dihydric or polyhydric aliphatic alcohols.
  • Suitable components c) are, for example, ethylene glycol, butylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol and / or trimethylolbenzene.
  • Component c) is preferably present in proportions of ⁇ 10% by weight, based on the total weight of the polyester polyol, particularly preferably ⁇ 5% by weight and very particularly preferably ⁇ 2% by weight.
  • component c) is in proportions of> 0.5% by weight and ⁇ 10% by weight, based on the total weight of the polyester polyol, particularly preferably> 0.5% by weight and ⁇ 5 Wt .-% and most preferably> 0.5 wt .-% and ⁇ 2 wt .-% before.
  • monocarboxylic acids such as benzoic acid, caproic acid, oleic acid and / or ricinoleic acid can be used.
  • hydroxycarboxylic acids can also be used as reactants in the preparation of a polyester polyol having terminal hydroxyl groups.
  • Suitable hydroxycarboxylic acids are, for example, hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid or hydroxystearic acid or mixtures thereof.
  • component d it is also possible to use lactones for the preparation of the polyesterpolyols.
  • lactones Preferably, caprolactone is used.
  • polycarboxylic acids with a functionality> 2 can be used.
  • Suitable polycarboxylic acids of component d) are, for example, pyromellitic acid, pyromellitic dianhydride, trimellitic acid, trimellitic anhydride, as well as trimer fatty acids, such as, for example, Pripol 1040 from Croda.
  • component d) are mono- and / or polycarboxylic acids having a functionality of> 2, more preferably ricinoleic acid and / or trimer fatty acids.
  • Component d) is preferably present in proportions of ⁇ 10% by weight, based on the total weight of the polyesterpolyol, particularly preferably ⁇ 5% by weight and very particularly preferably ⁇ 2% by weight.
  • component d) is in proportions of> 0.5% by weight and ⁇ 10% by weight, based on the total weight of the polyester polyol, more preferably> 0.5% by weight and ⁇ 5 Wt .-% and most preferably> 0.5 wt .-% and ⁇ 2 wt .-% before.
  • the sum of components c) and d) is preferably ⁇ 20% by weight, particularly preferably ⁇ 10% by weight and very particularly preferably ⁇ 5% by weight, based on the total weight of the polyester polyol.
  • Single or more of the compounds suitable as component a) to d) may be biobased, i. be made from renewable raw materials and / or by means of at least one fermentative process step.
  • the polyesterpolyol is preferably obtainable from at least a) one or more linear, unbranched dicarboxylic acids with> 8 and ⁇ 18 C atoms and / or dimer fatty acids and / or phthalic acid, isophthalic acid and / or terephthalic acid and the carboxylic acid equivalents of the abovementioned, b) one or more linear and / or branched aliphatic diols which have> 6 and ⁇ 18 C atoms, c) optionally one or more alcohols which are selected from difunctional or polyhydric aromatic alcohols with> 8 C atoms and / or aliphatic diols with> 2 and ⁇ 5 C atoms and / or trihydric or polyhydric aliphatic alcohols and d) optionally at least one further synthesis component which is selected from monocarboxylic acids, polycarboxylic acids having a functionality> 2 and / or hydroxycarboxylic acids and / or the carboxylic acid equivalents
  • the polyesterpolyol is obtainable from at least ai)> 5% by weight, based on the total weight of the polyesterpolyol, of at least one aliphatic dicarboxylic acid which has> 30 and ⁇ 44 carbon atoms and / or their carboxylic acid equivalents and a2) at least one further aromatic and / or aliphatic dicarboxylic acid a2) and / or its dicarboxylic acid equivalent, which is different from al), the sum of the proportions of al) and a2) being 100% by weight (corresponding to component a) added, b) one or more linear and / or branched aliphatic diols having> 6 and ⁇ 18 C atoms, c) optionally one or more alcohols selected from di- or polyhydric aromatic alcohols having> 8 C atoms and / or aliphatic diols having> 2 and ⁇ 5 C atoms and / or trihydric or more aliphatic alcohols and
  • the polyesterpolyol is obtainable from at least ai)> 5% by weight, based on the total weight of the polyesterpolyol, of at least one dimer fatty acid and / or its carboxylic acid equivalent and a2) at least one further aromatic and / or aliphatic dicarboxylic acid a2) and / or their dicarboxylic acid equivalent, which is selected from linear, unbranched dicarboxylic acids having> 8 and ⁇ 18 C atoms and / or phthalic acid, isophthalic acid and / or terephthalic acid, and the carboxylic acid equivalents of the aforementioned, wherein the sum of the proportions of al ) and a2) to 100 wt .-% (corresponding to component a) added, b) one or more linear and / or branched aliphatic diols, which are selected from 1,8-octanediol, 1, 10-decanediol, 1,
  • the polyester polyol is exclusively from components a), b), c) and d), more preferably exclusively from components a), b) and c) and very particularly preferably exclusively from components a) and b) constructed.
  • the compound A) has a number average functionality of isocyanate groups of> 2.6 and ⁇ 4.
  • Isocyanates or modifications of isocyanates having a number average functionality of isocyanate groups of> 2.6 and ⁇ 4, for example based on 1, 4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2 are suitable according to the invention as compound A) , 2,4 and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes (H12-MDI) 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 (TDI), 1,5-naphthylene diisocyanate
  • modifications such as allophanate, uretdione, urethane, isocyanurate, biuret, iminooxadiazinedione or oxadiazinetrione containing compounds based on the diisocyanates mentioned, as well as polynuclear compounds, such as polymeric MDI (pMDI) and combinations of all mentioned compounds.
  • pMDI polymeric MDI
  • the compound A) comprises or consists of an aliphatic polyisocyanate.
  • the compound A) comprises or consists of hexamethylene diisocyanate and / or a polyisocyanate based on HDI having a functionality of> 2.6, this being Polyisocyanate particularly preferably has a biuret, allophanate, isocyanurate, Iminooxadiazindion- or Oxadiazintrion Modell.
  • the compound A) comprises or consists of hexamethylene diisocyanate and / or a biuret and / or isocyanurate of hexamethylene diisocyanate.
  • the compound A) has a content of isocyanate groups of> 10 and ⁇ 50 wt .-%, preferably of> 15 and ⁇ 40% by weight, particularly preferably of> 18 and ⁇ 25% by weight.
  • the isocyanate groups of compound A) may also be partially or completely blocked until they react with the isocyanate-reactive groups so that they can not react directly with the isocyanate-reactive group. This ensures that the reaction takes place only at a certain temperature (blocking temperature).
  • blocking temperature Typical blocking agents are found in the prior art and are selected so that they split off again at temperatures between 60 and 220 ° C, depending on the substance, from the isocyanate group and only then react with the isocyanate-reactive group.
  • blocked NCO values are also be blocked NCO values.
  • NCO values are mentioned in the invention, this is always based on the unblocked NCO value. Most are blocked up to ⁇ 0.5%.
  • Typical blocking agents are for example caprolactam, methyl ethyl ketoxime, pyrazoles such as 3,5-dimethyl-l, 2-pyrazole or 1-pyrazole, triazoles such as 1,2,4-triazole, diisopropylamine, diethyl malonate, diethylamine, phenol or its derivatives or imidazole.
  • the mixture may also contain further polymeric compounds i) containing at least 2 isocyanate-reactive groups, these being preferred for ⁇ 20% by weight, based on the total weight of the polyester polyols B) and the compounds i) ⁇ 15 wt .-% and particularly preferably ⁇ 10 wt .-% present. Further preferably, the mixture contains no compounds i).
  • polymeric compounds i) for the purposes of this invention are meant compounds having a number average molecular weight of> 400 g / mol.
  • the isocyanate-reactive groups of compound i) are functional groups that can react to form covalent bonds with isocyanate groups.
  • the isocyanate-reactive groups are particularly preferably hydroxyl and / or amine groups.
  • the compound i) has a number-average functionality of isocyanate-reactive groups of> 2.0 and ⁇ 4, wherein the isocyanate-reactive groups are preferably hydroxyl and / or amine groups, more preferably hydroxy groups.
  • the compound i) may preferably have an OH number> 27 and ⁇ 120 mg KOH / g, more preferably> 35 and ⁇ 90 mg KOH / g.
  • polyetherpolyols polyetheramines, polyetheresterpolyols, polycarbonatepolyols, polyethercarbonatepolyols, polybutadiene derivatives and polysiloxanes, and mixtures thereof.
  • I) are preferably polyether, polycarbonate and polyetherester polyols, polybutadiene polyols and / or polysiloxane polyols and more preferably polycarbonate polyols.
  • the mixture may also comprise monofunctional compounds ii) which have an isocyanate-reactive group.
  • monofunctional compounds are ethanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol mono-propyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol or 1-hexadecanol or mixtures thereof.
  • the mixture may additionally contain chain extenders and / or crosslinking agents iii), which are proportionally added to compound B).
  • chain extenders and / or crosslinking agents iii which are proportionally added to compound B.
  • compounds having a functionality of 2 to 3 and a molecular weight of 62 to 400 g / mol are preferably used.
  • aromatic or aliphatic aminic chain extenders for example diethyltoluenediamine (DETDA), 3,3'-dichloro-4,4'-diaminodiphenylmethane (MBOCA), 3,5-diamino-4-chloro-isobutylbenzoate, 4- Methyl 2,6-bis (methylthio) -1,3-diaminobenzene (Ethacure 300), trimethylene glycol di-p-aminobenzoate (Polacure 740M) and 4,4'-diamino-2,2'-dichloro-5 , 5'-Diethyldiphenylmethane (MCDEA) can be used.
  • DETDA diethyltoluenediamine
  • MOCA 3,3'-dichloro-4,4'-diaminodiphenylmethane
  • MOCA 3,3'-dichloro-4,4'-diaminodipheny
  • MBOCA 3,5-diamino-4-chloro-isobutylbenzoate.
  • Components suitable for chain extension according to the invention are organic diamines or polyamines.
  • component iii) compounds which, in addition to a primary amino group, also have secondary amino groups or, in addition to an amino group (primary or secondary), also OH groups, can be used.
  • 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 having an isocyanate-reactive group such as methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, morpholine, piperidine, or suitable substituted derivatives thereof, amide amines from diprimary amines and monocarboxylic acids, monoketim of diprimary amines, primary / tertiary amines, such as ⁇ , ⁇ -dimethylaminopropylamine. Often these have a thixotropic effect due to their high reactivity, so that the rheology is changed so that the mixture has a higher viscosity on the substrate.
  • non-aminic chain extenders which are often used are, for example, 2,2'-thiodiethanol, 1,2-propanediol, 1,3-propanediol, glycerol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol.
  • A) and B) and optionally i) have low levels of free water, residual acids and metal contents.
  • the residual water content of B) is preferably ⁇ 1% by weight, more preferably ⁇ 0.7% by weight (based on B)).
  • the residual acid content of B) is preferably ⁇ 1% by weight, more preferably ⁇ 0.7% by weight (based on B).
  • the residual metal contents caused, for example, by residues of catalyst constituents used in the preparation of the starting materials should preferably be less than 1000 ppm and more preferably less than 500 ppm, based on A) or B).
  • the ratio of isocyanate-reactive groups to isocyanate groups in the mixture is preferably between 1: 3 to 3: 1, more preferably between 1: 1.5 to 1.5: 1, most preferably between 1: 1, 3 to 1, 3: 1 and more preferably between 1: 1, 02 to 1: 0.95.
  • the components A) and B), and optionally i), ii) and iii) can be reacted with one another in one step, the so-called one-shot process.
  • the prepolymer process can also be used in the reaction of A) with B).
  • a part A) is reacted with B) to form a prepolymer and later reacted further with further component B).
  • the prepolymer thus prepared can be further processed directly or first filled and stored and later used as component A).
  • the mixture may additionally contain auxiliaries and additives.
  • auxiliaries and additives are crosslinkers, thickeners, solvents, thixotropic agents, stabilizers, antioxidants, light stabilizers, emulsifiers, surfactants, adhesives, plasticizers, water repellents, pigments, fillers rheology improvers, plasticizers, degassing and defoaming agents, wetting additives and catalysts and fillers.
  • Typical catalysts are organometallic compounds such as tin salts or amines or amidines. Very particular preference is given to using organotin compounds as catalysts.
  • the mixture furthermore comprises C) a solvent which has a vapor pressure at 20 ° C. of> 0.1 and ⁇ 200 mbar and D) a wetting additive.
  • the mixture also comprises a filler E).
  • aqueous and organic solvents can be used, more preferably organic solvents are used.
  • a solvent can be used which has a vapor pressure at 20 ° C. of> 0.1 mbar and ⁇ 200 mbar, preferably> 0.2 mbar and ⁇ 150 mbar and particularly preferably> 0.3 mbar and ⁇ 120 mbar. It is particularly advantageous that the films of the invention can be produced on a roller coating system.
  • the wetting additive D in an amount of 0.05 to 1.0 wt .-%, based on the total weight of the mixture, in the mixture.
  • Typical wetting additives are available, for example, from Altana (Byk additives such as: polyester-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane or acrylate copolymers, and, for example, CeFo fluorotelomers).
  • the mixture comprises fillers E) with a high dielectric constant.
  • these are ceramic fillers, in particular barium titanate, strontium titanate, copper titanate, calcium titanate, titanium dioxide and piezoelectric ceramics such as quartz or lead zirconium titanate, and mixed oxides of all compounds mentioned above and organic fillers, especially those having a high electrical polarizability, for example phthalocyanines, poly-3-hexylthiophene , By adding these fillers, the dielectric constant of the polyurethane film can be increased.
  • a higher dielectric constant can also be achieved by introducing electrically conductive fillers below the percolation threshold.
  • electrically conductive fillers below the percolation threshold.
  • examples of such materials are, besides metals such as silver, aluminum and copper, carbon black, graphite, graphene, fibers, single 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.
  • carbon black types with a particularly high BET surface area are preferred.
  • additives for increasing the dielectric constant and / or the electrical breakdown field strength can also be added after the filming of polyurethanes. This can be done, for example, by generating one or more further layers or by penetration of the polyurethane film, for example, by diffusion.
  • the polyurethane film is separated from the carrier.
  • the steps I) to IV) are repeated continuously.
  • the polyurethane film may have a layer thickness of 0.1 ⁇ to 1000 ⁇ , preferably from 1 ⁇ to 500 ⁇ , more preferably from 5 ⁇ to 200 ⁇ and most preferably from 10 ⁇ to 100 ⁇ .
  • the application of the mixture of step I) to the support in step II) can be carried out, for example, by knife coating, brushing, casting, spinning, spraying, extrusion in a roll-to-roll process.
  • the mixture is applied to the carrier with a squeegee (such as a squeegee, quark, or the like), rollers (such as anilox rollers, gravure rollers, burnishing rollers, or the like) or a nozzle.
  • the nozzle may be part of a nozzle application. It is also possible to operate several commissioned works simultaneously or in succession. Several layers can be applied simultaneously with a commissioned work.
  • a nozzle is used, and more preferably a residence time optimized and / or recirculation-free nozzle.
  • the distance of the nozzle to the carrier is less than three times the thickness of the wet film, preferably less than twice the thickness of the wet film, and more preferably less than one and a half times the thickness of the wet film. If, for example, 150 ⁇ m of wet film is coated (if the wet film contains 20% by weight of solvent, this corresponds to 120 ⁇ m of cured film), then the distance between the nozzle and the substrate should be selected to be less than 300 ⁇ m. If the distance of the nozzle to the support is chosen as described above, a roller coater can be used to make the films.
  • a wet film with a thickness of 10 to 300 ⁇ m, preferably of 15 to 150 ⁇ m, more preferably of 20 to 120 ⁇ m, and very particularly preferably of 20 to 80 ⁇ m can be produced in step II).
  • the wet film is cured in step III) by being passed through a first drying section, which preferably has a temperature> 40 ° C and ⁇ 120 ° C, more preferably> 60 ° C and ⁇ 110 ° C and especially preferably> 60 ° C and ⁇ 100 ° C.
  • the wet film can also be passed through a second drying section after the first drying section, which preferably has a temperature> 60 ° C and ⁇ 130 ° C, more preferably> 80 ° C and ⁇ 120 ° C and particularly preferably> 90 ° C and ⁇ 120 ° C has.
  • the wet film can also be passed through a third drying section which preferably has a temperature of> 110 ° C. and ⁇ 180 ° C., more preferably> 110 ° C. and ⁇ 150 ° C. and particularly preferably> 110 ° C. ⁇ 140 ° C has.
  • Drying can be carried out in suspension or in roller dryers, such as those offered by, for example, Krönert, Coatema, Drytec or Polytype on the market.
  • the typical rate at which the wet film on the support passes through the drying section (s) is> 0.5 m / min and ⁇ 600 m / min, more preferably> 0.5 m / min and ⁇ 500 m / min and more preferably> 0.5 m / min and ⁇ 100 m / min.
  • the dry section length and the supply air of the dry sections are adapted to the speed.
  • the total residence time of the wet film in the dry section or sections is> 10 seconds and ⁇ 60 minutes, preferably> 30 seconds and ⁇ 40 minutes, more preferably> 40 seconds and ⁇ 30 minutes, and most preferably> 40 seconds and ⁇ 10 mins.
  • the dielectric polyurethane film according to the invention can be provided with further functional layers, for example conductive layers, barrier layers against solvents and gases, and / or adhesive layers. This can be done on one side or on both sides, in one layer or in several layers one above the other, by complete or by surface partial coating.
  • further functional layers for example conductive layers, barrier layers against solvents and gases, and / or adhesive layers. This can be done on one side or on both sides, in one layer or in several layers one above the other, by complete or by surface partial coating.
  • Glass, release paper, films and plastics from which the produced polyurethane dielectric film can be easily separated are particularly suitable as carriers for the production of a polymer film from the reaction mixture.
  • Particularly preferred paper or films are used. Paper can be coated on one or both sides, for example, with silicone or plastics be.
  • the coating and / or the film can be made, for example, of plastics such as polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, teflon, polystyrene, polybutadiene, polyurethane, acrylester-styrene-acrylonitrile, acrylonitrile / butadiene / acrylate, acrylonitrile-butadiene Styrene, acrylonitrile / chlorinated polyethylene / styrene, acrylonitrile / methyl methacrylate, butadiene rubber, butyl rubber, casein plastics, artificial horn, cellulose acetate, cellulose hydrate, cellulose nitrate, chloroprene rubber, chitin, chitosan, cyclo-olefin copolymers, epoxy resin, ethylene oxide Ethyl acrylate copolymer, ethylene
  • these plastics can also be used directly as support materials and / or additionally provided with further internal or external release agents or layers.
  • the layers may have barrier functions or may also contain conductive structures which may optionally be transferred to the polyurethane dielectric film.
  • the plastics may be axially or biaxially oriented or stretched and may be pretreated by pressure or corona.
  • the films can also be reinforced. Typical reinforcements are fabrics such as textile or glass fibers.
  • a carrier made of glass, plastic or paper and preferably made of silicone or plastic-coated paper can be used.
  • the film or paper can be peeled off directly after coating and reused.
  • the film may be circulated and the dielectric polyurethane film transferred directly to a new carrier during stripping.
  • the carrier is provided with a structure. This is also called an imprint.
  • the embossing is such that the structure on the dielectric Polyurethane film transfers in such a way that the embossing is formed only in the surface of the dielectric polyurethane film.
  • the embossing is smooth when the film is stretched.
  • the embossment is made such that an electrode layer on the film is stretched when stretched without significantly stretching that layer itself.
  • the embossment is preferably embossed in a roll-to-roll process in the carrier. For example, hot or coagulated hot through a roll into a thermoplastic is applied here. Typical embossings are described for example in EP 1 919 071.
  • a further subject of the present invention is a dielectric polyurethane film obtainable by the process according to the invention.
  • the polyurethane dielectric film of the present invention is also useful for the production of multi-layered electroactive polymer film systems known in the art comprising layers of dielectric polyurethane and, for example, conductive electrode layer. Such systems are described, for example, in WO-A 2014/001272 or WO-A 2014/006005.
  • a method for producing an electromechanical transducer in which a dielectric polyurethane film is produced in a first step by a method according to the invention and in a second step an electrode is arranged on opposite sides of the dielectric polyurethane film.
  • the electrodes can be applied, for example, via a printing process such as ink-jet, flexographic printing, screen printing or via a doctor blade, a nozzle or roller and via a metallization in a vacuum.
  • Typical materials are carbon based or based on metals such as silver, copper, aluminum, gold, nickel, zinc or other conductive metals as well as materials.
  • the metal can be applied as a salt or as a solution, as a dispersion or emulsion and also as a precursor.
  • the electrode layer on the layers is preferably applied so that it can be contacted from the sides and not over the dielectric film edge, otherwise there will be breakdowns. It is usual to allow a safety margin between the electrode and the dielectric so that the electrode area is smaller than the dielectric area.
  • the electrode is structured such that a conductor track is led out for electrical contacting.
  • the converter can be advantageously used in a variety of configurations for the production of sensors, actuators and / or generators.
  • Another object of the present invention is therefore an electronic and / or electrical device, in particular a module, automaton, instrument or a component comprising an electromechanical transducer according to the invention.
  • the present invention relates to the use of an electromechanical transducer according to the invention in an electronic and / or electrical device, in particular in an actuator, sensor or generator.
  • the invention in a variety of different applications in the electro-mechanical and electro-acoustic field, in particular in the field of energy 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 can be realized.
  • Typical examples include pressure sensors, electroacoustic transducers, microphones, loudspeakers, vibration transducers, light deflectors, diaphragms, optical fiber modulators, pyroelectric detectors, capacitors and control systems, and "intelligent" floors, as well as systems for converting mechanical energy, particularly rotating or oscillating motions electrical power.
  • NCO contents were determined volumetrically in accordance with DIN EN ISO 11909, unless expressly stated otherwise. Hydroxyl numbers (OHN in mg KOH / g substance) were determined according to DIN 53240 (December 1971).
  • the indicated viscosities were determined by means of rotational viscometry according to DIN 53019 at 23 ° C. using a rotational viscometer from Anton Paar Germany GmbH, Germany, Helmuth-Hirth-Str. 6, 73760 Ostfildern.
  • the determination of the stress relaxation was also carried out on the tractor Zwicki; the instrumentation corresponds to the attempt to determine the permanent strain.
  • the sample used was a strip-shaped sample of the dimension 60 ⁇ 10 mm 2 , which was clamped with a clamp spacing of 50 mm. After a very fast deformation to 55 mm, this deformation was kept constant for a period of 30 minutes and during this time the force curve was determined.
  • the stress relaxation after 30 minutes is the percentage decrease in stress, relative to the initial value immediately after deformation to 55 mm.
  • the determination of the glass transition temperature was carried out by means of a dynamic mechanical analysis (DMS 6100 from SEIKO, German representation: THASS GmbH, Pfingstweide 21, 61169 Friedberg) under forced oscillations according to DIN 51513.
  • the glass transition temperature is the maximum of the loss modulus curve.
  • the electrical resistance was determined by means of a laboratory setup from Keithley Instruments (Keithley Instruments GmbH, Landsberger Strasse 65, D-82110 Germering Germany) Model No .: 6517 A and 8009 according to ASTM D 257, a method for determining the insulation resistance of materials , Fracture field strength was determined according to ASTM D 149-97a using a model HypotMAX high voltage power source supplied by Associated Research Inc, 13860 W Laurel Drive, Lake Forest, IL 600045-4546, USA, and a self-constructed sample holder. The sample holder contacts the homogeneous-thickness polymer samples with little mechanical preload and prevents the operator from coming in contact with the stress.
  • the non-prestressed polymer film is statically loaded in this structure with increasing voltage until an electrical breakdown takes place through the film.
  • the result of measurement is the voltage reached at breakthrough, based on the thickness of the polymer film in [V / ⁇ ]. There are 5 measurements per slide and the mean value is given. Substances used and abbreviations:
  • Phthalic anhydride molecular weight 2000 g / mol, ester group content 7.6 mol / kg and aromatic content 62.7 wt .-%, Bayer MaterialScience AG, Leverkusen, DE
  • Phthalic anhydride My-Chem GmbH & Co KG
  • Pripol 1009 hydrogenated dimer fatty acid, Croda Europe Ltd. Titanium tetrabutoxide: Sigma-Aldrich
  • Hostaphan RN 2SLK release film from Mitsubishi based on polyethylene terephthalate with silicone coating. A 300 mm wide film was used. polyester production
  • Table 1 shows the starting materials used for the preparation of the polyester polyols 1 to 4, the ester group contents and aromatic proportions of the resulting polyester polyols.
  • Aromatic content [% by weight] 33.3 29.4 22.6 0
  • reaction temperature after addition at about 130 ° to 140 ° C. in each case being raised to 230 ° C. and at this temperature, the reaction continued until no more water of reaction distilled off, which was the case after a running time of about 20 hours.
  • the reaction was completed by adding 40 mg of stannous chloride dihydrate, by applying Vacuum the pressure gradually over about 2 hrs. lowered to last 15 mbar and the reaction continued at 200 ° C for a further 50 hours
  • Viscosity 1500 mPas (75 ° C)
  • Viscosity 1910 mPas (75 ° C)
  • Viscosity 1050 mPas (75 ° C)
  • Table 2 shows the properties of the polyurethane films produced from the individual polyesters determined by the abovementioned measuring methods. It was found that the films according to the invention offer distinct advantages over those of the prior art.
  • the combination of the deep glass point with a good electrical resistance and a high breakdown field strength is particularly advantageous.
  • the Films of the invention can be used in particular for the production of electromechanical converters with particularly good efficiencies, which can also be used at the usual ambient temperatures, especially in winter.
  • the polyurethane films have good mechanical strength and high elasticity.
  • Aromatic content 33.3 29.4 22.6 0 62.7

Abstract

L'invention concerne un procédé de fabrication d'un film de polyuréthane diélectrique à partir d'un mélange comprenant : A) un composé contenant des groupes isocyanate ayant une teneur en groupes isocyanate comprise entre ≥ 10 et ≤ 50 % en poids et une fonctionnalité moyenne en nombre des groupes isocyanate comprise entre ≥ 2,6 et ≤ 4; et B) un polyester-polyol ayant un indice OH compris entre ≥ 27 et ≤ 120 mg de KOH/g, déterminé selon la norme DIN 53240, caractérisé en ce qu'il présente une teneur en groupes ester compris entre ≥ 1 et ≤ 7 mol/kg et une proportion en structures aromatiques de ≤ 50 % en poids. De plus, l'invention concerne le film de polyuréthane diélectrique pouvant être obtenu par ce procédé. L'invention concerne par ailleurs un procédé de fabrication d'un transformateur électrochimique et un transformateur électrochimique pouvant être obtenu par ledit procédé.
EP15719757.5A 2014-05-12 2015-05-08 Films diélectriques eap à bas point de transition vitreuse et à base de polyester-polyols Withdrawn EP3143061A1 (fr)

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US7034432B1 (en) 1997-02-07 2006-04-25 Sri International Electroactive polymer generators
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MX2013001484A (es) 2010-08-09 2013-03-12 Bayer Ip Gmbh Conversor electromecanico que incluye un polimero de poliuretano con unidades de poliester y/o de policarbonato.
EP2509126A1 (fr) 2011-04-07 2012-10-10 Bayer Material Science AG Utilisation de polyuréthanes thermoplastiques pour la production d'énergie électrique à partir d'énergie des vagues
CN104379643A (zh) 2012-06-27 2015-02-25 拜耳材料科技股份有限公司 介电聚氨酯薄膜
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