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    • 专利摘要:
    The present invention relates to an ionic interpenetrating polymer network comprising at least one elastomer and an ionic supramolecular structure comprising the reaction product of at least two chemical compounds wherein each of said compounds has at least two functional groups and wherein said compounds are able to undergo Lewis acid-base reactions. The interpenetrating polymer network may be used as dielectric electroactive polymers (DEAPs) having a high dielectric permittivity.
    公开号:DK201570405A1
    申请号:DK201570405
    申请日:2015-06-29
    公开日:2015-07-13
    发明作者:Søren Hvilsted；Anne Ladegaard Skov；Lídia Gonzalez Búrdalo
    申请人:Univ Danmarks Tekniske；
    IPC主号:
    专利说明:

    TITLE: ©F INVENTION
    Dielectric eiectroactive polymers comprising an ionic supramoiecular structure FIELD OF THE INVENTION
    The present invention relates to an sonic interpenetrating polymer network comprising at least one elastomer anp -an ionic supramoiecular structure, said Ionic supramoiecular structure comprising the reaction product of at lea#two: chemical compounds wherein each of said compounds had: at least two functional groups: and wherein said compounds are able 'to undergo Lewis acid-base reactions.' the invention relates ip particular to an ionic interpenetrating: polymer network compnsmg an elastomeric matrix: Incorporating,: an loslic supramoiecular structure for use in electroactive peiymers (EAPs) having a high dieiectrie permittivity.
    BACKGROUND OF THE INVENTION
    Eiecfcroactlye polymers (ears) are polymers that exhibit a change In size or shape when stimulated by an electric held or reversibly generate energy when motibhedyTypicatiy·,. an EAR is able to undergo; a majorReformation while sustaining large forces.
    The development of elastomeric materials with high dielectric permittivity has attracted increased interest over the last years due to their use in e g, dielectric eiectroactive polymers (DEAF's).
    Dielectric eiectroactive polymers are materials in which actuation Is caused by electrostatic forces on an elastomeric him sandwiched between two electrodes which squeeze the elastomer upon application of ah electric held. When an electric voltage is applied, an electrostatic pressure is exerted on the film, reducing Its thickness end expending its area due to the applied electric field. Examples of EAR'S are dielectric elastomers. DieSectric eiectroactive polymers are used e,g. as actuators as so-called 'mrtifsciai muscles'’ and as generators In energy-haKestlhg.
    However, a drawback of DEAP’s for a wide, range of applications is the high operation voltage, which tends to be several thousand volts when actuation streins higherthan £-3% are wanted. The operation voltage can be reduced by reducing the thlcimess of the elastomer film, decreasing tins mechanical stiffness of the materialer increasing the 'relative .dielectric permittivity thereof, A reduction of-the thickness to less than 5pm seems, however,: not possible for mass-pfodlKed films (Matysek et a!... in Proc. SPIE-EAPAD, San Diego, p. 76420D (2010:);}- A reduction of the:: stiffness has been: shewn in a tri-block copolymer using block specific oil as piasticteer (Shankar sf aL, Nacromoi- Riapld·Comrb';(2007)}. An increase in relative dieiectrio permittivity (e!') of a material can lead to high electrical energy: density with lowered operas voltages. Permittivity enhancement and stiffness reduction was shown by blending a conductsrsg pOiy(3-bexyitbiapbene) into a commefeialiy available polydimethylsiidjcane (PBHS) elastomer (Carpi et ai., Adv, Fuoct Mater, id, 235-241 (2008}}- Another approach to enhance dielectric permittivity is attaching or grafting smali molecules with high permanent dipoles into an eiagtgmer matrix (Kussmaul ef ai., Adv.
    Punkt. Hater., 2011.. 2.1, 4589-4594).
    However, the prior art dieiectric electroactive polymers exhibit a reiative dielectric permittivity (c.} of oniy about 5-20 at 0.1 Hz and it is envisaged that the energy density of DEAP's should be substantially higher in order to he commercialiy interesting. Thus the dieiectric permittivity seems to be an important tuning parameter for obtaining DEAPis with a high energy density. OBJECT ©F THE invention:
    It is ah object of embodiments of the invention to provide an ionic intetpenefrating poiymer network haying asubstantiaily enhanced relative dielectric permittivity for use as Dieiectric EiectroActive Poiymer (DEAR): compared: to prior art DEAP% While showing: oniy little dielectric ioss.
    SUMMARY OF THE INVENTION
    It has been found by the present inyentor(s) that by providing an ionic snpramoleculaf structure comprising the reaction product of at least two chemical compounds wherein each Of said compounds has at least: two functional groups and wherein said compounds are able to undergo Lewis acid-base reactions and incorporate said supramolebular structure into an eiastomier, an ionic interpenetrating poiymer network may he obtained having greatly improved feiatiye dieteetric permittivity.
    So, In a first aspect the present invention relates to an ionic interpenetratingpoiymer network comprising: i) At least one elastomer selected from the group consisting of silicone rubber, fluorosllicone rubber, poiy {met h)aery!ate rubber, chk>roprene rubber, polybutadiene rubber, poly(ethyiene oxide) rubber, poly(propylene oxide) rubber, polyurethane n.ibber and mixtures thereof; and iQ An ionic suprarnoiecuiar structure comprising the reaction product of at least two chemical eampounds wherein each of said compounds has at ieast two functional groups and wherein said cornpounds are able to undergo Lewis add-base reactions. in a second aspect the present Invention relates to a method for preparing the ionic interpenetrating; polymer network according to the loveotion comprising the steps of; i) mixing said at least two chemical compounds, optionally by the addition of heat, to obtain said Ionic suprameieedlar structure; and it) Mixing the ionic supramoiecuiar structure obtained in step I),
    Optionally by the addition of heat, with at least one elastomer. in a third aspect the present Invention relates to a method for preparing the ionic interpenetrating polymer network according to the invention comprising the Step of mixing said at least two chemical compounds with at least one elastomer, optionally by the addition of heat.
    Ida fourth aspect the present Invention relates; to a use of the sonic interpenetrating polymer network according to the invention as dielectric electroactive polymer (DEAF).
    LgiSENOS TO THE: FIGURE
    Fig, 1 shows the relative dielectric permittivity as a function of frequency for the ionic interpenetrating polymer nebeprks according to examples 2.2a and 2.2b, respectlveiy, and
    Fig. 2 shows the dielectric loss as a funtTlbn of frequency for the some ionic Interpenetrating polymer networks.
    DETAILED DISCLOSURE ØF THE INVENTION
    Definitions
    In the present context the term "ionic supramoieculat structure" refers1 to moieeuies: formed by bonding smaller molecules or molecular subunits together via ionic Ponding.
    In the present context the term "ionic interpenetrating polymer network" refers to com positions comprising kt feast one polymer and ah ionic supra molecular structure as defined above at least partially interlaced on a polymer scale.
    In the present context the term "elastomer" refers to compositions of matter that: have a glass transition temperature;, jg, aj which there is an increase in the thermal expansion coefficient, and includes both amorphous polymer elastomers and thermoplastic elastomers (thermoplastics}. An elastomer exhibits an elasticity deriving from the ability of the polymer chains of the elastomer to reconfigure themselves to distribute an applied stress. A commercially available elastomer may, in addition to the polymer Itself, include fillers and additives, Sondimlting examples of fillers are e.g, reinforcing fillers such as silica and carbon black as well as filiem with e^g, color enhancement such as titanium dioxide.
    In the present context the term: "backbone'' of the at least two chemical compounds means the continuous chain: of the molecule: Ifr question.
    In the present context the term "poiy(ethyiene .glycol)'';, abbreviated "PEG", refers to a compound of the formula HO-CHs"(CHj"0“CHi)(v-:CHrOH, wherein n Is from 2 to ISO. PEG'S are often labelled according to their molecular weight, and thus e.g. PEGdOS refers to a poly{ethyiene glycol} having a molecular 'weight Of approximately 400 daltons.
    In the present context the term "poly(propylene glycol)", abbreylated "PPG”, refers to a compound of the 'formula· HO<H(CB3)-CHrG-(CHr€H(CHs}'O}^HrGH(CH3)~0-'CHr-Cti(CH3)-OH> wherein n is from 2 to ISO.
    In the present; context the term "poiysiioxane" refers to a compound Of the form RjSiO, wherein R is a hydrocarbon group.
    In the present context the term "polydimethylsiioXanef, abbreviated "PDHS", refers te a compound of the formula CH^SkCHs^Ql^SiCCrfi)^ where n Is the number of repeating units,
    In the present .context the term “poiyuretiane%:;:iafei)revlaté(|'>W:!' refers to a compound having repeat units of the formula “[β·0"€(0}“Μ(Η)“β,··Ν(Η}'-€(03 ·0'ν]ή··ί wherein R and R' are alkyl or aryf groups and n is the number of repeating units. ,In:ihe present context the term "aikyr means a linear, cyclic or branched hydrocarbon group having 1 to 24 carbon atoms, such as methyl, ethyl, propyl, /so-propyi, cyciopropyl, butyl, /so··butyl, /err butyl, cycfohutyl, pentyl, eyciopentyi, hexyl, and cyciohexyi.
    The term''aikyiene* is used in the following to specify moieties derived from alkanes in which two ft atoms have been removed to larm a cliradical species. The simpiest aikylene Is methylene -CHr, and other afkyienes include ethylene -€R2-CHS··, propylene and butyiene -QH»-. The term "'afliyiene” includes branched, linear and cyclic alkyienes, with linear aikyienes being most preferred.
    In the present context the term "alkenyl" means a iineah cyclic or branched hydrocarbon groups having 2 to 24 carbon atoms, and comprising fat least} one unsaturated bond. Examples ol aikenyl groups are vinyl, ailyi, butenyi, pentenyi, hexenyl, heptenyl, octenyl, nonenyl and decaenyi. Preferred examples of aikenyl are vinyl, allyi, butenyi, especially ally!.
    The term *alkenyien#':fe used in the following to specify/moieties· derived' from alkenes in which two H atoms have beep removed to form a d|pdica! species,: Examples Include ethehyiene “CHy==CH2- and propenylene moieties, The term· "aikenylene" Includes branched:, ifoeac and cyclic alkenylene, with linear alkenylen© being:most preferred.
    The term "halogen" includes frupro, chloro, bromg, and iodp.
    In the present context the term; "ary!'' refers to an unsaturated cyeiic system. Ary! groups may cdrrspnse From 4-12 atoms, suitably from &-8:atoms, most suitably 6 attains, "Aryl" 1$ preferably phenyl (--¾¾).
    In the present context, the term "aromatic" is intended to mean a carbocyclic ring system, such as phenyl.· naphthyl, 1,2,3,4-tetrahydronaphthyi, antbfacy!, phenahthracyi, pyrenyf, benzopyrenyi, fiuorenyi and xanthenyl.
    In the present context the term "beter oaromatic* is intended to mean an aromatic carbocydic ring system where one or more of the carbon atoms have been replaced with heteroatoms, e.g. nitrogen (“N- or -NH-), sulphur, and/or oxygen atoms. Examples of such heteroaryl groups are oxazoiyl, isoxazoiyi, fchiazoiy!, isetbiazoiyi, pyrroiyl, imidazoiyi, pyrazolyi, pyridinyi, pyrimidinyi, pyrazinyi, pyridazinyf, triazinyi, coumaryl, furanyi, thienyl, quirsoiyi, benzøthiazølyl, benzøtriazøiyl, befizodiazolyi,.^ørixooxoi^iyi,· phthaiazinyi, phthalahyi, triazolyb tatt-azolyi: isoqyinoiyb acndsnyi, earbazolyi, dihenzazepinyi, Indolyl, benzdpymzoiyf, phenoxazdnyi. Pdteicuiatiy interesting heteroaryl·groupS;areΓben^:lmiddzø:iyi/::0X:8^Qίyiy itexazolyiythiazoiyi^ feothiazdlyl, pyrroiyi, imldazolyl, pyrazolyl,. pyridinyl, pyrimidinyi, pyrazinyi, pyridazioyi, furyi, thienyl, qninoiyl, triazoiyI, tetrazoIyI, iscquinolyl, indoiyi in particular benzimidbzolyi, pyrroiyi, imidazoiyl, pyridinyl^pyrimidfny!,. furyi, thienyl, quinoiyi, tetrazolyl, and isoquinolyl.
    In· the present context the term “dendrimer" denotes repetitively branched molecules. A dendrimer is typically symmetric around a core and often adapts a spherical three-dimensional morphology. Examples of dendrimers include poly (ethylene I mine) dendrimers and pdly(propyiene imine) dendrimersv Dendrimers of dliferent generations cap he prepared. The generation number,. :such as Gl, G2, and 63, respectsyely, indicates the number gf different branch points such that generation GO is a simple star* generation Gl will be a star with the ends of the chains acting as branch points and so forth.
    In the present content the term V" is synonomous with the term *$.* and stands for relative dielectric permittivity, bé, the ratio of the amount of electrical energy stored in a material by an applied voltage, relative to that stored in a vacuum. The term''h’eiatfve diefectrtc permittivity" is used in the present conteid; interehangeahiy with the term “relative permittivity"·
    Specific efribodhnønts af thø immtiort'
    In an embodiment of the invention the elastomer is at least one silicone rubber selected from the group consisting of RTV (Room Temperature Vulcanizing) silicone mbbefSj HTV (High Temperature Vulcanizing) silicone rubbers and LSR (tiguid Silicone Rubbers).
    In an embodiment of the Invention the elastomer is a silicone rubber selected from the group consisting of poiysiioxanes, such as a poiyalkyisi ioxane, preferably polydimethyls!!oxane (POMS). A preferred silicone rubber is an RTV silicone such as silica-reinforced ROMS (PoiyDiMethyiSiidXane)- An example of a commercially available silfcateeihfbrced PDMS is Sylgard r-184 frorn Dow Coming or Eiastosii RT62S from Wacker Chemie AG.
    In an embodiment of the invention the ionic supramoiecuiar structure comprises the reaction product of at least two chemical compounds, of which at least one of said compounds comprises a backbone selected from the group consisting of poly (ethylene) glycol, poiyf propylene) glycol, polyslloxane, poiyalkyislloxane, poiyurethane and mixtures thereof. in an embodiment of the invention the backbone is selected from the group consisting of poly(ethyiene) giycol (PEG), poly (propylene) glycol (PPG), polydimethyisiloxane and mixtures thereof. Thus PEG and PPG backbones provide good flexibility and iow Tg's which is advantageous in terms potentially good compatibility,
    Ih: an embodiment of the mventign the ionic suprsmoleculpr structure comprises the reaction product of at least fcwo: chemical com pounds, wherein at least one of these comprises at least two amina) functional groups and: is selected from the group consisting of Wherein R* is selected from: the group consisting of linear and branched Chalky! and :¾. j^alkenyt:and cyc):ic::C3. <^iky! and C^alkenyi, optionally substituted by ope or more substituents selected from: the group consisting of halogen, amino, hitro, hydroxy!, and GFS; rii- or thamino-Gio^aikylamine, wherein the alkyl moiety thereof IS lineårer branched €,, aralkyl or cyclic C^alkyl) optionally substituted by one or more substituents selected from the group consisting of halogen, amino, nitro, hydroxyl, and $F$;: di- or friamlno-Cy, s^alkeoylanme, wherein the:alkenyl moiety thereof is linear or branched Ca^alkenyl of cyclic Cj,;Maikepy!, opfionaliy substituted: by one; or more substituents selected: from the group consisting of halogen, amino, nitro, hydroxyl, and Ct, : di-, tri- or tetraamino-substituted aromatic or heteroaromatic compounds, which compounds are optionally substituted by one or more substituents selected from the group consisting of halogen, amino, nitro, hydroxyl, and 0¾ polyfethylene imine) dendrlmers; polypropylene Imine) dendrimers’ polyfethyiene glycol) diamine; poly(propylene glycol) diamine; polyfethylene giycoi)/poiy(propyiene glycol) diamine; poly(ethyiene giycol) triamine; polyCpropylene giycol): tpamina; poiyfethylene glycol )/ppiy (propylene giyeoi) triamine; and amind-Ci-saikyl terminated polyaikylsiioxane.
    In an embodiment of the invention said chemical compound comprising at least two amine functional groups is selected from the; group consisting of i;3-diaminopropanef 4,4-diaminohutane, I,S-diamihopenfa:he, hexamethylene diamine (HMPA), l,10~decanediamine; 3,4,6-'tnaminopyhmidine (TAP), (tris-t-aminoethyi) amine (ΤΆΕΑ), 3;3-diaminobenzidine, (DAS), poiyCpropyfene imine) dendrirner (G:f:),:poiy(pfopy!ene imlhe) dendrirner (G2), poiyfpropyiene imine) dendrimer (03), polypropylene:giycoi) diandne, poiyCethytene giycol) diamine, polyethylene giycol)/poiy(propyle.ne giycoi) diamine, polypropylene glyCoi) triamine, poiy(etbyiene glycol) triamine, poiy(ethyiene giyco!)/po!y (propylene glycol) triamine, aminopropyi terminated polydimethyisiloxahe (^DM:S) and ebpoSymers of aftdnoaikyfmethyisiiDxane and dirnethyisiioxane., such as copolymers of amihodrdpyidiei'hySsiloxane and dimethylsifoxane. Commercially available: pbiyefcherammes ;1notude)ar»lp.^of'the:deff«m.lnes# D; Series (DAOQ, D2000;), Jeffamines® ED Series such as ED2DQ3, Jeffamines® EDR Series (EOR-148, EDR-176), jeffamlhes® triamines (T series) (T403, 131300, T5Q00) from Huntsman, and commercially available ammoaikylterminated pslyaikyisiloxafies, such as arriinopropyiterrninated poiydi methyls! ioxanes, include DMS At 5 and DMS A31. from Geiest, Inc.. The polypropylene [mine) dendrimer CGI), polyCpropyiene imihe) dendrimer (G2)r po!y(prppyiene imlne) dendrimer (G3) may be obtained commeraaiiy from SYMO-dhem The Netharlands- in an embodiment of the Invention the ionic supramdigcular structure comprises the reaction product of least two chemical compounds, wherein at least one of these comprises at : least two carboxy, sulfonic or phosphonlc acid functions! groups or anhydrides thereof and is selected from the: group consisting of dl-, tri- or tetra-carboxy-, di-, tri- or tetra-suilonic or di-f tri- or tetrapbosphonic acid-substituted linear or branched, saturated or unsatufated aliphatic, aromatic or heteroardmahc compounds optipnaliy substituted by one or more substituents selected from the group consisting of halogen, amino, nltro, hydroxy!, and GFS; aii<Ylenediaminetetracarboyy!ic acid; dlalkylenefriamipepenfacarboYylic acid, po!y(ethylene giycdijbisearboxymethyl ether, polypropylene giycoi)biscarboxymethyi ether, α,ω-disuimnate-funetignelized ppiyiethylene glycol) and QiO-disyifonafe-functionaifeed poly(propylene glycol),
    In an embodiment of the Invention said chemical compound comprising at least two: carboxy, sulfonic or phosphonlc acid functionai groups is selected from the group consisting of citric acid (CA), tricarbailyiic acid (T C AA), trimesie acid (TMA), ethylenedsaminetetraacetic acid (£DTA), diethylenetriaminepentaacetilc add CDÉTFA), ppfytethylene g!ycoi)biscarboxyrnefhyi ether, poiy(prøpyierte giycoijhiscarboxyniethyd ether, o.ro-disuifonate-functsoHallzed poiy(ethy!ene glycof), a,u>--disu!1onate-iunctionalized poiytpropyiene giycoS) and o,u>-d i ca r boxy I ate - fu η ct i one Sized di methyl siioxane.
    Further non-limiting examples of the above chemicahcdmpound comprising at least two carboxy or sulfonic acid functionai groups include a Chemical compound selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutatlc acid, adipic aCid, pimdic add, suberic acid, ^elfp-'8dd,.e^adc;'a04»'-;unddcanediofc acid, dodecanadiode acid, tridecahedioic add, tetradecanddloie acid, bexadecanedioic add, fumaric acid, maleic acid, maleic anhydride, phthaiic acid, phthaiic anhydride, Ssophthalic acid, and terepthalic add, and 1,4·, 2,3··, and 2,6-haphthaienedicarboxyiic acid in an embodiment accørding tbtheldyénhbh the iodic,idterpenefratShg polymer network further comprises one or more additives, such as fillers or reinforcing substances. in an embodiment of the invention said additive is selected from the group consisting of particles such as Sit)·., TiDn BaTSO*, CaCuyThOia, or resins such as Vinyl Q resins from Gefest Inc. In a preferred embodiment of the invention the additive is SiO». Such additives may be present in a commercially available elastomer or may be added tø the ionic Interpenetrating poiymer network separately. The amount of additive necessary wlii vary widely depending on die ionic interpenetrating polymer network in question but usualiy is in the range 0 -40% by weight, such as 5 -30% by weight, such as 10*25% by weight of the ionic interpenetrating poiymer network. in an embodiment of the invention the ionic interpenetrahug poiymer network has a relative dielectric permittivity p at 0.1 Hz. of at least IMS1, such as at least lx tø2, preferably at least 1x105, such as at least IxtO4, more preferred at ieast 1x10s, such as at least 1χ10δ. Thus it has surprisingly been found that the ionic interpenetrating polymer networks according to the invention provide unexpected properties such as a high dielectric permittivity over a broad range of frequencies combined with a low degree of dieiecfric dissipation. This means that the ionic interpenetrating poiymer networks witbe highly efficient without; any substantia! loss of dielectric energy. Furthermore the ionic interpenetrating poiymer networks according to the invention are contemplated to maintain their elastic moduli and thus their desired mechanical properties.
    In an embodiment of the invention the preparation of the ionic supramoiecuiar structure is performed by mixing of stoichiometric amounts of said at least two chemical compounds.
    In an embodiment of the invention the preparation of the ionic supramoiecuiar structure is performed by mixing a molar surplus of either one of said at least two chemical compounds, such as wherein one of said at least two chemical compounds is present in a molar ratio of at least 1.25:1 over the at least one further compound, such as a ratio of about 1.5:1, such as a ratio of about 2:1,
    In an erabbdiihehf of the invention the preparation of the ionic supramoiecuiar structure is performed in the absence Of a solvent. Thus preparation of the ionic supramoiecuiar structure may be performed by simple: mixing of said at feast two chemicai compounds beat with or without heating. The degree of heating needed, If any, depends on the specific chemicai compounds used.
    In an embodiment of the invention the preparation of the ionic interpenetrating polymer network is performed as a 'twO"Sté^s"'procéss>;: wherein step one comprises preparation of the ionic supramoiecuiar structure by mixing of said at least two chemicai compounds, followed! by mixing of said ionic supramoiecuiar structure with at least one elastomer, in another embodiment of the invention the preparation of the ionic interpenetrating polymer network is performed as a one-step process comprising the step of mixing said at least two chemical compounds with at least one elastomer. |p an em bodi ment øf the Invention the preparation: of the Sonic interpenetrating polymer network is performed by miking ofamounts o said tonic sopramølecutar structure and said ét least one elastomer in the range .12 9 to 2:1 by weight, such as in the range 1:4 to 1:3, preferably a boot: 1:1 by weight. The preparation of the ionic interpenetrating polymer network is preferably performed by mixing of about egnai amounts by weight of said ionic suprømpieoniar structure and said at: toast one elastomer.
    In an embodiment of the invention the preparation of the ionic interpenetrating polymer network; Is: performed in the absence of a solvent, thus :preparation of the ionic interpenetrating polymer network may be performed by providing the elastomer and adding said at least two chemica! compounds neat whereby the ionic supramoiecular structure Is formed in situ. Subsequent mixing to obtain a homogenous mixture is performed, with or without heating, whereupon the ionlc interpenetrating polymer network is cured; in a marmer known per se, such as by beating to a temperature in the rang · 62-1:30°¾ such as about 70-12.0^0, such as about 70-110:¾ such as about 60-100¾ su't as about 70-90¾ such as about; 80°C for #;;pertod of time depending: on the elastomer used, such as: a period of time of about; 12.-24 hours, such: as about 20 hours:
    In an embodiment of the invention the curing may take place by means of Ub‘ radiation in a manner known per so.
    In an embodiment of the invention the ionic supramoiectilar strs.}cture is covalently grafted to at least, one elastomer. in order to graft the ionic supramolecuiar structure onto an elastomer the ionic supramoiecuSaf structures may be derlvattoed to comprise oiefinic terminated groups, e.g. by converdng some of the primary amino groups of the amines suggested into ally! end groups whereupon, due to said vinyi and aliyl end groups, the elastomer, such as a PDMS chain and the ionic supramoiecuiar structures wii! be abie to be grafted into Si-H groups in a competitive reaction.
    The invention is disclosed in more detail below by means of the following non-limiting examples. EXAMPLE 1
    General description of the preparation Of ionic supramoleeuiar polymers A number of different ionic supramolecuiar polymers having the compositions as listed in Tabie 3 below wore prepared as follows.. Silica (SiO;>) was used as mode! for a silicone elastomer.
    The ionic supramolecpiar structures (entries Λ- 7, 9 and 19- 22. below) were prepared by simple mixing Of stoichiometric amounts of HMDA or TAEA or poly ( propylene irftine) dendrimers (P&J.-S1 and PPI:£S2) and the different dicarboxylic; acids (DiCDDN--PEi3 250 and 600, respectively) without the use of solvent followed by manual stirring. A network formation was directly observable as the formation of these ionic systems was exothermic. Furthermore, a viscosity increase of the mixtures could be observed. In the case of the tonic supramolecuiar structure (entry if) heating was needed sinceDsCOOH-PEG 4756 Is 3 solid. The ionic supramolecuiar structures (entries 12-18) were prepared by simply mixing followed by magnetically stirring of stoichiometric amounts of the difoerentdeffamines# used (D4G0 and 02000) and the different carho^irc^acids.f^/TGAA, THA, E8TA and ΡΕΤΡΑ) without the use of solvent. No heating developed in these eases. The mixtures were subjected te heating for 25 min at i0OeC, 25min at lSø“C and finally 30 min at 20øttC since the carboxylic adds (GA, TCAA, TMA, ΕΪ3ΤΑ and DETPA) are solid arid have moderste-hlgh melting points, Once the carboxylic acids were melted and hence ionic supramoiecuiar structures formed, an increase of viscosity was observed. The ionic supramolecuiar structures including 10% of hydrophobic fumed 5¾ particles (entries 8 and 10) were prepared by formation of the ionic supramoiecuiar structures by simple mixing followed by manual stirring without the use of solvent as the first step, and secondly, the silica particles were addsxE A Speed Mixer instrument was used in order fo get homogeneously dispersed mixtures. The instrument was set at 3GO0 rpm for 3min. This procedure was repeated 5^-8 times. The numbers reporting the various ratios of the constituents of the mixtures employed always refer to the particular functionality,
    The relative permittivities of the ionic supramolecuiar Structures obtained above were determined by means of dielectric relaxation spectroscopy on a Novocontrol Aipha~A high performance frequency ahaiyzer. The results thereof appear from Table 1 below.
    Table 1, Relative permittivities of ionic supramofecuiar structures.
    EXAMPLE 2
    Ionic Interpenetrating Polymer Networks (IPN-s > ionic interpenetrating polymer networks (IPNs) were prepared fey mining a equal amounts by weight of the elastomer Elastoslids RTS25 A/B from Wacker Cbemie AG and different supramoiecufar structures. Eiastosii® RT625 A/B is a two parts kit to be used in a 9:1 ratio of Part A to Part B as the manufacturer recommends. The supramolecular structures were formed by simple mixing of stoichiometric amounts of poiyf propylene imine) dendrimsr (PPI Gl} and two dicarboxyiic acids (DiCOOH-PEG 2SO and 600, respectiveiy} without any use of solvent, 2.1. Preparation of elastomer
    EiastosiK ,' RT625 A/B was used in the ratio 9: 3 by mixing 9.0396g of A and 3,0064g of B. The mixture was prepared 'using a Speed Mixer instrument set at 3500 rprn for 60s, 2.2 Preparafibn gf ipnie iPterpenetrsting;: polymer networks
    The ionic interprenetrating polymer networks |IFN$) were prepared by miking of equal amounts fey weight: of Eiastosii RT625 A/B and the ionite networks formed in situ (PPI Gl a DiCOGH-PEQ: 600 or PPlGl + DiCOOH-PEG 250} as follows: 2,2:-0 Eiastosii RT625 A/B-4 :£.PPI G3.-DiG00B-PEG: 250 (3::2)} 1,2911 g of Eiastosii RT625 A/B as prepared above In 2,1 was placed In a mixer, and the PPI dendrimer Gl (0:, 50S7g) and finally the dicarboxyiic add ©iCOOH--PEG2SO (0.79S8g) 'were added. The, mixture was put into the speed mixer fbrjmfn at SSQOrpm, Afterwards, the mixture was cured in the oven at 80->C for 2ih. The thickness of the samples was about 2.5-3 mm. 2,2b Eiastosii RT625 A/E + (PPI Gl - SiCGQH - PEG 600 (:3:2}) 3.23.35 g of Eiastosii: PT625 A/B as prepared above In 2,1 was placed in a mixer, and the PPI dendrimer Gl fO<2SS4g) and fenaliy the dicarboxyiic acid DiGOOH-PEGSOO (0,9 90g) were added. The mixture was put into the speed mixer for 3mln at 35OOrpm. Afterwards, the mixture was cured in the oven at SCrC for 21b.
    The relative permittivities of the ionSe interpenetrating polymer networks obtained above were determined by means of dielectric relaxation spectroscopy on a Nøvoeontref Alpha-A high porfbrmahce frequonev' nnaiyzer. The results thereof appear from Table 2 below and figure i.
    EXAMPLE 3
    The following ionic supramolecular structures were prepared analogously to the procedure described In Example i. Heating was not applied 10 this example.
    The relative permittivities of the above supramolecular structures were determined as described in Example 2.
    Table 3, Relative permittivities of sonic ssupramofecuiar structures.
    EXAMPLE 4
    Preparation of ionic suprambiecuiar structures containing: aminopropyi terminated polyd I m et by Isi ioxanas and DiCQQH--PEG>
    The fpilowing ionic supramoieeuiar structures were prepared in a manner analogously to the procedure of example 1. Heating was not applied in this examplte
    The relative permittivities of the; above supramoieeuiar structures were determined as described in Example 2.
    Table 4, Relative permittivities of ionic supramofecuiar structures.
    EXAMPLE S
    The following Ionic supramolecular structures were prepared In a mariner analogously to the procedure of example 1, Heating was not applied In this example.
    The relative permittivities of the above supramolecular structures were determined as described in Example 2.
    Table 5, Relative permittivities of ionic supramofecuiar structures.
    EXAMPLE 6 containing multifunctional carboxylic acids and aminqjsropyi terminated poiydfmethyisHpxaiies-
    The following ionic suprBmoieeuiar structures were prepared in a manner anaiogdtssiy to the procedure of example 1. The mixtures were sylgecCed to heating for 25 min at 106¾ 25 min at iSOXTand fidaliy 30 min at 2CKFC since the carboxyiic acids (CA, TCAA, THA, EDTA and DETPA) are solid at mom temperature and have moderate·high melting points.
    Their relative permittivities were determined as described in example 2.
    Tabte 6,-Relative permittivities of ionic supramofecuiar structures.
    EXAMPLE 7
    Preparation of ionic supramolecuSar structures containing dlphosphgnic PEG acids
    The following ionic supramoSeeuiar structures were prepared in a manner analogously to the procedure of example l. Heating was not applied in this example.
    The relative permittivities of these were determined as described in example 2.
    Table 7. Relative permittivities of ionic supramofecuiar structures.
    EXAMPLE 8
    Preparation: of ionic supramoiecuiar structures prepared with carboxylate fynetionai siiicones,
    The following ionic supramofecyiar structures were prepared in a manneraoaiogousiy to the procedure of example i. Heating was not appiied in this example.
    Their relieve pem>asviB«Were determine« as «0*»*ssemf>te 2 end «“*** ^ below.
    Table 8, Relative permittivities of ionic supramofecuiar structures.
    EXAMPLE 9
    Preparation of ionic supramoSacuiar structures-of aminopropyimathyisiloxane" dimathyisliaxane copolymers and different dicarpoxyiate or diphosphpniP 'cornpppnds
    Thefpifpwipg ionic supreroolecuiar structures wore prepared in a manner anaiogousiy to the: procedure of example 1. Beating was not applied in this example.
    Their relative permittivities were determined as described in example 2 and appear from table 9 below,
    Table 9, Relative permittivities {/) of Ionic suprarnofecufar structures,
    - EXAMPLE 10
    Preparation of non* ionic supramoiecuiar structures
    The below non-ionic supramoiecuiar structures were prepared in a manner analogously to the procedure of example 1, however with one of the components in excess (non-stoicbiometric ratio). Their relative permittivities appear from the table below, entries 2 and 3, compared to a corresponding ionic supramoiecuiar structure, entry l, taken from entry 7 in table 1, Heating was not appiied in this example.
    Tabte 10. Relative permittivities (s') of ionic supramoiecuiar structures.
    EXAMPLE 11
    Preparation of ionic interpenetrating networks
    The foliowing Isniotntensenetrat^iig.:' networks were prepared fn a manner analogously to the procedure described in example 2f however wherein the curing time was 1 day at 80sC and about 6 hours at 110 °C. The thickness of the samples ranged from 0.8-1.6 mm.
    Their relative permittivities were determined as described in example 2 and appear from the table below.
    Tabte il. Relative permittivities (s') of ionic supramoiecuiar structures.
    EXAMPLE 12
    The following Ionic interpenetrating networks were prepared in a manner analogously to the procedure described in example 2, however wherein the curing Lime was 1 day at SO^C and 3 hours at 110 ''C. The thickness of the samples ranged from 0,9--1,8 mm. Their relative permittivities were determined as described in example 2 end appear from the table below.
    Tabte 12. Relative permittivities (s') of Ionic suprsmoiecufar structures.
    权利要求:
    Claims (11)
    [1] 2. The |:on|C:interpenetrafing polymer network according tø claim 1, wherein the elastomer is: a silicone rubber selected from the group consisting of polysiioxanes, such as at poiyaifcyisitoxane, preferably polydimethyisMoxan^fPDMS;.
    [2] 3, The ionic interpenettating/poiymef network according to claim l or 2, wherein the ionic supramolecular structure; comprises: the reaction product of at least two chemical compounds, of which at least one of said compounds comprises a backbone selected from the group: consisting of poly (ethylene) glycol, poly (propylene) glycol, polysiioxane, pdiyaikyisiloxane, polyurethane and mixtures thereof, A. The labic irTerpenet rating polymer network according to claim 3, wherein the backbone is· selected:from the group consistlng of pdly(ethyiene) glycol, poly(propylene) glycol, polydimethyisiloxane and mixtures thereof, S) Tha ibnfe Interpenetrating polymer network according to any onerof the preceding claims,, wherein one of said chemical compounds comprises at least two amine functional groups and is selected from the group consisting of NMr:8*f|NHaf wherein R1 Is selected from the group:consisting of linear and branched Cx.24aikys and QaAdkenyl and cyclic Cs. s«alkyi and Cs^olkenyi, optionally substituted: by one or more substituents selected from the group consisting of halogen,: amino, nitre, hydroxyl, and CFw di- of triamibb-Gx.z^aikyiamine, wherein the alkyl moiety thereof is linear or branched chalky* or cyclic Cs.a*aikyl, optionally: substituted by one or more substituents selected from the group consisting of halogen, amino, nitro, hydroxyl, and Cf%', di- or tnamino-Cs.24aikenylamine, wherein the alkenyl moiety thereof is linear or branched Cj-jidlkenyl or cyclic Ga. ^alkenyl, optionaliy substituted by one or more substituents selected from the group consisting of halogen, amino, retro, hydroxyl, and CF3; dk tri~ or tetraamino-sikstituted aromatic or heteroaromatic compounds,, which compounds are optiohaiiy substituted by ores or moresubsfituebis selected from the: group consisting of halogen, amino, nitro, hydroxyl and CF^; poiyfetbyiene Imine) dendrimers; poly(propyiene irrens) dendrimers; pOlyCethyiene glycø!) diamine; poiYtpropySeneglycoi} dlardlne; paiy(ethylene glycoi)/rx&gt;ly (propylene glycd!) diamine; poSyCethyiene giyeoi) triamine; poiyfpropylene glycol) tnamind; porAerhylene g:iyco!)/paiy{:propy!ene glycol} triamine; and amirø-G^saiky! terminated polyalkylslloxane.
    [3] 6, The ionic Interpenetrating polymer network according to claim 5, wherein said chemical compound comprising at least two amine functional groups is selected from: the group consisting of l,:3~dlaminøprapane, ik-diaminøbutane* kS'-diamsn&amp;pentane, hexamethyiene diamine jHMDA), ikO-decanediamine, I^S^riamlng^ (tris- 2 ami noethyl} amine1 (IAEA), Sk'-diaminobenzidine (DAS), poly (propylene imine) dendrimer (Gi), poly (propy lene imine) dendrimer (02),. poiyfpropylene imine) dendrimer (03), poly (propylene glycol) diamine, polyCethyiene glycol) giyeoi)/poly (propylene glycol) diamine, polypropylene glycol) triamine., polyCethyiene glycol) triamine, polyCethyiene glycol)/poiy(propyleneglycol) tnamtne, amlnopropyf terminated poiydimethyisiloxane (ATOMS) and copolymers of aminc^lkyimethyisiloxane and dimethyisiloxanei such as cppolymers of arolnopropyimethyisiloxane a nd di methyl si ioxane.
    [4] 7. The ionic interpenetrating polymer network according to any one of the preceding claims, wherein one of said chemical compounds comprises at ieast two carboxy, sulfonic or ; phosphoric acid functional groups and is selected from the group consisting of dk tri- or tetra-carboxy-, &quot;dl·, tri- or tetra-sulfonic ordl·, tri- ortetraphosphonic acid-substituted linear or branched, saturated or unsaturated aliphatic, aromatic or heteroaromatic compounds optionally substituted by one or more subsbtuehts seiected from the group consisting of halogen, amino, nitro, hydroxyl, and .)0(¾ alkylenediandrietetracarhoxyiic acid; dlaikylenetriaminepentacarboxylie add, poly(ethyiene giyeoi)l^scarboxy rsethyi etbery pplyipropylene giycQi)biscarboxymefhyl ether, o^misollbnate-ronctionaiixed polyfethyiena glycol) and a,w^disy!fonate~functionalfzed polypropylene glycol), B:, The ionic interpenetrating polymer network: according to claim 7, wherein said chemical compound: comprising at least two carboxy, suitable or phosphoric add functional groups is selected from the group consisting of citric acid (CA), triearhailyiic: acid (TCAA), trimesic acid (TMA), ethylenédisminetptraaceic acid (EDTA), diethylenetriamlhepentaaeetiC: acid (DETPA), poiy(ethyiene giycoi)biscarboxyP5ethyl ether, poiyfpropylene giycoilbiscarhoxymethylethef, a^-dispSfonate-functiortallxedi poiyfethySane glycoi), o,ak .diSuff0hate^fiJn'i$io^3li2'ød:'poly(^FOpyienei glybøij and afW'dscarboxyiate-'funetSdngiizaci dimethylsildxane,
    [5] 9, The ionic: interpenetrating polymer network· according to any one of the preceding claims, further comprising one or more additives*,preferably wherein said additive is selected from the grayp consisting pf particles such as SiOa,. Ts02,, BaTiOsf CaCusTSiiOsg^preferahiy SiCb,
    [6] 10, The ionic iinterpénetrating: polymer network according to any one of the preeediog claims, having a relative dielectric permittivity crat 0,1 Hz of at least XxM&gt; such as at least : IxlO a pmferahly at least 1x10s, such as pt feast more preferred at least 1x101 such as at least 1x10^,
    [7] 11, A method: for preparing: the ionic interpenetrating polymer network according to any one of the preceding claims comprising: the steps of: i) mixing: said at least two chemical compounds, optionally by the addition of heat, to obtain said loose suprarnotecuiar structure; and lij Mixing the ionic supramaidcular structure obtained in step i), optionally by the addition of heat, with at least one elastomer.
    [8] 12, A method for preparing the ionic interpenetrating polymer network according to any pne of claims 1-ΊΘ comprising the step of mixing said at least two chemical compounds with at least one elastomer, optionally by dm addition of heat.
    [9] 13, The method acco rd i n g to claim 11 or i 2, wherein said at least two chemical compounds are used in stoichiometric amounts of said at ieast two chemicai compounds.
    [10] 14, The method according to. any one of claims 11 to 13, wherein the preparation of the ionic interpenetrating polymer network according to any one of claims 1 to 10 is performed by mixing of amounts of said ionic supramoiecuiar structure and said at least one elastomer in the range 1:9 to 2:1 by weight, such as in the range 1:4 to 1:3, preferably about 1:1 by weight.
    [11] 15, A use Of the ionic interpenetrating polymer network according to any one of claims: 1 to 10 as dielectric eiectroactive polymer:(DEAP),
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    同族专利:
    公开号 | 公开日
    ES2616105T3|2017-06-09|
    BR112015013204A2|2017-07-11|
    PT2928963T|2017-02-21|
    AU2013354100A1|2015-07-02|
    IL239257A|2017-06-29|
    EP2928963A1|2015-10-14|
    AU2013354100B2|2016-11-10|
    ZA201504283B|2016-04-28|
    EP2928963B1|2016-11-16|
    KR20150091400A|2015-08-10|
    DK178648B1|2016-10-17|
    CA2894003A1|2014-06-12|
    CN104981516A|2015-10-14|
    WO2014086885A1|2014-06-12|
    JP2016501303A|2016-01-18|
    US9607731B2|2017-03-28|
    MX2015007145A|2016-03-21|
    US20150318074A1|2015-11-05|
    CL2015001550A1|2016-02-26|
    CN104981516B|2017-09-15|
    SG11201504440WA|2015-07-30|
    IL239257D0|2015-07-30|
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    法律状态:
    2019-08-15| PBP| Patent lapsed|Effective date: 20181204 |
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