EP3116936A1 - High permittivity polymers based on functionalized silicones - Google Patents
High permittivity polymers based on functionalized siliconesInfo
- Publication number
- EP3116936A1 EP3116936A1 EP15711646.8A EP15711646A EP3116936A1 EP 3116936 A1 EP3116936 A1 EP 3116936A1 EP 15711646 A EP15711646 A EP 15711646A EP 3116936 A1 EP3116936 A1 EP 3116936A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- repeating units
- polymer
- alkyl
- group
- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/098—Forming organic materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/857—Macromolecular compositions
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
Definitions
- the present invention relates to high permittivity silicone-based polymers, to methods of manufacturing such silicone-based polymers, methods of manufacturing elastomers containing such polymers and to the use thereof, particularly the use in dielectric elastomer actuators.
- Dielectric elastomers and their use in actuators (DEA) are known.
- DEA actuators
- Known elastomers meet the mechanical requirements for actuators, however, they suffer from a low permittivity
- ⁇ ' can be increased when dipoles are attached to polymer chain .
- Racles et al (Smart Mater. Struct, 2013, 22, 104004) disclose that silicone functionalized by cyanopropyl groups showed an increase in the ⁇ ' from 2.3 for the unmodified to about 7 for the modified silicone.
- Kruger et al ( O2013/038093 and WO2013/113593 ) also describe the use of cyanopropyl groups to increase the ⁇ ' as well as their application in DEA.
- Kruger et al. (US2013/0253146 Al) discloses silicones containing an electronic dipole covalently bonded to the silicone chain.
- Silicones functionalized via thiol-ene reaction are also known. Fahem et al (Microelectronic Engineering 2013, 74) describes Thiol-ene polymers useful for organic FETs. Boileau et al (FR2708272) describes specific silicon resins useful as adhesives. Boutevin et al (J. of Fluorine Chemistry, 1986, 425) describes the synthesis of fluorinated polysiloxanes, and specifically discloses a cyclic tetramer (p.430, structure 13). Mosch (US5057589) discloses polysiloxanes having C B + perfluoralkylgroups as the materials being useful as oil- and water repellents.
- the present invention to mitigate at least some of these drawbacks of the state of the art.
- the invention further aims providing a synthesis of such elastomers that is easy, cheap, and allows up-scaling.
- silicon based elastomer is known in the field; it particularly describes a polymer having- [Si-O] n- repeating units and elastic properties.
- silicon is known in the field; it particularly describes an oligomer or a polymer having -[Si-0]n- repeating units and side groups covalently attached, as defined below.
- thiolen reaction is known in the field; it particularly describes the addition of a thiol to a carbon-carbon double bond in the presence of a radical initiator. It is done under irradiation such as, for example, UV-irradiation, ionizing radiation (e.g. gamma ray or x-ray irradiation), microwave irradiation and the like. Thermal thiolene reaction is also well-known to a person skilled in the art.
- free radial initiator is known in the field and includes photoinitiators and thermal initiators.
- a "photoinitiator” refers to a chemical that initiate free radial reaction by the use of light, such as, for example, from the class of phenones.
- photoinitiators suitable in the context of this invention include: 2,2- dimethoxy-2-phenylaceto-phenone , acetophenone , anison, antraquinonem benzyl, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzoin methyl ether, benzophenone, benzophenone/1-hydroxycyclohexyl phenyl ketone (50/50 blend, 3, 3' , 4, 4' -benzophenonetetracarboxylic dianhydride, benzoylbiphenyl , 2-benzyl-2- ( diumetylamino ) - ' -morpholinobutyrophenone, , ' -bis (diethylamino) benzophenone, 4 , 4 ' -bis (dimethylamino) benzophenone, camphor- quinone, 2-chlorothioxanthen-9-one, dibenzosuberen
- thermal initiator refers to a chemical that initiates radial reaction by the use of heat energy, such as, for example, from the class of diazo-compounds and from the class of orgainic peroxides.
- Specific thermal initiators include: 2,2'- azobisisobutyronitrile (AIBN) , cyclohexyl analogs of AIBN, 2,2'-azobis ( 4-methoxy-2 , 4 -dimethyl valeronitrile) (V70) and mixtures thereof, organic peroxides like di-tert-butyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, acetone peroxide, cumene peroxide, terz-amyl peroxybenzoate, 4 , 4-azobis ( 4-cyanovaleric acid),
- alkyl is known and includes linear and branched alkyls. Unless otherwise specified, alkyls do not contain functional groups, i.e. they are unsubustituted .
- the term alkyl denotes both, monovalent radicals (i.e. end-groups, such as - CH2CH3) and divalent radicals (i.e. spacers, such as - CH2CH2-) .
- X C1-C20 alkyl includes methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec. -butyl, iso- butyl and tert. -butyl; particularly methyl.
- aryl is known and includes phenyl and naphtyl. Unless otherwise specified, aryls do not contain functional groups, i.e. they are unsubustituted . Again, the term includes monovalent and divalent radicals.
- FIG. 1A shows the synthesis of poly (dimethyl- methylvinyl) siloxane whereby, different end groups (R) can be introduced by using functionalized end-blockers (BL) [first step] . These end-blockers are selected such that the thiolene addition is not disturbed or they are introduced after the dipole attachment.
- the poly (dimethyl- methylvinyl ) siloxane copolymer is reacted with functionalized thiols [second step] .
- R represents a functional end-group and D represents a group with a large dipole moment, both as outlined herein.
- Figure IB shows a specific example of the functionalization with mercaptopropanenitrile .
- Figure 1C shows 1 H NMR spectra of the poly ( dimethyl- metyhlvinyl ) siloxane (bottom) and of the prepared polymer by thiolene addition of mercaptopropanenitrile (top) .
- the disappearance of the vinyl protons at about ⁇ 6 ppm, indicated by an arrow, is a clear proof of quantitative conversion .
- Figure ID shows dielectric properties of silicones containing different percentages of methyl ethylthiopropanenitrile siloxy repeat units (19%, 8%, 4.4%, 1.7%, 0%); X-axis: frequency [Hz]. The arrow indicates an increasing amount of CN groups.
- Figure IE shows the synthesis of polar silicones by thiolene addition starting from silicones containing thiol groups and a polar vinyl compound; substituents as in fig. 1A.
- Figure 2A shows the synthesis of polymethylvinylsiloxane containing different end groups and its functionalization by thiolene addition using different proportions of thiol/dipole functionali zed thiol.
- R represents an end group, such as OH;
- R " N represents a C1-C20 alkyl;
- D represents a group with a large dipole moment as outlined herein .
- Figure 2B shows a specific example of this embodiment using mercaptopropanenitrile .
- Figure 2C shows 1 H NMR spectra of the copolymers prepared starting from polymethylvinylsiloxane and mercapto- propanenitrile / butanethiol containing different percentages of methylethylthiopropanenitrile siloxy repeat units. From bottom to the top: starting material (reference), 0, 10, 20, 30, 40, 50, 100%.
- Figure 2D shows dielectric properties of functionalized silicones that contain different percentages of methyl ethylthiopropanenitrile siloxy and methyl ethylthiobutane siloxy repeat units. The permittivity is increasing with increasing the proportion of methyl ethylthio- propanenitrile siloxy units.
- X-axis frequency [Hz].
- Figure 3A shows in-situ thiolene functionalization and cross-linking of polymethylvinylsiloxane or poly (dimethyl- methylvinyl) siloxane in thin films.
- Figure 3B briefly describes the inventive procedure leading to silicone-based elastomers with superior properties.
- Figure 3C shows stress-strain curves of the prepared material according to the third embodiment (radical induced cross-linking) , whereby about 50% of the vinyl groups were reacted with mercaptopropanenitrile .
- Y-axis stress [N/mm2] ;
- Figure 3D shows dielectric properties of films of modified silicones according to the third embodiment.
- Figure 3E shows the stress-strain curves for materials A, B1-B3 and CI, C2 as well as of commercially available VHB4905 and Elastosil RT 745 from standard tensile tests at 500 mm min-1. The stress-strain curves were averaged from three independent tests. The strain at break for VHB and Elastosil was 850% and 770%, respectively.
- Figure 3F shows Permittivity (bottom) , loss factor (middle), and conductivity (top) of material C2, Elastosil RT 745, and VHB 4905 foil as a function of frequency at room temperature.
- Figure 3G shows the measured lateral actuation strain of a membrane actuator.
- the actuators were made by a silicone film prestrained 20% and fixed between two circular frames (25 mm diameter). Circular electrodes (8 mm) of carbon black powder were applied to each side of the film.
- Figure 3H shows lateral actuation strain membrane actuators for materials A, C2 and Elastosil RT 745 (each with 28.6% prestrain) as well as of VHB 4905 foil (300% prestrain) as a function of the applied voltage (top) and the lateral actuation strain of materials CI and Elastosil (both without prestrain) (bottom) .
- Figure 31 shows long term stability of a film measured at 1000 V. The actuators survived thousands of cycles, x-axis time in seconds.
- Fig. 4 outlines synthesis of starting materials, in case z represents 2 or 3.
- the invention in more general te ms , in a first aspect, relates to polymers comprising 1 - 100 % of repeating units of fo ula (I)
- X represents an alkyl group, preferably a C1-C12 alkyl, or a C6-C10 aryl group, or a -X-S-Y-D z group
- X represents a spacer, preferably selected from the group consisting of C2-C12 alkyl, C2-C12 alkyl interrupted by C6-C10 aryl, C2-C12 alkyl interrupted by C6-C10 aryl whereby said aryl being substituted by 1-4 C1-C4 alkyl
- S represents sulphur
- Y represents a spacer, preferably selected from the group consisting of C1-C20 alkyl, C1-C20 alkyl interrupted by C6-C10 aryl, C1-C20 alkyl interrupted by C6-C10 aryl whereby said aryl being substituted by 1-4 C1-C4 alkyl; C1-C20 alkyl interrupted by a carboxyl group, C1-C20 alkyl interrupted by amide group;
- D represents a polar group, preferably selected from the group consisting of CN, N0 2 , NO, CF 3 , F, CI, Br, OCN and SCN;
- z represents the integer 1, 2 or 3, preferably 1.
- Polymers according to this invention preferably comprise 3 or more repeating units as defined herein, particularly preferably 10 or more repeating units as defined herein.
- the polymer comprises repeating units where Rl represents C1-C12 alkyl, particularly methyl. In case the polymer comprises 100% of these repeating units , the resulting polymer is a homo- polymer. In case the polymer comprises less than 100% of these repeating units, the resulting polymer is a copolymer .
- the polymer comprises repeating units where Rl represents a group -X-S-Y-D z . In case the polymer comprises 100% of these repeating units, the resulting polymer is a homo-polymer. In case the polymer comprises less than 100% of these repeating units, the resulting polymer is a co-polymer. In a further advantageous embodiment, the polymer comprises repeating units where Rl represents C1-C12 alkyl, particularly methyl and repeating units where Rl represents a group -X-S-Y-D z . In this embodiment, the polymer is a copolymer, depending on its manufacturing a random co-polymer or block-copolymer .
- the polymer comprises repeating units where X represents 1 , 2-ethandiyl and/or 1 , 1-ethandiyl .
- Polymers according to this embodiment are obtained when thiol-ene reaction is performed using a vinyl-compound as starting material. Typically, the 1,2- ethandiyl is predominantly formed.
- the polymer comprises repeating units where X represents 1 , 2-propanediyl and/or 1, 3-propanediyl .
- Polymers according to this embodiment are obtained when thiol-ene reaction is performed using an allyl-compound as starting material. Typically, the 1,3- propanediyl is predominantly formed.
- the polymer comprises repeating units where z represents 1, i.e. repeating units having one polar group D
- the polymer comprises repeating units where z represents 2 or 3, i.e. repeating units having two or three polar groups D in its side chain.
- z represents 2 or 3, i.e. repeating units having two or three polar groups D in its side chain.
- Exemplary groups Y-D z are shown below,
- D is as defined above, preferably C . If z represents 2 or 3, Y preferably represents branched C1-C20 alkyl. If z represents 2 or 3, the D groups are preferably the same, such as CN .
- the polymer comprises repeating units of formula (I), where D represents CN, R 1 represents methyl, X represents 1,2- ethanediyl and Y represents 1 , 2-ethanediyl .
- these polymers are available by a straightforward synthesis, show superior permittivity and good elastic properties. This aspect of the invention shall be explained in further detail below, with particular reference to
- the invention relates to polymers as described herein having a permittivity above 3, preferably above 4, particularly preferably above 7, very particularly preferable above 10. Even higher values can be reached.
- the polymers described herein have outstanding electrical properties.
- the invention relates to polymers as described herein having moduli of elasticity of 50 kPa to 2 MPa (preferably: 50 kPa to 5 MPa) and strain limits between 50 to 800% preferably 300% and higher.
- the polymers described herein have very good mechanical properties .
- the invention relates to polymers as described herein having a molecular weight in the range of Mw 500-500000 g/mol, preferably 500-150000 g/mol more preferably 1000-150000 g/mol and even more preferably 1000-100000 g/mol.
- Mw 500-500000 g/mol preferably 500-150000 g/mol more preferably 1000-150000 g/mol and even more preferably 1000-100000 g/mol.
- the invention relates to polymers as described herein, said polymers being cross- linked .
- the invention relates to polymers as described herein additionally containing fillers, such as nanoparticles .
- Suitable nanoparticles are known in the field and include silica, titania, ferroelectric ceramics, BaTi0 3 .
- Suitable amounts of fillers may be determined by routine experiments, but are typically in the range of up to 50 vol% (preferably: 1 to 30 vol%) .
- Such fillers may be added to fine-tune mechanical properties, particularly for reinforcing the inventive polymers .
- the invention provides for polymers comprising 1 - 100 % of repeating units of formula (I) and 99 to 0% of repeating units of formula (II)
- R 1 , X, Y, D, z are as defined above and
- R 2 represents, independent from each other, alkyl, such as C1-C12 alkyl, or aryl.
- alkyl such as C1-C12 alkyl, or aryl.
- Such polymers are available by the methods outlined below and depicted in fig. 1A and IB and IE.
- such polymers possess end-groups R 6 , selected from the group consisting of hydroxyl, vinyl, allyl, acryl, methacryl, thiol, C1-C12 alkyl thiol groups, amino- Cl-C12-alkyl groups, halogenated- Cl-C12-alkyl groups, epoxy groups, C1-C12 alkyl oxirane groups, C1-C12 alkyl-carboxy groups, hydrogen. Accordingly, such polymers are of formula (1-1)
- R 1 , R 2 , R 6 , X, Y, D z are as defined above;
- m 0 to 99% repeating units
- n 1 to 100% repeating units.
- R 2 represents methyl.
- R 6 represents hydroxyl, vinyl, hydrogen, C1-C12 alkyl thiol.
- the invention provides for polymers comprising 1 - 100 % of repeating units of formula (I) and 0-99 % of repeating units of formula (III)
- R 1 , X, Y, D, z are as defined above and
- R 3 represents, independent from each other, C1-C12 alkyl, or C6-C10 aryl, or a X-S-Y-H group.
- R 3 preferably represents methyl
- H represents hydrogen
- such polymers possess end-groups R 6 as defined above. Accordingly, such polymers are of formula (1-2)
- R 1 , R 2 , R 6 , X, Y, D, z are as defined above;
- n 0-99% repeating units
- n 1-100% repeating units.
- the invention provides for polymers comprising 1 - 100 % of repeating units of formula (I) and 0-99 % of repeating units of formula (III) and of 1-50 of formula (IV)
- X represents either a single bond or a spacer selected from the group of C1-C12 alkanediyl; preferably a single bond.
- these polymers are cross-linked. Due to the double bond in formula (IV) such cross-linking is achieved by radical polymerisation, adding a UV or thermally active initiator.
- the invention also provides for polymers comprising the above repeating units of formula (I) , (III) and (IV) characterized in that the polymer is cross-linked.
- Fig. 3 A outlines possible mechanisms and structures of such cross-linked polymers.
- the invention in a second aspect, relates to a process for manufacturing of polymers as described herein, comprising the step of reacting a suitable thiol-component with a suitable alkene-component with way of a thiolene reaction.
- the invention thus relates to the use of the thiol-ene reaction for manufacturing silicon- based dielectric elastomers.
- the present invention uses the robust thiol-ene addition instead of using a hydrosilylation reaction for the dipole attachment to the silicone chain for this purpose.
- polysiloxanes that contain methylvinylsiloxy repeat units in their chains and defined functional end groups are prepared first.
- the vinyl groups are then used to functionalize the silicone with polar groups by thiolene addition chemistry.
- This synthetic approach has a number of advantages. Most importantly, the polymer synthesis
- ⁇ can be used for any kind of thiol-functionalized compound .
- first aspect 1 st to 4 th embodiment shall be explained in further detail below, specifically referring to the polymers disclosed above, first aspect 1 st to 4 th embodiment :
- poly (dimethyl-methylvinyl ) siloxane) is prepared by cationic or anionic copolymerization of octamethylcyclotetrasiloxane (D4) with 1,3,5,7- tetramethyl-1, 3, 5, 7-tetravinylcyclotetrasiloxane (V4) (fig. 1A) .
- D4 octamethylcyclotetrasiloxane
- V4 1,3,5,7- tetramethyl-1, 3, 5, 7-tetravinylcyclotetrasiloxane
- the mole fraction of Si-vinyl in the polymer chain can easily be tuned by varying the proportion between D4 and V4.
- the molecular weight is controlled by the amount of end-blocker and initiator used. The end-blocker is selected such that the introduced end functional group would not interfere with the thiolene reaction. Suitable end-groups are listed above as R6, for example, hydrogen or hydroxyl groups .
- polar groups D are subsequently attached by thiolene addition with suitable thiols containing small or large dipoles.
- the dielectric properties of the final material are tuned by changing the amount and type of polar thiol used (depending on the composition of the initial poly (dimethyl-methylvinyl) siloxane) .
- the hydroxyl/hydro end group of the functionalized silicone can be replaced by other functional end groups by using reactions that are known in the art (In the context of this invention, such functional end groups include vinyl, allyl, acryl , methacryl , thiol, C1-C12 alkyl thiol, amino- Cl-C12-alkyl groups, halogenated- Cl-C12-alkyl groups , epoxy groups , hydrogen) . These end groups are used as described below.
- the molecular weight of the functionalized silicone has a direct impact on the mechanical properties o the material , polymers with high Mw are preferred to ensure good elastic properties, whereas low molecular weight polymers are preferred in combination with chain extenders.
- “Chain extenders” are molecules that carry two reactive end groups and allow formation of a copolymer with the low molecular weight polymer.
- silica or other nanoparticles may be added.
- Method B Functionalization of thiol containing silicones by thiolene addition with functionalized dipoles that carry a double bond .
- silica or other nanoparticles may be added.
- Mw 500 to 150000 g/mol
- cationic or anionic polymerization fig. 2A
- Molecular weight and end functionality are controlled by using different amount and type of suitable end-blockers as well as by the amount of the initiator used.
- Second step These polymers were subsequently used in a thiolene reaction using a mixture of thiol that carry a polar group and an alkyl thiol. To avoid uncontrolled cross-linking, slightly larger than stoichiometric amounts of thiols to vinyl groups were used.
- Figure 2C shows the X H NMR spectrum of the prepared polymers. The proportion between the two thiols was changed which allows fine tuning the dielectric properties of the resulting polymers (fig. 2D) .
- Third step (optional)
- the hydroxyl end group of the functionalized silicone can be replaced by other functional end groups by using reactions that are well known in the art (e.g. vinyl, allyl, acryl, methacryl, thiol, alkyl thiol, amino alkyl groups, epoxy groups, etc). These end groups are used directly for crosslinking high molecular weight polymers. When low molecular weight polymers are used suitable chain extenders and cross-linkers are added, whereby chains growth and crosslinking occur in a single step .
- Forth step These polymers were cross-linked in thin films, whereby a large variety of chemical reactions can potentially be used for cross-linking.
- silica or other nanoparticles may be added.
- Second step vinyl functionalized polymers or copolymers were mixed together with the thiols carrying polar groups and an UV initiator (e.g. 2 , 2-dimethoxy-2- phenylacetophenone, DMPA) .
- an UV initiator e.g. 2 , 2-dimethoxy-2- phenylacetophenone, DMPA
- Second step The resulting mixture is poured into a Teflon mold and irradiated, whereby the dipole attachment and the crosslinking occur at the same time.
- silica and/or cross-linkers with two or more thiol groups were used. This led to a substantial improvement in that soft elastomers with high permittivity and good elastic properties were obtained (fig. 3B) .
- the invention relates to the use of the polymers as described herein and to devices comprising such polymers.
- the invention provides for the use of polymers as described herein as a dielectric material and to devices comprising such polymers.
- the invention provides for the use of polymers as described herein in dielectric elastomer actuators (DEA) and to DEAs comprising such polymers, particularly in the form of a cross-linked film.
- DEAs are known per se; they consist of a thin elastomeric film sandwiched between two compliant electrodes. When a voltage is applied, an electrostatic pressure is acting on the film which is compressed. Since elastomers conserve their volume upon deformation, the film is elongated perpendicular to the applied electric field. This process is reversible; after removal of the field the polymer relaxes back to its original form.
- the invention therefore provides for devices selected from the group consisting of actuators, robotics, prosthetic and rehabilitation devices (such as implantable prosthetic and rehabilitation devices) , vehicles and aeroflight capable devices, energy harvesting devices, sensors, optical devices, comprising the polymers as described herein .
- the invention provides for the use of polymers as described herein in generators and to generators comprising such polymers, particularly in the form of a film.
- Devices that convert mechanical energy into electrical energy (“generators") are known per se.
- the inventive dielectric elastomers are used to generate electrical energy when mechanical work is done against the electric field. An external mechanical force is used to stretch the dielectric elastomer, followed by charging of the stretched film. It is thereafter allowed to contract by using the elastic forces. Thus mechanical forces are working against the electric field pressure and the electrical energy increases.
- the invention provides for the use of polymers as described herein in capacitors and transistors and to capacitors and transistors comprising such polymers, particularly in the form of a film. Due to its high permittivity, the polymers as described herein are also suited for such applications.
- the invention provides for the use of polymers as described herein in optical devices and to optical devices comprising such polymers, particularly in the form of a film. Due to its high permittivity, the polymers as described herein are also suited for such applications.
- the following examples are provided. These examples are provided with no intend to limit the scope of the invention.
- Table 1 The amounts of reagents and reaction conditions used for the synthesis of different polymers contacting different amount of polar CN groups and their composition, molecular weights and distributions.
- a mixture of poly (dimethyl-methylvinyl) siloxane-a, ⁇ - ⁇ (0.5 g) , toluene ( 2 ml), mercapropropionitril (0.48 g) , 2 , 2 ' - (Ethylenedioxy) diethanethiol (5 ⁇ ) and 2,2- dimethoxy-2-phenylacetophenone (5 mg) was casted to a film and subsequently the crosslinking and dipole grafting was initiated by UV-irradiation for few minutes. The cross- linked film was dried at elevated temperature for several hours .
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US2960492A (en) * | 1954-12-07 | 1960-11-15 | Morton Maurice | Sulfur-containing organosiloxane polymers, and processes for making the same |
DE3903005A1 (en) | 1989-02-02 | 1990-08-16 | Pfersee Chem Fab | METHOD FOR THE PRODUCTION OF MODIFIED POLYSILOXANES, THE POLYSILOXANES SO MANUFACTURED, THE USE THEREOF AND THE MATERIALS SO TREATED |
FR2708272B1 (en) | 1993-07-26 | 1995-09-01 | Rhone Poulenc Chimie | Silicone resins with thermo- or hydro-reversible crosslinking nodes. |
DE102010046343A1 (en) | 2010-09-23 | 2012-03-29 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Dielectric polymers with increased permittivity, process for their preparation and uses thereof |
FR2980173B1 (en) | 2011-09-16 | 2013-10-25 | Aircelle Sa | REPLACEMENT OF NACELLE FOR TURBOJET ENGINE |
DE102012001808A1 (en) | 2012-01-31 | 2013-08-01 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polymer compound with blended polar-functionalized oligomer, process for its preparation and use |
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