CN100509960C - Electrostriction polymer laminar nano composite material, preparation method and application thereof - Google Patents
Electrostriction polymer laminar nano composite material, preparation method and application thereof Download PDFInfo
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- CN100509960C CN100509960C CN 200610080969 CN200610080969A CN100509960C CN 100509960 C CN100509960 C CN 100509960C CN 200610080969 CN200610080969 CN 200610080969 CN 200610080969 A CN200610080969 A CN 200610080969A CN 100509960 C CN100509960 C CN 100509960C
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Abstract
The present invention relates to one kind of electrostrictive layered nanometer composite polymer material, which is prepared with electrostrictive polymer, layered nanometer inorganic material, organic intercalative agent, cross-linking agent, catalyst and protonating agent, and through curing at 40-120 deg.c to form 10-1000 micron thick film and the subsequent drawing orientation. When 10-100 V/micron electric field is applied in the direction perpendicular to the film plane, one strain in 1-100 % may generate in the direction perpendicular to the electric field direction and the drawing direction, with the deformation being eliminated fast after the electric field is eliminated. The electrostrictive composite polymer material may be applied in electric driver, pump and sensor related to artificial muscle, and compared with available technology, the present invention has the advantages of simple preparation and lower driving voltage.
Description
Technical field
The invention belongs to the organic/inorganic composite material field, specifically relate to a kind of Electrostriction polymer laminar nano composite material, and its production and use.
Background technology
Electrostrictive polymers is can produce stretching motion under effect of electric field, thereby realizes a kind of polymer materials of electric energy-mechanical energy conversion.Electrostrictive polymers is owing to the mode of motion of similar muscle in its electric energy-mechanical energy conversion is called as artificial thews material.In U.S. Pat 6911764 and US6940211, material and device that a kind of electric energy based on electrostrictive polymers-mechanical energy transforms are disclosed, this electrostrictive polymers material mainly is the electrostriction material based on single component, its driving voltage is higher, output stress, makes its performance compare bigger gap in addition with muscle.2005, the U.S. hold in the world first the people with based on the breaking off with the fingers and thumb in the wrist trial of strength of the artificial arm of electrostrictive polymers, although the trigger voltage that artificial arm needs up to thousands of volts, the result still comes to an end with the mankind's triumph.The electrostrictive property of existing electrostrictive polymers is still waiting to improve.
Summary of the invention
The objective of the invention is to overcome the higher and output stress smaller defect of driving voltage of existing electrostrictive polymers, have than low driving voltage and bigger output stress Electrostriction polymer laminar nano composite material thereby provide a kind of.
Another object of the present invention is to provide a kind of preparation method of above-mentioned Electrostriction polymer laminar nano composite material.
A further object of the present invention is to provide the purposes of above-mentioned Electrostriction polymer laminar nano composite material.
The objective of the invention is to realize by the following technical solutions:
Electrostriction polymer laminar nano composite material provided by the invention, its be a mixture that comprises electrostrictive polymers, nano lamellar inorganic materials, organic intercalation agent, linking agent, catalyzer, protonating agent 40～120 ℃ of curing obtain thick be 10～1000 microns film material, then through the one dimension stretch orientation and rete; Apply the electric field of 10～100V/ μ m in direction perpendicular to membrane plane, can be in the strain that produces 1～100% perpendicular to electric field and tensile direction.
The invention provides a kind of preparation method of above-mentioned Electrostriction polymer laminar nano composite material, comprise following step:
1) with electrostrictive polymers 100 weight part, nano lamellar inorganic materials 0.1～20 weight part, organic intercalation agent 0.1～20 weight part, linking agent 1～5 weight part, catalyzer 0.01～0.2 weight part, protonating agent 0.2～5 weight part are filmed on quartz substrate after mixing evenly, carry out 1～10 hour curing reaction at 40～120 ℃ then, obtain thickness and be 10～1000 microns matrix material rete;
Described electrostrictive polymers is the oligopolymer of silicon rubber or acrylic elastomer;
Laminated insulation body material, layered semiconductor material or stratiform conductor material that described nano lamellar inorganic materials is 50～1000 nano-scales; Preferably, described laminated insulation material is polynite; Described layered semiconductor material is a molybdenumdisulphide; Described layered conductive material is a lamellar graphite;
Described organic intercalation agent is an organic amine, for example cetyl trimethylammonium bromide, cetylamine or trolamine;
Described linking agent is tetraethoxy, phenylformic acid amine or 1,2-propylene diamine;
Described catalyzer is a dialkyl group dicarboxylic acid tin;
Described protonating agent is hydrochloric acid, phosphoric acid or sulfuric acid;
2) the matrix material rete that step 1) is obtained makes the matrix material rete be orientated along draw direction along one dimension direction stretch orientation, obtains Electrostriction polymer laminar nano composite material of the present invention.
Electrostriction polymer laminar nano composite material of the present invention has improved the mechanical property and the processing characteristics of matrix material significantly by add polynite, molybdenumdisulphide or lamellar graphite in electrostrictive polymers; Because orientation stratiform inorganic materials produces induction field, can significantly improve the electric driveability of Electrostriction polymer laminar nano composite material.Apply the electric field of 10～100V/ μ m in direction perpendicular to membrane plane, can be in the strain that produces 1～100% perpendicular to electric field and tensile direction; After removing electric field, the very fast answer of deformation energy.Be that Electrostriction polymer laminar nano composite material of the present invention has under extra electric field drives deformation reversible character.
Electrostriction polymer laminar nano composite material provided by the invention, can be applied to the electricity relevant with artificial-muscle drives, pump and sensor field, as with described Electrostriction polymer laminar nano composite material, method by spin-coating or spraying is at coated on both sides carbon back conductive resin, obtaining the two sides is conductive resin, the centre is the artificial thews material of the sandwich structure of Electrostriction polymer laminar nano composite material of the present invention, and this sandwich structure is orientated nano-lamellar structure by the tensile shear effect with draw direction along parallel in Electrostriction polymer laminar nano composite material.Sandwich structure is applied the electric field of strength of electric field 10～100V/ μ m, can make Electrostriction polymer laminar nano composite material in the deformation that produces 1～100% perpendicular to electric field and tensile direction, thus output mechanical energy.
Compared with prior art, the advantage of Electrostriction polymer laminar nano composite material provided by the invention is that it is easy to prepare, and has reduced driving voltage, can bigger output stress under lower driving voltage.
Embodiment
Embodiment 1
With particle diameter is that the sodium-based montmorillonite 2g of 1000 nanometers joins in the 38ml distilled water, 60～70 ℃ of following vigorous stirring, forms stable suspension system.With 0.2g hexadecyl trimethyl ammonium bromide, 1g concentration is that 37% concentrated hydrochloric acid and 10ml water mix, and makes the quaternary amine aqueous solution.Under the intense stirring condition, the above-mentioned quaternary amine aqueous solution slowly is added drop-wise in the aqueous solution of polynite.Filter, washing filter residue to filtrate does not have chlorion, filter residue and drying is ground obtain organo montmorillonite.With being dispersed in 200 gram mass concentration under this organo montmorillonite violent stirring is in the tetrahydrofuran solution of 20wt% polymethoxy siloxanes, adds linking agent tetraethoxy 0.4g, and catalyzer dialkyl group dicarboxylic acid tin 0.01g is evenly mixed.This mixed liquid is filmed in quartz substrate, under 50～60 ℃ of conditions, solidified 10 hours, obtain thickness and be 10 microns nano-composite material membrane.This matrix material rete is carried out one dimension 50～100% stretch orientations, obtain Electrostriction polymer laminar nano composite material I of the present invention.
With this Electrostriction polymer laminar nano composite material I, method by spin-coating or spraying is at the coated on both sides carbon back conductive resin of film, obtaining the two sides is the artificial thews material of the sandwich structure of conductive resin, the middle Electrostriction polymer laminar nano composite material I of the present invention of being, and this sandwich structure is orientated nano-lamellar structure by stretching with draw direction along parallel in Electrostriction polymer laminar nano composite material.Sandwich structure is applied the electric field of strength of electric field 10～100V/ μ m, can make Electrostriction polymer laminar nano composite material in the deformation that produces 1～50% perpendicular to electric field and tensile direction, thus output mechanical energy.Thereby as seen, the driving voltage of Electrostriction polymer laminar nano composite material provided by the invention is lower, and output stress is bigger.
Embodiment 2
With particle diameter is that the sodium-based montmorillonite 20g of 1000 nanometers joins in the 38ml distilled water, 60～70 ℃ of following vigorous stirring, forms stable suspension system.With 20g trolamine, 5g concentration is that 98% sulfuric acid and 10ml water mix, and makes the quaternary amine aqueous solution.Under the intense stirring condition, the above-mentioned quaternary amine aqueous solution slowly is added drop-wise in the aqueous solution of polynite.Filter, washing filter residue to filtrate does not have chlorion, filter residue and drying is ground obtain organo montmorillonite.With being dispersed in 1000 gram mass concentration under this organo montmorillonite violent stirring is in the tetrahydrofuran solution of 10wt% acrylic elastomer, adds linking agent phenylformic acid amine 5g, and catalyzer dialkyl group dicarboxylic acid tin 0.01g is evenly mixed.This mixed liquid is filmed in quartz substrate, and solvent slowly after the volatilization at ambient temperature, reheat to 70 ℃ solidified 5 hours, obtained thickness and be 1000 microns nano-composite material membrane.This matrix material rete is carried out one dimension 50～200% stretch orientations, obtain Electrostriction polymer laminar nano composite material II of the present invention.
With this Electrostriction polymer laminar nano composite material II, method by spin-coating or spraying is at the coated on both sides carbon back conductive resin of film, obtaining the two sides is the artificial thews material of the sandwich structure of conductive resin, the middle Electrostriction polymer laminar nano composite material II of the present invention of being, and this sandwich structure is orientated nano-lamellar structure by the tensile shear effect with draw direction along parallel in Electrostriction polymer laminar nano composite material.Sandwich structure is applied the electric field of strength of electric field 10～100V/ μ m, can make Electrostriction polymer laminar nano composite material in the deformation that produces 1～100% perpendicular to electric field and tensile direction, thus output mechanical energy.
Embodiment 3
Will 2.0 under the condition of argon shield, add in the tetrahydrofuran solution of 20ml n-Butyl Lithium in the gram molybdenumdisulphide, stir after 1 hour in the Dropwise 5 00ml deionized water.Filter, filter residue and drying is ground obtain organic stratiform molybdenumdisulphide.With being dispersed in 200 gram mass concentration under this organo montmorillonite violent stirring is in the tetrahydrofuran solution of 20wt% polymethoxy siloxanes, adds linking agent tetraethoxy 0.4g, and catalyzer dialkyl group dicarboxylic acid tin 0.01g is evenly mixed.This mixed liquid is filmed in quartz substrate, under 50～60 ℃ of conditions, solidified 10 hours, obtain thickness and be 10 microns nano-composite material membrane.This matrix material rete is carried out one dimension 50～100% stretch orientations, obtain Electrostriction polymer laminar nano composite material III of the present invention.
With this Electrostriction polymer laminar nano composite material III, method by spin-coating or spraying is at the coated on both sides carbon back conductive resin of film, obtaining the two sides is the artificial thews material of the sandwich structure of conductive resin, the middle Electrostriction polymer laminar nano composite material III of the present invention of being, and this sandwich structure is orientated nano-lamellar structure by stretching with draw direction along parallel in Electrostriction polymer laminar nano composite material.Sandwich structure is applied the electric field of strength of electric field 10～50V/ μ m, can make Electrostriction polymer laminar nano composite material in the deformation that produces 1～50% perpendicular to electric field and tensile direction, thus output mechanical energy.
Embodiment 4
2.0 gram lamellar graphite materials are added in the 20ml vitriol oil, and ultrasonic agitation obtains Ionized lamellar graphite after 1 hour.With 0.2g quaternary amine, 1g concentration is that 37% concentrated hydrochloric acid and 10ml water mix, and makes the quaternary amine aqueous solution.The aqueous solution that vigorous stirring gets under the condition lamellar graphite slowly drips in the aqueous solution of quaternary amine.Filter, be washed to no chlorion and sulfate ion, filter residue and drying is ground obtain organo montmorillonite.With being dispersed in 1000 gram mass concentration under this organo montmorillonite violent stirring is in the tetrahydrofuran solution of 10wt% acrylic elastomer, adds linking agent 1,2-propylene diamine 5g, and catalyzer dialkyl group dicarboxylic acid tin 0.01g is evenly mixed.This mixed liquid is filmed in quartz substrate, and solvent slowly after the volatilization at ambient temperature, reheat to 70 ℃ solidified 5 hours, obtained thickness and be 1000 microns nano-composite material membrane.This matrix material rete is carried out one dimension 50～200% stretch orientations, obtain Electrostriction polymer laminar nano composite material IV of the present invention.
With this Electrostriction polymer laminar nano composite material IV, method by spin-coating or spraying is at the coated on both sides carbon back conductive resin of film, obtaining the two sides is the artificial thews material of the sandwich structure of conductive resin, the middle Electrostriction polymer laminar nano composite material IV of the present invention of being, and this sandwich structure is orientated nano-lamellar structure by the tensile shear effect with draw direction along parallel in Electrostriction polymer laminar nano composite material.Sandwich structure is applied the electric field of strength of electric field 10～50V/ μ m, can make Electrostriction polymer laminar nano composite material in the deformation that produces 1～100% perpendicular to electric field and tensile direction, thus output mechanical energy.
Claims (8)
1, a kind of Electrostriction polymer laminar nano composite material, it is what obtain by following method:
1) with electrostrictive polymers 100 weight part, nano lamellar inorganic materials 0.1～20 weight part, organic intercalation agent 0.1～20 weight part, linking agent 1～5 weight part, catalyzer 0.01～0.2 weight part, protonating agent 0.2～5 weight part are filmed on quartz substrate after mixing evenly, carry out 1～10 hour curing reaction at 40～120 ℃ then, obtain thickness and be 10～1000 microns matrix material rete;
Described electrostrictive polymers is the oligopolymer of silicon rubber or acrylic elastomer;
Laminated insulation body material, layered semiconductor material or stratiform conductor material that described nano lamellar inorganic materials is 50～1000 nano-scales;
Described organic intercalation agent is an organic amine;
Described linking agent is tetraethoxy, phenylformic acid amine or 1,2-propylene diamine;
Described catalyzer is a dialkyl group dicarboxylic acid tin;
Described protonating agent is hydrochloric acid, phosphoric acid or sulfuric acid;
2) the matrix material rete that step 1) is obtained makes the matrix material rete be orientated along draw direction along one dimension direction stretch orientation, obtains Electrostriction polymer laminar nano composite material of the present invention.
2, Electrostriction polymer laminar nano composite material as claimed in claim 1 is characterized in that: described laminated insulation material is polynite; Described layered semiconductor material is a molybdenumdisulphide; Described layered conductive material is a lamellar graphite.
3, Electrostriction polymer laminar nano composite material as claimed in claim 1 is characterized in that: described organic amine is hexadecyl trimethyl ammonium bromide, cetylamine or trolamine.
4, the preparation method of the described Electrostriction polymer laminar nano composite material of a kind of claim 1 comprises following step:
1) with electrostrictive polymers 100 weight part, nano lamellar inorganic materials 0.1～20 weight part, organic intercalation agent 0.1～20 weight part, linking agent 1～5 weight part, catalyzer 0.01～0.2 weight part, protonating agent 0.2～5 weight part are filmed on quartz substrate after mixing evenly, carry out 1～10 hour curing reaction at 40～120 ℃ then, obtain thickness and be 10～1000 microns matrix material rete;
Described electrostrictive polymers is the oligopolymer of silicon rubber or acrylic elastomer;
Laminated insulation body material, layered semiconductor material or stratiform conductor material that described nano lamellar inorganic materials is 50～1000 nano-scales;
Described organic intercalation agent is an organic amine;
Described linking agent is tetraethoxy, phenylformic acid amine or 1,2 one propylene diamine;
Described catalyzer is a dialkyl group dicarboxylic acid tin;
Described protonating agent is hydrochloric acid, phosphoric acid or sulfuric acid;
2) the matrix material rete that step 1) is obtained makes the matrix material rete be orientated along draw direction along one dimension direction stretch orientation, obtains Electrostriction polymer laminar nano composite material of the present invention.
5, the preparation method of Electrostriction polymer laminar nano composite material as claimed in claim 4 is characterized in that: described laminated insulation material is polynite; Described layered semiconductor material is a molybdenumdisulphide; Described layered conductive material is a lamellar graphite.
6, the preparation method of Electrostriction polymer laminar nano composite material as claimed in claim 4 is characterized in that: described organic amine is hexadecyl trimethyl ammonium bromide, cetylamine or trolamine.
7, the described Electrostriction polymer laminar nano composite material of one of claim 1～3 is in the application of relevant electricity driving, pump and sensor field of artificial-muscle.
8, purposes as claimed in claim 7, it is characterized in that: with the described Electrostriction polymer laminar nano composite material of one of claim 1～3, method by spin-coating or spraying is at coated on both sides carbon back conductive resin, obtaining the two sides is that conductive resin, centre are the artificial thews material of the sandwich structure of Electrostriction polymer laminar nano composite material, and this sandwich structure is orientated nano-lamellar structure by the tensile shear effect with draw direction along parallel in Electrostriction polymer laminar nano composite material; Sandwich structure is applied the electric field of strength of electric field 10～100V/ μ m, make Electrostriction polymer laminar nano composite material in the deformation that produces 1～100% perpendicular to electric field and tensile direction, thus output mechanical energy.
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| CN101958394B (en) * | 2009-07-17 | 2011-11-30 | 清华大学 | Electrostriction composite material and electrostriction element |
| CN101847466B (en) * | 2010-03-22 | 2011-07-20 | 朱惠欣 | Method for preparing carbon series conductive slurry added with nano material and application |
| CN102551918B (en) * | 2012-02-21 | 2014-11-19 | 上海海事大学 | Electroshock extension artificial muscle movement device |
| CN106604482B (en) * | 2016-11-25 | 2018-06-12 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of AC electroluminescence device |
| CN107541072B (en) * | 2017-08-22 | 2019-10-18 | 华南理工大学 | High temperature circulation drawing force causes the silicon rubber composite material and preparation method thereof of electric conductivity enhancing |
| CN113416332B (en) * | 2021-06-23 | 2023-03-24 | 青岛科技大学 | Preparation method of high-thermal-conductivity three-phase composite film under assistance of electric field |
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| US11433648B2 (en) | 2016-07-27 | 2022-09-06 | The Penn State Research Foundation | Multilayered dielectric composites for high temperature applications |
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