CN104959988B - Muscle driving module based on temperature responsiveness hydrogel - Google Patents
Muscle driving module based on temperature responsiveness hydrogel Download PDFInfo
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- CN104959988B CN104959988B CN201510291994.1A CN201510291994A CN104959988B CN 104959988 B CN104959988 B CN 104959988B CN 201510291994 A CN201510291994 A CN 201510291994A CN 104959988 B CN104959988 B CN 104959988B
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- Medicinal Preparation (AREA)
- Manipulator (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a muscle driving module based on temperature responsiveness hydrogel; the muscle driving module comprises a driving layer based on the temperature responsiveness hydrogel, a flexible protection layer wrapping the driving layer, and an electrothermal layer arranged between the driving layer and the flexible protection layer. The muscle driving module uses flexible material to serve as a muscle auxiliary device, thus preventing machinery damage on human body; an electrothermal driving mode can drive the material to deform, and is easily controlled, thus obtaining different driving forms.
Description
Technical field
The present invention relates to technical field of hydrogel, and in particular to a kind of muscle based on temperature-responsive hydrogel drives mould
Block.
Background technology
Hydrogel material is a kind of to be filled in the soft material that polymer mesh structure is formed by hydrone.Because it has
The characteristic such as wet, soft, is widely used in the fields such as bioengineering, drug delivery, organizational project.Intelligent aqueous gel material is water-setting
One kind of glue, its change to external environment condition is very sensitive, if the factor such as ambient temperature, pH, photosignal, special chemical molecule
Generation minor variations, intelligent aqueous gel itself can occur the change of corresponding physical arrangement or chemical constitution.Therefore, because
Intelligent aqueous gel can rapidly indicate the change of some external environmental factors, under certain environmental stimuli, change its volume or
Other qualitative responses are made, there is the intelligent aqueous gel of excellent mechanical performances can apply to the knot such as biology, medical science for some
Muscle drive module in structure.
Typical intelligent aqueous gel material is divided into temperature-responsive water-setting according to its response to different external environments
Glue, pH responsiveness aquagels, ionic strength responsiveness aquagel etc..With a kind of typical temperature-responsive hydrogel, (poly- N- is different
Propylacrylamide hydrogel) as a example by, it is with the rising of temperature, when temperature reaches its response temperature (32 DEG C -35 DEG C), water
Macromolecular chain in gel will occur drastically phenomenon of losing water, so as to the volume for causing hydrogel diminishes, if afterwards by the external world
The temperature of environment is reduced, and the macromolecular chain in hydrogel will once again return to hydrophily, so as to the water swelling from external environment,
Volume becomes big.
Intelligence change in intelligent aqueous gel volume, and its mechanical characteristic similar to human muscle so as to have very big
Possibly as muscle drive material be widely used.However, most of hydrogel with good intelligent characteristic is in mechanics
All it has been short of in performance, they are perhaps too soft, it is impossible to produce too big driving force, it is perhaps too fragile, it is easily broken
Failure.Deficiency in mechanical property causes its ability and application in terms of driving to be restricted.Document " Highly
Stretchable and tough hydrogels " (NATURE 2012) disclose a kind of double-network hydrogel material, and it is
The hydrogel with high tensile property and excellent toughness by prepared by two kinds of macromolecule networks are by way of complementing each other
Material, two kinds of macromolecule networks of this material are respectively a kind of a kind of rigid macromolecule network and chemical bond friendships of ionomer
The flexible macromolecule network of connection.Hydrogel is prepared by way of two kinds of macromolecule network mechanical property complementations, can be reached
Strengthen the purpose of hydrogel mechanical property.Therefore, it can by way of dual macromolecule network is combined with intelligent aqueous gel,
Prepare and can be used to produce the intelligent aqueous gel with excellent mechanical performances compared with large driving force.
On the other hand, hydrogel material major part is required for the maintenance of water environment, the corresponding environmental stimuli of intelligent aqueous gel
Major part is also to be provided by water environment.Such as the heating of temperature-responsive hydrogel, realize often through the mode of hot water is added；pH
Responsiveness aquagel produces response by changing the pH value of the aqueous solution.Such response forms limit the application of hydrogel,
Once because departing from water environment, hydrogel no longer will can realize its original intelligent function.In order to evade necessity of water environment
Property for the restriction of intelligent aqueous gel, in temperature-responsive hydrogel, extendable circuit can be added, by circuit generate heat
Mode stimulating temperature-responsive hydrogel so as to respond.So, water environment is broken away from the application of intelligent aqueous gel
Constraint, be beneficial to it and be applied in more fields.
The content of the invention
For the deficiencies in the prior art, the invention provides a kind of muscle based on temperature-responsive hydrogel drives mould
Block.
A kind of muscle drive module based on temperature-responsive hydrogel, including the driving based on temperature-responsive hydrogel
Layer, it is characterised in that also including being coated on the flexible cover sheet driven outside layer, and located at drive layer and flexible cover sheet it
Between electrothermal layer.
In the actually used break-make for making the drive module to pass through control electrothermal layer with additional control circuit, the control circuit
Electric situation with control drive layer mode of heating (temperature, temperature changing speed etc.), so as to produce different heating effects to pierce
Sharp temperature-responsive hydrogel (driving layer) produces different contractive effects, reaches the mesh of the driving effect of regulation and control drive module
, it is easy to accomplish and it is with low cost.
The muscle drive module operation principle of the present invention is as follows：When prepare drive layer hydrogel temperature raise reach it is specific
When more than temperature spot, there is dehydration in hydrogel, produce the power shunk；Temperature is replied, and through contrary process, hydrogel water suction is produced
The power of raw expansion.
The muscle drive module of the present invention has following performance requirement to preparing the temperature-responsive hydrogel for driving layer：
With preferable response characteristic, can pass through to change the larger volume deformation of external environment acquisition.With preferable
Mechanical property, can bear larger external force and not destroy, and external force is embodied in and can bear 4～5 times of deformations, modulus about 30KPa.
Preferably, the temperature-responsive hydrogel includes the first network monomer and the second network monomer of crosslinking, its
In, the network structure that first network monomer is formed is flexible network, and with temperature response characteristics, what the second network monomer was formed
Network structure is rigid network.
The present invention increases the intelligent characteristic of temperature-responsive on the good mechanical foundation of double-network hydrogel, there is provided a kind of
The new hydrogel for having temperature-responsive concurrently with excellent mechanical performances.Two kinds of networks be respectively flexible temperature-responsive network and
Rigid network, by flexible network and rigid combination good mechanical property is provided, by the intelligent to solidifying of flexible network
Glue gives intelligent characteristic.
The network structure that first network monomer is formed in the present invention is flexible network, and with temperature response characteristics, with the
One monomer introduces flexible network and temperature individual features ensures that the hydrogel for finally giving has temperature accordingly special as base material
Property.
The first network monomer of the present invention can be acrylic acid, vinyl alcohol etc., preferably, the first network monomer is
NIPA.
The second network monomer of the present invention increases the mechanical property of the hydrogel for finally giving as the source of rigid network
Can, can be 2- acrylamide-2-methylpro panesulfonic acids, SSS etc..Preferably, the second network monomer is
Sodium alginate.
Preferable effect is reached to ensure to be interacted between flexible network and rigid network, with reasonable mechanical property
Can, further preferably, the NIPA is 6～15 with the mass ratio of sodium alginate:1, the quality hundred of the water
Divide than being 80%～90%.
Said temperature responsiveness aquagel is prepared via a method which method, comprises the steps：
(1) crosslinking agent of first network monomer, the second network monomer, light trigger and first network monomer is dissolved in
Mixed solution is obtained in water；
(2) mixed solution is made to be centrifuged after uniformly mixing with the crosslinking agent and crosslinking accelerator of the second network monomer；
(3) to the solution casting die after centrifugation, being placed in imposing a condition down carries out cross-linking reaction and obtains hydrogel.
Step (1) prepares mixed solution in the present invention, and step (2) makes the crosslinking of mixed solution and the second network monomer
Agent and crosslinking accelerator are required to stir to reach the purpose of uniform dissolution, generally or so stirring half an hour when uniformly mixing.
When carrying out cross-linking reaction, first network monomer, the second network monomer, crosslinking agent are (including the friendship of first network monomer
Connection agent and the crosslinking agent of the second network monomer) and light trigger, the species of crosslinking accelerator, and corresponding proportion relation, directly
Connect the property for having influence on the hydrogel for finally preparing.
Preferably, first network monomer is NIPA in the step (1), the second network monomer is sea
The mass ratio of mosanom, its first network monomer and the second network monomer is 6～15:1.
The crosslinking agent of described first network monomer is N, and N'- methylene-bisacrylamides, quality is about first network list
The 0.02%-0.1% of weight.
The crosslinking agent of the second network monomer is ionic crosslinker, preferably, adopting Ca ion (Ca in the present invention2+),
Specifically adopt CaCO3, its quality is the 5～20% of the quality of the second network monomer (sodium alginate).Due to CaCO3It is water insoluble,
Need to discharge Ca using method for releasing in situ2+, add and CaCO in step (2) in the present invention3In gluconic acid etc. quality
Ester makes CaCO3Ca is not discharged2+。
Further preferably, described light trigger is ammonium persulfate, and quality is the quality of NIPA
0.5-5%, preferably 0.8%.Described crosslinking accelerator is N, and N, N', N'- methyl ethylenediamine, quality is N- isopropyl propylene
The 0.1% of the quality of acid amides.
Preferably, the reaction condition for carrying out cross-linking reaction is as follows：
Temperature is 0～10 DEG C, and intensity of illumination is more than 500 lumens, and cross-linking reaction time is 1h.
Intensity of illumination is more than more than the luminous flux of the light source that 500 lumens actually carry out being adopted during illumination in the present invention
500 lumens.
Due to adding N, after N, N', N'- tetramethylethylenediamine, NIPA just starts to be cross-linked to form network,
And Ca2+Plus membership make sodium alginate be cross-linked to form network rapidly, therefore during its two kinds of network monomers are uniformly dissolved first
It is added without.Due to NIPA monomer, at high temperature solubility is reduced so as to separate out from water, therefore traditional friendship
Connection process preparation technology (requiring higher temperature agent illumination) can be so that NIPA network cannot be cross-linked to form, this
In bright middle employing low temperature (5～10 DEG C) environment, by the way of compared with strong illumination it is cross-linked to form gel network.
Preferably, the thickness of the driving layer is 0.5mm-2mm.
Flexible cover sheet selects as far as possible thin, survivable, not restrained deformation, preferably, described flexible cover sheet adopts
Prepared with VHB9473, thickness is 0.1mm～0.3mm, more preferably 0.25mm.
The electrothermal layer is the heating dish being made up of some heatings.Electrothermal layer is required to the deformation for driving layer
And there is corresponding deformation, it is therefore desirable to cause circuit that there is certain ductility by specific arrangement mode, as
It is preferred that, the S-type arrangement of described heating.
For ease of carrying out position arrangement, preferably, the heating of the present invention mostly is hot water radiation wire.
Compared with prior art, the invention has the advantages that：
(1) mechanical wounding to human body can be avoided as muscle servicing unit using flexible material
(2) by way of electrothermal drive driving material to deform, and electrothermal drive is easily controllable, and then can obtain not
Same drive form；
(3) in the way of other flexible material encapsulation, increase device lifetime, and avoid driving contact of the material with human body.
Description of the drawings
Fig. 1 is the structural representation of the muscle drive module based on i.e. temperature-responsive hydrogel of the present embodiment；
Fig. 2 is the arrangement schematic diagram of resistance wire in electrothermal layer；
View when Fig. 3 a are the drive module driving spherical structure of the present embodiment in a state of nature；
View when Fig. 3 b are the drive module driving spherical structure of the present embodiment in contraction state.
Specific embodiment
Describe the present invention below in conjunction with the drawings and specific embodiments.
If Fig. 1 is that the muscle in the present embodiment based on temperature responsive intelligent hydrogel (i.e. temperature-responsive hydrogel) drives
The structural representation of dynamic model block, including based on temperature responsive intelligent hydrogel interlayer 1 (i.e. based on temperature-responsive hydrogel
Drive layer), the extendable electrothermal layer 2 being attached on temperature responsive intelligent hydrogel interlayer, and up and down two-layer by temperature
Responsive intelligent hydrogel is wrapped in flexible cover sheet therein 3.
Being used to prepare in the present embodiment drives the temperature-responsive hydrogel of layer as follows：
Including the first network monomer and the second network monomer of crosslinking, the network structure that first network monomer is formed is flexibility
Network, and with temperature response characteristics, the network structure that the second network monomer is formed is rigid network.The hydrogel of the present embodiment
The mass percent of middle water is 80%, wherein, first network monomer is NIPA, and the second network monomer is marine alga
Sour sodium.
The temperature-responsive hydrogel of the present embodiment is prepared via a method which to obtain：
(1) by NIPA, sodium alginate, NIPA crosslinking agent N, N'- di-2-ethylhexylphosphine oxides
Acrylamide and light trigger ammonium persulfate dissolve together to mixed solution, wherein, NIPA and alginic acid
The mass ratio of sodium is 13:1, N, N'- methylene-bisacrylamide is the 0.8% of the quality of NIPA, light-initiated
The quality of agent ammonium persulfate is the 0.8% of the quality of NIPA.
(2) the crosslinking agent CaCO of sodium alginate is added in the mixed solution prepared in step (1)3After shaking up, plus
Entering glucolactone and N, N, N', N'- tetramethylethylenediamine carries out shaking up Quick spin after dissolving and removes bubble.
CaCO3Quality for sodium alginate quality 10%, the quality and CaCO of glucolactone3Quality it is equal；
The quality of crosslinking accelerator N, N, N', N'- methyl ethylenediamine is the 0.1% of the quality of NIPA.
The mass percent of water is 80% in the solution that step (2) dissolving is obtained in the present embodiment.
(3) the solution injection mould after centrifugation is carried out into mold, in being subsequently placed in cryogenic box, and gives intense light irradiation to be crosslinked
Reaction.The condition that cross-linking reaction is carried out in the present embodiment is as follows：
Reaction temperature is 5 DEG C, and intensity of illumination is (using the white LED lamp conduct of 50W in the present embodiment more than 500 lumens
Light source, and carry out light source during cross-linking reaction to the distance of reactant be 1m.), a length of 1h during reaction.
Circuit in extending electrothermal layer is mainly resistance wire, and resistance wire is powered when using make electric heating once produce heat
Heating-up temperature responsive intelligent hydrogel interlayer so as to which temperature raises dehydration shrinkage.
Circuit is required to deform with the deformation of hydrogel interlayer, it is therefore desirable to made by specific arrangement mode
Obtain circuit and there is certain ductility.As shown in Fig. 2 resistance wire is the arrangement of s shapes in the present embodiment.
The characteristics of flexible cover sheet is needed with thin, soft, good toughness, so can just play protection and drive layer hydrogel, but
The effect of hydrogel driving is not limited again, and the present embodiment neutrality protective layer is prepared using VHB9473 (3M companies).
The muscle drive module of the present embodiment can be prepared via a method which to obtain：
First with one layer of VHB9473 film to prepare the bottom that intelligent aqueous gel drives the drive module of layer, one layer is prepared
Temperature responsive intelligent hydrogel, the extending circuit arranged is placed on the gel layer for preparing, then by another layer
VHB9473 films are covered thereon, and the part that upper and lower two-layer VHB9473 edge has more is bound tightly together, and synthesize driving
The prototype structure of supplementary module.
To ensure that flexible cover sheet fully wrapped around can firmly drive layer, during preparation, two panels is selected to be slightly larger in dimension than driving layer
VHB9473 films, be respectively placed in drive layer upper and lower both sides, then the part that periphery has more closely is bonded together, i.e.,
Drive layer completely to wrap up middle hydrogel, can effectively prevent the water loss in hydrogel material.
Temperature responsive intelligent hydrogel interlayer is the main body of whole module, and its operation principle is as follows：When hydrogel temperature
When rising reaches more than specified temp point, there is dehydration in hydrogel, produce the power shunk；Temperature is replied, through contrary process,
Hydrogel water suction produces the power of expansion.
Driving supplementary module in the present embodiment is composite wafer structure, and can be wrapped in need to drive various can deformation
Three-dimensional structure outside, power-up by way of, the temperature responsive intelligent hydrogel in electrothermal layer heat driven module so as to
Shrink, can reach the effect for driving whole three-dimensional structure to shrink, Fig. 3 a and Fig. 3 b is the driving ball of the drive module of the present embodiment
The use state schematic diagram of shape structure both shrinks.Preferably, the spherical structure of the present embodiment can use animal's bladder, drive
Dynamic model block can reach the effect that auxiliary bladder contraction flesh extrudes urine.
The drive module of the present embodiment is additionally provided with control circuit, the break-make Denso that the control circuit passes through control electrothermal layer
The mode of heating (temperature, temperature changing speed etc.) of control electrothermal layer is put, so as to produce different heating effects to stimulate temperature
Responsiveness aquagel (driving layer) produces different contractive effects, reaches the purpose of the driving effect of regulation and control drive module.
Above-described specific embodiment has been described in detail to technical scheme and beneficial effect, Ying Li
Solution is to the foregoing is only presently most preferred embodiment of the invention, is not limited to the present invention, all principle models in the present invention
Interior done any modification, supplement and equivalent etc. are enclosed, be should be included within the scope of the present invention.
Claims (4)
1. a kind of muscle drive module based on temperature-responsive hydrogel, including the driving based on temperature-responsive hydrogel
Layer, it is characterised in that also including being coated on the flexible cover sheet driven outside layer, and located at drive layer and flexible cover sheet it
Between electrothermal layer；The temperature-responsive hydrogel includes the first network monomer and the second network monomer of crosslinking, wherein, first
The network structure that network monomer is formed is flexible network, and with temperature response characteristics, the network knot that the second network monomer is formed
Structure is rigid network；The thickness of the driving layer is 0.5～2mm；The electrothermal layer is the heating being made up of some heatings
Disk, the S-type arrangement of all heatings；
The temperature-responsive hydrogel is prepared via a method which, comprises the steps：
(1) crosslinking agent of first network monomer, the second network monomer, light trigger and first network monomer is dissolved in water
Obtain mixed solution；
(2) mixed solution is made to be centrifuged after uniformly mixing with the crosslinking agent and crosslinking accelerator of the second network monomer；
(3) to the solution casting die after centrifugation, being placed in imposing a condition down carries out cross-linking reaction and obtains hydrogel；
Wherein, the second network monomer is sodium alginate；The crosslinking agent of the second network monomer is CaCO3, its quality is the second net
The 5～20% of the quality of network monomer；The reaction condition setting for carrying out cross-linking reaction is as follows：Temperature is 0～10 DEG C, and intensity of illumination is big
In 500 lumens, cross-linking reaction time is 1h.
2. the muscle drive module of temperature-responsive hydrogel is based on as claimed in claim 1, it is characterised in that described first
Network monomer is NIPA.
3. the muscle drive module of temperature-responsive hydrogel is based on as claimed in claim 1, it is characterised in that the flexibility
The thickness of protective layer is 0.1mm～0.3mm.
4. it is as claimed in claim 1 to plant based on the muscle drive module of temperature-responsive hydrogel, it is characterised in that described
Flexible cover sheet is prepared using VHB9473.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510291994.1A CN104959988B (en) | 2015-05-29 | 2015-05-29 | Muscle driving module based on temperature responsiveness hydrogel |
Applications Claiming Priority (1)
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| CN107101736B (en) * | 2017-06-08 | 2019-08-27 | 南京航空航天大学 | Temperature-detecting device |
| CN109620689B (en) * | 2019-01-10 | 2020-06-05 | 浙江大学 | Flexible device based on soft composite membrane and continuous human body surface massage method |
| CN110172126B (en) * | 2019-03-13 | 2020-09-01 | 浙江大学 | Artificial muscle driving module based on double-network hydrogel and dielectric elastomer and preparation method thereof |
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| WO2012075033A2 (en) * | 2010-11-29 | 2012-06-07 | President And Fellows Of Harvard College | Environmentally responsive optical microstructured hybrid actuator assemblies and applications thereof |
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