阅读说明：本技术 离子导电双网络水凝胶及其制备方法和应用 (Ionic conduction double-network hydrogel and its preparation method and application ) 是由 袁伟忠 杨博文 于 2019-08-01 设计创作，主要内容包括：本发明提供了一种离子导电双网络水凝胶及其制备方法和应用,制备方法为以水溶性盐电解液提供导电离子,氢键交联的琼脂为第一交联网络,化学交联的聚2-(甲基丙烯酰基氧基)乙基-二甲基-(3-磺酸丙基)氢氧化铵为第二交联网络,通过紫外光引发得到；本发明的离子导电双网络水凝胶可以在温度-应变双重传感器或电致发光装置中应用；本发明的离子导电双网络水凝胶具有高透明性、高拉伸强度、高断裂伸长率、温度和应变双重传感性、传感范围广和灵敏系数高的特点,在可视化可穿戴设备、弹性电致发光、智能人工皮肤等领域具有广阔的应用前景；本发明的制备方法简单易行,制备周期短,原料绿色环保,可工业化生产,从而具有很好的推广应用价值。(The present invention provides a kind of ionic conduction double-network hydrogels and its preparation method and application; preparation method is provides conductive ion with water soluble salt electrolyte; the agar of hydrogen bond crosslinks is the first cross-linked network; poly- 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide of chemical crosslinking is the second cross-linked network, light-initiated is obtained by ultraviolet；Ionic conduction double-network hydrogel of the invention can be applied in temperature-strain dual sensor or el light emitting device；Ionic conduction double-network hydrogel of the invention has the characteristics that high transparency, high tensile, high elongation at tear, temperature and strain dual sensing, sensing scope is wide and sensitivity coefficient is high, has broad application prospects in fields such as visualization wearable device, elastic electroluminescent, intelligent artificial skins；Of the invention preparation method is simple, and short preparation period, raw material is environmentally protective, can industrialized production, thus have good application value.)

1. a kind of ionic conduction double-network hydrogel, it is characterised in that: it includes following component:

2. ionic conduction double-network hydrogel according to claim 1, it is characterised in that: the conductive salt is selected from chlorination One or more of lithium, sodium chloride, magnesium chloride, lithium sulfate, lithium perchlorate, sodium perchlorate, magnesium sulfate and sodium tetraborate.

3. ionic conduction double-network hydrogel according to claim 1, it is characterised in that: the photoinitiator is selected from 2- hydroxyl Base -2- methyl phenyl ketone, 2- hydroxy-methyl phenyl-propane -1- ketone, 2- hydroxy-2-methyl -1- phenyl -1- acetone and 2- ketone penta One or more of diacid.

4. ionic conduction double-network hydrogel according to claim 1, it is characterised in that: the crosslinking agent is N, and N'- is sub- Methyl-is bis--acrylamide.

5. a kind of preparation method of ionic conduction double-network hydrogel according to any one of claims 1-4, it is characterised in that: It includes the following steps:

(1), by poly- 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide and agar by mole In deionized water than 9:1-7:3 dissolution, conductive salt, photoinitiator and crosslinking agent is added, circulation is vacuumized except oxygen simultaneously three times It is passed through nitrogen, and is reacted under nitrogen and shading, mixed liquor is obtained；

(2), mixed liquor injection is in a mold and cooling, it is then transferred under ultraviolet light and irradiates, be removed from the molds, obtain To ionic conduction double-network hydrogel.

6. preparation method according to claim 5, it is characterised in that: in step (1), the temperature of the reaction is 70-95 DEG C, the time of the reaction is 2-4h.

7. preparation method according to claim 5, it is characterised in that: in step (2), the mold is by two pieces of transparent nothings Color organic glass interlayer silica gel strip formed rectangular chamber, the silica gel strip with a thickness of 0.1-2mm.

8. preparation method according to claim 5, it is characterised in that: in step (2), the temperature of the cooling is 4 DEG C, institute Stating the cooling time is 0.5-1.5h；And/or

In step (2), the wavelength of the ultraviolet light is 365nm, intensity 22.4mW/cm², the time of the irradiation is 7- 15min。

9. a kind of ionic conduction double-network hydrogel as described in claim 1 is in temperature-strain dual sensor or electroluminescent hair Application in electro-optical device.

10. application according to claim 9, it is characterised in that: the temperature-strain dual sensor is led by the ion Electric double-network hydrogel coating silicone oil composition, temperature sensitive range is 0-70 DEG C, and strain sensing range is 0-2000%, and strain passes Sense sensitivity coefficient is 0-4.8；And/or

The el light emitting device by the ionic conduction double-network hydrogel film and dimethyl silicone polymer, zinc sulphide It is formed with the mixture film of copper, the film of the ionic conduction double-network hydrogel is respectively placed in top layer and bottom, described poly- The mixture film of dimethyl siloxane, zinc sulphide and copper is placed in middle layer, the film of the ionic conduction double-network hydrogel With a thickness of 0.1-2mm, the mixture film of the dimethyl silicone polymer, zinc sulphide and copper with a thickness of 40-120 μm, institute State the mixture of dimethyl silicone polymer and zinc sulphide and copper in the mixture film of dimethyl silicone polymer, zinc sulphide and copper Mass ratio be 1:1-1:3.

Technical field

The invention belongs to high molecular materials and smart electronics field, and in particular to a kind of ionic conduction dual network water-setting Glue and its preparation method and application.

Background technique

Recent advanced intelligent flexible electronic devices emerge in multitude, and such as electronic skin, scalable sensor, robot and are based on The actuator etc. of soft material.These flexible electronic devices usually require that high mechanically deform matching degree, including bending, folding, distortion And stretching.Generally, these intelligent electronic devices are passed through by elastomeric substrate such as dimethyl silicone polymer (PDMS) and Ecoflex Composite electron conductive filler (liquid metal, silver nanowires, graphene, carbon nanotube, conducting polymer etc.) constructs conductive threshold and seeps It is prepared by network.Yu et al reports a kind of design through structure and uses the compound dimethyl silicone polymer of Carbon Nanotube Array Transparent flexible strain transducer (Yu Y, Luo Y, Guo A, et al.Flexible and transparent strain sensors based on super-aligned carbon nanotube films[J].Nanoscale,2017,9(20): 6716-6723.).Wang et al reports a kind of layer/polyaniline conductive polymeric strain sensing hydrogel, improves sensor Tensility (Wang T, Zhang Y, Liu Q, et al.A self-healable, highly stretchable, and solution processable conductive polymer composite for ultrasensitive strain and pressure sensing[J].Advanced Functional Materials,2018,28(7):1705551.).So And although realizing high sensitivity, complex structural designs, strain sensing narrow range, transparency is low, cannot be super flexible wearable The data visualization of product provides further development.Moreover, their stretchable range is relatively low (usually less than 500%), This greatly limits its sensing scopes.

As biosystem imitator, stretchable hydrogel ion conductor attracts attention recently, becomes out The flexible another means for being especially stretchable device of hair.Patent of invention CN 109294133A discloses a kind of sol-gel method The stretchable self-healing hydrogel flexibility strain transducer being prepared.As a kind of soft object containing solid and liquid simultaneously Matter, hydrogel have the behavior of more human like body skin.Hydrogel usually has intrinsic retractility and the transparency.By water-setting Glue can form ion and transmit electric current as ion conductor by the water of its high embedding amount to dissolve conductive salt ion, and ionic liquid It will not be leaked from hydrogel.Conductive ion is usually obtained from the salt of dissolution, such as lithium chloride or sodium chloride.Hydrogel matrix Inherently affect the mechanical performance of system.Traditional only water-setting matrix ion conductor intensity with one-component or structure Low, elongation at break is low, is not able to satisfy the performance requirement of super drawing conductive material of new generation.The poly- poly- 2- of amphoteric ion polymer (methylacryloyl oxygroup) ethyl-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide is a kind of biodegradable bio-compatible Natural polyelectrolyte, can be used as Hydrogel Component, the high sensitivity that a large amount of conductive ions ensure aqueous ionomer gel be provided.Chemistry The poly- 2- of poly- amphoteric ion polymer (methylacryloyl oxygroup) ethyl-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide of crosslinking Contain amino and sulfonic acid group in side group, a large amount of hydrogen bond can be formed with agar, generate physical cross-linked network, is formed multiple weak dynamic State network.By introducing dual network structure and its sacrificing the energy dissipation mechanism of key, the hydrogel mechanical performance of formation will substantially It improves.When gel is stretched, first network becomes rigid and crisp due to swelling effect, and reply external force is first broken sacrifice, largely Dissipated the power being applied on gel, and the second network then is used to bridge the first network of fracture to maintain the globality of gel, Key is sacrificed in Recovery Process to rebuild.Thus double-network hydrogel has been assigned strong mechanical performance, to improve hydrogel in reality Tolerance in application environment.Conductive ion and high-strength dual network gel-in-matrix is mutually compound, high performance ion can be obtained Conductor is with a wide range of applications in wearable device, intelligent sensing field.

Summary of the invention

Aiming at the shortcomings in the prior art, primary and foremost purpose of the invention is to provide a kind of ionic conduction double-network hydrogel.

A second object of the present invention is to provide the preparation methods of above-mentioned ionic conduction double-network hydrogel, i.e., with water solubility Salt electrolyte (i.e. conductive salt) provides conductive ion, and (i.e. hydrogen bond crosslinks are the molecular structure pendant groups due to agar to hydrogen bond crosslinks It is mostly hydroxyl, intermolecular to spontaneously form hydrogen bond after being dissolved in water) agar be the first cross-linked network, be chemically crosslinked (i.e. ultraviolet It is light-initiated) poly- 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide be the second cross-linked network By ultraviolet light-initiated final product ionic conduction double-network hydrogel quickly is prepared in network.

Third object of the present invention is to provide the applications of above-mentioned ionic conduction double-network hydrogel.

In order to achieve the above objectives, solution of the invention is:

A kind of ionic conduction double-network hydrogel comprising following component:

Preferably, conductive salt is selected from lithium chloride, sodium chloride, magnesium chloride, lithium sulfate, lithium perchlorate, sodium perchlorate, magnesium sulfate One or more of with sodium tetraborate.

Preferably, photoinitiator is selected from 2- hydroxy-2-methyl propiophenone, 2- hydroxy-methyl phenyl-propane -1- ketone, 2- hydroxyl Base-2- methyl-1-one or more of phenyl-1- acetone and 2-oxoglutaric acid.

Preferably, crosslinking agent N, N'- methylene-bis-acrylamide.

A kind of preparation method of above-mentioned ionic conduction double-network hydrogel comprising following steps:

(1), poly- 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide and agar are pressed Molar ratio 9:1-7:3 dissolves in deionized water, and conductive salt, photoinitiator and crosslinking agent is added, and circulation vacuumizes deoxygenation three times Gas is simultaneously passed through nitrogen, and is reacted under nitrogen and shading, and mixed liquor is obtained；

(2), mixed liquor injection is in a mold and cooling, it is then transferred under ultraviolet light and irradiates, be removed from the molds, obtain To ionic conduction double-network hydrogel.

Preferably, in step (1), the temperature of reaction is 70-95 DEG C, and the time of reaction is 2-4h.

Preferably, in step (2), mold is the rectangular cavity formed by two pieces of clear, colorless organic glass interlayer silica gel strips Room, silica gel strip with a thickness of 0.1-2mm.

Preferably, in step (2), cooling temperature is 4 DEG C, and the cooling time is 0.5-1.5h.

Preferably, in step (2), the wavelength of ultraviolet light is 365nm, intensity 22.4mW/cm², irradiation time 7- 15min。

A kind of above-mentioned ionic conduction double-network hydrogel is in temperature-strain dual sensor or el light emitting device Using.

Preferably, temperature-strain dual sensor is made of ionic conduction double-network hydrogel coating silicone oil, temperature sensing Range is 0-70 DEG C, and strain sensing range is 0-2000%, and strain sensing sensitivity coefficient is 0-4.8.

Preferably, el light emitting device by ionic conduction double-network hydrogel film and dimethyl silicone polymer, vulcanization The mixture film (PDMS/ZnS:Cu film) of zinc and copper composition, the film of ionic conduction double-network hydrogel are respectively placed in top Layer and bottom, the mixture film (PDMS/ZnS:Cu film) of dimethyl silicone polymer, zinc sulphide and copper are placed in middle layer, from The film of subconductivity double-network hydrogel with a thickness of 0.1-2mm, the mixture film of dimethyl silicone polymer, zinc sulphide and copper (PDMS/ZnS:Cu film) with a thickness of 40-120 μm, the mixture film (PDMS/ of dimethyl silicone polymer, zinc sulphide and copper ZnS:Cu film) in the mixture (ZnS:Cu) of dimethyl silicone polymer (PDMS) and zinc sulphide and copper mass ratio be 1:1- 1:3。

By adopting the above scheme, the beneficial effects of the present invention are:

The first, the present invention uses natural polysaccharide material agar and the poly- 2- of biocompatible material (methylacryloyl oxygroup) second Base-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide by introducing conductive ion and dual network structure, while utilizing ultraviolet initiation Polymerization, obtained ionic conduction double-network hydrogel have high transparency, high tensile, high elongation at tear, temperature and answer Become dual sensing, the feature that sensing scope is wide and sensitivity coefficient is high, in visualization wearable device, elastic electroluminescent, intelligence The fields such as energy artificial skin have broad application prospects.

The second, of the invention preparation method is simple, and short preparation period, raw material is environmentally protective, can industrialized production, from And there is good application value.

Detailed description of the invention

Fig. 1 is the tensile strength schematic diagram (abscissa of the ionic conduction double-network hydrogel of the embodiment of the present invention 1 Strain is strain, and ordinate Stress is stress).

Fig. 2 is the compressive strength schematic diagram (abscissa of the ionic conduction double-network hydrogel of the embodiment of the present invention 1 Compression strain is compression strain, and ordinate Compression stress is compression stress).

Fig. 3 is the strain sensing schematic diagram (abscissa of the ionic conduction double-network hydrogel of the embodiment of the present invention 1 Strain is strain, and left ordinate Resistance is resistance, and right ordinate Gauge factor is the scale factor).

Fig. 4 is that the ionic conduction double-network hydrogel base el light emitting device light emission luminance of the embodiment of the present invention 1 characterizes Schematic diagram (abscissa Voltage is voltage, and ordinate Luminance is brightness).

Specific embodiment

The present invention provides a kind of ionic conduction double-network hydrogels and its preparation method and application.

<ionic conduction double-network hydrogel>

Ionic conduction double-network hydrogel of the invention includes following component:

Wherein, conductive salt be selected from lithium chloride, sodium chloride, magnesium chloride, lithium sulfate, lithium perchlorate, sodium perchlorate, magnesium sulfate and One or more of sodium tetraborate.

Photoinitiator is selected from 2- hydroxy-2-methyl propiophenone, 2- hydroxy-methyl phenyl-propane -1- ketone, 2- hydroxyl -2- first One or more of base -1- phenyl -1- acetone and 2-oxoglutaric acid.

Crosslinking agent is N, N'- methylene-bis-acrylamide.

<preparation method of ionic conduction double-network hydrogel>

The preparation method of ionic conduction double-network hydrogel of the invention includes the following steps:

(1), poly- 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide and agar are pressed Molar ratio 9:1-7:3 dissolves in deionized water, and conductive salt, photoinitiator and crosslinking agent is added, and circulation vacuumizes deoxygenation three times Gas is simultaneously passed through nitrogen, and carries out under nitrogen protection and shading, adjusts the temperature of reaction, and carry out magnetic agitation, is mixed Liquid；

(2), transparent mixed liquor being uniformly mixed to be injected in molding die with syringe, surrounding is fixed with binder clip, It is transferred in refrigerator later cooling；The mold for loading cooling obtained colloidal sol is transferred under ultra-violet curing instrument and is irradiated, taking-up is unloaded Fall mold, obtains ionic conduction double-network hydrogel.

The visible transparent rate of the ultra-drawn ionic conduction double-network hydrogel of the high transparency is 90-98%, break-draw Intensity is 120-580KPa, compressive strength 340-770KPa, break-draw strain 400-2000%, elasticity modulus 4.5 ×10⁴-2.0×10⁵KPa。

Wherein, in step (1), the temperature of reaction can be 70-95 DEG C, preferably 70 DEG C；The time of reaction can be 2-4h, preferably 2h.

In step (2), mold is the rectangular chamber formed by two pieces of clear, colorless organic glass interlayer silica gel strips, silica gel The thickness of item can be 0.1-2mm, preferably 0.1mm.

In step (2), cooling temperature is 4 DEG C, and the cooling time can be 0.5-1.5h, preferably 0.5h.

In step (2), the wavelength of ultraviolet light is 365nm, intensity 22.4mW/cm², the time of irradiation can be 7- 15min, preferably 7min.

<application of ionic conduction double-network hydrogel>

Ionic conduction double-network hydrogel of the invention can be in temperature-strain dual sensor or el light emitting device Using.

Wherein, temperature-strain dual sensor is made of ionic conduction double-network hydrogel coating silicone oil, is had simultaneously Temperature and strain dual sensing.In fact, strain sensing range is 0-2000%, strain sensing sensitivity coefficient is 0-4.8, is answered Change-sensitivity is positively correlated.Temperature sensitive range is 0-70 DEG C, and temperature-resistance relationship is negatively correlated, and temperature change is to strain The influence of sensor has linear relationship.

El light emitting device by ionic conduction double-network hydrogel film and PDMS/ZnS:Cu film (i.e. poly dimethyl The mixture film of siloxanes, zinc sulphide and copper) composition, for a kind of layer assembly structure of two kinds of films, two layers of ion is led The film of electric double-network hydrogel is respectively placed in top layer and bottom, poly- PDMS/ZnS:Cu film (i.e. dimethyl silicone polymer, sulphur Change the mixture film of zinc and copper) be placed in middle layer, the film of ionic conduction double-network hydrogel with a thickness of 0.1-2mm, electricity Photoluminescence emitting voltage is 3-220V, frequency 100-1600Hz；PDMS/ZnS:Cu film with a thickness of 40-120 μm.PDMS/ The mass ratio of PDMS and ZnS:Cu particle is 1:1-1:3 in ZnS:Cu film.

The present invention is further illustrated with reference to embodiments.