阅读说明：本技术 用于发光显示器的离子导电电化学发光水凝胶及其制备方法 (Ionic conduction electrochemical luminescence hydrogel and preparation method thereof for active display ) 是由 李菲 郭晓锦 李迎春 李亚北 于 2019-07-15 设计创作，主要内容包括：本发明公开了一种用于发光显示器的离子导电电化学发光水凝胶及其制备方法。该电化学发光水凝胶是通过将氯化钠/三联吡啶氯化钌/三正丙胺吸附在阴离子型聚丙烯酰胺水凝胶的三维网络结构中而形成的复合电化学发光水凝胶。具体是将单体丙烯酰胺、单体丙烯酸钠、交联剂甲叉双丙烯酰胺、导电介质氯化钠、电化学发光体系三联吡啶氯化钌/三正丙胺、引发剂过硫酸铵和加速剂四甲基乙二胺混合形成红色透明溶液,室温下或烘箱加热成胶。本发明制备的电化学发光水凝胶有效固定了电化学发光物质,不仅保留水凝胶良好的透光性和可拉伸性,还具有良好的导电性、均一性和电化学发光性质,该水凝胶可应用于发光显示器,具有可循环、低引发电压等优点。(The ionic conduction electrochemical luminescence hydrogel and preparation method thereof that the invention discloses a kind of for active display.The electrochemical luminescence hydrogel is the luminous hydrogel of composite electrochemical formed and sodium chloride/Tris(2,2'- bipyridyl) ruthenium (II) chloride/Tri-n-Propylamine is adsorbed in the three-dimensional net structure of anion-polyacrylamide hydrogel.Monomeric acrylamide, monomeric acrylic sodium, crosslinking agent methylene diacrylamide, conducting medium sodium chloride, electrochemiluminescsystem system Tris(2,2'- bipyridyl) ruthenium (II) chloride/Tri-n-Propylamine, initiator ammonium persulfate and accelerator tetramethylethylenediamine are specifically mixed to form red, transparent solution, at room temperature or baking oven heats plastic.Electrochemical luminescence hydrogel prepared by the present invention effectively secures electrochemical luminescence substance, not only retain the good translucency of hydrogel and tensility, also there is good electric conductivity, homogeneity and electrochemical luminescence property, the hydrogel can be applied to active display, have many advantages, such as recyclable, low initiation voltage.)

1. a kind of ionic conduction electrochemical luminescence hydrogel, it is characterised in that: the ionic conduction electrochemical luminescence hydrogel includes Anion-polyacrylamide hydrogel substrate, and the electrochemical luminescence substance and ion that are dispersed in the hydrogel substrate are led Dielectric.

2. a kind of ionic conduction electrochemical luminescence hydrogel according to claim 1, it is characterised in that: the ionic conduction electricity Chemiluminescence hydrogel is by the way that electrochemical luminescence substance and ion conducting medium are adsorbed on anion-polyacrylamide water The luminous hydrogel of the composite electrochemical formed in the three-dimensional net structure of gel, wherein electrochemical luminescence substance is selected from three Pyridine ruthenic chloride/Tri-n-Propylamine electrochemiluminescsystem system, ion conducting medium is selected from sodium chloride, in anion-polyacrylamide The concentration of Tris(2,2'- bipyridyl) ruthenium (II) chloride is 0.1mM~10mM in the cross-linking system of hydrogel, the concentration of Tri-n-Propylamine be 1mM~ 100mM, the concentration of sodium chloride are 0.1M~1M.

3. a kind of ionic conduction electrochemical luminescence hydrogel according to claim 1, it is characterised in that: the ionic conduction electricity The conductivity of chemiluminescence hydrogel is 0.005s/m~0.05s/m.

4. a kind of ionic conduction electrochemical luminescence hydrogel according to claim 1, it is characterised in that: the ionic conduction electricity The luminous current potential of chemiluminescence hydrogel is 1.0V~5.0V.

5. a kind of preparation method of ionic conduction electrochemical luminescence hydrogel, it is characterised in that: the following steps are included:

1) acrylamide, sodium acrylate and crosslinking agent are uniformly mixed in water, obtain solution a；

2) electrochemical luminescence substance is uniformly mixed with solution a, obtains solution b；

3) ion conducting medium is uniformly mixed with solution b, obtains solution c；

4) by solution c, initiator and accelerator be uniformly mixed obtain solution d, in solution d the concentration of acrylamide be 2.0M~ 2.5M, the concentration of sodium acrylate are 0.3M~0.4M, concentration 0.01M~0.15M of crosslinking agent, the concentration of initiator be 3mM~ 5mM, the concentration of accelerator are 60mM~70mM；

5) hydrogel for being dispersed with electrochemical luminescence substance and ion conducting medium is generated by solution d by cross-linking reaction.

6. a kind of preparation method of ionic conduction electrochemical luminescence hydrogel according to claim 5, it is characterised in that: described In step 1), crosslinking agent is selected from methylene diacrylamide, acrylamide: methylene diacrylamide: the mass ratio of sodium acrylate is 100:(1~15): (20~25).

7. a kind of preparation method of ionic conduction electrochemical luminescence hydrogel according to claim 5, it is characterised in that: described Electrochemical luminescence substance is in Tris(2,2'- bipyridyl) ruthenium (II) chloride/Tri-n-Propylamine electrochemiluminescsystem system, the solution d, terpyridyl The concentration of ruthenic chloride is 0.1mM~10mM, and the molar concentration of Tri-n-Propylamine is 1mM~100mM.

8. a kind of preparation method of ionic conduction electrochemical luminescence hydrogel according to claim 5, it is characterised in that: described For ion conducting medium in sodium chloride, the solution d, the concentration of sodium chloride is 0.1M~1M.

9. a kind of preparation method of ionic conduction electrochemical luminescence hydrogel according to claim 5, it is characterised in that: described In step 4), initiator is selected from ammonium persulfate, and accelerator is selected from tetramethylethylenediamine, acrylamide: ammonium persulfate: tetramethyl second The mass ratio of diamines is 100:(0.5~1): (0.1~10).

10. a kind of preparation method of ionic conduction electrochemical luminescence hydrogel according to claim 5, it is characterised in that: institute Step 5) is stated specifically includes the following steps: solution d is stood 0.5~3 hour, or solution d is placed in 50~70 DEG C of baking ovens ≤ 1 hour, obtain ionic conduction electrochemical luminescence hydrogel.

Technical field

The invention belongs to composite material synthesis and application fields, are related to a kind of ionic conduction electrification for active display Learn the hydrogel (NaCl/Ru (bpy) that shines₃Cl₂/ TPA/APAM hydrogel) preparation.

Background technique

Electrochemical luminescence is obtained due to highly sensitive, stability and simplicity in the fields such as bioanalysis and environmental analysis Extensive research.Ru(bpy)₃Cl₂/ TPA has good recyclability, stability as classical electrochemiluminescsystem system And luminous intensity, can preferably it meet applied to electrochemical luminescence device growing inexpensive, disposable or repeatable Using the demand of display, it is expected to the substitute as Organic Light Emitting Diode.

Hydrogel is the general designation of a kind of cross-linked polymer that can be swollen and cannot be dissolved in water in water, wherein anion The features such as type polyacrylamide (APAM) hydrogel has both adsorptivity, flocculability, dispersibility, in the fields such as food, environment Using very wide.The conductive hydrogel branch important as hydrogel has good electric conductivity, translucency, tensility Deng can be used as the inexpensive base material of active display, greatly widened hydrogel in the energy, electronic console, electricity The application in the fields such as detection.

Conductive hydrogel can be divided into Common hydrogels, electronic conduction hydrogel and ionic conduction hydrogel.Its intermediate ion is led Electric hydrogel usually combines ionic liquid or inorganic ion (such as sodium chloride) and hydrogel to improve leading for hydrogel Electrically, but ionic liquid have the shortcomings that poorly water-soluble, toxicity greatly, higher cost, limit its application.Sodium chloride have from Sub- migration rate height, good water solubility, environmental-friendly, at low cost, chemical and thermal stability is high, good biocompatibility, can be extensive The advantages that production, is not only to improve the ideal chose of hydrogel electric conductivity, and the water holding capacity of hydrogel can be improved.

Simple physical doping cannot be effectively fixed medium (electrochemiluminescsystem system and conductive ion) at present, manufactured Composite electrochemical shines hydrogel (such as aqueous phase) under use environment, and the medium adulterated is easy diffusion and is lost, and affects it Display performance improves application cost.

Summary of the invention

The purpose of the present invention is to provide a kind of ionic conduction electrochemical luminescence hydrogel for active display and its Preparation method.The present invention introduces electrostatic adsorption using anion-polyacrylamide hydrogel backbone, preferably fixed electricity Chemiluminescent substance (such as Ru (bpy)₃ ²⁺), to obtain the stable electrochemical luminescence hydrogel of performance.

In order to achieve the above objectives, the invention adopts the following technical scheme:

A kind of ionic conduction electrochemical luminescence hydrogel, the ionic conduction electrochemical luminescence hydrogel include that anionic is poly- Acrylamide (APAM) hydrogel substrate, and the electrochemical luminescence object being dispersed in the three-dimensional net structure of the hydrogel substrate Matter and ion conducting medium.

Preferably, the ionic conduction electrochemical luminescence hydrogel is by the way that electrochemical luminescence substance and ionic conduction are situated between Matter is adsorbed on the three-dimensional net structure of anion-polyacrylamide hydrogel and the composite electrochemical that is formed shines hydrogel, In, electrochemical luminescence substance is selected from Tris(2,2'- bipyridyl) ruthenium (II) chloride/Tri-n-Propylamine electrochemiluminescsystem system (Ru (bpy)₃Cl₂/ TPA), from Subconductivity medium is selected from sodium chloride (NaCl), the terpyridyl chlorination in the cross-linking system of anion-polyacrylamide hydrogel The molar concentration of ruthenium is 0.1mM~10mM, and the molar concentration of Tri-n-Propylamine is 1mM~100mM, and the molar concentration of sodium chloride is 0.1M~1M.

Preferably, the conductivity of the ionic conduction electrochemical luminescence hydrogel is 0.005s/m~0.05s/m.

Preferably, the luminous current potential of the ionic conduction electrochemical luminescence hydrogel is 1.0V~5.0V.

The preparation method of above-mentioned ionic conduction electrochemical luminescence hydrogel, comprising the following steps:

1) by monomeric acrylamide (AM), monomeric acrylic sodium (NaAA) and crosslinking agent methylene diacrylamide (MBAA) in It is uniformly mixed in water, obtains solution a；

2) by electrochemical luminescence substance Tris(2,2'- bipyridyl) ruthenium (II) chloride (Ru (bpy)₃Cl₂) and Tri-n-Propylamine (TPA) and solution a it is mixed It closes uniformly, obtains red, transparent solution b；

3) ion conducting medium sodium chloride (NaCl) is uniformly mixed with red, transparent solution b, obtains red, transparent solution c；

4) red, transparent solution c, initiator ammonium persulfate (APS) and accelerator tetramethylethylenediamine (TEMED) is abundant Mixing, obtains final mixed solution d；In the solution d, the molar concentration of AM is 2.0M~2.5M, and the molar concentration of NaAA is The molar concentration of the molar concentration 0.01M~0.15M, APS of 0.3M~0.4M, MBAA are 3mM~5mM, the molar concentration of TEMED For 60mM~70mM；

5) thermal crosslinking treatment (as continued at room temperature or being heated to higher temperature) is carried out to final mixed solution d, obtained Red, transparent hydrogel.

Preferably, in the step 1), the mass ratio of AM:MBAA:NaAA is 100:(1~15): (20~25), to guarantee The APAM hydrogel formed after crosslinking has the mechanical property for being suitable for and the adsorption capacity to the dopant in cross-linking system.

Preferably, in the solution d, Ru (bpy)₃Cl₂Molar concentration be 0.1mM~10mM, the molar concentration of TPA is 1mM~100mM, to guarantee electrochemical luminescence hydrogel (NaCl/Ru (bpy)₃Cl₂/ TPA/APAM hydrogel) there is preferable electricity Chemiluminescence property.

Preferably, in the solution d, the molar concentration of conducting medium NaCl is 0.1M~1M, to guarantee electrochemical luminescence Hydrogel (NaCl/Ru (bpy)₃Cl₂/ TPA/APAM hydrogel) there is preferable electric conductivity.

Preferably, in the step 4), the mass ratio of AM:APS:TEMED is 100:(0.5~1): (0.1~10), to protect Demonstrate,prove electrochemical luminescence hydrogel (NaCl/Ru (bpy)₃Cl₂/ TPA/APAM hydrogel) reasonable plastic speed and hydrogel hardness.

Preferably, the thermal crosslinking treatment specifically includes the following steps: solution before polymerizeing (the i.e. described solution d) in 20~ 0.5~3 hour is stood at 30 DEG C；Or (the i.e. described solution d) is placed in 50~70 DEG C of baking ovens≤1 hour solution before polymerizeing.

Preferably, the temperature of the baking oven is 60~65 DEG C.

The beneficial effects of the present invention are embodied in:

The present invention is prepared for a kind of electrochemical luminescence hydrogel (such as NaCl/Ru (bpy)₃Cl₂/ TPA/APAM hydrogel), system Preparation Method is easy to operate, and reaction condition is mild, and preparation cost is low, is conducive to produce in batches.Not only make full use of anionic poly- The porous three-dimensional net structure of acrylamide gel comes Uniform Doped electrochemical luminescence substance and ion conducting medium, Er Qieli Electrostatic adsorption is introduced with the negative electricity skeleton of the hydrogel effectively to adsorb the dopants such as electrochemical luminescence substance It is fixed.The electrochemical luminescence hydrogel can be applied to active display field, have many advantages, such as recyclable, low initiation voltage.

Further, obtained NaCl/Ru (bpy)₃Cl₂It is good that/TPA/APAM hydrogel not only retains hydrogel Photosensitiveness and tensility also have good electric conductivity, electrochemical luminescence property and homogeneity.

Further, by control crosslinking agent MBAA dosage (ratio is unsuitable too low), solution before polymerizeing is avoided to be unable to plastic.

Further, it by controlling the dosage (ratio should not be too large) of ion conducting medium NaCl, avoids because being quenched Influence the luminous intensity of electrochemical luminescence substance in hydrogel.

Detailed description of the invention

Fig. 1 is NaCl/Ru (bpy) prepared by the embodiment of the present invention 1₃Cl₂/ TPA/APAM electrochemical luminescence hydrogel is answered Use schematic diagram；Wherein: 1 is ionic conduction electrochemical luminescence hydrogel, and 2 be conductive copper adhesive tape.

Fig. 2 is NaCl/Ru (bpy) prepared by the embodiment of the present invention 1₃Cl₂The pattern audio-visual picture of/TPA/APAM hydrogel.

Fig. 3 is NaCl/Ru (bpy) prepared by the embodiment of the present invention 1₃Cl₂The infrared spectrogram of/TPA/APAM hydrogel.

Fig. 4 is NaCl/Ru (bpy) prepared by the embodiment of the present invention 1₃Cl₂/ TPA/APAM hydrogel and APAM hydrogel Microscopic appearance figure.

Fig. 5 is NaCl/Ru (bpy) prepared by the embodiment of the present invention 1₃Cl₂The electrochemical luminescence figure of/TPA/APAM hydrogel (0-1.5V)。

Fig. 6 is NaCl/Ru (bpy) prepared by the embodiment of the present invention 1₃Cl₂The electrochemical luminescence figure of/TPA/APAM hydrogel (0-3.0V)。

Fig. 7 is NaCl/Ru (bpy) prepared by the embodiment of the present invention 1₃Cl₂/ TPA/APAM hydrogel and polyacrylamide PAAm hydrogel diffusion experiment (in water) result figure.

Fig. 8 is NaCl/Ru (bpy) prepared by the embodiment of the present invention 1₃Cl₂The electrochemical luminescence of/TPA/APAM hydrogel is straight See figure.

Specific embodiment

Invention is further described in detail with reference to the accompanying drawings and examples.The embodiment is for explaining this hair It is bright, rather than limiting the scope of the invention.

(1) ionic conduction electrochemical luminescence hydrogel (NaCl/Ru (bpy) is prepared₃Cl₂/ TPA/APAM hydrogel)

By by sodium chloride/Tris(2,2'- bipyridyl) ruthenium (II) chloride/Tri-n-Propylamine (NaCl/Ru (bpy)₃Cl₂/ TPA) it adsorbs into APAM water The luminous hydrogel of composite electrochemical is formed in gel three-dimensional network structure.Specifically by monomer (AM, NaAA), crosslinking agent MBAA, ion conducting medium NaCl, electrochemiluminescsystem system Ru (bpy)₃Cl₂/ TPA, initiator A PS and accelerator TEMED are successively It is mixed to form red, transparent solution, red, transparent solution is subjected to thermal crosslinking treatment, forms red, transparent hydrogel.