CN115260544A - Rapid forming method of multi-crosslinked 3D gel material - Google Patents
Rapid forming method of multi-crosslinked 3D gel material Download PDFInfo
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- CN115260544A CN115260544A CN202210882514.9A CN202210882514A CN115260544A CN 115260544 A CN115260544 A CN 115260544A CN 202210882514 A CN202210882514 A CN 202210882514A CN 115260544 A CN115260544 A CN 115260544A
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- 238000000034 method Methods 0.000 title claims abstract description 63
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 38
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2405/04—Alginic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
Abstract
The invention provides a rapid forming method of a multi-crosslinked 3D gel material, which comprises the steps of adding an ethylene diamine tetraacetic acid disodium calcium solution into a solution containing sodium alginate and carboxymethyl chitosan to obtain a mixed solution; and immersing the working electrode into the mixed solution for electrochemical deposition to obtain the multi-crosslinked 3D gel material. The anode metal ions generated by the anode of the invention are chelated with polymer molecules to form a first layer of gel, and meanwhile, the excessive anode metal ions initiate competitive chelation,stimulation of EDTA & Na2Ca release Ca2+The source cross-links with the polymer molecules to form a second layer of transparent gel; under the action of an electric field and concentration driving, a concentration gradient of metal ions is formed in the gel, so that the gel material has a gradient layered structure. The gel material prepared by the invention has an interpenetrating network structure and a bimetallic ion chelating and crosslinking effect, the thickness and the mechanical property are greatly improved, the generation efficiency is improved by about 10 times compared with the traditional preparation method, and the gel material is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of gel materials, in particular to a rapid forming method of a multi-crosslinked 3D gel material.
Background
At present, hydrogel materials are widely applied in the biomedical field. Among them, the calcium alginate hydrogel material shows obvious advantages in the biomedical field because of its high water absorption capacity, high biocompatibility and biodegradability. Calcium alginate hydrogels are typically prepared by the chelation and rapid gelation of sodium alginate with calcium ions. In the prior art, a calcium salt (such as calcium chloride and calcium carbonate) is directly mixed with a sodium alginate solution to form hydrogel, or sodium alginate fibers are injected into the calcium chloride solution to form hydrogel. In the method, the property of the finally formed gel material is influenced by the speed of adding calcium ions into the sodium alginate solution, if the calcium ions are added too fast, uneven gel can be formed, the continuity of the gel structure is lost, and if the calcium ions are added too slowly, the production efficiency of the gel material is too low; in addition, calcium ions are completely freely diffused in sodium alginate, and therefore, it is difficult to precisely control the release amount of calcium ions to be chelated with sodium alginate; this makes controlling the structural uniformity and shape of hydrogel materials extremely challenging.
The invention patent (application number is CN 201610881153.0) discloses alginic acid/chitosan blending sponge and a preparation method, micron or nanometer insoluble calcium salt powder and sodium alginate solution are mixed uniformly to form suspension; slowly adding the chitosan acid solution into the suspension, stirring to form alginic acid/chitosan gel, and freeze-drying to obtain the blended sponge. According to the method, nano calcium salt is used as a calcium ion source, an acid environment is provided through acid treatment to dissolve the calcium salt, calcium ions are released, and then the calcium ion source is chelated with alginic acid and chitosan to form the hydrogel material. However, in the method, the nano calcium salt particles and the sodium alginate solution are easy to be gelatinized and are easy to be mixed and distributed unevenly; and when the hydrogel is dissolved in an acid solution, gas is generated, great influence is caused on the uniformity of the internal structure of the formed gel, and a cavity or a defect structure is formed in the gel material, so that the gel shows a semitransparent state, has poor mechanical property and cannot meet the requirement of a complex scene.
In view of the above, there is a need to design an improved method for rapid molding of multiple cross-linked 3D gel materials to solve the above problems.
Disclosure of Invention
The invention aims to provide a rapid forming method of a multi-crosslinked 3D gel material, which prepares an interpenetrating polymer network structure material by taking two-component polymer molecules as a deposition precursor through an electrochemical deposition method; anodic metal ions generated after anodic oxidation and Ca provided by disodium calcium ethylene diamine tetraacetate2+A source that generates a multiply cross-linked 3D gel material on the electrode surface by competitive chelation and multiple cross-linking; the method can accurately control and improve the growth rate and the thickness of the gel material, and the prepared gel material has excellent mechanical properties.
In order to achieve the above object, the present invention provides a method for rapidly forming a multiple cross-linked 3D gel material, comprising the steps of:
s1, dissolving disodium calcium ethylene diamine tetraacetate powder in deionized water to prepare a solution, and adding the solution into a precursor solution to obtain a mixed solution; the solute of the precursor solution comprises sodium alginate; the mass ratio of the ethylene diamine tetraacetic acid disodium calcium to the sodium alginate in the mixed solution is 1 (0.5-1.2);
s2, immersing the working electrode into the mixed solution obtained in the step S1, performing electrochemical deposition, taking out the electrode after the electrochemical deposition is finished, and stripping gel from the surface of the electrode to obtain a multi-crosslinked 3D gel material; the anode of the working electrode is metal A, the cathode of the working electrode is metal B, and the activity of the metal B is weaker than that of the metal A.
As a further improvement of the invention, in the step S1, the solute of the precursor solution further comprises carboxymethyl chitosan, and the mass ratio of the carboxymethyl chitosan to the sodium alginate is 1 (0.5-1.2).
As a further improvement of the present invention, in step S2, after the multi-crosslinked 3D gel material is obtained, it is immersed in a calcium chloride solution to be cured, so as to increase the degree of crosslinking, and impurity ions are washed away.
As a further improvement of the present invention, in step S1, the mass fraction of each component in the mixed solution is 0.5% to 1.2%, preferably 1%; the weight percentage of the disodium calcium ethylene diamine tetraacetate in the disodium calcium ethylene diamine tetraacetate solution is 1-3.5%, and the preferable weight percentage is 3%.
As a further improvement of the invention, in step S2, the effective area of the single side of the sheet electrode of the working electrode is 0.4cm2～100cm2(ii) a During electrodeposition, the working potential is 4-10V; the deposition time is 1-10 min.
As a further improvement of the invention, the thickness of the prepared multi-crosslinked 3D gel material is 0.1-2.5 mm.
As a further improvement of the present invention, in step S2, the anode metal a of the working electrode includes one of iron, copper, zinc, nickel, silver, and aluminum; the anode and the cathode are respectively connected to an electrochemical workstation; the distance between the anode and the cathode is 8-15 mm, and the immersion depth of the electrodes is 20-40 mm.
As a further improvement of the invention, in the electrodeposition in step S2, a mask method is used to control the deposition region and the non-deposition region, so as to realize the overall patterning of the gel material and prepare a multi-crosslinked 3D gel material with different patterns.
As a further improvement of the present invention, in step S1, the prepared mixed solution is stored at 4 ℃ for later use.
As a further improvement of the present invention, in step S2, after the electrode is taken out, the electrode is rinsed three times with deionized water to remove the excessive impurities.
The invention has the beneficial effects that:
1. the invention provides a rapid molding method of a multi-crosslinked 3D gel material, which comprises the steps of adding an ethylene diamine tetraacetic acid disodium calcium solution into a precursor solution containing carboxymethyl chitosan and sodium alginate to obtain a mixed solution; immersing a working electrode into the mixed solution for electrochemical deposition to obtain a multi-crosslinked 3D gel material; the prepared multi-crosslinked 3D gel material is immersed in a calcium chloride solution to increase the crosslinking degree of calcium ions and polymers. The gel material prepared by the invention has an interpenetrating network structure and a double-metal ion chelating and crosslinking function, shows a layering phenomenon, greatly improves the whole thickness, and improves the generation efficiency by about 10 times compared with the traditional gel material preparation method; the composite material also has good biocompatibility and degradability, is pollution-free, can be rapidly prepared in batches, and is suitable for industrial production.
2. According to the invention, alginic acid and carboxymethyl chitosan are used as deposition precursors by an electrochemical deposition method, and a double-component polymer molecule is used for preparing a double-network structure material, so that the mechanical properties of the gel material are improved. In the deposition process, anodic metal ions generated after anodic oxidation and Ca provided by disodium calcium ethylene diamine tetraacetate2+A source that generates a multiply cross-linked 3D gel material on the electrode surface by competitive chelation and multiple cross-linking; in addition, there are anodic metal ions and Ca as the distance from the solution to the anode varies2+A concentration gradient of anode metal ions, e.g. Cu, near the anode side2+A cross-linked dense layer of Ca on the side away from the anode electrode2+The cross-linked structure loose layer enables the formed 3D gel material to show a better layered structure, so that the gel material has unique physical and chemical properties and can meet the application requirements of complex scenes.
3. The invention provides a novel calcium ion source-disodium calcium ethylene diamine tetraacetate, which can be uniformly mixed with alginic acid, has relatively sensitive pH responsiveness, and can obviously improve the efficiency of gel formation by electrodeposition; the preparation method matched with the electrochemical deposition method solves the problems that calcium salt particles are not uniformly mixed and distributed in the traditional mode, the uniformity of the internal structure of the formed gel is affected, and the mechanical property is poor. In addition, the disodium calcium ethylene diamine tetraacetate is used as a calcium source, and after the calcium ethylene diamine tetraacetate is mixed with alginic acid, calcium ions cannot be immediately chelated with the calcium ethylene diamine tetraacetate, and the calcium ethylene diamine tetraacetate needs to be induced under certain conditions; therefore, the calcium source does not have the problem that the structure of the prepared gel material is discontinuous because the traditional calcium salt reacts with alginic acid too fast.
4. In the electrochemical deposition process, interpenetrating polymer structure double-layer hydrogel with different sizes and shapes is obtained by controlling the working potential, the deposition time and the electrode shape; the precipitation amount of metal ions of the anode is controlled by transferring electric quantity to accurately control and improve the growth rate and the thickness of the gel material; and the deposition area and the non-deposition area can be controlled by using a mask method, so that the 3D gel material with different patterns is prepared by integrally patterning the gel, and the multi-crosslinked 3D gel material is quickly prepared by further folding and assembling to form complex 3D gel. The preparation method disclosed by the invention is mild in reaction and simple in preparation process, can be used for preparing multifunctional composite hydrogel films with different shapes by changing electric signals and deposition parameters, and has a huge application prospect in the field of medical use.
Drawings
Fig. 1 is a schematic diagram of the forming mechanism of the multiple cross-linked 3D gel material of the present invention.
FIG. 2 is an optical and electron micrograph of a multiple crosslinked 3D gel material according to example 1 of the present invention; wherein (a) is an optical picture, (b) is an electron microscope microscopic picture, and (c) is an energy spectrum picture.
Fig. 3 is a graph showing optical images and thickness test results of 3D gel materials prepared in example 1 of the present invention and comparative examples 1 to 3.
Fig. 4 is a schematic diagram of a process for forming a multi-crosslinked 3D gel material according to example 2 of the present invention and a macroscopic picture.
Fig. 5 is an optical picture of a multiple cross-linked 3D gel material prepared in example 3 of the present invention.
Fig. 6 is an effect view of folding the gel materials of different shapes prepared in example 3 of fig. 5 (a).
Fig. 7 is a front and side view of gel materials prepared using different anode metals in examples of the present invention and comparative examples.
Fig. 8 is a graph showing the thickness measurement result of each gel material in fig. 7.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
A rapid prototyping method of a multiple cross-linked 3D gel material comprises the following steps:
s1, dissolving calcium disodium ethylene diamine tetraacetate (EDTA. Na)2Ca) powder is dissolved in deionized water to prepare a solution, the solution is added into the precursor solution to obtain a mixed solution, and the mixed solution is stored at 4 ℃ for standby; wherein the solute of the precursor solution comprises Sodium Alginate (SA); the mass ratio of the calcium disodium ethylene diamine tetraacetate and the sodium alginate in the mixed solution is 1 (0.5-1.2);
particularly, the solute of the precursor solution also comprises carboxymethyl chitosan (CMC), and the mass ratio of the carboxymethyl chitosan to the sodium alginate is 1 (0.5-1.2); alginic acid and carboxymethyl chitosan are used as deposition precursors, and a double-component polymer molecule is used for preparing a double-network structure material, so that the mechanical property of the finally prepared gel material is improved;
s2, immersing the working electrode into the mixed solution obtained in the step S1, performing electrochemical deposition, taking out the electrode after the electrochemical deposition is finished, disconnecting the electrode from a power supply, washing the electrode with deionized water for three times, and stripping gel from the surface of the electrode to obtain a multi-crosslinked 3D gel material; and (3) immersing the multi-crosslinked 3D gel material into a calcium chloride solution for solidification so as to increase the crosslinking degree and wash away impurities EDTA and sodium ions.
The anode of the working electrode is metal A, the cathode of the working electrode is metal B, and the activity of the metal B is weaker than that of the metal A, so that in the electrochemical deposition process, the metal A serving as the anode can be electrolyzed and oxidized to generate anode metal ions, the anode metal ions close to the anode and polymer molecules generate chelation and quickly form a first layer of gel film, meanwhile, excessive anode metal ions can initiate competitive chelation, and the acidic environment generated by side reaction with accompanying electrolyzed water can stimulate EDTA & Na2Ca release Ca2+And (3) spontaneously and further chelating and crosslinking with polymer molecules to form a second layer of transparent gel. In addition, under the driving action of electric field and concentration, anode metal ions and Ca are formed in the gel2+Such that the formed multiple cross-linked 3D gel material has a gradient layered structure. By controlling the release amount of the anode metal ions, the production efficiency, the thickness and the structural uniformity of the gel material can be controlled; overcomes the defect that the gel forming process and the formed structure can not be controlled in the traditional method.
The traditional electrochemical method has low efficiency and poor mechanical property, is usually limited by a single polymer component and the influence of low crosslinking degree of the single polymer component, and the thickness of the generated gel film is limited by the change of local microenvironment of electrochemical reaction, so that thicker gel is difficult to form. Although the thickness can be increased to some extent by increasing the voltage or time for applying the current, the uniformity of the thin film material to be formed is seriously affected by the generation of bubbles due to the excessively violent reaction. The invention improves the generation efficiency by about 10 times compared with the traditional method by combining the electrochemical deposition method, the deposition system and the competitive chelation of the bimetallic ions, and the prepared gel material has uniform structure and greatly improved thickness.
In some specific embodiments, metal a includes iron, copper, zinc, nickel, silver, and aluminum; the metal B is a platinum wire.
In particular, anodic oxygenThe anode metal ions generated after the reaction and Ca provided by the disodium calcium ethylene diamine tetraacetate2+A source of anodic metal ions and Ca according to distance from the anode by competitive chelation and multiple cross-linking, simultaneously under the action of electric field induced diffusion2+A concentration gradient exists such that multiple cross-linked 3D gel materials are generated at the electrode surface. The presence of anodic metal ions may play a role in reacting with Ca2+And the competitive chelation with the polymer ensures that the layer interface of the prepared 3D gel material is tightly and firmly connected, thereby having better service performance.
EDTA·Na2Ca is used as a new calcium ion source, can be uniformly mixed with alginic acid, has relatively sensitive pH responsiveness, and can remarkably improve the efficiency of gel formation by electrodeposition; by matching with an electrochemical deposition method, the problems that calcium salt particles are not uniformly mixed and distributed in the traditional mode, the uniformity of the internal structure of the formed gel is affected, and the mechanical property is poor are solved. In addition, the disodium calcium ethylene diamine tetraacetate is used as a calcium source, and after the calcium ethylene diamine tetraacetate is mixed with alginic acid, calcium ions cannot be immediately chelated with the calcium ethylene diamine tetraacetate, and the calcium ethylene diamine tetraacetate needs to be induced under certain conditions; therefore, the calcium source does not have the problem that the conventional calcium salt reacts with alginic acid too quickly to cause discontinuous structure of the prepared gel material.
Specifically, in step S1, the mass fraction of each component in the mixed solution is 0.5% to 1.2%, preferably 1%. The weight percentage of the disodium calcium ethylene diamine tetraacetate in the disodium calcium ethylene diamine tetraacetate solution is 1 to 3.5 percent, and the preferred weight percentage is 3 percent. The mass fraction of the solute in each solution is related to the degree of polymer reaction, and the structure and the mechanical property of the prepared gel material are further influenced.
Specifically, in step S2, the effective area of the working electrode on one side of the sheet electrode is 0.4cm2～100cm2(ii) a During electrodeposition, the working potential is 4-10V; the deposition time is 1-10 min; the thickness of the prepared multi-crosslinked 3D gel material is 0.1-2.5 mm. During electrochemical deposition, interpenetrating structure double-layer hydrogel with different sizes and shapes is obtained by controlling the working potential, the deposition time and the electrode shape; controlling the precipitation of anodic metal ions by transferring the electrical quantityThe amount is precisely controlled and the growth rate and thickness of the gel material are increased.
The anode and the cathode of the working electrode are respectively connected to an electrochemical workstation; the distance between the anode and the cathode is 8-15 mm, and the immersion depth of the electrodes is 20-40 mm. During the electrochemical deposition process, the distance between the solution and the anode is different, and anode metal ions and Ca exist2+The side close to the anode side is a structural compact layer crosslinked by anode metal ions, and the side far away from the copper electrode is Ca2+A crosslinked structured bulk layer; the formed 3D gel material shows a better layered structure, as shown in FIG. 1, which is a schematic diagram of the forming mechanism of the gel material of the invention; the gel material prepared by the invention can show unique physical and chemical properties and meet the application requirements of complex scenes.
In the electrochemical deposition, a mask method can be used for controlling a deposition area and a non-deposition area, so that the gel is integrally patterned, the 3D gel materials with different patterns are prepared, and the 3D gel materials with the multi-layer gradient structure are rapidly prepared by further folding and assembling to form complex 3D gel. The method has mild reaction and simple preparation process, can prepare the multifunctional composite hydrogel films with different shapes by changing electric signals and deposition parameters, and has huge application prospect in the field of transdermal drug delivery dressings.
Example 1
The embodiment provides a method for rapidly forming a multi-crosslinked 3D gel material, which comprises the following steps:
s1, weighing 0.3g of disodium calcium ethylene diamine tetraacetate powder, and dissolving the powder in 100mL of deionized water to obtain EDTA-Na2A Ca solution; respectively weighing 0.3g of CMC and 0.3g of SA, respectively adding 100mL of deionized water to prepare a CMC solution and an SA solution, mixing the CMC solution and the SA solution, and magnetically stirring the mixture for 1 hour at normal temperature to obtain a CMC/SA solution; EDTA-Na2Adding the Ca solution into the CMC/SA solution, and uniformly mixing to obtain the CMC/SA/EDTA-Na with three components of which the mass fractions are all 1 percent (w/v)2The mixed solution of Ca is preserved for standby at 4 ℃;
s2, measuring 20mL of CMC/SA/EDTA & Na2Ca mixed solution asIn order to deposit the solution, a working electrode with a copper sheet as an anode and a platinum wire as a cathode is immersed into the deposition solution, the distance between the positive electrode and the negative electrode is 10mm, and the immersion depth of the electrodes is 30mm; and (3) carrying out electrodeposition by adopting a constant potential working mode, setting the deposition potential to be 10V, setting the deposition area to be 8mm multiplied by 20mm, electrifying for 3 minutes, disconnecting the electrode from the electrochemical workstation after the deposition process is finished, taking out the electrode from the solution, washing by using deionized water, and taking down the whole prepared double-layer gel material by using tweezers to obtain the multi-crosslinked 3D gel material.
Fig. 2 shows an optical image and an electron microscope image of the multiple cross-linked 3D gel material of the present embodiment, wherein (a) is an optical image, (b) is an electron microscope microscopic image, and (c) is a spectrum image. As can be seen from the graph (a), the gel has two layers of blue and transparent, the blue being Cu2+The characteristic color is Ca2+The characteristic color is crosslinked, and the gradient that the blue color gradually becomes lighter from the copper electrode to the outside can be seen; in the diagram (b), the double-layer gel has a microscopic double-layer structure, wherein the side close to the copper electrode is dense and is a dense layer, and the side far away from the copper electrode is loose and is a loose layer; as can be seen from FIG. (c), the dense layer is mainly Cu2+The crosslinked, loose layer is mainly Ca2+Cross-linked and Cu is present with distance from the copper electrode2+And Ca2+The concentration gradient of (1). The results showed that a double-group of polymer molecules (alginic acid and carboxymethyl chitosan) was used as a deposition precursor, a copper electrode was used, and EDTA · Na was added2Ca as additional Ca2+A source that causes the gel to spontaneously form a second layer of gel.
Example 2
This example provides a method for rapid prototyping of a multiple-crosslinked 3D gel material, which differs from example 1 in that no CMC is added in step S1, but only SA/EDTA & Na2Ca solution is used as deposition solution; the rest is substantially the same as embodiment 1, and will not be described again.
The gel material obtained in example 2 was deposited to a thickness of about 0.68mm, and compared to example 1, cu was generated due to the anodic oxidation reaction2+Will communicate with SAThe molecules are rapidly crosslinked, resulting in a thin and dark green inner layer gel, and EDTA & Na2Ca releases Ca under the stimulation of solution environment2+A source that twice crosslinks with SA to form a second clear layer gel on the outer layer; however, since example 2 is a deposition system of a single polymer, the thickness of the resulting gel is reduced compared to example 1.
Comparative example 1
Comparative example 1 provides a method of forming a 3D gel material, which is different from example 1 in that EDTA & Na is not added in step S12Ca, only CMC/SA solution is used as the deposition solution, and the rest is substantially the same as example 1, and is not repeated herein.
Comparative example 2
Comparative example 2 provides a method for forming a 3D gel material, which is different from example 1 in that EDTA & Na is not added in step S12Ca and SA are substantially the same as those in example 1 except that a CMC solution is used as a deposition solution, and are not described again.
Comparative example 3
Comparative example 3 provides a method for forming a 3D gel material, which is different from example 1 in that EDTA & Na is not added in step S12Ca and CMC, which are substantially the same as those in example 1 except that SA solution is used as the deposition solution, are not described herein again.
Comparative example 4
Comparative example 4 provides a method for forming a 3D gel material, which is different from example 1 in that both the anode and the cathode of the working electrode are platinum wires in step S2, and the rest is substantially the same as example 1, and thus, detailed description thereof is omitted.
Fig. 3 is a graph showing optical images and thickness test results of the 3D gel materials prepared in example 1 and comparative examples 1 to 3; the gel material thickness of comparative example 2 was taken as 100% in fig. 3. It can be seen from the figure that the thickness of the gel material produced by the deposition solution of the CMC or SA component is lower under the same other conditions, while the thickness of the gel produced by deposition is significantly improved by the existence of the CMC/SA double-polymer system, and meanwhile, the additional Ca is used2+A source of CMC/SA/EDTA-Na by competitive chelation and secondary crosslinking2The thickness of the Ca system deposition was 1.8 times that of the CMC/SA system deposition gel. From the results, it was revealed that a double-group polymer molecule (alginic acid and carboxymethyl chitosan) was used as a deposition precursor, a copper electrode was used, and EDTA · Na was added2Ca as additional Ca2+The source can obviously improve the whole thickness and the generation efficiency of the gel.
In comparative example 4, when the anode and cathode of the working electrode were both platinum wires, there was no anode metal Cu2+Ion generation, only electrolytic water reaction, but EDTA Na is still stimulated by the weak acidic environment formed near the anode2Part of Ca in Ca2+Released, formed a highly transparent gel with polymer molecules, having a thickness of about 0.55mm, whereas in example 1, when a platinum wire was used for the cathode and a metallic copper electrode was used for the anode, both anodic oxidation reaction and electrolytic water side reaction occurred, and the formed gel exhibited an inner blue color and an outer transparent layer having a distinct layered structure, and the gel thickness of example 1 was 1.8mm, which was also greatly improved compared to comparative example 4.
Example 3
Example 3 provides a rapid prototyping method of a multiple cross-linked 3D gel material, which is different from example 1 in that, in step S2, during the electrodeposition process, the deposition area is 4mm × 4mm, the power is applied for 10 minutes, and the copper electrode is modified by using an insulating mask of 3 mm; the rest is substantially the same as embodiment 1, and will not be described again.
Fig. 4 is a schematic diagram and a macroscopic view of a process for forming the multi-crosslinked 3D gel material of example 3. In example 3, the copper electrode was modified with a 3mm insulating mask so that the deposited gel grew in the intended spatial direction. As can be seen from FIG. 4, by controlling the gel growth by the mask method of example 3, a 3D gel material having a shape similar to "mushroom" can be prepared, as seen by color, where "pileus" is Ca2+A loose layer with crosslinked gel as main component and transparent color, and the "stipe" is Cu2+The compact layer with crosslinked gel as the main component is blue; 3D gel illustrating that certain spatial structures can be prepared by maskingThe gel widens the application range of the gel material.
Example 4
FIG. 5 shows an optical image of the multiple cross-linked 3D gel material obtained in example 4. In example 4, the copper electrode was modified with insulating masks of different sizes and shapes so that the deposited gel grew in the desired spatial direction. As can be seen from FIG. 5, after the modification by the mask method, the obtained gel has a spatial structure and a distinct color gradient, and the gel can be generated even in the non-deposition area of the modified mask; the mask-modified region was in a clear color of Ca2+The loose layers, which are mainly crosslinked gel, are connected to each other through the loose layers, so that the deposition regions can be connected to each other, thereby obtaining a desired pattern, color, and spatial structure. The 3D gel material with different patterns can be prepared by using different templates to realize the overall gel patterning by using a mask method.
Referring to fig. 6, when the gel materials with different shapes prepared in example 4 of fig. 5 (a) are folded, it can be seen that the dense layers of the gel material deposition areas are connected with each other through the loose layers of the non-deposition areas, so that the deposition areas can form a whole space, and the joints have good mechanical properties, and can be folded at least 90 degrees without breaking; the desired configuration, such as the space cube of fig. 6, can be obtained by folding and assembling. The double-layer gel material prepared by the mask method has excellent mechanical property, can be further folded and assembled to form complex 3D gel, and can meet the application of certain complex scenes.
Examples 5 to 9
Examples 5 to 9 provide a rapid prototyping method of a multi-crosslinked 3D gel material, which is different from example 1 in that, in step S2, anodes of the working electrodes of examples 5 to 9 are silver, zinc, nickel, aluminum, and iron pieces, respectively; the rest is substantially the same as embodiment 1, and will not be described again.
Comparative examples 5 to 9
Comparative examples 5 to 9 provide a method of molding a gel material, which is different from example 1 in that EDTA & Na is not added in step S12Ca, only CMC/SA solution was used as the deposition solution, and in step S2, anodes of the working electrodes of comparative examples 5 to 9 were silver, zinc, nickel, aluminum, and iron pieces, respectively; the rest is substantially the same as embodiment 1, and will not be described again.
Referring to fig. 7 to 8, fig. 7 is a front view and a side view of a gel material prepared by using different anode metals in examples and comparative examples; fig. 8 is a graph showing the thickness measurement result of each gel material in fig. 7. As can be seen from fig. 7, when the anodes are respectively copper, silver, zinc, nickel, aluminum and iron, gel materials with different colors can be prepared; in addition, EDTA & Na was added regardless of the metal of the anode2In the examples of Ca, gel materials having a layered structure were obtained, and the gel materials prepared using zinc and aluminum as anodes did not delaminate significantly because the gel materials had high transparency and exhibited no color change. As is clear from FIG. 8, EDTA/Na was added separately2Ca provides Ca2+When the source is used, the thickness of each gel material is improved; the thickness of the gel material prepared by taking copper and zinc as the anode is improved to the greatest extent.
In summary, the invention provides a method for rapidly forming a multi-crosslinked 3D gel material, which comprises the steps of adding an ethylene diamine tetraacetic acid disodium calcium solution into a precursor solution containing carboxymethyl chitosan and sodium alginate to obtain a mixed solution; and immersing the working electrode into the mixed solution for electrochemical deposition to obtain the multi-crosslinked 3D gel material. According to the invention, alginic acid and carboxymethyl chitosan are used as deposition precursors by an electrochemical deposition method to prepare the material with the double-network structure, so that the mechanical property of the gel material is improved. Anodic metal ions and EDTA & Na generated after anodic oxidation of working electrode2Ca supplied by Ca2+Source, generated on the electrode surface by competitive chelation and multiple cross-linkingA multiply cross-linked 3D gel material; in addition, under the driving action of electric field and concentration, there are anode metal ions and Ca2+The formed 3D gel material shows a better layered structure and unique physical and chemical properties by the concentration gradient of (2), and can meet the application requirements of complex scenes. The invention introduces EDTA & Na2Ca is used as a new calcium ion source, can be uniformly mixed with alginic acid, has relatively sensitive pH responsiveness, and can obviously improve the efficiency of gel formation by electrodeposition. The overall thickness and the mechanical property of the prepared 3D gel material are greatly improved, and the generation efficiency is improved by about 10 times compared with that of the traditional electrochemical deposition method; the composite material also has good biocompatibility and degradability, is pollution-free, can be rapidly prepared in batches, and is suitable for industrial production.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A method for rapidly forming a multi-crosslinked 3D gel material is characterized by comprising the following steps:
s1, dissolving disodium calcium ethylene diamine tetraacetate powder in deionized water to prepare a solution, and adding the solution into a precursor solution to obtain a mixed solution; the solute of the precursor solution comprises sodium alginate; the mass ratio of the ethylene diamine tetraacetic acid disodium calcium to the sodium alginate in the mixed solution is 1 (0.5-1.2);
s2, immersing the working electrode into the mixed solution obtained in the step S1, performing electrochemical deposition, taking out the electrode after the electrochemical deposition is finished, and stripping gel from the surface of the electrode to obtain a multi-crosslinked 3D gel material; the anode of the working electrode is metal A, the cathode of the working electrode is metal B or graphite, and the activity of the metal B is weaker than that of the metal A.
2. The method for rapidly forming the multiple cross-linked 3D gel material according to claim 1, wherein in step S1, the solute of the precursor solution further comprises carboxymethyl chitosan, and the mass ratio of the carboxymethyl chitosan to the sodium alginate is 1 (0.5-1.2).
3. The method for rapidly forming a multiple-crosslinked 3D gel material according to claim 1, wherein in step S2, after the multiple-crosslinked 3D gel material is obtained, the multiple-crosslinked 3D gel material is immersed in a calcium chloride solution for solidification so as to increase the crosslinking degree and wash away impurity ions.
4. The method for rapid prototyping of multiple cross-linked 3D gel material as recited in claim 1, wherein in step S1, the mass fraction of each component in the mixed solution is 0.5% to 1.2%, preferably 1%; the weight percentage of the disodium calcium ethylene diamine tetraacetate in the disodium calcium ethylene diamine tetraacetate solution is 1-3.5%, and the preferable weight percentage is 3%.
5. The method for rapid prototyping of multiple cross-linked 3D gel material as in claim 1, wherein in step S2, the effective area of the working electrode on one side of the sheet electrode is 0.4cm2～100cm2(ii) a During electrodeposition, the working potential is 2-10V; the deposition time is 1-10 min.
6. The method for rapid prototyping of multiple cross-linked 3D gel materials as set forth in claim 5 wherein the multiple cross-linked 3D gel materials are produced with a thickness of 0.1 to 2.5mm.
7. The method for rapid prototyping of multiple cross-linked 3D gel material as recited in claim 1 wherein in step S2 the anodic metal a of the working electrode comprises one of iron, copper, zinc, nickel, silver and aluminum; the anode and the cathode are respectively connected to an electrochemical workstation; the distance between the anode and the cathode is 8-15 mm, and the immersion depth of the electrodes is 20-40 mm.
8. The method for rapidly forming a multi-crosslinked 3D gel material according to claim 1, wherein in the step S2 of electrodeposition, a mask method is used to control a deposition region and a non-deposition region, so as to realize overall patterning of the gel material and obtain the multi-crosslinked 3D gel material with different patterns.
9. The method for rapid prototyping of multiple cross-linked 3D gel material as recited in claim 1, wherein the mixed solution is prepared at step S1 and stored at 4 ℃ for further use.
10. The method for rapid prototyping of multiple cross-linked 3D gel materials as in claim 1, wherein in step S2, after the electrodes are taken out, the electrodes are rinsed three times with deionized water to remove excess impurities.
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