CN110904490A - Preparation method of carboxylated cellulose nanofiber hydrogel - Google Patents
Preparation method of carboxylated cellulose nanofiber hydrogel Download PDFInfo
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- CN110904490A CN110904490A CN201911129256.1A CN201911129256A CN110904490A CN 110904490 A CN110904490 A CN 110904490A CN 201911129256 A CN201911129256 A CN 201911129256A CN 110904490 A CN110904490 A CN 110904490A
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/04—Electrophoretic coating characterised by the process with organic material
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- 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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- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
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Abstract
The invention discloses a preparation method of carboxylated cellulose nanofiber hydrogel, which is characterized by comprising the following steps of: step 1): preparing a carboxylated cellulose nanofiber suspension for later use; step 2): preparing an anode material and a cathode material as an anode and a cathode of electrophoretic deposition respectively; step 3): immersing the anode material and the cathode metal material into the carboxylated cellulose nanofiber suspension, and applying direct current to carry out electrophoretic deposition on the carboxylated cellulose nanofiber; step 4): and (4) after the deposition is finished, obtaining the carboxylated cellulose nanofiber hydrogel on the anode. The invention adopts the carboxylated cellulose nanofiber suspension for electrophoretic deposition to obtain a thicker hydrogel product with a nanofiber-shaped three-dimensional network structure.
Description
Technical Field
The invention belongs to the field of electrochemistry of high polymer materials, and particularly relates to a preparation method of carboxylated cellulose nanofiber hydrogel.
Background
The application of the electrodeposition method to prepare hydrogel in the prior art is provided in the Chinese patent with the application number of 201610767359.0 and the name of 'an electrodeposition method of carboxymethyl cellulose', and the method for preparing the hydrogel of carboxymethyl cellulose by adopting the electrodeposition method is proposed. And the unique 3D nano network structure of the nano material can endow the material with more and wider application.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of carboxylated cellulose nanofiber hydrogel, the thickness of the hydrogel prepared by the method can reach centimeter level, and the microstructure presents a three-dimensional nano network structure.
The technical scheme adopted by the invention is as follows:
a preparation method of a carboxylated cellulose nanofiber hydrogel is characterized by comprising the following steps:
step 1): preparing a carboxylated cellulose nanofiber suspension for later use;
step 2): preparing an anode material and a cathode material as an anode and a cathode of electrophoretic deposition respectively;
step 3): immersing the anode material and the cathode metal material into the carboxylated cellulose nanofiber suspension, and applying direct current to carry out electrophoretic deposition on the carboxylated cellulose nanofiber;
step 4): and (4) after the deposition is finished, obtaining the carboxylated cellulose nanofiber hydrogel on the anode.
Further, the carboxylated cellulose nanofiber suspension is a carboxylated cellulose nanofiber suspension.
Furthermore, the carboxylated cellulose nanofiber suspension is a carboxylated cellulose nanofiber suspension with the concentration of 0.1-0.5 percent by mass fraction.
Further, in the step 3), the distance between the anode material and the cathode material is 10 mm-50 mm.
Still further, in the step 3), the distance between the anode material and the cathode material is 15 mm-20 mm.
Further, in the step 3), the direct current is a constant current direct current or a constant voltage direct current.
Further, in the step 3), when the direct current is a constant current direct current, the current in the anode metal material and the cathode material is 0.1 mA-2 mA.
Still further, in the step 3), when the direct current is a constant current direct current, the current in the anode metal material and the cathode material is 0.25 mA-1 mA.
Further, in the step 3), when the direct current is a constant voltage direct current, the voltage applied between the anode metal material and the cathode material is 1V to 5V.
Further, in the step 3), the deposition time of the carboxylated cellulose nanofibers is 10min to 120 min.
Still further, in the step 3), the deposition time of the carboxylated cellulose nanofibers is 60-120 min.
Further, the anode material is made of metal between zinc and silver in a metal activity order table. The metal used for the anode material can be zinc, iron, tin, lead, copper and silver.
Further, the anode metal material is a wire or a sheet made of iron, copper or silver.
Still further, the cathode material is a platinum wire, a platinum sheet or a stainless steel needle.
The principle of the invention is as follows:
since the carboxylated cellulose nanofiber suspension is prepared by oxidizing a part of hydroxyl groups of cellulose to carboxyl groups by the Tempo oxidation method, the carboxylated cellulose nanofibers used have a negative charge. Under the action of an electric field between the cathode and the anode, the nano fibers with negative electricity can move directionally and aggregate at the anode to form hydrogel. Meanwhile, when the anode adopts metal between zinc and silver in a metal activity sequence table, the anode loses electrons to precipitate metal cations, and the metal cations and the carboxylated cellulose nanofiber hydrogel are subjected to ion crosslinking to form the composite hydrogel.
The invention can obtain the following technical effects:
1. by adopting the carboxylated cellulose nanofiber suspension for electrophoretic deposition, compared with the solution deposition, the hydrogel obtained by utilizing the nanofiber suspension for electrophoretic deposition has a larger size, and the probable reason is that the hydrogel is endowed with higher porosity and water content by a three-dimensional network structure formed by stacking the nanofibers and a good ion conduction channel is provided, so that a thicker hydrogel product can be obtained.
2. The electrophoretic deposition of natural polymer nano material suspension has deposition layer thickness reaching micron level only due to bubble and deposition resistance. According to the invention, by setting electrochemical parameters and processing the nanofiber suspension, the thickness of the deposition layer can reach centimeter level, and the deposition layer can be stripped from the surface of the electrode, so that the method has higher application value.
3. Compared with other methods for preparing the nanofiber/metal composite gel, the method has the characteristics of mild reaction conditions, simple and rapid preparation process, environmental friendliness and controllable gel morphology.
4. The invention can obtain metal composite nanofiber hydrogel with different thicknesses, sizes and shapes by controlling output voltage/current, deposition time, anode shape and anode metal types, and can be applied to the fields of carriers, bioengineering, tissue engineering, environmental protection and the like.
5. Most electrophoretic deposition techniques are applied to proteins or SiO2Etc. on the inorganic particles. And the electrophoretic deposition under the condition needs to be carried out under the condition of high voltage. The present invention applies electrophoretic deposition techniques to negatively charged carboxylated cellulose nanofibers and the voltage required for deposition is as low as 1V. The technical range of electrophoretic deposition is expanded, and the method is more environment-friendly.
6. Most of the natural polymer materials subjected to electrodeposition are in solution deposition to obtain a film structure with a uniform structure, the natural polymer nano materials are modified to enable the surfaces of the natural polymer nano materials to have charges, a 3D network structure with the nano structure can be obtained by an electrophoretic deposition method, the specific surface area is large, the density is low, the performances such as light, electricity, heat, biology and the like are stronger, and the advantages of the nano structure can endow the materials with more and more extensive applications.
Drawings
FIG. 1 is a schematic diagram of the preparation of hydrogel by using a preparation method of carboxylated cellulose nanofiber hydrogel according to the present invention.
FIG. 2-1 is a picture of the appearance of the pure carboxylated cellulose nanofiber hydrogel obtained in example 1;
FIG. 2-2 is a scanning electron micrograph of the hydrogel shown in FIG. 2-1.
FIG. 3-1 is a photograph of the carboxylated cellulose nanofiber/Fe composite hydrogel obtained in example 2 just after deposition;
FIG. 3-2 is a photograph of the appearance of the hydrogel of FIG. 3-1 after a period of time;
FIG. 3-3 is a scanning electron micrograph of the hydrogel shown in FIG. 3-1.
FIG. 4-1 is a front view of the carboxylated cellulose nanofiber/Cu composite hydrogel obtained in example 3;
FIG. 4-2 is a photograph showing the appearance of the side of the hydrogel shown in FIG. 4-1;
FIG. 4-3 is a scanning electron micrograph of the hydrogel shown in FIG. 4-1.
FIG. 5-1 is a picture of the appearance of the carboxylated cellulose nanofiber/Ag composite hydrogel obtained in example 4;
FIG. 5-2 is a scanning electron micrograph of the hydrogel shown in FIG. 5-1.
Detailed Description
Example 1
Step 1): preparing a carboxylated cellulose nanofiber suspension with the mass percentage concentration of 0.25% for later use;
step 2): preparing a stainless steel needle with the diameter of 1.5mm as an anode material and a platinum wire with the diameter of 0.5mm as a cathode material, and respectively using the stainless steel needle and the platinum wire as an anode and a cathode for electrophoretic deposition;
step 3): immersing the anode material and the cathode metal material into the carboxylated cellulose nanofiber suspension, wherein the insertion depth is 6mm, the distance is 20mm, constant-current direct current is applied, the current value is 0.25mA, and the electrophoretic deposition of the nanofibers is carried out, and the deposition time is 120 min;
step 4): and (4) after the deposition is finished, obtaining the carboxylated cellulose nanofiber hydrogel on the stainless steel needle anode.
The diameter of the obtained carboxylated cellulose nanofiber hydrogel on the anode can reach 1.2cm (see figure 2-1), the hydrogel is in a nanofiber-shaped three-dimensional network structure (see figure 2-2), and the hydrogel is subjected to CO treatment2The specific surface area after supercritical drying can reach 300m2More than g.
Example 2
Step 1): preparing a carboxylated cellulose nanofiber suspension with the mass percentage concentration of 0.25% for later use;
step 2): preparing iron wires with the diameter of 1.5mm and the purity of 99.99 percent as anode materials and platinum wires with the diameter of 0.5mm as cathode materials, and respectively using the iron wires as an anode and a cathode for electrophoretic deposition;
step 3): immersing the anode material and the cathode metal material into the carboxylated cellulose nanofiber suspension, wherein the insertion depth is 10mm, the distance is 20mm, constant-current direct current is applied, the current value is 0.25mA, and electrophoretic deposition of the carboxylated cellulose nanofiber is carried out, and the deposition time is 120 min;
step 4): and after the deposition is finished, obtaining the carboxylated cellulose nanofiber hydrogel on the iron wire anode.
The carboxylated cellulose nanofiber hydrogel obtained on the anode is a carboxylated cellulose nanofiber/Fe composite hydrogel, the diameter of the carboxylated cellulose nanofiber/Fe composite hydrogel can reach 0.8cm (see figures 3-1 and 3-2), the carboxylated cellulose nanofiber/Fe composite hydrogel is in a nanofiber-like three-dimensional network structure (see figure 3-3), and the carboxylated cellulose nanofiber/Fe composite hydrogel is subjected to CO treatment2The specific surface area after supercritical drying can reach 300m2More than g.
Example 3
Step 1): preparing a carboxylated cellulose nanofiber suspension with the mass percentage concentration of 0.1% for later use;
step 2): preparing a copper sheet with the size of 20mm multiplied by 50mm multiplied by 0.2mm and the purity of 99.99 percent as an anode material and a platinum sheet with the size of 15mm multiplied by 20mm multiplied by 0.1mm as a cathode material respectively as an anode and a cathode of electrophoretic deposition;
step 3): immersing the anode material and the cathode metal material into the carboxylated cellulose nanofiber suspension, wherein the insertion depth is 15mm, the distance is 15mm, constant-current direct current is applied, the current value is 1.0mA, and electrophoretic deposition of the carboxylated cellulose nanofiber is carried out, and the deposition time is 60 min;
step 4): after the deposition is finished, obtaining the carboxylated cellulose nanofiber hydrogel on the copper sheet anode.
The carboxylated cellulose nanofiber hydrogel obtained on the anode is a carboxylated cellulose nanofiber/Cu composite hydrogel, the average thickness of the carboxylated cellulose nanofiber/Cu composite hydrogel can reach 4mm (see figures 4-1 and 4-2), the carboxylated cellulose nanofiber/Cu composite hydrogel is in a nanofiber-like three-dimensional network structure (see figure 4-3), and the carboxylated cellulose nanofiber/Cu composite hydrogel is subjected to CO treatment2The specific surface area after supercritical drying can reach 300m2More than g.
Example 4
Step 1): preparing a carboxylated cellulose nanofiber suspension with the mass percentage concentration of 0.5% for later use;
step 2): preparing a silver wire with the diameter of 2.0mm and the purity of 99.99 percent as an anode material and a platinum wire with the diameter of 0.5mm as a cathode material as an anode and a cathode of electrophoretic deposition respectively;
step 3): immersing the anode material and the cathode metal material into the carboxylated cellulose nanofiber suspension, wherein the insertion depth is 10mm, the distance is 15mm, constant-current direct current is applied, the current value is 0.33mA, and electrophoretic deposition of the carboxylated cellulose nanofiber is carried out, and the deposition time is 120 min;
step 4): and after the deposition is finished, obtaining the carboxylated cellulose nanofiber hydrogel on the silver wire anode.
The carboxylated cellulose nanofiber hydrogel obtained on the anode is a carboxylated cellulose nanofiber/Ag composite hydrogel with the diameter of 1cm (see figure 5-1), has a nanofiber-like three-dimensional network structure (see figure 5-2), and is subjected to CO treatment2The specific surface area after supercritical drying can reach 300m2More than g.
By changing the anode metal material, hydrogel of other composite metals can be obtained.
The invention utilizes electrophoretic deposition technology, utilizes carboxyl cellulose nanofiber suspension, controls different parameters based on different anode metals and electrode templates, and prepares different types, different shapes, different sizes and different thicknesses of carboxyl cellulose nanofiber/metal composite hydrogel. The reaction condition is mild, the preparation process is simple and quick, and the method is environment-friendly and can be applied to the fields of carriers, bioengineering, tissue engineering, environmental protection and the like.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention. The anode metal comprises metal between zinc and silver in a metal activity sequence table, and the nano-fiber comprises natural high-molecular carboxylated nano-fiber, such as carboxylated chitin nano-fiber, carboxymethyl cellulose nano-fiber and the like.
Claims (10)
1. A preparation method of a carboxylated cellulose nanofiber hydrogel is characterized by comprising the following steps:
step 1): preparing a carboxylated cellulose nanofiber suspension for later use;
step 2): preparing an anode material and a cathode material as an anode and a cathode of electrophoretic deposition respectively;
step 3): immersing the anode material and the cathode metal material into the carboxylated cellulose nanofiber suspension, and applying direct current to carry out electrophoretic deposition on the carboxylated cellulose nanofiber;
step 4): and (4) after the deposition is finished, obtaining the carboxylated cellulose nanofiber hydrogel on the anode.
2. The method for producing a carboxylated cellulose nanofiber hydrogel according to claim 1, wherein the carboxylated cellulose nanofiber suspension is a carboxylated cellulose nanofiber suspension having a concentration of 0.1 to 0.5 mass%.
3. The method for preparing the carboxylated cellulose nanofiber hydrogel according to claim 1, wherein in the step 3), the distance between the anode material and the cathode material is 10mm to 50 mm.
4. The method for preparing the carboxylated cellulose nanofiber hydrogel according to claim 1, wherein the direct current in the step 3) is constant current direct current or constant voltage direct current.
5. The method for preparing the carboxylated cellulose nanofiber hydrogel according to claim 4, wherein in the step 3), when the direct current is a constant-current direct current, the current in the anode metal material and the cathode material is 0.1 mA-2 mA.
6. The method for preparing the carboxylated cellulose nanofiber hydrogel according to claim 5, wherein in the step 3), when the direct current is a constant-current direct current, the current in the anode metal material and the cathode material is 0.25 mA-1 mA.
7. The method for preparing the carboxylated cellulose nanofiber hydrogel according to claim 4, wherein in the step 3), when the direct current is a constant voltage direct current, the voltage applied between the anode metal material and the cathode material is 1V to 5V.
8. The method for preparing the carboxylated cellulose nanofiber hydrogel according to any one of claims 2 to 6, wherein the deposition time of the carboxylated cellulose nanofibers in step 3) is 10 to 120 min.
9. The method for preparing a carboxylated cellulose nanofiber hydrogel according to any one of claims 1 to 8, wherein said anode material is made of a metal between zinc and silver in the metal activity order list.
10. The method for preparing carboxylated cellulose nanofiber hydrogel according to any one of claims 1 to 8, wherein the cathode material is platinum wire, platinum sheet or stainless steel needle.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022191190A1 (en) * | 2021-03-09 | 2022-09-15 | 日本製紙株式会社 | Method for producing coating of cellulose nano-fibers and/or chitin nano-fibers |
| WO2023048157A1 (en) * | 2021-09-22 | 2023-03-30 | 国立大学法人大阪大学 | Rigid polymer molded body and method for producing rigid polymer molded body |
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| CN104562074A (en) * | 2015-01-09 | 2015-04-29 | 武汉理工大学 | Preparation method of anodic-electrodeposition chitosan gel on basis of coordination action |
| CN106222718A (en) * | 2016-08-30 | 2016-12-14 | 武汉理工大学 | A kind of electro-deposition method of carboxymethyl cellulose |
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| CN101874043A (en) * | 2007-11-26 | 2010-10-27 | 国立大学法人东京大学 | Cellulose nanofiber and process for production thereof, and cellulose nanofiber dispersion |
| CN104562074A (en) * | 2015-01-09 | 2015-04-29 | 武汉理工大学 | Preparation method of anodic-electrodeposition chitosan gel on basis of coordination action |
| CN106222718A (en) * | 2016-08-30 | 2016-12-14 | 武汉理工大学 | A kind of electro-deposition method of carboxymethyl cellulose |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022191190A1 (en) * | 2021-03-09 | 2022-09-15 | 日本製紙株式会社 | Method for producing coating of cellulose nano-fibers and/or chitin nano-fibers |
| JPWO2022191190A1 (en) * | 2021-03-09 | 2022-09-15 | ||
| JP7367264B2 (en) | 2021-03-09 | 2023-10-23 | 日本製紙株式会社 | Method for producing cellulose nanofiber and/or chitin nanofiber coating |
| WO2023048157A1 (en) * | 2021-09-22 | 2023-03-30 | 国立大学法人大阪大学 | Rigid polymer molded body and method for producing rigid polymer molded body |
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