CN112300410A - Hydrogel composite material with porous structure and preparation and application thereof - Google Patents
Hydrogel composite material with porous structure and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of hydrogel composite materials, and discloses a hydrogel composite material with a porous structure, and preparation and application thereof. The hydrogel composite material is CNF/CC/Eu/TTA, and a rare earth complex formed by TTA and Eu is connected with a three-dimensional network structure formed by CNF and CC in a covalent bond mode. The CNF is cellulose nanofiber, the CC is carboxylated chitosan, the Eu is rare earth europium ion, and the TTA is sodium salt obtained by deprotonating 2-thenoyltrifluoroacetone. The cellulose nanofibers are bound to the carboxylated chitosan through hydrogen bonds. The rare earth europium ions are coordinated with carboxyl functional groups of the carboxylated chitosan, so that the carboxylated chitosan hydrogel is stably connected with a hydrogel network skeleton in a covalent bond mode, TTA is further coordinated with the rare earth europium ions, an excellent red fluorescent hydrogel material is formed, the excellent compressive strain performance is shown, and the carboxylated chitosan red fluorescent hydrogel material can be used as an environment-friendly identification material.
Description
Technical Field
The invention relates to the technical field of hydrogel composite materials, in particular to a hydrogel composite material with a porous structure and preparation and application thereof.
Background
The rare earth complex has excellent luminescence property, but the simple rare earth complex is greatly limited in practical application, and the application range of the rare earth complex can be expanded by introducing the rare earth complex into some matrix materials. The traditional method is to dope the rare earth complex into some artificial synthetic polymers or silica and other matrix materials. The inherent disadvantages of these matrices are poor biocompatibility and not readily biodegradable. In addition, in the rare earth composite material prepared by the traditional method, the mechanical property of the material also needs to be further improved. Reports on rare earth complex hydrogel materials which have good mechanical properties and excellent luminescence properties are rare at present.
Disclosure of Invention
In view of the above, the present invention provides a hydrogel composite material with a porous structure and good mechanical properties, and further provides a preparation method and an application of the hydrogel composite material, in order to overcome at least one of the defects of the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a hydrogel composite material with a porous structure, wherein the hydrogel composite material is CNF/CC/Eu/TTA, and a rare earth complex formed by TTA and Eu is connected with a three-dimensional network structure formed by CNF and CC in a covalent bond mode. The CNF is cellulose nanofiber, the CC is carboxylated chitosan, the Eu is rare earth europium ion, and the TTA is sodium salt obtained by deprotonating 2-thenoyltrifluoroacetone. Specifically, the CNF and the CC are connected through a hydrogen bond to form the three-dimensional network structure, the Eu and the carboxyl functional group of the CC are connected in a covalent bond mode, and the beta-diketone functional group of the TTA and the Eu are covalently bonded to form the rare earth complex.
The carboxylated chitosan and the cellulose nanofiber are used as the matrix, so that the price is low, and the carboxylated chitosan and cellulose nanofiber are easy to obtain on a large scale; in addition, the carboxylated chitosan and the cellulose nanofiber belong to natural biological macromolecules, are easy to degrade and belong to environment-friendly materials. The cellulose nanofiber is combined with the carboxylated chitosan through hydrogen bonds to form a three-dimensional network structure, the rare earth europium ions are coordinated with the carboxyl functional groups of the carboxylated chitosan, so that the cellulose nanofiber is stably connected with the hydrogel network framework in a covalent bond mode and is uniformly distributed, the TTA is further coordinated with the rare earth europium ions, the rare earth complexes are connected into the biomacromolecule network framework in a covalent bond mode, the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided, an excellent red fluorescent hydrogel material is formed, and the red fluorescent hydrogel material has good mechanical properties. The decomposition temperature of the hydrogel composite was 283 ℃.
The second aspect of the present invention provides a method for preparing the hydrogel composite material with porous structure, comprising the following steps:
s1, adding CC into the CNF sol, and stirring at room temperature until the CC is fully dissolved;
s2, adding epoxy chloropropane and sodium hydroxide into the sol obtained in the step S1, and fully and uniformly stirring;
s3, pouring the sol obtained in the step S2 into a mold, and then freezing at-25 ℃;
s4, unfreezing the jelly obtained in the step S3 in water, and washing with a large amount of deionized water to obtain hydrogel;
s5, soaking the hydrogel obtained in the step S4 in a hydrochloric acid solution, and then washing with a large amount of deionized water;
s6, soaking the hydrogel obtained in the step S5 in EuCl3In aqueous solution, then washing with a large amount of deionized water to obtainA Eu-containing hydrogel;
s7, soaking the Eu-containing hydrogel obtained in the step S6 into a sodium salt solution obtained after deprotonation of 2-thenoyltrifluoroacetone, and then washing with a large amount of deionized water to obtain the hydrogel composite material.
The invention adopts the freezing-unfreezing simple and easy method to prepare the hydrogel material, and connects the carboxylated chitosan and the cellulose nanofiber with the rare earth complex through covalent bonds, so that the rare earth europium complex can be uniformly distributed in a biomacromolecule matrix skeleton network, and the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided. The experiment is simple and easy to implement, the post-treatment of the material is extremely convenient, the deionized water washing mode is basically adopted, the practicability of the organic solvent is greatly reduced, the environmental protection requirement is met, and the obtained hydrogel composite material can be used as an environment-friendly identification material. The method has good processability, and materials with different forms can be obtained by designing different moulds according to different requirements, so that the form of the hydrogel material can be freely designed according to requirements, and the obtained hydrogel material shows excellent compressive strain performance. The preparation method can be applied to other rare earth ion luminescent systems and natural biological macromolecule systems.
The following are preferred embodiments of the above preparation method:
in the step S1, the mass percentage concentration of CC is preferably 0.5-4%; more preferably, the mass percentage concentration of CC is 0.6-3%.
In the step S2, the volume ratio concentration of the epoxy chloropropane is preferably 5-20%, and the molar concentration of the sodium hydroxide is preferably 0.4-1.5M; more preferably, the volume ratio concentration of the epichlorohydrin is 6-15%, and the molar concentration of the sodium hydroxide is 0.5-1.2M.
In the step S3, the freezing time is preferably 24-72 h; more preferably, the freezing time is 30-60 h.
In the step S5, the molar concentration of the hydrochloric acid is preferably 0.1-1.2M; more preferably, the molar concentration of the hydrochloric acid is 0.2-1.0M.
In step S6, EuCl3Mole of rare earth europium ion in aqueous solutionThe preferred molar concentration is 0.01-0.15M; more preferably, EuCl3The molar concentration of the rare earth europium ions in the aqueous solution is 0.02-0.12M.
In the step S7, the preferable molar concentration of the sodium salt solution after deprotonation of the 2-thenoyltrifluoroacetone is 0.01-0.08M; more preferably, the molar concentration of the sodium salt solution after deprotonation of the 2-thenoyltrifluoroacetone is 0.02-0.06M.
In a third aspect, the present invention provides the use of a hydrogel composite of the above porous structure. The hydrogel composite material obtains a red emission spectrum under the excitation of 350nm, the maximum emission peak is at 613nm, the red emission peak is a pure positive red fluorescence emission peak of a typical rare earth europium complex, and the color purity is high. Meanwhile, the hydrogel composite material has good mechanical properties, shows excellent compressive strain performance and can be applied as a red fluorescent material.
Compared with the prior art, the invention has the following beneficial effects:
firstly, the carboxylated chitosan and the cellulose nanofiber are connected with the rare earth complex through covalent bonds by using a simple and easy method, so that the rare earth europium complex can be uniformly distributed in a biomacromolecule matrix skeleton network, and the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided.
Secondly, the hydrogel material of the invention obtains red emission spectrum under 350nm excitation, the maximum emission peak is at 613nm, which is the pure positive red fluorescence emission peak of the typical rare earth europium complex, and the color purity is high.
Thirdly, the hydrogel material of the invention adopts carboxylated chitosan and cellulose nanofiber as the matrix, has low price and is easy to obtain in a large scale. In addition, the carboxylated chitosan and the cellulose nanofiber belong to natural biological macromolecules, are easy to degrade and belong to environment-friendly materials.
Fourthly, the hydrogel material has good mechanical property and shows the characteristic of good compressive strain.
Finally, the preparation method of the invention comprises the following steps: 1) the preparation of the hydrogel material is simple freezing-unfreezing preparation, and is simple and feasible. 2) The material has good processability, and different shapes of materials can be obtained by designing different dies according to different requirements; 3) the post-treatment of the hydrogel material preparation basically adopts a deionized water washing mode, so that the practicability of an organic solvent is greatly reduced, and the environmental protection requirement is met; 4) the preparation method can be applied to other rare earth ion luminescent systems and natural biological macromolecule systems.
Drawings
FIG. 1 is a thermogram of a hydrogel composite of porous structure after drying.
FIG. 2 is a scanning electron microscope image of the hydrogel composite material with a porous structure after being dried.
FIG. 3 is a diagram showing the distribution of Eu element after drying the hydrogel composite having a porous structure.
Figure 4 is a diagram of a hydrogel composite with a porous structure under daylight illumination.
FIG. 5 is a graph of a hydrogel composite of porous structure under UV light.
FIG. 6 is a fluorescence spectrum of a hydrogel composite having a porous structure.
Figure 7 is a graph of the compressive stress of a hydrogel composite having a porous structure.
Detailed Description
The invention provides a hydrogel composite material with a porous structure and preparation and application thereof. The hydrogel composite material is CNF/CC/Eu/TTA, and a rare earth complex formed by TTA and Eu is connected with a three-dimensional network structure formed by CNF and CC in a covalent bond mode. The CNF is cellulose nanofiber, the CC is carboxylated chitosan, the Eu is rare earth europium ion, and the TTA is sodium salt obtained by deprotonating 2-thenoyltrifluoroacetone.
Specifically, the cellulose nanofibers are connected with the carboxylated chitosan through hydrogen bonds to form a stable three-dimensional network structure, the rare earth europium ions are coordinated with the carboxyl functional groups of the carboxylated chitosan, so that the cellulose nanofibers are stably connected with the hydrogel network skeleton in a covalent bond mode and are uniformly distributed, and the TTA is further coordinated with the rare earth europium ions through the beta-diketone functional groups of the TTA, so that the rare earth complexes are connected to the biomacromolecule network skeleton in a covalent bond mode, the fluorescence quenching phenomenon of the materials prepared by traditional physical doping is avoided, an excellent red fluorescent hydrogel material is formed, and the red fluorescent hydrogel material has good mechanical properties.
The preparation method of the hydrogel composite material with the porous structure comprises the following steps:
s1, adding CC with the mass percentage concentration of 0.5-4% into the CNF sol, and stirring at room temperature until the CC is fully dissolved;
s2, adding 5-20% volume ratio concentration epoxy chloropropane and 0.4-1.5M molar concentration sodium hydroxide into the sol obtained in the step S1, and fully and uniformly stirring;
s3, pouring the sol obtained in the step S2 into a proper mold, then putting the mold into a refrigerator, and freezing the mold for 24-72 hours at the temperature of-25 ℃;
s4, unfreezing the jelly obtained in the step S3 in water, and washing with a large amount of deionized water to obtain hydrogel;
s5, soaking the hydrogel obtained in the step S4 in a hydrochloric acid solution, and then washing with a large amount of deionized water;
s6, soaking the hydrogel obtained in the step S5 in EuCl with the molar concentration of rare earth europium ions being 0.01-0.15M3Washing in water solution with a large amount of deionized water to obtain Eu-containing hydrogel;
s7, soaking the Eu-containing hydrogel obtained in the step S6 into a sodium salt solution with the molar concentration of 0.01-0.08M and after deprotonation of 2-thenoyltrifluoroacetone, and then washing with a large amount of deionized water to obtain the hydrogel composite material.
S8, freeze-drying the hydrogel composite material obtained in the step S7 to obtain an aerogel material for electron microscope characterization and thermogravimetric testing.
Preferably, in the step S1, the mass percentage concentration of CC is 0.6-3%; in the step S2, the volume ratio concentration of the epoxy chloropropane is 6-15%, and the molar concentration of the sodium hydroxide is 0.5-1.2M; in the step S3, the freezing time is 30-60 h; in step S6, EuCl3The molar concentration of the rare earth europium ions in the aqueous solution is 0.02-0.12M; in step S7, the molar concentration of the sodium salt solution after deprotonation of 2-thenoyltrifluoroacetone is0.02-0.06M. And calculating the mass percentage concentration of the CC and the volume ratio concentration of the epichlorohydrin according to the CNF sol used in the step S1, wherein the mass of the CC in the calculation process is in g unit, and the volume of the epichlorohydrin and the volume of the CNF sol are in mL unit.
The hydrogel composite material with the porous structure is an excellent red fluorescent hydrogel material, a red emission spectrum is obtained under the excitation of 350nm, the maximum emission peak is at 613nm, the red emission peak is a pure positive red fluorescent emission peak of a typical rare earth europium complex, and the color purity is high. Meanwhile, the hydrogel composite material has good mechanical property, shows excellent compressive strain property, has the decomposition temperature of 283 ℃, and can be applied as a red fluorescent material.
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention is further described in detail with reference to the following specific embodiments.
Example 1
25mg of CC was added to 5mL of CNF sol and magnetically stirred at room temperature until CC was sufficiently dissolved. Then adding 0.25mL of epoxy chloropropane, stirring uniformly, adding 2mL of 0.4M sodium hydroxide solution, stirring uniformly, placing the sol in a refrigerator at the temperature of-25 ℃ for freezing for 24h, unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and soaking the obtained hydrogel material into 20mL of 0.01M EuCl3And (3) washing the hydrogel in the aqueous solution for 12 hours by using a large amount of deionized water, then soaking the hydrogel material in 20mL of 0.01M sodium salt solution after deprotonation of 2-thenoyltrifluoroacetone for 12 hours, and then washing by using a large amount of deionized water to obtain the hydrogel composite material.
Example 2
30mg of CC was added to 5mL of CNF sol and magnetically stirred at room temperature until CC was sufficiently dissolved. Then adding 0.3mL of epoxy chloropropane, stirring uniformly, then adding 2mL of 0.5M sodium hydroxide solution, stirring uniformly, placing the sol in a refrigerator at the temperature of-25 ℃ for freezing for 30h, then unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and then soaking the obtained hydrogel material into 20mL of 0.15M EuCl3In aqueous solution 12And h, washing the hydrogel by using a large amount of deionized water, soaking the hydrogel material in 20mL of 0.1M sodium salt solution after deprotonation of 2-thenoyltrifluoroacetone for 12h, and washing by using a large amount of deionized water to obtain the hydrogel composite material.
Example 3
150mg of CC was added to 5mL of CNF sol and magnetically stirred at room temperature until CC was sufficiently dissolved. Then adding 0.5mL of epoxy chloropropane, stirring uniformly, adding 2mL of 1.5M sodium hydroxide solution, stirring uniformly, placing the sol in a refrigerator at the temperature of-25 ℃ for freezing for 72h, unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and soaking the obtained hydrogel material into 20mL of 0.02M EuCl3And (3) washing the hydrogel in the aqueous solution for 12 hours by using a large amount of deionized water, then soaking the hydrogel material in 20mL of 0.02M sodium salt solution after deprotonation of 2-thenoyltrifluoroacetone for 12 hours, and then washing by using a large amount of deionized water to obtain the hydrogel composite material.
Example 4
200mg of CC was added to 5mL of CNF sol and magnetically stirred at room temperature until CC was sufficiently dissolved. Then adding 0.4mL of epoxy chloropropane, stirring uniformly, then adding 2mL of 1.2M sodium hydroxide solution, stirring uniformly, placing the sol in a refrigerator at the temperature of-25 ℃ for freezing for 60h, then unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and then soaking the obtained hydrogel material into 20mL of 0.12M EuCl3And (3) washing the hydrogel in the aqueous solution for 12h by using a large amount of deionized water, then soaking the hydrogel material in 20mL of 0.08M sodium salt solution after deprotonation of 2-thenoyltrifluoroacetone for 12h, and then washing by using a large amount of deionized water to obtain the hydrogel composite material.
Example 5
50mg of CC was added to 5mL of CNF sol and magnetically stirred at room temperature until CC was sufficiently dissolved. Then adding 0.75mL of epoxy chloropropane, stirring uniformly, then adding 2mL of 0.6M sodium hydroxide solution, stirring uniformly, placing the sol in a refrigerator at the temperature of-25 ℃ for freezing for 24h, then unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and then carrying out washingThe resulting hydrogel material was then soaked in 20mL of 0.03M EuCl3And (3) washing the hydrogel in the aqueous solution for 12 hours by using a large amount of deionized water, then soaking the hydrogel material in 20mL of 0.04M sodium salt solution after deprotonation of 2-thenoyltrifluoroacetone for 12 hours, and then washing by using a large amount of deionized water to obtain the hydrogel composite material.
Example 6
75mg of CC was added to 5mL of CNF sol and magnetically stirred at room temperature until CC was sufficiently dissolved. Then adding 1mL of epoxy chloropropane, stirring uniformly, then adding 2mL of 0.8M sodium hydroxide solution, stirring uniformly the sol, placing the sol in a refrigerator at the temperature of-25 ℃ for freezing for 48h, then unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and then soaking the obtained hydrogel material in 20mL of 0.05M EuCl3And (3) washing the hydrogel in the aqueous solution for 12h by using a large amount of deionized water, then soaking the hydrogel material in 20mL of 0.05M sodium salt solution after deprotonation of 2-thenoyltrifluoroacetone for 12h, and then washing by using a large amount of deionized water to obtain the hydrogel composite material.
Testing
(ii) thermal stability of hydrogel composite after drying
FIG. 1 is a thermogravimetric plot of the hydrogel composite after freeze-drying, from which it can be seen that the material has good thermal stability and a decomposition temperature of 283 ℃.
Morphology of hydrogel composite
To determine the morphology of the hydrogel, aerogel samples were obtained using freeze-drying techniques. The aerogel is observed in section by using a field emission scanning electron microscope, and as can be seen from fig. 2, the interior of the material has a macroporous structure. In order to determine the distribution of the rare earth europium element, a distribution diagram of the europium element is obtained by using a surface scanning technology, and as can be found from fig. 3, the europium element is uniformly distributed in the material, thereby proving that the rare earth complex is uniformly distributed in the biomacromolecule network framework.
(III) fluorescence Properties of hydrogel composites
Fig. 4 is a graph of hydrogel under sunlight, and fig. 5 is a graph under ultraviolet lamp irradiation, under which the hydrogel material emits pure red fluorescence. FIG. 6 shows the excitation and emission spectra of the hydrogel composite, and it can be seen from FIG. 6 that the excitation is the excited state in which the TTA ligand absorbs the UV light and transfers the energy to the rare earth europium ion after intersystem crossing. In an excitation spectrum, 4 f-4 f transition of rare earth europium ions is not found, which indicates that energy transfer is carried out through TTA groups and the transfer efficiency is high, thereby indirectly proving that TTA and the rare earth europium ions form a complex. From FIG. 6, it can be seen that an emission spectrum is obtained under excitation at 350nm, and the maximum emission peak is at 613nm, which is the red emission peak of a typical rare earth europium ion. The obtained material has high color purity and good monochromaticity. In the emission spectrum of fig. 6, no emission peak from the ligand is found, which further illustrates that TTA and the rare earth europium ion form a coordination compound, thereby achieving the purpose of organic covalent bonding, since the organic ligand needs to form a compound of a covalent bonding type with the rare earth ion in order to achieve energy transfer.
Shape memory Properties of (IV) hydrogel composites
FIG. 7 is a graph of the compressive stress of a hydrogel composite, from which it can be seen that the hydrogel material, after being compressed to different degrees, still maintains its original shape after the pressure is released, showing good shape memory properties.
In the above test, the fluorescence spectrum experiment was performed using a Hitachi F-4600 fluorescence spectrometer, and the scanning electron microscope was a NOVA/NANOSE EM-450 field emission electron microscope from FEI, USA; thermogravimetric experiments used a STA449F31 instrument.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The hydrogel composite material with the porous structure is characterized in that the hydrogel composite material is CNF/CC/Eu/TTA, and a rare earth complex formed by TTA and Eu is connected with a three-dimensional network structure formed by CNF and CC in a covalent bond mode; the CNF is cellulose nanofiber, the CC is carboxylated chitosan, the Eu is rare earth europium ion, and the TTA is sodium salt obtained by deprotonating 2-thenoyltrifluoroacetone.
2. The cellular structure hydrogel composite of claim 1, wherein the CNF and CC are hydrogen bonded to form the three-dimensional network structure, and/or the Eu and the carboxyl functional group of CC are covalently bonded, and/or the β -diketone functional group of TTA and Eu are covalently bonded to form the rare earth complex, and/or the decomposition temperature of the hydrogel composite is 283 ℃.
3. A method of preparing a cellular-structured hydrogel composite according to claim 1 or 2, comprising the steps of:
s1, adding CC into the CNF sol, and stirring at room temperature until the CC is fully dissolved;
s2, adding epoxy chloropropane and sodium hydroxide into the sol obtained in the step S1, and fully and uniformly stirring;
s3, pouring the sol obtained in the step S2 into a mold, and then freezing at-25 ℃;
s4, unfreezing the jelly obtained in the step S3 in water, and washing with a large amount of deionized water to obtain hydrogel;
s5, soaking the hydrogel obtained in the step S4 in a hydrochloric acid solution, and then washing with a large amount of deionized water;
s6, soaking the hydrogel obtained in the step S5 in EuCl3Washing in water solution with a large amount of deionized water to obtain Eu-containing hydrogel;
s7, soaking the Eu-containing hydrogel obtained in the step S6 into a sodium salt solution obtained after deprotonation of 2-thenoyltrifluoroacetone, and then washing with a large amount of deionized water to obtain the hydrogel composite material.
4. The method for preparing the hydrogel composite material with the porous structure according to claim 3, wherein in the step S1, the mass percentage concentration of CC is 0.5-4%; and/or in step S6, EuCl3The molar concentration of the rare earth europium ions in the aqueous solution is 0.01-0.15M; and/or in the step S7, the molar concentration of the sodium salt solution after deprotonation of the 2-thenoyltrifluoroacetone is 0.01-0.08M.
5. The method for preparing the hydrogel composite material with the porous structure according to claim 4, wherein in the step S1, the mass percentage concentration of CC is 0.6-3%; and/or in step S6, EuCl3The molar concentration of the rare earth europium ions in the aqueous solution is 0.02-0.12M; and/or in the step S7, the molar concentration of the sodium salt solution after deprotonation of the 2-thenoyltrifluoroacetone is 0.02-0.06M.
6. The method for preparing the hydrogel composite material with a porous structure according to claim 3, wherein in step S2, the volume ratio concentration of epichlorohydrin is 5-20%, and/or the molar concentration of sodium hydroxide is 0.4-1.5M.
7. The method for preparing the hydrogel composite material with a porous structure according to claim 6, wherein in step S2, the volume ratio concentration of epichlorohydrin is 6-15%, and/or the molar concentration of sodium hydroxide is 0.5-1.2M.
8. The method for preparing a hydrogel composite material with a porous structure according to claim 3, wherein the freezing time in step S3 is 24-72 hours.
9. The method for preparing a hydrogel composite material having a porous structure according to claim 8, wherein the freezing time in step S3 is 30-60 hours.
10. Use of a porous structured hydrogel composite according to claim 1 or 2 as red fluorescent material.
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