CN112375258A - Hydrogel material with shape memory function and preparation and application thereof - Google Patents
Hydrogel material with shape memory function and preparation and application thereof Download PDFInfo
- Publication number
- CN112375258A CN112375258A CN202011223562.4A CN202011223562A CN112375258A CN 112375258 A CN112375258 A CN 112375258A CN 202011223562 A CN202011223562 A CN 202011223562A CN 112375258 A CN112375258 A CN 112375258A
- Authority
- CN
- China
- Prior art keywords
- shape memory
- hydrogel material
- hydrogel
- cmc
- memory function
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000017 hydrogel Substances 0.000 title claims abstract description 105
- 239000000463 material Substances 0.000 title claims abstract description 94
- 230000006386 memory function Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 56
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 56
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 44
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 31
- 229920002678 cellulose Polymers 0.000 claims abstract description 26
- 239000001913 cellulose Substances 0.000 claims abstract description 26
- -1 rare earth terbium ion Chemical class 0.000 claims abstract description 23
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 19
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 16
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 16
- 239000002121 nanofiber Substances 0.000 claims abstract description 15
- XETSAYZRDCRPJY-UHFFFAOYSA-M sodium;4-aminobenzoate Chemical group [Na+].NC1=CC=C(C([O-])=O)C=C1 XETSAYZRDCRPJY-UHFFFAOYSA-M 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 238000007710 freezing Methods 0.000 claims description 14
- 230000008014 freezing Effects 0.000 claims description 14
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 235000015110 jellies Nutrition 0.000 claims description 9
- 239000008274 jelly Substances 0.000 claims description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 abstract description 7
- 238000004020 luminiscence type Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 18
- 229960004050 aminobenzoic acid Drugs 0.000 description 9
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 9
- 238000000295 emission spectrum Methods 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000004964 aerogel Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- 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
- 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
-
- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
-
- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to the technical field of hydrogel composite materials, and discloses a hydrogel material with a shape memory function, and preparation and application thereof. The hydrogel material is CNF/CMC/Tb/Ab, and a rare earth complex formed by Ab and Tb is connected with a cellulose network skeleton formed by CNF and CMC in a covalent bond mode; wherein Ab is sodium p-aminobenzoate, Tb is rare earth terbium ion, CMC is carboxymethyl cellulose, and CNF is cellulose nanofiber. The cellulose nanofiber is combined with carboxymethyl cellulose through a hydrogen bond to form a cellulose network framework, the rare earth terbium ion is coordinated with a carboxyl functional group in the carboxymethyl cellulose, so that the cellulose nanofiber is stably connected with the cellulose network framework in a covalent bond mode, the sodium p-aminobenzoate is further coordinated with the rare earth terbium ion, a green fluorescent material with excellent luminescence is formed, and the cellulose nanofiber shows an excellent shape memory function and can be used as a novel shape memory fluorescent material.
Description
Technical Field
The invention relates to the technical field of hydrogel composite materials, in particular to a hydrogel material with a shape memory function, and preparation and application thereof.
Background
In order to expand the application range of the luminescent rare earth complex, the rare earth complex is introduced into some host materials, so that the thermal stability and the mechanical property of the rare earth complex can be improved. The conventional approach is to dope rare earth complexes into some synthetic polymers or silica matrices. However, the disadvantages of silica and synthetic polymer materials are poor biocompatibility and difficult biodegradation. In addition, in the rare earth composite material prepared by the traditional method, the tensile resistance of the material needs to be further improved. Particularly, there are few reports of hydrogel materials having both shape memory function and excellent light emitting properties.
Disclosure of Invention
In view of the above, the present invention provides a hydrogel material with shape memory function, and a preparation method and an application thereof, in order to overcome at least one of the above disadvantages of the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a hydrogel material with a shape memory function, wherein the hydrogel material is CNF/CMC/Tb/Ab, and a rare earth complex formed by Ab and Tb is connected with a cellulose network skeleton formed by CNF and CMC in a covalent bond mode. Wherein Ab is sodium p-aminobenzoate, Tb is rare earth terbium ion, CMC is carboxymethyl cellulose, and CNF is cellulose nanofiber. Specifically, the CNF and the CMC are connected through hydrogen bonds to form the cellulose network skeleton, and the Tb and the carboxyl functional group of the CMC are connected in a covalent bond mode.
The invention selects carboxymethyl cellulose and cellulose nano-fiber as substrates, and is cheap and easy to obtain; moreover, the carboxymethyl cellulose and the cellulose nano-fiber belong to natural biological macromolecules, are easy to degrade and belong to environment-friendly materials. The cellulose nano-fiber is combined with carboxymethyl cellulose through hydrogen bond to form a cellulose network skeleton; the rare earth terbium ion is coordinated with the carboxyl functional group in the carboxymethyl cellulose, so that the coordination is stably connected with the hydrogel network framework in a covalent bond mode, the sodium p-aminobenzoate is further coordinated with the rare earth terbium ion, the rare earth terbium complex can be uniformly distributed in the framework network of the matrix, the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided, the excellent shape memory function is shown, and the decomposition temperature is 268 ℃.
The second aspect of the present invention provides a preparation method of the hydrogel material with shape memory function, comprising the following steps:
s1, adding CMC into the CNF sol, and stirring at room temperature until the CMC 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 TbCl3Washing in water solution with a large amount of deionized water to obtain Tb-containing hydrogel;
s6, soaking the Tb-containing hydrogel obtained in the step S5 into an Ab solution, and then washing the Tb-containing hydrogel with a large amount of deionized water to obtain the hydrogel material.
The invention adopts the freezing-unfreezing simple and easy method to prepare the hydrogel material, and the carboxymethyl cellulose, the cellulose nano-fiber and the rare earth complex are connected through covalent bonds, so that the rare earth terbium complex can be uniformly distributed in a skeleton network of a matrix, and the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided. The preparation method has simple steps, is easy to implement, and is simple and easy to implement after material post-treatment; has good processing type, and can be processed into different forms according to different requirements. 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 the CMC is preferably 1-5%; more preferably, the mass percentage concentration of the CMC is 1.5-4%.
In the step S2, the volume ratio concentration of the epoxy chloropropane is preferably 4-12%, and the molar concentration of the sodium hydroxide is preferably 0.5-2M; more preferably, the volume ratio concentration of the epichlorohydrin is 5-10%, and the molar concentration of the sodium hydroxide is 0.6-1.5M.
In the step S3, the freezing time is preferably 12-48 h; more preferably, the freezing time is 16-40 h.
In step S5, TbCl3The preferred molar concentration of the rare earth terbium ions in the aqueous solution is 0.01-0.1M; more preferably, TbCl3The molar concentration of the rare earth terbium ions in the aqueous solution is 0.02-0.08M.
In the step S6, the preferable molar concentration of the sodium p-aminobenzoate solution is 0.01-0.06M; more preferably, the molar concentration of the sodium p-aminobenzoate solution is 0.02-0.05M.
In a third aspect, the present invention provides the use of the hydrogel material with shape memory function described above.
The hydrogel material is a green fluorescent material with excellent luminescence, a green emission spectrum is obtained under 303nm excitation, the maximum emission peak is 544nm, the hydrogel material is a pure green fluorescent emission peak of a typical rare earth terbium complex, and the color purity is high. Therefore, the application of the hydrogel material with the shape memory function as a green fluorescent material is provided, and the hydrogel material can be particularly used for electron microscope characterization.
In addition, the hydrogel material has an excellent shape memory function, can quickly recover the shape after external pressure is relieved, and can be used as a novel shape memory fluorescent material. Therefore, the invention also provides the application of the hydrogel material with the shape memory function as the shape memory fluorescent material.
Compared with the prior art, the invention has the following beneficial effects:
firstly, the carboxymethyl cellulose, the cellulose nano-fiber and the rare earth complex are connected by a covalent bond by a simple and easy method, so that the rare earth terbium complex can be uniformly distributed in a skeleton network of a matrix, and the fluorescence quenching phenomenon of the material prepared by the traditional physical doping is avoided.
Secondly, the hydrogel material of the invention obtains a green emission spectrum under 303nm excitation, the maximum emission peak is at 544nm, the hydrogel material is a pure green fluorescence emission peak of a typical rare earth terbium complex, and the color purity is high.
In addition, the hydrogel material of the invention adopts carboxymethyl cellulose and cellulose nano-fiber as matrixes, and is cheap and easy to obtain. Moreover, the carboxymethyl cellulose and the cellulose nano-fiber belong to natural biological macromolecules, are easy to degrade and belong to environment-friendly materials.
Moreover, the hydrogel material has a good shape memory function, and can quickly recover the shape after external pressure is relieved.
Finally, the invention is in the preparation method: 1) the preparation of the hydrogel material is prepared by simple freezing-unfreezing, and the steps are simple; 2) the product has good processing type, and can be processed into different forms according to different requirements; 3) the post-treatment of the hydrogel material preparation is simple and easy to implement; 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 material with shape memory after drying.
FIG. 2 is a scanning electron microscope image of a hydrogel material with shape memory function after drying.
FIG. 3 is a distribution diagram of Tb elements after drying of hydrogel materials with shape memory function.
FIG. 4 is a diagram of a hydrogel material with shape memory under UV lamp irradiation.
FIG. 5 is a fluorescence spectrum of a hydrogel material having a shape memory function.
FIG. 6 is a graph of the compressive stress of a hydrogel material having shape memory.
Detailed Description
The invention provides a hydrogel material with a shape memory function, and preparation and application thereof. The hydrogel material is CNF/CMC/Tb/Ab, and a rare earth complex formed by Ab and Tb is connected with a cellulose network skeleton formed by CNF and CMC in a covalent bond mode; wherein Ab is sodium p-aminobenzoate, Tb is rare earth terbium ion, CMC is carboxymethyl cellulose, and CNF is cellulose nanofiber.
Specifically, the cellulose nanofiber is combined with carboxymethyl cellulose through a hydrogen bond to form the cellulose network framework, the rare earth terbium ion is coordinated with a carboxyl functional group in the carboxymethyl cellulose so as to be stably connected with the cellulose network framework in a covalent bond mode, and the sodium p-aminobenzoate is further coordinated with the rare earth terbium ion, so that the obtained rare earth terbium complex can be uniformly distributed in the network framework of the matrix, the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided, and the green fluorescent material with excellent luminescence is formed. The decomposition temperature of the hydrogel material was 268 ℃.
The preparation method of the hydrogel material with the shape memory function comprises the following steps:
s1, adding 1-5% by mass of CMC into the CNF sol, and stirring at room temperature until the CMC is fully dissolved;
s2, adding epoxy chloropropane with the volume ratio concentration of 4-12% and sodium hydroxide with the molar concentration of 0.5-2M 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 12-48 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 TbCl with the mole concentration of rare earth terbium ions of 0.01-0.1M3Washing the obtained product in an aqueous solution for 12-24 hours by using a large amount of deionized water to obtain Tb-containing hydrogel;
s6, soaking the Tb-containing hydrogel obtained in the step S5 into a sodium p-aminobenzoate solution with the molar concentration of 0.01-0.06M for 12-24 hours, and then washing with a large amount of deionized water to obtain the hydrogel material;
s7, freeze-drying the hydrogel material obtained in the step S6 to obtain an aerogel material for electron microscope characterization.
Preferably, in the step S1, the mass percentage concentration of the CMC is 1.5-4%; in the step S2, the volume ratio concentration of the epoxy chloropropane is 5-10%, and the molar concentration of the sodium hydroxide is 0.6-1.5M; in the step S3, the freezing time is preferably 16-40 h; in step S5, TbCl3The molar concentration of the rare earth terbium ions in the aqueous solution is 0.02-0.08M; in step S6, the molar concentration of the sodium p-aminobenzoate solution is 0.02-0.05M. And calculating the mass percentage concentration of the CMC and the volume ratio concentration of the epichlorohydrin according to the CNF sol used in the step S1, wherein the mass of the CMC 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 material with the shape memory function is a green fluorescent material with excellent luminescence, a green emission spectrum is obtained under the excitation of 303nm, the maximum emission peak is 544nm, the hydrogel material is a pure green fluorescence emission peak of a typical rare earth terbium complex, the color purity is high, and the hydrogel material can be used as a green fluorescent material and is particularly used for electron microscope characterization.
In addition, the hydrogel material has an excellent shape memory function, can quickly recover the shape after external pressure is relieved, and can be used as a novel shape memory 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
50mg of CMC was added to 5mL of the CNF sol and magnetically stirred at room temperature until the CMC was fully dissolved. Then adding 0.20mL of epoxy chloropropane, stirring uniformly, then adding 2mL of 0.5M sodium hydroxide solution, stirring uniformly the sol, placing the sol in a refrigerator at the temperature of-25 ℃ for freezing for 12h, then unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and then soaking the obtained hydrogel into 20mL of 0.01M TbCl3And (3) washing the hydrogel in the aqueous solution for 12h by using a large amount of deionized water, then soaking the hydrogel in 20mL of 0.01M aqueous solution of p-aminobenzoic acid for 12h, and then washing by using a large amount of deionized water to obtain the hydrogel material.
Example 2
100mg CMC was added to 5mL CNF sol and magnetically stirred at room temperature until the CMC was fully dissolved. Then adding 0.25mL of epoxy chloropropane, stirring uniformly, then adding 2mL of 0.6M sodium hydroxide solution, stirring uniformly the sol, 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 soaking the obtained hydrogel into 20mL of 0.02M TbCl3And (3) washing the hydrogel in the aqueous solution for 12h by using a large amount of deionized water, then soaking the hydrogel in 20mL of 0.06M aqueous solution of p-aminobenzoic acid for 12h, and then washing by using a large amount of deionized water to obtain the hydrogel material.
Example 3
300mg of CMC was added to 5mL of the CNF sol and magnetically stirred at room temperature until the CMC was fully dissolved. Then adding 0.50mL 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 36h, then unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and then soaking the obtained hydrogel into 20mL of 0.08M TbCl3And (3) washing the hydrogel in the aqueous solution for 12h by using a large amount of deionized water, then soaking the hydrogel in 20mL of 0.02M aqueous solution of p-aminobenzoic acid for 12h, and then washing by using a large amount of deionized water to obtain the hydrogel material.
Example 4
Adding 400mg CMCTo 5mL of CNF sol, magnetically stir at room temperature until the CMC is sufficiently dissolved. Then adding 0.6mL of epoxy chloropropane, stirring uniformly, then adding 2mL of 2.0M 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 into 20mL of 0.05M TbCl3And (3) washing the hydrogel in the aqueous solution for 12h by using a large amount of deionized water, then soaking the hydrogel in 20mL of 0.03M aqueous solution of p-aminobenzoic acid for 12h, and then washing by using a large amount of deionized water to obtain the hydrogel material.
Example 5
100mg CMC was added to 5mL CNF sol and magnetically stirred at room temperature until the CMC was fully dissolved. Then adding 0.5mL of epoxy chloropropane, stirring uniformly, then adding 2mL of 1.5M sodium hydroxide solution, stirring uniformly the sol, placing the sol in a refrigerator at the temperature of-25 ℃ for freezing for 16h, then unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and then soaking the obtained hydrogel into 20mL of 0.06M TbCl3And (3) washing the hydrogel in the aqueous solution for 12h by using a large amount of deionized water, then soaking the hydrogel in 20mL of 0.04M aqueous solution of p-aminobenzoic acid for 12h, and then washing by using a large amount of deionized water to obtain the hydrogel material.
Example 6
250mg of CMC was added to 5mL of the CNF sol and magnetically stirred at room temperature until the CMC was fully dissolved. Then adding 0.25mL of epoxy chloropropane, stirring uniformly, then adding 2mL of 1.0M sodium hydroxide solution, stirring uniformly the sol, placing the sol in a refrigerator at the temperature of-25 ℃ for freezing for 40h, then unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and then soaking the obtained hydrogel into 20mL of 0.1M TbCl3And (3) washing the hydrogel in the aqueous solution for 12h by using a large amount of deionized water, then soaking the hydrogel in 20mL of 0.05M aqueous solution of p-aminobenzoic acid for 12h, and then washing by using a large amount of deionized water to obtain the hydrogel material.
Testing
(ii) thermal stability of hydrogel Material after drying
FIG. 1 is a thermogravimetric plot of the hydrogel material after freeze-drying, from which it can be seen that the material has good thermal stability with a decomposition temperature of 268 ℃.
Morphology of (II) hydrogel materials
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 rare earth terbium ions, a distribution diagram of terbium elements is obtained by using a surface scanning technology, and the uniform distribution of the terbium elements in the material can be found from fig. 3, so that the uniform distribution of the rare earth complexes in the biomacromolecule network framework is proved.
(III) fluorescence Properties of hydrogel Material
FIG. 4 is a graph of a luminescent hydrogel under UV light, and from FIG. 4, it can be seen that the hydrogel material emits pure green fluorescence under UV light. FIG. 5 is an excitation and emission spectrum of a luminescent hydrogel material, and from FIG. 5, it can be seen that excitation is an excited state in which energy is transferred to the rare earth terbium ion by absorbing ultraviolet light through the p-aminobenzoic acid ligand, and by intersystem crossing. In the excitation spectrum, 4 f-4 f transition of rare earth terbium ion is not found, which indicates that the energy transfer is carried out through a p-aminobenzoic acid group and the transfer efficiency is high, thereby indirectly proving that the p-aminobenzoic acid and the rare earth terbium ion form a complex. From FIG. 5, it can be seen that an emission spectrum is obtained with excitation at 303nm, and the maximum emission peak is at 544nm, which is the green emission peak of a typical rare earth terbium ion. The obtained material has high color purity and good monochromaticity. In the emission spectrum of FIG. 5, no emission peak from the ligand is observed, which further illustrates that the aminobenzoic acid and the rare earth terbium ion form a coordination compound, thereby achieving the purpose of organic covalent bonding, because the organic ligand needs to form a compound of covalent bonding type with the rare earth ion for energy transfer.
(IV) shape memory Properties of hydrogel Material
FIG. 6 is a graph of the compressive stress of a luminescent hydrogel material, from which it can be seen that the hydrogel material, after being compressed to different degrees, still maintains its original morphology 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 material with the shape memory function is characterized in that the hydrogel material is CNF/CMC/Tb/Ab, and a rare earth complex formed by Ab and Tb is connected with a cellulose network skeleton formed by CNF and CMC in a covalent bond mode; wherein Ab is sodium p-aminobenzoate, Tb is rare earth terbium ion, CMC is carboxymethyl cellulose, and CNF is cellulose nanofiber.
2. Hydrogel material with shape memory function according to claim 1, wherein the CNF is hydrogen bonded to CMC to form the cellulose network backbone, and/or the Tb is covalently bonded to carboxyl functional groups of CMC; and/or the hydrogel material has a decomposition temperature of 268 ℃.
3. A method for preparing a hydrogel material with shape memory function according to claim 1 or 2, comprising the following steps:
s1, adding CMC into the CNF sol, and stirring at room temperature until the CMC 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 TbCl3Washing in water solution with a large amount of deionized water to obtain Tb-containing hydrogel;
s6, soaking the Tb-containing hydrogel obtained in the step S5 into a sodium p-aminobenzoate solution, and then washing with a large amount of deionized water to obtain the hydrogel material.
4. The method for preparing the hydrogel material with the shape memory function according to claim 3, wherein in the step S1, the mass percentage concentration of CMC is 1-5%; and/or in step S5, TbCl3The molar concentration of the rare earth terbium ions in the aqueous solution is 0.01-0.1M; and/or in the step S6, the molar concentration of the sodium p-aminobenzoate solution is 0.01-0.06M.
5. The method for preparing the hydrogel material with the shape memory function according to claim 4, wherein in the step S1, the mass percentage concentration of CMC is 1.5-4%; and/or in step S5, TbCl3The molar concentration of the rare earth terbium ions in the aqueous solution is 0.02-0.08M; and/or in the step S6, the molar concentration of the sodium p-aminobenzoate solution is 0.02-0.05M.
6. The method for preparing the hydrogel material with the shape memory function according to claim 3, wherein in step S2, the volume concentration of epichlorohydrin is 4-12%, and/or the molar concentration of sodium hydroxide is 0.5-2M.
7. The method for preparing the hydrogel material with the shape memory function according to claim 6, wherein in step S2, the volume concentration of epichlorohydrin is 5-10%, and/or the molar concentration of sodium hydroxide is 0.6-1.5M.
8. The method for preparing a hydrogel material with a shape memory function according to claim 3, wherein the freezing time in step S3 is 12-48 h.
9. The method for preparing a hydrogel material with a shape memory function according to claim 8, wherein the freezing time in step S3 is 16-40 h.
10. Use of a hydrogel material with shape memory function according to claim 1 or 2 as a shape memory fluorescent material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011223562.4A CN112375258A (en) | 2020-11-05 | 2020-11-05 | Hydrogel material with shape memory function and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011223562.4A CN112375258A (en) | 2020-11-05 | 2020-11-05 | Hydrogel material with shape memory function and preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112375258A true CN112375258A (en) | 2021-02-19 |
Family
ID=74578388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011223562.4A Pending CN112375258A (en) | 2020-11-05 | 2020-11-05 | Hydrogel material with shape memory function and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112375258A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276801A (en) * | 2021-12-23 | 2022-04-05 | 广东省科学院微生物研究所(广东省微生物分析检测中心) | Cellulose-based binuclear rare earth organic polymer composite material with controllable fluorescence and preparation method and application thereof |
| CN114292411A (en) * | 2021-12-17 | 2022-04-08 | 广东省科学院化工研究所 | Organic rare earth luminescent material and preparation method and application thereof |
| CN114316335A (en) * | 2021-12-31 | 2022-04-12 | 中国林业科学研究院林产化学工业研究所 | Fluorescent hydrogel with antibacterial activity, actuator and preparation method |
| CN114921241A (en) * | 2022-04-14 | 2022-08-19 | 新疆农业大学 | Preparation method and application of manganese-containing complex cellulose-based fluorescent functional material |
| CN115353672A (en) * | 2021-12-10 | 2022-11-18 | 云南师范大学 | Luminous hydrogel material with shape memory function and preparation and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277124A (en) * | 2014-05-07 | 2015-01-14 | 山东省医疗器械研究所 | Lanthanide rare earth coordinated cellulose medical material and preparation method thereof |
| CN106807448A (en) * | 2017-02-28 | 2017-06-09 | 华南理工大学 | A kind of metallic catalyst of nano-cellulose based aquagel load for trichlorophenol in water body of degrading and preparation method thereof |
| CN108264579A (en) * | 2018-01-05 | 2018-07-10 | 云南师范大学 | A kind of hydrogel material containing big ring rare earth compounding, preparation method and application |
| CN109897317A (en) * | 2019-03-06 | 2019-06-18 | 南京林业大学 | A kind of Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe and its preparation method and application |
-
2020
- 2020-11-05 CN CN202011223562.4A patent/CN112375258A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277124A (en) * | 2014-05-07 | 2015-01-14 | 山东省医疗器械研究所 | Lanthanide rare earth coordinated cellulose medical material and preparation method thereof |
| CN106807448A (en) * | 2017-02-28 | 2017-06-09 | 华南理工大学 | A kind of metallic catalyst of nano-cellulose based aquagel load for trichlorophenol in water body of degrading and preparation method thereof |
| CN108264579A (en) * | 2018-01-05 | 2018-07-10 | 云南师范大学 | A kind of hydrogel material containing big ring rare earth compounding, preparation method and application |
| CN109897317A (en) * | 2019-03-06 | 2019-06-18 | 南京林业大学 | A kind of Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe and its preparation method and application |
Non-Patent Citations (7)
| Title |
|---|
| FAN W 等: "Hierarchical porous cellulose/lanthanide hybrid materials as luminescent sensor", 《JOURNAL OF RARE EARTHS》 * |
| YE J 等: "Fluorescence probe based carboxymethyl cellulose/Tb(III) nanocomposites for detection of Mn2+ with simpleness, rapidness and high sensitivity", 《CARBOHYDRATE POLYMER》 * |
| 代天卫 等: "一种形状记忆水凝胶材料的制备及其应用", 《云南化工》 * |
| 吴强等: "纳米纤维素晶体-聚乙烯醇水凝胶的制备及性能表征", 《功能高分子学报》 * |
| 李晓茹: "超吸水性纤维素基水凝胶的制备及其性能研究", 《纺织科学与工程学报》 * |
| 杨德超: "纤维素基/稀土多功能材料的制备与表征", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 范文涛: "多糖/稀土杂化功能材料的制备与表征", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115353672A (en) * | 2021-12-10 | 2022-11-18 | 云南师范大学 | Luminous hydrogel material with shape memory function and preparation and application thereof |
| CN114292411A (en) * | 2021-12-17 | 2022-04-08 | 广东省科学院化工研究所 | Organic rare earth luminescent material and preparation method and application thereof |
| CN114276801A (en) * | 2021-12-23 | 2022-04-05 | 广东省科学院微生物研究所(广东省微生物分析检测中心) | Cellulose-based binuclear rare earth organic polymer composite material with controllable fluorescence and preparation method and application thereof |
| CN114316335A (en) * | 2021-12-31 | 2022-04-12 | 中国林业科学研究院林产化学工业研究所 | Fluorescent hydrogel with antibacterial activity, actuator and preparation method |
| CN114921241A (en) * | 2022-04-14 | 2022-08-19 | 新疆农业大学 | Preparation method and application of manganese-containing complex cellulose-based fluorescent functional material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112375258A (en) | Hydrogel material with shape memory function and preparation and application thereof | |
| CN110510605B (en) | Nitrogen-rich group functionalized graphene, and preparation method and application thereof | |
| CN101955631B (en) | Preparation method of polyaniline modified multi-wall carbon canotube/epoxy resin composite material | |
| CN108264579B (en) | Hydrogel material containing macrocyclic rare earth complex, preparation method and application | |
| CN107163933B (en) | A kind of even porous rare earth composite material of emitting red light, preparation method and application | |
| CN112321851B (en) | Lignin rare earth composite luminescent material and preparation and application thereof | |
| CN112300410B (en) | Hydrogel composite material with porous structure and preparation and application thereof | |
| Peng et al. | Green fabrication of high strength, transparent cellulose-based films with durable fluorescence and UV-blocking performance | |
| CN109942892A (en) | A kind of hud typed dielectric filler of over-branched polyamidoamine enveloped carbon nanometer tube and preparation method thereof | |
| CN107312536B (en) | Red luminescent rare earth composite material, preparation method and application | |
| CN113683811A (en) | Efficient flame-retardant phosphorylated chitosan aerogel and preparation method thereof | |
| CN112341638B (en) | Hydrogel material with porous structure and preparation and application thereof | |
| CN109233807B (en) | Rare earth composite luminescent hydrogel material and preparation method and application thereof | |
| CN115353672B (en) | Luminous hydrogel material with shape memory function and preparation and application thereof | |
| KR101566811B1 (en) | Transparent Composite Films Reinforced with Luminescent Nanofillers and Process for Preparing the Same | |
| CN105131024A (en) | Preparation method for novel rare-earth fluorescent gel adopting PVA as main body and application thereof | |
| CN107099285A (en) | A kind of green emitting hydrogel and preparation method | |
| CN114561011B (en) | Self-emulsifying ionic aqueous polyamide imide and preparation method thereof, carbon fiber sizing agent and preparation method and application thereof | |
| You et al. | Solid-state fluorescent composite phosphor based on cellulose grafted with carbon dots for temperature sensing | |
| CN114292495B (en) | Epoxy resin composite material and preparation method and application thereof | |
| CN112280092A (en) | High-toughness porous composite hydrogel material and preparation and application thereof | |
| CN115301166A (en) | Green luminescent hydrogel material with high mechanical property and preparation and application thereof | |
| CN110256725B (en) | HEC/PVA interpenetrating network aerogel and preparation method thereof | |
| CN115304786A (en) | Luminescent hydrogel material with high resilience performance and preparation and application thereof | |
| CN115337876B (en) | Porous structure luminous hydrogel material and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210219 |