CN105504312A - Method for quickly preparing carboxymethylcellulose-based luminous self-healing hydrogel - Google Patents
Method for quickly preparing carboxymethylcellulose-based luminous self-healing hydrogel Download PDFInfo
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- CN105504312A CN105504312A CN201610019603.5A CN201610019603A CN105504312A CN 105504312 A CN105504312 A CN 105504312A CN 201610019603 A CN201610019603 A CN 201610019603A CN 105504312 A CN105504312 A CN 105504312A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/164—Aluminum halide, e.g. aluminium chloride
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides a method for quickly preparing carboxymethylcellulose-based luminous self-healing hydrogel. The method includes the steps that firstly, a citric acid (PCAD) luminous compound with blue and green fluorescence is synthesized through a solid phase reaction, a luminous compound water solution containing an Al3+ cross-linking agent is dropwise added to a carboxymethylcellulose transparent solution, and after the mixture stands for 24 hours under room temperature, the transparent light yellow carboxymethylcellulose hydrogel is obtained. The hydrogel with excellent self-healing performance and good luminous performance and tensile performance at the same time is synthesized through a simple two-step preparation scheme, and the method has great application potential in the field of biomedicine and engineering.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly the method for the carboxymethyl cellulose-based luminous self-healing hydrogel of a kind of quick preparation.
Background technology
Self-healing hydrogel, as the novel soft intelligent material of one, can recover the structural integrity of self, mechanical property and other various functions, and then extend the work-ing life of material after being subject to environmental damage.In the recent period, research about self-healing hydrogel illustrate it as structured material biomedical sector (as, organizational project, cell therapy, tissue adhesive, surgical dressing etc.) and the application potential of engineering field (e.g., coating and sealing agent etc.).Although self-healing hydrogel has good self-healing performance, with regard to its future should be used for see, still existing must defect, such as, owing to lacking tracking monitor performance, makes it in use cannot obtain Real-Time Monitoring.On the other hand, the appearance of photosensitive photoluminescence hydrogel is just because of the real-time monitoring performance of himself causes everybody concern.The luminous hydrogel be made up of luminophore (quantum dot, carbon point, lanthanide ion) and polymer network, also have very large application potential at biomedical sector (bio-imaging, biosensor, temperature sensor) and engineering field (pH sensor, switch), but luminous hydrogel but seldom has self-healing performance.So self-healing performance and luminescent properties are integrated, preparing luminous self-healing hydrogel will have very large application potential.
The internal networking structure of self-healing hydrogel is mainly built by non-covalent interaction (such as, hydrogen bond action, electrostatic interaction, Host-guest interaction etc.) and dynamic covalent linkage (imine linkage, phenylhydrazone key, disulfide linkage etc.).At present, based on not only there is self-healing performance but also having that the hydrogel of luminescent properties is existing to be reported prepared by supramolecular polymer material (by electrostatic interaction and Host-guest interaction), but their mechanical property is poor, and supramolecular hydrogel has some unavoidable shortcomings, such as, the small molecules gel-forming substance used has certain toxicity, preparation method and purification step complexity, productive rate is not high.Above mentioned shortcoming not only limit the widely using property of supramolecular hydrogel as structured material, also makes it not reach environmental friendliness and mass-produced object.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide the method for the carboxymethyl cellulose-based luminous self-healing hydrogel of a kind of quick preparation, using abundance, environmental protection, degradable and the good carboxymethyl cellulose (CMC) of biocompatibility as gel base, have fast and convenient, environmental protection, economical and practical process characteristic, gained hydrogel collection self-healing performance, tensile property, luminescent properties are all over the body.
To achieve these goals, the technical solution used in the present invention is:
A method for the carboxymethyl cellulose-based luminous self-healing hydrogel of quick preparation, first has lemon acids (PCAD) luminophor of blue-green fluorescent by solid state reaction kinetics, then will containing Al
3+the luminophor aqueous solution of linking agent is added drop-wise in carboxymethyl cellulose clear solution, at room temperature, leaves standstill after 24 hours, obtains the light yellow carboxymethyl cellulose hydrogel of transparence.
Described lemon acids (PCAD) luminophor obtains in the following way: be put in mortar by Citric Acid, usp, Anhydrous Powder and carbonyl dimidazoles (CDI), at room temperature continue grinding, the color of mixture gradually by white yellowing, then becomes dark-brown and get final product.
The mol ratio of described Citric Acid, usp, Anhydrous Powder and carbonyl dimidazoles is 1:1.2.
Described Al
3+with Alcl
36H
2the form of O adds, in the luminophor aqueous solution, the mass volume ratio of Citric Acid, usp, Anhydrous Powder and deionized water is (0.28 ~ 0.82): 1g/mL, and the mass volume ratio of carbonyl dimidazoles and deionized water is (0.34 ~ 0.98): 1g/mL, Alcl
36H
2the mass volume ratio of O and deionized water is (0.48 ~ 0.96): 1g/mL.Described containing Al
3+after the luminophor aqueous solution of linking agent is added drop-wise to the mixing of carboxymethyl cellulose clear solution, PCAD and Alcl
3total concn C
tfor 10wt%, 15wt%, 20wt% or 25wt%.
Described containing Al
3+the luminophor aqueous solution of linking agent and the volume ratio of carboxymethyl cellulose clear solution are 1:10.
The mass concentration of described carboxymethyl cellulose clear solution is 6%.
Compared with prior art, present invention employs simple two steps and prepare scheme to synthesize the hydrogel simultaneously possessing excellent self-healing performance, good luminescent properties and tensile property.The blue-green fluorescent luminescent properties of this carboxymethyl cellulose hydrogel excellence mainly comes from adulterated citric acid derivant (PCAD); Self-healing capability mainly passes through Al
3+with carboxymethyl cellulose and the upper-COO of citric acid derivant (PCAD)
-between ion coordination dynamic reversible interact realize.The preparation method of this multi-functional carboxymethyl cellulose hydrogel is simple, and completes in the presence of water.Luminous self-healing hydrogel has application potential, such as, as the sealing agent holding volatile solvent soln vessel at biomedical and engineering field; As the tissue adhesive etc. for the treatment of gastric perforation.
Accompanying drawing explanation
Fig. 1 is that the carboxymethyl cellulose hydrogel of the present invention's electronic tensile machine to dumbbell shaped carries out Elongation test result schematic diagram, and wherein Fig. 1 a is containing different PCAD and Alcl
3the carboxymethyl cellulose hydrogel stress-strain curve of concentration, Fig. 1 b is containing different PCAD and Alcl
3at the healing efficiency of healing after 24 hours, 48 hours, (wherein HEs is stress healing efficiency to the carboxymethyl cellulose hydrogel of concentration, HE
lfor strain healing efficiency).
Fig. 2 is the fluorescence emission peak detected result schematic diagram of carboxymethyl cellulose hydrogel of the present invention under fluorescence spectrophotometer, wherein Fig. 2 a is exciting collection of illustrative plates and launching collection of illustrative plates of carboxymethyl cellulose hydrogel and citric acid derivant and luminophor (PCAD) aqueous solution, and Fig. 2 b is containing different PCAD and Alcl
3the transmitting collection of illustrative plates of the carboxymethyl cellulose hydrogel of concentration.
Embodiment
Hydrogel of the present invention is by carboxymethyl cellulose (CMC), Al
3+linking agent and citric acid derivant luminophor (PCAD) are prepared from, at room temperature, as luminophor (PCAD) and Al
3+the mixing solutions of linking agent is added drop-wise to after in cmc soln, Al
3+gradually diffuse in carboxymethyl cellulose clear solution with luminophor ,-the COO on carboxymethyl cellulose and luminophor (PCAD)
-with Al
3+between form interactional ion coordination key.Here, Al
3+serve as the physical crosslinking agent between carboxymethyl cellulose macromolecular chain; Luminophor itself has fluorescence, the carboxyl on its chain also can with Al
3+combined by ion coordination effect, therefore, luminophor (PCAD) and Al
3between interaction suitably can reduce Al
3+with-COO on carboxymethyl cellulose
-between strong ion coordination effect, make gel have self-healing performance.Carboxymethyl cellulose, luminophor and Al are controlled
3+between ratio, just can obtain the self-healing hydrogel with fine luminescent properties.
Hydrogel performance of the present invention: at room temperature, do not need to add the just energy self-healing of any other component, and healing efficiency is up to more than 90%; There is good tensile property, 3 times that former length can be moved to; There is excellent blue-green fluorescent; There is plasticity-, any shape can be made.
Below in conjunction with four specific embodiments, the preparation method to invention is described in detail:
Embodiment 1
The present embodiment comprises the following steps:
The first step, is mixed to form a transparent cmc soln (massfraction of carboxymethyl cellulose is 6%), carrys out standing froth breaking in the difform grinding tool that then tiled to by the carboxymethyl cellulose powder of drying and deionization aqueous phase.
Second step, 0.28g Citric Acid, usp, Anhydrous Powder and 0.34g carbonyl dimidazoles (CDI) (mol ratio is 1:1.2) are put in mortar, continue grinding until the color of mixture is gradually by white yellowing, become dark-brown again, now just have citric acid class luminophor (PCAD) and formed.Then in sample, add the deionized water of 1mL.Finally, then add 0.48gAlcl
36H
2o is as linking agent.Subsequently, PCAD and Alcl is obtained
3luminophore solution.
3rd step, by 0.5mLPCAD and Alcl
3luminophore mixing be added drop-wise in 5mL cmc soln, make PCAD and Alcl
3total concn C
t(t=AlCl
3+ PCAD) be 10wt%.Leave standstill after 24 hours, lurid carboxymethyl cellulose hydrogel will be formed.
Elongation test is carried out with the carboxymethyl cellulose hydrogel of electronic tensile machine to dumbbell shaped, as shown in Figure 1, PCAD and Alcl
3concentration C
t(t=AlCl
3+ PCAD) 2.8 times of former length can be stretched to for the hydrogel of 10wt%.Under room temperature, heal after 24 hours, the healing efficiency of sample is 72.3%, and the efficiency after time less than self-healing 12 adds 35.2%.As shown in Figure 2, record carboxymethyl cellulose hydrogel by fluorescence spectrophotometer and have obvious fluorescence emission peak at 483nm place.
Embodiment 2
The present embodiment comprises the following steps:
The first step, is mixed to form a transparent cmc soln (massfraction of carboxymethyl cellulose is 6%), carrys out standing froth breaking in the difform grinding tool that then tiled to by the carboxymethyl cellulose powder of drying and deionization aqueous phase.
Second step, 0.48g Citric Acid, usp, Anhydrous Powder and 0.57g carbonyl dimidazoles (CDI) (mol ratio is 1:1.2) are put in mortar, continue grinding until the color of mixture is gradually by white yellowing, become dark-brown again, now just have citric acid class luminophor (PCAD) and formed.Then in sample, add the deionized water of 1mL.Finally, then add 0.6gAlcl
36H
2o is as linking agent.Subsequently, PCAD and Alcl is obtained
3luminophore solution
3rd step, by 0.5mLAl
3+be added drop-wise in 5mL cmc soln with mixing of luminophore, make PCAD and Alcl
3total concn C
t(t=AlCl
3+ PCAD) be 15wt%.Leave standstill after 24 hours, lurid carboxymethyl cellulose hydrogel will be formed.
Elongation test is carried out with the carboxymethyl cellulose hydrogel of electronic tensile machine to dumbbell shaped, as shown in Figure 1, PCAD and Alcl
3concentration C
t(t=AlCl
3+ PCAD) 2.7 times of former length can be stretched to for the hydrogel of 15wt%.Under room temperature, heal after 24 hours, the healing efficiency of sample is 90.2%, and the efficiency after time less than self-healing 12 adds 37.9%.As shown in Figure 2, record carboxymethyl cellulose hydrogel by fluorescence spectrophotometer and have obvious fluorescence emission peak at 483nm place.
Embodiment 3
The present embodiment comprises the following steps:
The first step, is mixed to form a transparent cmc soln (massfraction of carboxymethyl cellulose is 6%), carrys out standing froth breaking in the difform grinding tool that then tiled to by the carboxymethyl cellulose powder of drying and deionization aqueous phase.
Second step, 0.64g Citric Acid, usp, Anhydrous Powder and 0.76g carbonyl dimidazoles (CDI) (mol ratio is 1:1.2) are put in mortar, continue grinding until the color of mixture is gradually by white yellowing, become dark-brown again, now just have citric acid class luminophor (PCAD) and formed.Then in sample, add the distilled water of 1mL.Finally, then add 0.8gAlcl
36H
2o is as linking agent.Subsequently, PCAD and Alcl is obtained
3luminophore solution.
3rd step, by 0.5mLAl
3+be added drop-wise in 5mL cmc soln with mixing of luminophore, make PCAD and Alcl
3total concn C
t(t=AlCl
3+ PCAD) be 20wt%.Leave standstill after 24 hours, lurid carboxymethyl cellulose hydrogel will be formed.
Elongation test is carried out with the carboxymethyl cellulose hydrogel of electronic tensile machine to dumbbell shaped, as shown in Figure 1, the concentration C of PCAD and Alcl3
t(t=AlCl
3+ PCAD) 1.3 times of former length can be stretched to for the hydrogel of 20wt%.Under room temperature, heal after 24 hours, the healing efficiency of sample is 87.13%, and the efficiency after time less than self-healing 12 adds 44.13%.As shown in Figure 2, record carboxymethyl cellulose hydrogel by fluorescence spectrophotometer and have obvious fluorescence emission peak at 483nm place.
Embodiment 4
The present embodiment comprises the following steps:
The first step, is mixed to form a transparent cmc soln (massfraction of carboxymethyl cellulose is 6%), carrys out standing froth breaking in the difform grinding tool that then tiled to by the carboxymethyl cellulose powder of drying and deionization aqueous phase.
Second step, 0.82g Citric Acid, usp, Anhydrous Powder and 0.98g carbonyl dimidazoles (CDI) (mol ratio is 1:1.2) are put in mortar, continue grinding until the color of mixture is gradually by white yellowing, become dark-brown again, now just have citric acid class luminophor (PCAD) and formed.Then in sample, add the distilled water of 1mL.Finally, then add 0.96gAlcl
36H
2o is as linking agent.Subsequently, PCAD and Alcl is obtained
3luminophore solution.
3rd step, by 0.5mLAl
3+be added drop-wise in 5mL cmc soln with mixing of luminophore, PCAD and Alcl
3concentration C
t(t=AlCl
3+ PCAD) be 25wt%.Leave standstill after 24 hours, lurid carboxymethyl cellulose hydrogel will be formed
Elongation test is carried out with the carboxymethyl cellulose hydrogel of electronic tensile machine to dumbbell shaped, as shown in Figure 1, PCAD and Alcl
3total concn C
t(t=AlCl
3+ PCAD) 0.9 times of former length can be stretched to for the hydrogel of 25wt%.Under room temperature, heal after 24 hours, the healing efficiency of sample is 68.3%, and the efficiency after time less than self-healing 12 adds 35.3%.As shown in Figure 2, record carboxymethyl cellulose hydrogel by fluorescence spectrophotometer and have obvious fluorescence emission peak at 483nm place.
The present invention prepares the hydrogel simultaneously with self-healing performance, luminescent properties and tensility energy first time.This multifunctional water gel will have at biomedical and engineering field well applies potential.
Claims (7)
1. prepare a method for carboxymethyl cellulose-based luminous self-healing hydrogel fast, it is characterized in that first be there is by solid state reaction kinetics lemon acids (PCAD) luminophor of blue-green fluorescent, then will containing Al
3+the luminophor aqueous solution of linking agent is added drop-wise in carboxymethyl cellulose clear solution, at room temperature, leave standstill after 24 hours, the light yellow carboxymethyl cellulose hydrogel of transparence.
2. prepare the method for carboxymethyl cellulose-based luminous self-healing hydrogel according to claim 1 fast, it is characterized in that, described lemon acids (PCAD) luminophor obtains in the following way:
Be put in mortar by Citric Acid, usp, Anhydrous Powder and carbonyl dimidazoles (CDI), at room temperature continue grinding, the color of mixture gradually by white yellowing, then becomes dark-brown and get final product.
3. prepare the method for carboxymethyl cellulose-based luminous self-healing hydrogel according to claim 2 fast, it is characterized in that, the mol ratio of described Citric Acid, usp, Anhydrous Powder and carbonyl dimidazoles is 1:1.2.
4. prepare the method for carboxymethyl cellulose-based luminous self-healing hydrogel according to claim 2 fast, it is characterized in that, described Al
3+with Alcl
36H
2the form of O adds, in the luminophor aqueous solution, the mass volume ratio of Citric Acid, usp, Anhydrous Powder and deionized water is (0.28 ~ 0.82): 1g/mL, and the mass volume ratio of carbonyl dimidazoles and deionized water is (0.34 ~ 0.98): 1g/mL, Alcl
36H
2the mass volume ratio of O and deionized water is (0.48 ~ 0.96): 1g/mL.
5. prepare the method for carboxymethyl cellulose-based luminous self-healing hydrogel according to claim 4 fast, it is characterized in that, described containing Al
3+the luminophor aqueous solution of linking agent and the volume ratio of carboxymethyl cellulose clear solution are 1:10.
6. according to claim 1 or 5, prepare the method for carboxymethyl cellulose-based luminous self-healing hydrogel fast, it is characterized in that, the mass concentration of described carboxymethyl cellulose clear solution is 6%.
7. prepare the method for carboxymethyl cellulose-based luminous self-healing hydrogel according to claim 4 fast, it is characterized in that, described containing Al
3+after the luminophor aqueous solution of linking agent is added drop-wise to the mixing of carboxymethyl cellulose clear solution, PCAD and Alcl
3total concn C
tfor 10wt%, 15wt%, 20wt% or 25wt%.
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Citations (4)
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| CN103012811A (en) * | 2012-12-21 | 2013-04-03 | 北京林业大学 | Preparation method for self-repairing cellulose hydrogel and hydrogel prepared through method |
| CN104039871A (en) * | 2011-06-03 | 2014-09-10 | 弗兰克·古 | Polysaccharide-based hydrogel polymers and uses thereof |
-
2016
- 2016-01-12 CN CN201610019603.5A patent/CN105504312B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000078846A1 (en) * | 1999-06-22 | 2000-12-28 | Access Pharmaceuticals, Inc. | Degradable cross-linking agents and cross-linked network polymers formed therewith |
| CN104039871A (en) * | 2011-06-03 | 2014-09-10 | 弗兰克·古 | Polysaccharide-based hydrogel polymers and uses thereof |
| CN102276854A (en) * | 2011-07-08 | 2011-12-14 | 西安交通大学 | Preparation method of high strength natural high-molecular hydrogel |
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| Title |
|---|
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