CN105504312B - The method for quickly preparing carboxymethyl cellulose-based luminous self-healing hydrogel - Google Patents
The method for quickly preparing carboxymethyl cellulose-based luminous self-healing hydrogel Download PDFInfo
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- CN105504312B CN105504312B CN201610019603.5A CN201610019603A CN105504312B CN 105504312 B CN105504312 B CN 105504312B CN 201610019603 A CN201610019603 A CN 201610019603A CN 105504312 B CN105504312 B CN 105504312B
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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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- 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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- 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
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
A kind of method for quickly preparing carboxymethyl cellulose-based luminous self-healing hydrogel, lemon acids (PCAD) luminophor by solid state reaction kinetics first with blue-green fluorescent, then will contain Al3+The luminophor aqueous solution of crosslinking agent is added drop-wise in carboxymethyl cellulose clear solution, at room temperature, after standing 24 hours, produce the light yellow carboxymethyl cellulose hydrogel of transparence, scheme is prepared present invention employs simple two step to synthesize and is provided simultaneously with the hydrogel of excellent self-healing performance, good luminescent properties and tensile property, has huge application potential in biomedical and engineering field.
Description
Technical field
It is more particularly to a kind of quickly to prepare carboxymethyl cellulose-based light certainly the invention belongs to technical field of polymer materials
The method of healing hydrogel.
Background technology
Self-healing hydrogel can recover the structure of itself as the new soft intellectual material of one kind after by environmental damage
Integrality, mechanically performance and other various functions, and then extend the service life of material.In the recent period, relevant self-healing water-setting
The research of glue illustrates it as structural material in biomedical sector (e.g., organizational project, cell therapy, tissue adhesive, outer
Section's dressing etc.) and engineering field (e.g., coating and sealant etc.) application potential.Although self-healing hydrogel has well certainly
Healing properties, but with regard to its following application from the point of view of, still suffer from must defect, for example, due to lacking tracking and monitoring performance, making
It can not be monitored in real time in use.On the other hand, photosensitive luminescence generated by light hydrogel appearance just because of
The real-time monitoring performance of its own causes everybody concern.By luminescent substance (quantum dot, carbon point, lanthanide ion) and polymer
The luminous hydrogel that network is constituted, in biomedical sector (bio-imaging, biology sensor, temperature sensor) and engineering field
(pH sensors, switch) also has very big application potential, but luminous hydrogel but seldom has self-healing performance.So, will
Self-healing performance is integrated with luminescent properties, prepares luminous self-healing hydrogel by with very big application potential.
The internal networking structure of self-healing hydrogel is mainly by non-covalent interaction (for example, hydrogen bond action, quiet
Electric interactions, Host-guest interaction etc.) and dynamic covalent bond (imine linkage, phenylhydrazone key, disulfide bond etc.) come what is built.At present, base
In prepared by supramolecular polymer material (by electrostatic interaction and Host-guest interaction) not only have self-healing performance again have
The hydrogel for having luminescent properties has been reported, but their mechanical performance is poor, and supramolecular hydrogel has some can not
The shortcoming avoided, for example, used small molecule gel-forming substance has, certain toxicity, preparation method and purification step are complicated, produce
Rate is not high.Above mentioned shortcoming not only limit supramolecular hydrogel as the widely using property of structural material, also make it
Purpose that is environment-friendly and largely producing is not reached.
The content of the invention
In order to overcome the shortcoming of above-mentioned prior art, quickly carboxymethyl cellulose is prepared it is an object of the invention to provide one kind
The method of the luminous self-healing hydrogel of plain base, with abundance, environmental protection, degradable and good biocompatibility carboxylic first
Base cellulose (CMC) is as gel base, with fast and convenient, environmental protection, economical and practical process characteristic, gained hydrogel
Collect self-healing performance, tensile property, luminescent properties for all over the body.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of method for quickly preparing carboxymethyl cellulose-based luminous self-healing hydrogel, passes through solid state reaction kinetics first
Lemon acids (PCAD) luminophor with blue-green fluorescent, then will contain Al3+The luminophor of crosslinking agent is water-soluble
Drop is added in carboxymethyl cellulose clear solution, at room temperature, after standing 24 hours, produces the light yellow carboxymethyl of transparence fine
Tie up hydrogel.
Lemon acids (PCAD) luminophor is obtained in the following way：By anhydrous citric acid and carbonyl dimidazoles
(CDI) it is put into mortar, persistently grinds at room temperature, the color of mixture is gradually by white yellowing, then become dark-brown
Produce.
The mol ratio of the anhydrous citric acid and carbonyl dimidazoles is 1:1.2.
The Al3+With Alcl3·6H2O form is added, in the luminophor aqueous solution, anhydrous citric acid and go from
The mass volume ratio of sub- water is (0.28~0.82)：The mass volume ratio of 1g/mL, carbonyl dimidazoles and deionized water is (0.34
~0.98)：1g/mL, Alcl3·6H2O and the mass volume ratio of deionized water are (0.48~0.96)：1g/mL.It is described containing
Al3+The luminophor aqueous solution of crosslinking agent is added drop-wise to after the mixing of carboxymethyl cellulose clear solution, PCAD and Alcl3It is total dense
Spend CtFor 10wt%, 15wt%, 20wt% or 25wt%.
It is described to contain Al3+The luminophor aqueous solution of crosslinking agent is 1 with the volume ratio of carboxymethyl cellulose clear solution：
10。
The mass concentration of the carboxymethyl cellulose clear solution is 6%.
Compared with prior art, prepare scheme present invention employs simple two step and be provided simultaneously with excellent self-healing to synthesize
Close the hydrogel of performance, good luminescent properties and tensile property.The excellent blue-green fluorescent of this carboxymethyl cellulose hydrogel
Luminescent properties are mostly derived from adulterated citric acid derivant (PCAD)；Self-healing capability mainly passes through Al3+It is fine with carboxymethyl
- COO on dimension element and citric acid derivant (PCAD)-Between ion coordination dynamic reversible interaction realize.It is this multi-functional
Carboxymethyl cellulose hydrogel preparation method it is simple, and complete in the presence of water.Luminous self-healing water-setting
Glue has application potential in biomedical and engineering field, for example, being used as the sealant for holding volatile solvent soln vessel；As controlling
Treat tissue adhesive of gastric perforation etc..
Brief description of the drawings
Fig. 1 is that the present invention carries out extension test result to the carboxymethyl cellulose hydrogel of dumbbell shaped with electronic tensile machine and shown
It is intended to, wherein Fig. 1 a are to contain different PCAD and Alcl3The carboxymethyl cellulose hydrogel stress-strain curve of concentration, Fig. 1 b
It is to contain different PCAD and Alcl3Healing efficiency (its of the carboxymethyl cellulose hydrogel of concentration after healing 24 hours, 48 hours
Middle HEs is stress healing efficiency, HElFor strain healing efficiency).
Fig. 2 is fluorescence emission peak testing result signal of the carboxymethyl cellulose hydrogel of the present invention under XRF
Figure, wherein Fig. 2 a are that carboxymethyl cellulose hydrogel and citric acid derivant i.e. luminophor (PCAD) aqueous solution excites figure
Spectrum and transmitting collection of illustrative plates, Fig. 2 b are to contain different PCAD and Alcl3The transmitting collection of illustrative plates of the carboxymethyl cellulose hydrogel of concentration.
Embodiment
The hydrogel of the present invention is by carboxymethyl cellulose (CMC), Al3+Crosslinking agent and citric acid derivant luminophor
(PCAD) it is prepared from, at room temperature, as luminophor (PCAD) and Al3+It is fine that the mixed solution of crosslinking agent is added drop-wise to carboxymethyl
After in the plain solution of dimension, Al3+Diffused into gradually in carboxymethyl cellulose clear solution with luminophor, carboxymethyl cellulose and
- COO on luminophor (PCAD)-With Al3+Between form the ion coordination key of interaction.Herein, Al3+Serve as carboxylic first
The Physical crosslinking agent of base cellulose macromolecule interchain；Luminophor has the carboxyl on fluorescence, its chain can also in itself
With Al3+Acted on and combined by ion coordination, therefore, luminophor (PCAD) and Al3Between interaction can suitably reduce
Al3+With-COO on carboxymethyl cellulose-Between strong ion coordination effect, make gel that there is self-healing performance.Carboxymethyl is controlled
Cellulose, luminophor and Al3+Between ratio, with regard to the self-healing hydrogel with fine luminescent properties can be obtained.
The hydrogel performance of the present invention：At room temperature, it is not necessary to add the just energy self-healing, and healing of any other component
Efficiency high is up to more than 90%；With good tensile property, 3 times of former length can be moved to；With excellent blue-green fluorescent；Have
Plasticity, can make any shape.
The preparation method of invention is described in detail with reference to four specific embodiments：
Embodiment 1
The present embodiment comprises the following steps：
The first step, dry carboxymethyl cellulose powder and deionized water are mixed to form a transparent carboxymethyl fibre
The plain solution of dimension (mass fraction of carboxymethyl cellulose is 6%), is then tiled into grinding tool of different shapes and is disappeared to stand
Bubble.
Second step, by 0.28g anhydrous citric acids and 0.34g carbonyl dimidazoles (CDI), (mol ratio is 1:1.2) it is put into mortar
In, lasting grinding is until the color of mixture is gradually by white yellowing, then becomes dark-brown, now just has citric acid class
Luminophor (PCAD) formation.Then 1mL deionized water is added into sample.Finally, 0.48g Alcl are added3·
6H2O is used as crosslinking agent.Then, PCAD and Alcl are obtained3Luminescent substance solution
3rd step, by 0.5mL PCAD and Alcl3Luminescent substance mixing be added drop-wise in 5mL cmc solns,
Make PCAD and Alcl3Total concentration Ct(t=AlCl3+ PCAD) it is 10wt%.After standing 24 hours, lurid carboxymethyl cellulose
Hydrogel will be formed.
Extension test is carried out to the carboxymethyl cellulose hydrogel of dumbbell shaped with electronic tensile machine, as shown in figure 1, PCAD and
Alcl3Concentration Ct(t=AlCl3+ PCAD) it can be stretched to 2.8 times of former length for 10wt% hydrogel.At room temperature, heal
After 24 hours, the healing efficiency of sample is 72.3%, and 35.2% is added than the efficiency after self-healing 12 hours.As shown in Fig. 2
Carboxymethyl cellulose hydrogel is measured with XRF obvious fluorescence emission peak at 483nm.
Embodiment 2
The present embodiment comprises the following steps：
The first step, dry carboxymethyl cellulose powder and deionized water are mixed to form a transparent carboxymethyl fibre
The plain solution of dimension (mass fraction of carboxymethyl cellulose is 6%), is then tiled into grinding tool of different shapes and is disappeared to stand
Bubble.
Second step, by 0.48g anhydrous citric acids and 0.57g carbonyl dimidazoles (CDI), (mol ratio is 1:1.2) it is put into mortar
In, lasting grinding is until the color of mixture is gradually by white yellowing, then becomes dark-brown, now just has citric acid class
Luminophor (PCAD) formation.Then 1mL deionized water is added into sample.Finally, 0.6g Alcl are added3·6H2O
It is used as crosslinking agent.Then, PCAD and Alcl are obtained3Luminescent substance solution
3rd step, by 0.5mL Al3+Mixing with luminescent substance is added drop-wise in 5mL cmc solns, makes PCAD
And Alcl3Total concentration Ct(t=AlCl3+ PCAD) it is 15wt%.After standing 24 hours, lurid carboxymethyl cellulose water-setting
Glue will be formed.
Extension test is carried out to the carboxymethyl cellulose hydrogel of dumbbell shaped with electronic tensile machine, as shown in figure 1, PCAD and
Alcl3Concentration Ct(t=AlCl3+ PCAD) it can be stretched to 2.7 times of former length for 15wt% hydrogel.At room temperature, heal
After 24 hours, the healing efficiency of sample is 90.2%, and 37.9% is added than the efficiency after self-healing 12 hours.As shown in Fig. 2
Carboxymethyl cellulose hydrogel is measured with XRF obvious fluorescence emission peak at 483nm.
Embodiment 3
The present embodiment comprises the following steps：
The first step, dry carboxymethyl cellulose powder and deionized water are mixed to form a transparent carboxymethyl fibre
The plain solution of dimension (mass fraction of carboxymethyl cellulose is 6%), is then tiled into grinding tool of different shapes and is disappeared to stand
Bubble.
Second step, by 0.64g anhydrous citric acids and 0.76g carbonyl dimidazoles (CDI), (mol ratio is 1:1.2) it is put into mortar
In, lasting grinding is until the color of mixture is gradually by white yellowing, then becomes dark-brown, now just has citric acid class
Luminophor (PCAD) formation.Then 1mL distilled water is added into sample.Finally, 0.8g Alcl are added3·6H2O makees
For crosslinking agent.Then, PCAD and Alcl are obtained3Luminescent substance solution
3rd step, by 0.5mL Al3+Mixing with luminescent substance is added drop-wise in 5mL cmc solns, makes PCAD
And Alcl3Total concentration Ct(t=AlCl3+ PCAD) it is 20wt%.After standing 24 hours, lurid carboxymethyl cellulose water-setting
Glue will be formed.
Extension test is carried out to the carboxymethyl cellulose hydrogel of dumbbell shaped with electronic tensile machine, as shown in figure 1, PCAD and
Alcl3 concentration Ct(t=AlCl3+ PCAD) it can be stretched to 1.3 times of former length for 20wt% hydrogel.At room temperature, heal
After 24 hours, the healing efficiency of sample is 87.13%, and 44.13% is added than the efficiency after self-healing 12 hours.Such as Fig. 2 institutes
Show, carboxymethyl cellulose hydrogel is measured with XRF obvious fluorescence emission peak at 483nm.
Embodiment 4
The present embodiment comprises the following steps：
The first step, dry carboxymethyl cellulose powder and deionized water are mixed to form a transparent carboxymethyl fibre
The plain solution of dimension (mass fraction of carboxymethyl cellulose is 6%), is then tiled into grinding tool of different shapes and is disappeared to stand
Bubble.
Second step, by 0.82g anhydrous citric acids and 0.98g carbonyl dimidazoles (CDI), (mol ratio is 1:1.2) it is put into mortar
In, lasting grinding is until the color of mixture is gradually by white yellowing, then becomes dark-brown, now just has citric acid class
Luminophor (PCAD) formation.Then 1mL distilled water is added into sample.Finally, 0.96g Alcl are added3·6H2O
It is used as crosslinking agent.Then, PCAD and Alcl are obtained3Luminescent substance solution
3rd step, by 0.5mL Al3+Mixing with luminescent substance is added drop-wise in 5mL cmc solns, PCAD and
Alcl3Concentration Ct(t=AlCl3+ PCAD) it is 25wt%.After standing 24 hours, lurid carboxymethyl cellulose hydrogel is just
It can be formed
Extension test is carried out to the carboxymethyl cellulose hydrogel of dumbbell shaped with electronic tensile machine, as shown in figure 1, PCAD and
Alcl3Total concentration Ct(t=AlCl3+ PCAD) it can be stretched to 0.9 times of former length for 25wt% hydrogel.At room temperature, more
After closing 24 hours, the healing efficiency of sample is 68.3%, and 35.3% is added than the efficiency after self-healing 12 hours.Such as Fig. 2 institutes
Show, carboxymethyl cellulose hydrogel is measured with XRF obvious fluorescence emission peak at 483nm.
It is of the invention to prepare for the first time while having the hydrogel of self-healing performance, luminescent properties and tensility energy.This
Good application potential will be had in biomedical and engineering field by planting multifunctional water gel.
Claims (4)
1. a kind of method for quickly preparing carboxymethyl cellulose-based luminous self-healing hydrogel, it is characterised in that first by solid
Lemon acids (PCAD) luminophor of phase reaction synthesis with blue-green fluorescent, then will contain Al3+Crosslinking agent it is luminous
Compound water solution is added drop-wise in carboxymethyl cellulose clear solution, at room temperature, after standing 24 hours, you can obtain transparence shallow
Yellow carboxymethyl cellulose hydrogel.
2. quickly preparing the method for carboxymethyl cellulose-based luminous self-healing hydrogel according to claim 1, its feature exists
In lemon acids (PCAD) luminophor is obtained in the following way：
Anhydrous citric acid and carbonyl dimidazoles (CDI) are put into mortar, persistently ground at room temperature, the color of mixture is gradually
By white yellowing, then become dark-brown and produce.
3. quickly preparing the method for carboxymethyl cellulose-based luminous self-healing hydrogel according to claim 2, its feature exists
In the mol ratio of the anhydrous citric acid and carbonyl dimidazoles is 1:1.2.
4. quickly preparing the method for carboxymethyl cellulose-based luminous self-healing hydrogel according to claim 1, its feature exists
In the mass concentration of the carboxymethyl cellulose clear solution is 6%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2743941C1 (en) * | 2020-07-29 | 2021-03-01 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method for producing biopolymeric hydrogel |
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2016
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Cited By (1)
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| RU2743941C1 (en) * | 2020-07-29 | 2021-03-01 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method for producing biopolymeric hydrogel |
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