CN106279724A - One class has the preparation method of the physical chitosan hydrogel of high intensity - Google Patents
One class has the preparation method of the physical chitosan hydrogel of high intensity Download PDFInfo
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- CN106279724A CN106279724A CN201610700807.5A CN201610700807A CN106279724A CN 106279724 A CN106279724 A CN 106279724A CN 201610700807 A CN201610700807 A CN 201610700807A CN 106279724 A CN106279724 A CN 106279724A
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Abstract
The present invention relates to the preparation method that a class has the physical chitosan hydrogel of high intensity, belong to functional high polymer material field.The hydrogel preparation method of the present invention, first dissolves chitosan in the aqueous solution of glacial acetic acid, stirs 0.5 3 hours under the conditions of 20～80 DEG C；Add function auxiliary element, stirring reaction 0.5 3 hours under the conditions of 20～80 DEG C；Finally reaction solution is held respectively with volatile akaline liquid, and be jointly placed in a closed environment, after reacting 0.5～10 hour at sealing lucifuge, obtain target product.The present invention is not required in chitosan solution other macromolecular material compound, only need to add little molecular functional composition, can obtain the hydrogel material with high intensity, can play degradation of chitosan characteristic of good performance simultaneously, and good functional of auxiliary ingredients.Additionally, this method preparation process is simple, low cost, it is suitable for promoting the use of.
Description
Technical field
The present invention relates to the preparation method that a class has the physical chitosan hydrogel of high intensity, belong to functional polymer material
Material field.
Background technology
Chitosan is a kind of by the natural macromolecular material extracted in the shell of the Crustacean such as shrimp, Eriocheir sinensis, is nature
Unique alkaline polysaccharide in boundary.Chitosan is because of its good biocompatibility, biodegradability, anthemorrhagic performance, anti-microbial property
Deng biology performance feature, it is applied widely in fields such as food, medicine, medical apparatus and instruments.
Utilize the 6-OH on chitosan molecule chain, 2-NH2Cross-linking reaction, the hydrogel with network-like structure can be obtained
Material, because it can retain the biological characteristics that chitosan is good, has again good hydrophilic, water retention property and obtains and extensively should
With.But prepared the process of hydrogel at present by chitosan, mainly use the chemical cross-linking agent such as epoxychloropropane, glutaraldehyde.On
Though the cross-linking reaction stating cross-linking agent is simple and easy to control, but owing to cross-linking agent is easily generated residual in hydrogel, have impact on hydrogel
Biocompatibility, easily causes cytotoxicity, thus is used by restriction.Additionally, due to the performance deficiency of chitosan itself, made
Standby hydrogel mechanical property is poor, it is impossible to form uniform and stable continuous gel.In order to improve the mechanical performance of hydrogel, often
The synthesis macromolecule such as polyvinylpyrrolidone, polyvinyl alcohol need to be added be combined.The introducing of above-mentioned polymer, makes prepared
The degradability of hydrogel is destroyed.
Chitosan/functional molecular composite solution is placed in alkaline atmosphere by the present invention first, by stifling effect, it is thus achieved that
There is the novel hydrogels material of good mechanical property and functional effect.
Summary of the invention
The invention aims to solve traditional method prepare aquagel and there is poor biocompatibility, degradable
Property the problem such as difference, and provide the preparation method of the physical chitosan hydrogel that a class has high intensity.
It is an object of the invention to be achieved through the following technical solutions.
One class of the present invention has the preparation method of the physical chitosan hydrogel of high intensity, and concrete preparation process is as follows:
1) dissolve chitosan in mass concentration be 0.1～5.0% glacial acetic acid aqueous solution in, 20～80 DEG C of conditions
Lower stirring 0.5-3 hour, chitosan mass concentration in glacial acetic acid aqueous solution is 0.1～10.0%；
2) to step 1) reaction solution that obtains adds account for reaction solution quality 0.1～the function auxiliary element of 10%,
Stirring reaction 0.5-3 hour under the conditions of 20～80 DEG C；
3) by step 2) volatile akaline liquid that the reaction solution that obtains is identical with reaction solution volume holds respectively,
And be jointly placed in a closed environment, after reacting 0.5～10 hour at sealing lucifuge, obtain target product；
Described function auxiliary element is: any in silver nitrate, copper chloride, Graphene, graphene oxide, CNT
A kind of；
Described volatile akaline liquid be mass concentration be 10%～40% ammonia or mass concentration be 10%～
The oxyammonia aqueous solution of 40%.
Beneficial effect
The present invention is not required in chitosan solution other macromolecular material compound, only need to add little molecular functional composition,
The hydrogel material with high intensity can be obtained, degradation of chitosan characteristic of good performance can be played simultaneously, also can play auxiliary
Good functional of furtherance part.Additionally, this method preparation process is simple, low cost, it is suitable for promoting the use of.
Detailed description of the invention
Below in conjunction with embodiment, present disclosure is further described.
Embodiment 1:
0.5 gram of chitosan is dissolved in the aqueous solution of glacial acetic acid that 99.5 gram mass concentration are 2%, under the conditions of 30 DEG C
Stir 0.5 hour.Weigh 0.3 gram of silver nitrate, add in above-mentioned chitosan solution, stir 1 hour under the conditions of 30 DEG C.Will stirring
The ammonia that mass concentration is 26% that good mixed solution is identical with mixed liquor volume holds respectively, and is jointly placed on sealing bag
Middle lucifuge obtains physical chitosan hydrogel after reacting 3 hours.
Embodiment 2:
2 grams of chitosans are dissolved in the aqueous solution of glacial acetic acid that 98 gram mass concentration are 4%, stir under the conditions of 60 DEG C
2 hours.Weigh 5 grams of graphene oxides, add in above-mentioned chitosan solution, stir 2 hours under the conditions of 60 DEG C.By be stirred
The ammonia that mass concentration is 28% that mixed solution is identical with mixed liquor volume holds respectively, and jointly be placed on sealing bag in keep away
Photoreaction obtained physical chitosan hydrogel after 3 hours.
Embodiment 3:
8 grams of chitosans are dissolved in the aqueous solution of the glacial acetic acid that 92 mass concentrations are 2%, under the conditions of 70 DEG C, stir 1
Hour.Weigh the CNT of 6 grams, add in above-mentioned chitosan solution, stir 1 hour under the conditions of 70 DEG C.By be stirred
The ammonia that mass concentration is 18% that mixed solution is identical with mixed liquor volume holds respectively, and jointly be placed on sealing bag in keep away
Photoreaction obtained physical chitosan hydrogel after 8 hours.
Embodiment 4:
0.3 gram of chitosan is dissolved in the aqueous solution of glacial acetic acid that 99.7 gram mass concentration are 0.1%, 30 DEG C of conditions
Lower stirring 0.5 hour.Weigh 0.5 gram of copper chloride, add in above-mentioned chitosan solution, stir 1 hour under the conditions of 30 DEG C.To stir
The aqueous hydroxylamine solution that mass concentration is 12% that the mixed solution mixed is identical with mixed liquor volume holds respectively, and jointly puts
In sealing bag, lucifuge obtains physical chitosan hydrogel after reacting 2 hours.Prepared physical chitosan hydrogel has well
Mechanical property and shape memory effect.
Following methods is used to test physical chitosan hydrogel embodiment 1 the obtained antibiotic property to different test strains
Can:
Physical chitosan hydrogel being swollen in distilled water, concentration is that 0.4g/mL is standby.It is seeded to put down by test strains
Plate, takes out after 37 DEG C of incubator 24h, is chosen to physiological saline solution by the antibacterial of inoculation aseptic cotton carrier, and regulation is to 0.5 Maxwell
The ratio bacterial concentration of turbid standard, and standby with M-H broth dilution 100 times.Utilize two-fold dilution's method that solution to be measured is diluted to 1:
5,1:10,1:20,1:40,1:80,1:160,1:320,1:640, put into equivalent bacterium solution, has examination with aseptic rubbery plug lid residence
Pipe, is placed in 37 DEG C of incubator effect 24h by above test tube.Take experimental liquid or diluent makees count plate, calculate pressing down of measured object
Bacterium rate.Minimal inhibitory concentration with the least concentration of the longest bacterium as measured object.
The physical chitosan hydrogel that embodiment 1 obtains is 2.5 × 10 to colibacillary minimum inhibitory concentration-3G/mL,
Minimum inhibitory concentration to staphylococcus aureus is 1.3 × 10-3g/mL.The physical chitosan hydrogel pair that embodiment 4 obtains
Colibacillary minimum inhibitory concentration is 4.0 × 10-2G/mL, the minimum inhibitory concentration to staphylococcus aureus is 2.5 × 10-3g/mL。
According to GB/T 1040.2-2006 " mensuration of plastic tensile performance " standard, tested hydrogel is utilized Standard Module
Cut into the sample of 1BB size in standard, the fracture strength being 50mm/min test hydrogel with draw speed.Embodiment 1
To the fracture strength of physical chitosan hydrogel be 0.78MPa, the fracture of the physical chitosan hydrogel that embodiment 2 obtains is strong
Degree is 1.16MPa, and the fracture strength of the physical chitosan hydrogel that embodiment 3 obtains is 1.37MPa, the shell that embodiment 4 obtains
The fracture strength of polysaccharide physical hydrogel is 0.63MPa.
Embodiment 5 (comparative examples of embodiment 1):
0.5 gram of chitosan is dissolved in the aqueous solution of glacial acetic acid that 99.5 gram mass concentration are 2%, under the conditions of 30 DEG C
Stir 0.5 hour.The mixed solution being stirred is positioned in airtight sealing bag, and addition mass concentration is 26% wherein
Ammonia, more whole obturator is positioned at lucifuge dark, after reacting 3 hours, obtains physical chitosan hydrogel.Made
Standby physical chitosan hydrogel has antibiotic property and good mechanical performance.Prepared physical chitosan hydrogel is to large intestine
The minimum inhibitory concentration of bacillus is 4.0 × 10-1G/mL, the minimum inhibitory concentration to staphylococcus aureus is 4.0 × 10-1g/
mL.The fracture strength of prepared physical chitosan hydrogel is 0.06MPa.
From the above results, compared with Example 1, it is being not added with Ag+In the case of carrying out being combined, prepared chitosan
The mechanical strength of physical hydrogel significantly reduces.Illustrate that adding little molecule is combined, and can improve above-mentioned physical chitosan hydrogel
Mechanical strength.Additionally, compared with Example 1, it is being not added with Ag+In the case of carrying out being combined, prepared chitosan physics water-setting
The minimum inhibitory concentration of glue significantly increases, and illustrates to use auxiliary ingredients Ag+It is combined and prepares hydrogel, be remarkably improved hydrogel
Antiseptic.
Embodiment 6 (comparative examples of embodiment 1):
0.5 gram of chitosan is dissolved in the aqueous solution of glacial acetic acid that 99.5 gram mass concentration are 2%, under the conditions of 30 DEG C
Stir 0.5 hour.Weigh 0.3 gram of silver nitrate, add in above-mentioned chitosan solution, stir 1 hour under the conditions of 30 DEG C.Will stirring
Good mixed solution is placed on after keeping in Dark Place 3 hours in sealing bag and obtains chitosan complex silver hydrogel.Prepared chitosan
Complex silver hydrogel has good antibiotic property, but mechanicalness is very poor.Prepared chitosan complex silver hydrogel is to large intestine bar
The minimum inhibitory concentration of bacterium is 2.5 × 10-3G/mL, the minimum inhibitory concentration to staphylococcus aureus is 2.5 × 10-3g/mL。
Prepared physical chitosan hydrogel poor mechanical properties, it is impossible to prepare batten, it is impossible to measure mechanical property.
From the above results, compared with Example 1, Ag is only being added+It is combined, does not use alkaline gas to smoke
In the case of steaming, although prepared chitosan complex silver hydrogel can keep certain anti-microbial property, but its mechanical strength
Very poor.Illustrate only by chitosan and Ag+Complex reaction, do not use alkaline gas fumigate, it is impossible to obtain that there is good mechanics
The physical hydrogel of intensity.
In conjunction with the embodiments 1 with embodiment 5, embodiment 6 compare visible, only at addition and the alkali of functional auxiliary ingredients
Property gas stifling common effect under, just can obtain the chitosan physics water-setting with excellent mechanical performances and anti-microbial property
Glue.
Claims (1)
1. a class has the preparation method of physical chitosan hydrogel of high intensity, it is characterized in that: concrete preparation process is as follows:
1) dissolve chitosan in mass concentration be 0.1～5.0% glacial acetic acid aqueous solution in, stir under the conditions of 20～80 DEG C
Mixing 0.5-3 hour, chitosan mass concentration in glacial acetic acid aqueous solution is 0.1～10.0%；
2) to step 1) reaction solution that obtains adds account for reaction solution quality 0.1～the function auxiliary element of 10%, 20
～stirring reaction 0.5-3 hour under the conditions of 80 DEG C；
3) by step 2) volatile akaline liquid that the reaction solution that obtains is identical with reaction solution volume holds respectively, and altogether
With being placed in a closed environment, after reacting 0.5～10 hour at sealing lucifuge, obtain target product；
Described function auxiliary element is: any one in silver nitrate, copper chloride, Graphene, graphene oxide, CNT
Kind；
Described volatile akaline liquid be mass concentration be 10%～40% ammonia or mass concentration be 10%～40%
Oxyammonia aqueous solution.
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| CN201610700807.5A CN106279724B (en) | 2016-08-22 | 2016-08-22 | One kind has the preparation method of the physical chitosan hydrogel of high intensity |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880184A (en) * | 2019-02-27 | 2019-06-14 | 浙江理工大学 | A kind of preparation method of polymolecularity fibroin-chitosan -3- methylimidazole salt hexyl thiophene-multi-walled carbon nanotube gel |
| CN111944519A (en) * | 2020-08-14 | 2020-11-17 | 大连工业大学 | Method for preparing chemiluminescence hydrogel |
| CN112851983A (en) * | 2020-12-31 | 2021-05-28 | 东华大学 | Electrostatic spraying film of hydrogel and preparation method and application thereof |
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| CN1833731A (en) * | 2005-03-17 | 2006-09-20 | 李毅彬 | Making method of and use of antibiotic surgical dressing |
| CN101215389A (en) * | 2008-01-14 | 2008-07-09 | 浙江大学 | Chitosan hydrogel and preparation method thereof |
| CN103601898A (en) * | 2013-11-07 | 2014-02-26 | 浙江科技学院 | Temperature-sensitive chitosan-carboxymethylcellulose gel and preparation method thereof |
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| CN1833731A (en) * | 2005-03-17 | 2006-09-20 | 李毅彬 | Making method of and use of antibiotic surgical dressing |
| CN101215389A (en) * | 2008-01-14 | 2008-07-09 | 浙江大学 | Chitosan hydrogel and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880184A (en) * | 2019-02-27 | 2019-06-14 | 浙江理工大学 | A kind of preparation method of polymolecularity fibroin-chitosan -3- methylimidazole salt hexyl thiophene-multi-walled carbon nanotube gel |
| CN111944519A (en) * | 2020-08-14 | 2020-11-17 | 大连工业大学 | Method for preparing chemiluminescence hydrogel |
| WO2022032714A1 (en) * | 2020-08-14 | 2022-02-17 | 大连工业大学 | Method for preparing chemiluminescent hydrogel |
| CN112851983A (en) * | 2020-12-31 | 2021-05-28 | 东华大学 | Electrostatic spraying film of hydrogel and preparation method and application thereof |
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| CN106279724B (en) | 2018-11-06 |
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