CN106279724B - One kind has the preparation method of the physical chitosan hydrogel of high intensity - Google Patents
One kind has the preparation method of the physical chitosan hydrogel of high intensity Download PDFInfo
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- CN106279724B CN106279724B CN201610700807.5A CN201610700807A CN106279724B CN 106279724 B CN106279724 B CN 106279724B CN 201610700807 A CN201610700807 A CN 201610700807A CN 106279724 B CN106279724 B CN 106279724B
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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
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Abstract
The present invention relates to the preparation methods of a kind of physical chitosan hydrogel with high intensity, belong to functional polymer material field.The hydrogel preparation method of the present invention, dissolves chitosan in the aqueous solution of glacial acetic acid, is stirred 0.5-3 hours under the conditions of 20~80 DEG C first；Function auxiliary element is added, is stirred to react under the conditions of 20~80 DEG C 0.5-3 hours；Finally reaction solution and volatile akaline liquid are held respectively, and are placed on jointly in a closed environment, after the sealing place of being protected from light is reacted 0.5~10 hour, obtains target product.The present invention is not required to compound other high molecular materials in chitosan solution, and small molecule functional components only need to be added, you can obtains the hydrogel material with high intensity, while can play degradation of chitosan characteristic of good performance and the good functionality of auxiliary ingredients.In addition, this method preparation process is simple, and it is at low cost, it is suitable for promoting the use of.
Description
Technical field
The present invention relates to the preparation methods of a kind of physical chitosan hydrogel with high intensity, belong to functional polymer material
Material field.
Background technology
Chitosan is a kind of natural macromolecular material by being extracted in the shell of the shellfish such as shrimp, crab, is nature
Unique alkaline polysaccharide in boundary.Chitosan is because of its good biocompatibility, biodegradability, anthemorrhagic performance, anti-microbial property
Equal biology performances feature, is applied widely in fields such as food, drug, medical instruments.
Utilize the 6-OH in chitosan molecule chain, 2-NH2Cross-linking reaction, can get with network-like structure hydrogel
Material because it can retain the good biological characteristics of chitosan, and is obtained and is answered extensively with good hydrophilic, water retention property
With.But the process of hydrogel is prepared by chitosan at present, mainly uses the chemical cross-linking agents such as epoxychloropropane, glutaraldehyde.On
Though the cross-linking reaction for stating crosslinking agent is simple and easy to control, since crosslinking agent is also easy to produce residual in hydrogel, hydrogel is affected
Biocompatibility easily causes cytotoxicity, thus is used by limitation.Further, since the performance deficiency of chitosan itself, made
Standby hydrogel mechanical property is poor, can not form uniform and stable continuous gel.In order to improve the mechanical performance of hydrogel, often
It is compound that the synthesis macromolecule progress such as polyvinylpyrrolidone, polyvinyl alcohol need to be added.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 for the first time, by fumigating effect, is obtained
Novel hydrogels material with good mechanical property and functional effect.
Invention content
Preparing aquagel the purpose of the present invention is to solve conventional method, there are poor biocompatibilities, degradable
Property it is poor the problems such as, and provide the preparation method of a kind of physical chitosan hydrogel with high intensity.
The purpose of the present invention is what is be achieved through the following technical solutions.
One kind of the present invention has the preparation method of the physical chitosan hydrogel of high intensity, specific preparation process as follows：
1) it dissolves chitosan in the aqueous solution for the glacial acetic acid that mass concentration is 0.1~5.0%, in 20~80 DEG C of conditions
Lower stirring 0.5-3 hours, mass concentration of the chitosan in glacial acetic acid aqueous solution are 0.1~10.0%；
2) the function auxiliary element for accounting for reaction solution quality 0.1~10% is added in the reaction solution obtained to step 1),
It is stirred to react under the conditions of 20~80 DEG C 0.5-3 hours；
3) the reaction solution volatile akaline liquid identical with reaction solution volume that step 2) obtains is held respectively,
And be placed on jointly in a closed environment, after the sealing place of being protected from light is reacted 0.5~10 hour, obtain target product；
The function auxiliary element is：It is arbitrary in silver nitrate, copper chloride, graphene, graphene oxide, carbon nanotube
It is a kind of；
The volatile akaline liquid be the ammonium hydroxide that mass concentration is 10%~40% or mass concentration be 10%~
40% oxyammonia aqueous solution.
Advantageous effect
The present invention is not required to compound other high molecular materials in chitosan solution, and small molecule functional components only need to be added,
The hydrogel material with high intensity is can be obtained, while degradation of chitosan characteristic of good performance can be played, can also be played auxiliary
The good functionality of furtherance part.In addition, this method preparation process is simple, and it is at low cost, it is suitable for promoting the use of.
Specific implementation mode
Present disclosure is further described with reference to embodiment.
Embodiment 1：
0.5 gram of chitosan is dissolved in the aqueous solution of the glacial acetic acid of 99.5 gram masses a concentration of 2%, under the conditions of 30 DEG C
Stirring 0.5 hour.0.3 gram of silver nitrate is weighed, is added in above-mentioned chitosan solution, is stirred 1 hour under the conditions of 30 DEG C.It will stirring
The ammonium hydroxide that good mixed solution mass concentration identical with mixed liquor volume is 26% is held respectively, and is placed on hermetic bag jointly
In be protected from light 3 hours after obtain physical chitosan hydrogel.
Embodiment 2：
2 grams of chitosans are dissolved in the aqueous solution of the glacial acetic acid of 98 gram masses a concentration of 4%, are stirred under the conditions of 60 DEG C
2 hours.5 grams of graphene oxides are weighed, are added in above-mentioned chitosan solution, are stirred 2 hours under the conditions of 60 DEG C.By what is be stirred
The ammonium hydroxide that mixed solution mass concentration identical with mixed liquor volume is 28% is held respectively, and is placed in hermetic bag and is kept away jointly
Light reaction obtains physical chitosan hydrogel after 3 hours.
Embodiment 3：
8 grams of chitosans are dissolved in the aqueous solution for the glacial acetic acid that 92 mass concentrations are 2%, 1 is stirred under the conditions of 70 DEG C
Hour.The carbon nanotube for weighing 6 grams is added in above-mentioned chitosan solution, is stirred 1 hour under the conditions of 70 DEG C.By what is be stirred
The ammonium hydroxide that mixed solution mass concentration identical with mixed liquor volume is 18% is held respectively, and is placed in hermetic bag and is kept away jointly
Light reaction obtains physical chitosan hydrogel after 8 hours.
Embodiment 4：
0.3 gram of chitosan is dissolved in the aqueous solution of the glacial acetic acid of 99.7 gram masses a concentration of 0.1%, in 30 DEG C of conditions
Lower stirring 0.5 hour.0.5 gram of copper chloride is weighed, is added in above-mentioned chitosan solution, is stirred 1 hour under the conditions of 30 DEG C.It will stir
The aqueous hydroxylamine solution that the mixed solution mixed mass concentration identical with mixed liquor volume is 12% is held respectively, and is put jointly
Physical chitosan hydrogel is obtained after being protected from light 2 hours in hermetic bag.Prepared physical chitosan hydrogel has good
Mechanical property and shape memory effect.
Using the following methods test physical chitosan hydrogel that obtains embodiment 1 to the antibiotic property of different strains to be tested
Energy：
Physical chitosan hydrogel is swollen in distilled water, a concentration of 0.4g/mL is spare.Strain to be tested is seeded to flat
Plate, 37 DEG C of incubators take out, the bacterium of inoculation are chosen with aseptic cotton carrier into sterile saline afterwards for 24 hours, are adjusted to 0.5 Maxwell
Than the bacterial concentration of turbid standard, it is used in combination 100 times of M-H broth dilutions spare.Solution to be measured is diluted to 1 using two-fold dilution's method:
5,1:10,1:20,1:40,1:80,1:160,1:320,1:640, it is put into equivalent bacterium solution, has examination with sterile rubbery plug lid residence
The above test tube is placed in 37 DEG C of incubator effects for 24 hours by pipe.It takes experimental liquid or dilution to make count plate, calculates the suppression of measured object
Bacterium rate.Using the minimum concentration of not long bacterium as the minimal inhibitory concentration of measured object.
The physical chitosan hydrogel that embodiment 1 obtains is 2.5 × 10 to the minimum inhibitory concentration of Escherichia coli-3G/mL,
Minimum inhibitory concentration to staphylococcus aureus is 1.3 × 10-3g/mL.The physical chitosan hydrogel pair that embodiment 4 obtains
The minimum inhibitory concentration of Escherichia coli is 4.0 × 10-2G/mL, the minimum inhibitory concentration to staphylococcus aureus are 2.5 × 10-3g/mL。
According to GB/T 1040.2-2006《The measurement of plastic tensile performance》Tested hydrogel is utilized standard module by standard
The sample for cutting into 1BB sizes in standard is the fracture strength that 50mm/min tests hydrogel with tensile speed.Embodiment 1
The fracture strength of the physical chitosan hydrogel arrived is 0.78MPa, and the fracture for the physical chitosan hydrogel that embodiment 2 obtains is strong
Degree is 1.16MPa, and the fracture strength for the physical chitosan hydrogel that embodiment 3 obtains is 1.37MPa, the shell that embodiment 4 obtains
The fracture strength of glycan physical hydrogel is 0.63MPa.
Embodiment 5 (comparative examples of embodiment 1)：
0.5 gram of chitosan is dissolved in the aqueous solution of the glacial acetic acid of 99.5 gram masses a concentration of 2%, under the conditions of 30 DEG C
Stirring 0.5 hour.The mixed solution being stirred is positioned in closed hermetic bag, and it is 26% that mass concentration is added wherein
Ammonium hydroxide, then entire obturator is positioned over and is protected from light dark place, reaction obtains physical chitosan hydrogel after 3 hours.It is 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 are 4.0 × 10-1g/
mL.The fracture strength of prepared physical chitosan hydrogel is 0.06MPa.
By the above results as it can be seen that compared with Example 1, being not added with Ag+Carry out it is compound in the case of, prepared chitosan
The mechanical strength of physical hydrogel significantly reduces.Illustrate that addition small molecule is compound, above-mentioned physical chitosan hydrogel can be improved
Mechanical strength.In addition, compared with Example 1, being not added with Ag+Carry out it is compound in the case of, prepared chitosan physics water-setting
The minimum inhibitory concentration of glue significantly increases, and illustrates to use auxiliary ingredients Ag+It is compound to prepare hydrogel, it is remarkably improved hydrogel
Antiseptic.
Embodiment 6 (comparative examples of embodiment 1)：
0.5 gram of chitosan is dissolved in the aqueous solution of the glacial acetic acid of 99.5 gram masses a concentration of 2%, under the conditions of 30 DEG C
Stirring 0.5 hour.0.3 gram of silver nitrate is weighed, is added in above-mentioned chitosan solution, is stirred 1 hour under the conditions of 30 DEG C.It will stirring
Good mixed solution is placed in hermetic bag be kept in dark place 3 hours after obtain 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 are 2.5 × 10-3g/mL。
Prepared physical chitosan hydrogel poor mechanical properties, can not prepare batten, can not measure mechanical property.
By the above results as it can be seen that compared with Example 1, Ag is only being added+It carries out compound, is smoked without using alkaline gas
In the case of steaming, although prepared chitosan complex silver hydrogel can keep certain anti-microbial property, its mechanical strength
It is very poor.Illustrate only through chitosan and Ag+Complex reaction, it is stifling without using alkaline gas, be unable to get with good mechanics
The physical hydrogel of intensity.
It 1 is compareed in conjunction with the embodiments as it can be seen that the only addition in functional auxiliary ingredients and alkali with embodiment 5, embodiment 6
Property gas stifling collective effect under, just can get with excellent mechanical performances and anti-microbial property chitosan physics water-setting
Glue.
Claims (1)
1. one kind has the preparation method of the physical chitosan hydrogel of high intensity, it is characterized in that：Specific preparation process is as follows：
1) it dissolves chitosan in the aqueous solution for the glacial acetic acid that mass concentration is 0.1~5.0%, is stirred under the conditions of 20~80 DEG C
It mixes 0.5-3 hours, mass concentration of the chitosan in glacial acetic acid aqueous solution is 0.1~10.0%；
2) the function auxiliary element for accounting for reaction solution quality 0.1~10% is added in the reaction solution obtained to step 1), 20
It is stirred to react under the conditions of~80 DEG C 0.5-3 hours；
3) the reaction solution volatile akaline liquid identical with reaction solution volume that step 2) obtains is held respectively, and altogether
With being placed in a closed environment, after the sealing place of being protected from light is reacted 0.5~10 hour, target product is obtained；
The function auxiliary element is：It is any one in silver nitrate, copper chloride, graphene, graphene oxide, carbon nanotube
Kind；
The volatile akaline liquid is the ammonium hydroxide that mass concentration is 10%~40% or mass concentration is 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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| CN106279724B true CN106279724B (en) | 2018-11-06 |
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| 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 |
| CN112851983B (en) * | 2020-12-31 | 2022-07-29 | 东华大学 | Electrostatic spraying film of hydrogel and preparation method and application thereof |
Citations (4)
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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 |
| CN105820352A (en) * | 2016-04-06 | 2016-08-03 | 南京林业大学 | Method for preparing electropositive chitin nanofiber hydrogel and aerogel |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105820352A (en) * | 2016-04-06 | 2016-08-03 | 南京林业大学 | Method for preparing electropositive chitin nanofiber hydrogel and aerogel |
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