CN106800662A - A kind of preparation method of chitosan gel rubber based material - Google Patents
A kind of preparation method of chitosan gel rubber based material Download PDFInfo
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- CN106800662A CN106800662A CN201710049556.3A CN201710049556A CN106800662A CN 106800662 A CN106800662 A CN 106800662A CN 201710049556 A CN201710049556 A CN 201710049556A CN 106800662 A CN106800662 A CN 106800662A
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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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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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
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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 invention discloses a kind of method that chitosan gel rubber based material is directly prepared from chitin, the material includes hydrogel and aeroge.Chitin is dissolved in the solvent of alkali-urea, heated sealed realizes that the homogeneous deacetylated of chitin obtains shitosan base gel, after shitosan base gel is removed into alkali lye urea with the method that non-solvent is replaced, the aquagel being physical crosslinking；To chemical cross-linking agent is added in chitin solution, heated after stirring, the shitosan base gel being yield a partially cross-linked, after solvent is replaced and removes alkali lye urea, obtain the aquagel of physical chemistry double cross connection；Shitosan aeroge is obtained by drying the solvent in removing aquagel and shitosan organogel.Chitin of the shitosan in nature, with excellent biocompatibility, biodegradability, chitosan gel rubber based material has huge application prospect in biologic medical field.
Description
Technical field
The present invention relates to a kind of preparation method of chitosan gel rubber based material, belong to field of new.
Background technology
In recent years, shitosan in flexible electronic device, stops as unique positively charged natural polysaccharide in nature
The application study in the fields such as blood, medicament transport, water process, METAL EXTRACTION and recovery achieves major progress.Shitosan is crust
The deacetylated product of element, when N- deacetylations（Degree of Deacetylation）When more than 55%, shitosan can only
It is dissolved in acidic aqueous solution.Chitosan gel rubber based material includes hydrogel, gelatinous fibre, the gel micro-ball of hygrometric state, the airsetting of dry state
Glue, dry film, silk etc..Traditional chitosan gel rubber based material be with shitosan acidic aqueous solution as starting point, by physics and
Material prepared by the method for chemistry, it is exactly weaker mechanical property that they have a weakness.Develop a kind of superior shell of physical property
Polysaccharide gel based material, can expand range of application and the field of chitosan gel rubber based material.
The industrial shitosan for preparing is after extracting chitin from biologies such as shrimp, crab, squid, silkworm chrysalises, then in high concentration
In strong alkali aqueous solution（Such as 40~50wt% sodium hydroxide solutions）Heating is by the deacetylated preparation of out-phase.Prepared from chitin
On the one hand shitosan consumes substantial amounts of alkali, and the on the other hand purifying and drying to shitosan can consume substantial amounts of acid and the energy.
From from the point of view of industrial production, prepare chitosan material from the shitosan of purifying and directly made compared to from chitin
Standby chitosan material has obvious short slab.Therefore, a kind of method pair that chitosan material is directly prepared from chitin is developed
It is significant for from the aspect of improve production efficiency, environmental protection, energy-saving and emission-reduction, increase economic well-being of workers and staff etc..
The content of the invention
The technical problem to be solved in the present invention is to overcome high energy consumption in existing chitosan gel rubber material preparation process not
Economic problems, there is provided a kind of safe, low energy consumption, meet the side by preparing chitosan from chitin gel rubber material of Green Chemistry
Method.Deacetylated by chitin solution original position, direct construction chitosan gel rubber material can omit the purification and acid of shitosan
Dissolving, saves ample resources, and have more excellent physical property from the chitosan material of alkali systems structure.
The present invention is in order to solve the above technical problems, the dissolving method first to chitin solution is optimized：
The dicyandiamide solution for using is aqueous alkali, alkali-aqueous solution of urea, alkali-thiourea solution, or alkali-urea-thiocarbamide water
Solution；Dicyandiamide solution is mixed with chitin, and be refrigerated to it is below freezing, it is above freezing defrosting and obtain chitin solution.
As one preferably, chitin solution is dissolved in potassium hydroxide-aqueous solution of urea by chitin and is obtained, wherein
Concentration of potassium hydroxide is 2wt~27wt%, preferably 15wt-22wt%；Urea concentration be 0.1~20wt%, preferably 4~
12wt%；Balance of water.
As another preferably, chitin solution is dissolved in potassium hydroxide-thiourea solution by chitin and is obtained, its
Middle concentration of potassium hydroxide is 2wt~27wt%, preferably 15wt-22wt%；Thiourea concentration be 0.1~10wt%, preferably 3~
6wt%；Balance of water.
As another preferably, chitin solution is dissolved in NaOH-aqueous solution of urea by chitin and is obtained, its
Middle naoh concentration is 2wt~25wt%, preferably 6wt-14wt%；Urea concentration be 0.1~20wt%, preferably 4~
12wt%；Balance of water.
As another preferably, chitin solution is dissolved in NaOH-thiourea solution by chitin and is obtained, its
Middle naoh concentration is 2wt~25wt%, preferably 6wt-14wt%；Thiourea concentration be 0.1~10wt%, preferably 3~
6wt%；Balance of water.
The present invention aquagel is prepared by the chitin solution for obtaining prepared above method be：
Chitin solution is obtained into transparent slight deacetylated chitin basic hydrogel in 40 ~ 80 DEG C of heating half an hour；After
Continuous heating, the deacetylation of chitin continues to increase, and chitin is changed into and is soluble in acidic aqueous solution after 2 hours
Alkaline chitosan hydrogel；By in the non-solvent of alkaline chitosan hydrogel immersion shitosan, regeneration obtains physics friendship after washing
The aquagel of connection.
The heating is that chitin solution is in 40 ~ 80 DEG C of temperature, is persistently added with microwave or other mode of heatings
Heat or intermittent-heating.
The present invention also provides the preparation method that a kind of chemically and physically crosslinking double cross joins aquagel.
Under less than the gelling temperature of chitin solution, crosslinking agent and stirred to being added in the chitin solution of stabilization,
It is 0.1 with the mol ratio of chitin to control crosslinking agent:1~2.5:1, more than 2 hours shapes are then heated under conditions of 40 ~ 80 DEG C
Into part chemical crosslinking it is deacetylated after chitosan gel rubber, then by the gel be placed in the non-solvent of shitosan 30 minutes with
On be physical crosslinking, the double cross being then chemically and physically crosslinked with pure water joins aquagel.
During aquagel prepared above, the non-solvent of the shitosan, can be water, organic solvent or
The mixed solution of person's water and organic solvent, in preferred technique, this kind of suitable coagulator includes alcohol ketone ester or its mixture.
It is preferred to do coagulator using methyl alcohol, ethanol, acetone.
The non-solvent of shitosan can also be the water for adding cation, preferably containing monovalent cation such as Li+、Na+、K+
The aqueous solution, sodium chloride, potassium chloride, lithium chloride, potassium sulfate, sodium sulphate etc. can be dissolved in water and be obtained by such solution.
The present invention shitosan aeroge is prepared by the aquagel for obtaining prepared above method be：By shitosan water
Water in gel is replaced into organic liquid, obtains shitosan organogel；Aquagel or shitosan organogel are done
Dry removing liquid obtains shitosan aeroge.
It is described be alkane, halogenated hydrocarbon for replacing the organic solvent of aquagel, alcohols, ketone, esters, contain
Nitrogen organic, sulfurous organic compound, or various solvents mixture.In the organic solvent being enumerated above, gather from shell is improved
Sugared performance and cost angle consider, and preferably use alkanes, ketone and alcohol compound, more preferably using methyl alcohol, ethanol or
Acetone.
Above in the preparation process of shitosan aeroge, the described link that dries can be using conventional drying means, example
Such as using carbon dioxide, methyl alcohol, ethanol, acetone as the supercritical drying of supercritical fluid, or constant pressure and dry and freezing are carried out
Dry and remove liquid medium.
Nitrogen adsorption-desorption test obtains shitosan aeroge specific surface area and reaches 460m2/g。
Aquagel, the aeroge obtained for the present invention, to it can also carry out surface hydroxyl or amino changes
It is property, such as carboxy methylation, hydroxyethylation, quaternized.Can synthesize in aquagel or add macromolecule, filler,
Inorganic matter etc..Macromolecule such as cellulose, collagen, alginic acid, PLA, polyacrylate, PVA etc..Filler such as carbon black, sweet
Oil, propane diols, butanediol or PEG400 etc..Fibre reinforced materials such as glass fibre, carbon fiber, cellulose can also be added brilliant
Palpus, chitin whisker etc..Inorganic matter such as silica, iron oxide, ferroso-ferric oxide, clay, titanium dioxide, Graphene etc..
Can synthesize or add a kind of or filler at least one of these additives.
The present invention provides a kind of inexpensive, and pollution-free, easy method obtains high-quality chitin solution, and utilizes this first
Shell element solution prepares the shitosan aeroge with high-specific surface area using corresponding method.The advantage of the invention is that：Adopted
Solvent is KOH, NaOH, urea（Thiocarbamide）And water, production process nontoxic pollution-free, low energy consumption, be conducive to environmental protection and
Operator's health；It is the more excellent hydrogel for preparing, aeroge physical property relative to the sour solvent system of shitosan.
This new method not only production technology environmental protection, low cost, and excellent product performance, it is to the great prominent of prior art
It is broken, it is suitable for industrialized production and practical application, have broad application prospects.
Brief description of the drawings
Fig. 1 display embodiment of the present invention 20 double crosses join the atomic force microscopy of aquagel.It is observed that
Gel inside has uniform microcellular structure；
Fig. 2 shows the stereoscan photograph of the shitosan aeroge of the embodiment of the present invention 26；
There is the deacetylated solid state nmr carbon spectrum for being changed into shitosan after a heating treatment in Fig. 3 display chitins.
Specific embodiment
Embodiment 1
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 81g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 1g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution, be put into during setting temperature is 60 DEG C of convection oven, heating 2h makes its gelation and deacetylated.Will be de-
The chitosan gel rubber of acetylation is placed in 72h in 75% ethanol water, and the aquagel that washing is physical crosslinking is measured
Tensile strength is 0.3MPa, and breaking strain is 110%, and moisture content is 92wt%, and deacetylation is 51%.
Embodiment 2
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 81g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 1g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution, be put into during setting temperature is 40 DEG C of convection oven, heating 12h makes its gelation and deacetylated.Will be de-
The chitosan gel rubber of acetylation is placed in 72h in deionized water, and the aquagel that washing is physical crosslinking measures compression strong
It is 1.3MPa to spend, and breaking strain is 83%, and moisture content is 97wt%, and deacetylation is 58%.
Embodiment 3
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 81g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 1g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution, be put into during setting temperature is 50 DEG C of convection oven, heating 12h makes its gelation and deacetylated.Will be de-
The chitosan gel rubber of acetylation is placed in 72h in deionized water, and the aquagel that washing is physical crosslinking measures compression strong
It is 1.3MPa to spend, and breaking strain is 79%, and moisture content is 96wt%, and deacetylation is 62%.
Embodiment 4
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 81g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 1g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution, be put into during setting temperature is 70 DEG C of convection oven, heating 12h makes its gelation and deacetylated.Will be de-
The chitosan gel rubber of acetylation is placed in 72h in deionized water, and the aquagel that washing is physical crosslinking measures compression strong
It is 2.7MPa to spend, and breaking strain is 78%, and moisture content is 94wt%, and deacetylation is 75%.
Embodiment 5
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 81g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 1g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution, be put into during setting temperature is 80 DEG C of convection oven, heating 12h makes its gelation and deacetylated.Will be de-
The chitosan gel rubber of acetylation is placed in 72h in deionized water, and the aquagel that washing is physical crosslinking measures compression strong
It is 3MPa to spend, and breaking strain is 76%, and moisture content is 92wt%, and deacetylation is 77%.
Embodiment 6
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 81g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 1g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution, be put into during setting temperature is 60 DEG C of convection oven, heating 12h makes its gelation and deacetylated.Will be de-
The chitosan gel rubber of acetylation is placed in 72h in deionized water, and the aquagel that washing is physical crosslinking measures compression strong
It is 0.07MPa to spend, and breaking strain is 68%, and moisture content is 97wt%, and deacetylation is 44%.
Embodiment 7
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 81g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 2g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution, be put into during setting temperature is 60 DEG C of convection oven, heating 12h makes its gelation and deacetylated.Will be de-
The chitosan gel rubber of acetylation is placed in 72h in deionized water, and the aquagel that washing is physical crosslinking measures compression strong
It is 0.33MPa to spend, and breaking strain is 76%, and moisture content is 96wt%, and deacetylation is 59%.
Embodiment 8
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 81g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 3g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution, be put into during setting temperature is 60 DEG C of convection oven, heating 12h makes its gelation and deacetylated.Will be de-
The chitosan gel rubber of acetylation is placed in 72h in deionized water, and the aquagel that washing is physical crosslinking measures compression strong
It is 1.2MPa to spend, and breaking strain is 79%, and moisture content is 95wt%, and deacetylation is 75%.
Embodiment 9
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 81g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 3g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution, be put into during setting temperature is 60 DEG C of convection oven, heating 12h makes its gelation and deacetylated.Will be de-
The chitosan gel rubber of acetylation is placed in 72h in deionized water, and the aquagel that washing is physical crosslinking measures compression strong
It is 1.19MPa to spend, and breaking strain is 79%, and moisture content is 95wt%, and deacetylation is 75%.
Embodiment 10
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 81g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 5g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution, be put into during setting temperature is 60 DEG C of convection oven, heating 8h makes its gelation and deacetylated.Will be de-
The chitosan gel rubber of acetylation is placed in 72h in deionized water, and the aquagel that washing is physical crosslinking measures compression strong
It is 2.4MPa to spend, and breaking strain is 77%, and moisture content is 95wt%, and deacetylation is 77%.
Embodiment 11
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 81g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 5g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution, be put into during setting temperature is 60 DEG C of convection oven, heating 4h makes its gelation and deacetylated.Will be de-
The chitosan gel rubber of acetylation is placed in 72h in deionized water, and the aquagel that washing is physical crosslinking measures compression strong
It is 2.2MPa to spend, and breaking strain is 81%, and moisture content is 95wt%, and deacetylation is 74%.
Embodiment 12
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 81g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 5g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution, be put into during setting temperature is 60 DEG C of convection oven, heating 48h makes its gelation and deacetylated.Will be de-
The chitosan gel rubber of acetylation is placed in 72h in deionized water, and the aquagel that washing is physical crosslinking measures compression strong
It is 4.7MPa to spend, and breaking strain is 80%, and moisture content is 92wt%, and deacetylation is 82%.
Embodiment 13
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 81g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 5g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution be put into during setting temperature is 60 DEG C of convection oven, heating 12h makes its gelation and deacetylated.Will be de-
The chitosan gel rubber of acetylation is placed in 72h in deionized water, and the aquagel that washing is physical crosslinking measures compression strong
It is 2.9MPa to spend, and breaking strain is 78%, and moisture content is 94wt%, and deacetylation is 76%.
Embodiment 14
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 18g potassium hydroxide, 5g urea, 77g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 5g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.- 20 DEG C to chitin solution in add and 1g epoxychloropropane and stir 2h, solution is filled after evacuation and centrifugal degassing
Enter in bottle and seal, be put into during setting temperature is 60 DEG C of convection oven, heating 24h occurs chemical crosslinking and deacetylated anti-
Should.Reacted gel is placed in 72h in 75wt% ethanol solutions and forms physical crosslinking, then washing obtains double cross-linked chitosans
Hydrogel.The moisture content for measuring double cross connection chitosan gel rubber is 75%, and tensile strength is 2.5MPa, and elongation strain is 60%.
（Comparative example 1）
The mixed solvent of 18g potassium hydroxide, 5g urea, 77g water is cooled to -20 DEG C in advance, 5g chitins is added after being cooled to -20 in advance℃Keep 12h.Thaw at room temperature, that is, obtain transparent chitin solution.- 20 DEG C to chitin solution in add 5g epoxies
Chloropropane simultaneously stirs 2h, solution is fitted into bottle after evacuation and centrifugal degassing seals, and is put into during setting temperature is 60 DEG C of convection oven,
There is chemical crosslinking and deacetylation in heating 24h.After soaking one week in deionized water, the chemical crosslinking shitosan for obtaining
Hydrogel mechanical property is very weak, only tens of kPa.
Embodiment 15
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 18g potassium hydroxide, 5g urea, 77g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 5g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.- 20 DEG C to chitin solution in add and 2g epoxychloropropane and stir 2h, solution is filled after evacuation and centrifugal degassing
Enter in bottle and seal, be put into during setting temperature is 60 DEG C of convection oven, heating 12h occurs chemical crosslinking and deacetylated anti-
Should.Reacted gel is placed in 72h in 5wt% ethanol solutions and forms physical crosslinking, then washing obtains double cross-linked chitosan water
Gel.The moisture content of the double cross connection chitosan gel rubber prepared under the conditions of this is 80%, and compressive strength is 8.3MPa, and compression strain is
94%。
Embodiment 16
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 18g potassium hydroxide, 5g urea, 77g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 5g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.- 20 DEG C to chitin solution in add and 0.5g epoxychloropropane and stir 2h, by solution after evacuation and centrifugal degassing
It is fitted into bottle and seals, be put into during setting temperature is 60 DEG C of convection oven, heating 12h occurs chemical crosslinking and deacetylated
Reaction.Reacted gel is placed in 72h in 5wt% ethanol solutions and forms physical crosslinking, then washing obtains double cross-linked chitosans
Hydrogel.The moisture content of the double cross connection chitosan gel rubber prepared under the conditions of this is 86%, and compressive strength is 4.5MPa, compression strain
It is 92%.
Embodiment 17
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 18g potassium hydroxide, 5g urea, 77g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 5g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.- 20 DEG C to chitin solution in add and 1g epoxychloropropane and stir 2h, solution is filled after evacuation and centrifugal degassing
Enter in bottle and seal, be put into during setting temperature is 60 DEG C of convection oven, heating 4h occurs chemical crosslinking and deacetylated anti-
Should.Reacted gel is placed in 72h in 5wt% ethanol solutions and forms physical crosslinking, then washing obtains double cross-linked chitosan water
Gel.The moisture content of the double cross connection chitosan gel rubber prepared under the conditions of this is 94%, and compressive strength is 7.5MPa, and compression strain is
88%。
Embodiment 18
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 18g potassium hydroxide, 5g urea, 77g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 5g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.- 20 DEG C to chitin solution in add and 1g epoxychloropropane and stir 2h, solution is filled after evacuation and centrifugal degassing
Enter in bottle and seal, be put into during setting temperature is 60 DEG C of convection oven, heating 8h occurs chemical crosslinking and deacetylated anti-
Should.Reacted gel is placed in 72h in 5wt% ethanol solutions and forms physical crosslinking, then washing obtains double cross-linked chitosan water
Gel.The moisture content of the double cross connection chitosan gel rubber prepared under the conditions of this is 90%, and compressive strength is 14.1MPa, and compression strain is
89%。
Embodiment 19
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 18g potassium hydroxide, 5g urea, 77g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 5g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.- 20 DEG C to chitin solution in add and 1g epoxychloropropane and stir 2h, solution is filled after evacuation and centrifugal degassing
Enter in bottle and seal, be put into during setting temperature is 60 DEG C of convection oven, heating 48h occurs chemical crosslinking and deacetylated anti-
Should.Reacted gel is placed in 72h in 5wt% ethanol solutions and forms physical crosslinking, then washing obtains double cross-linked chitosan water
Gel.The moisture content of the double cross connection chitosan gel rubber prepared under the conditions of this is 89%, and compressive strength is 13.6MPa, and compression strain is
91%。
Embodiment 20
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 18g potassium hydroxide, 5g urea, 77g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 5g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.- 20 DEG C to chitin solution in add and 1g epoxychloropropane and stir 2h, solution is filled after evacuation and centrifugal degassing
Enter in bottle and seal, be put into during setting temperature is 60 DEG C of convection oven, heating 12h occurs chemical crosslinking and deacetylated anti-
Should.Reacted gel is placed in 72h in 5wt% ethanol solutions and forms physical crosslinking, then washing obtains double cross-linked chitosan water
Gel.The moisture content of the double cross connection chitosan gel rubber prepared under the conditions of this is 88%, and compressive strength is 14MPa, and compression strain is
90%。
Embodiment 21
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 18g potassium hydroxide, 5g urea, 77g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 5g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.- 20 DEG C to chitin solution in add and 2g epoxychloropropane and stir 2h, solution is filled after evacuation and centrifugal degassing
Enter in bottle and seal, be put into during setting temperature is 40 DEG C of convection oven, heating 12h occurs chemical crosslinking and deacetylated anti-
Should.Reacted gel is placed in 72h in 5wt% ethanol solutions and forms physical crosslinking, then washing obtains double cross-linked chitosan water
Gel.The moisture content of the double cross connection chitosan gel rubber prepared under the conditions of this is 96%, and compressive strength is 4MPa, and compression strain is
85%。
Embodiment 22
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 18g potassium hydroxide, 5g urea, 77g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 5g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.- 20 DEG C to chitin solution in add and 2g epoxychloropropane and stir 2h, solution is filled after evacuation and centrifugal degassing
Enter in bottle and seal, be put into during setting temperature is 80 DEG C of convection oven, heating 12h occurs chemical crosslinking and deacetylated anti-
Should.Reacted gel is placed in 72h in 5wt% ethanol solutions and forms physical crosslinking, then washing obtains double cross-linked chitosan water
Gel.The moisture content of the double cross connection chitosan gel rubber prepared under the conditions of this is 92%, and compressive strength is 6MPa, and compression strain is
91%。
Embodiment 23
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 18g potassium hydroxide, 5g urea, 77g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 5g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.- 20 DEG C to chitin solution in add and 2g epoxychloropropane and stir 2h, solution is filled after evacuation and centrifugal degassing
Enter in bottle and seal, be put into during setting temperature is 80 DEG C of convection oven, heating 2h occurs chemical crosslinking and deacetylated anti-
Should.Reacted gel is placed in 72h in 5wt% ethanol solutions and forms physical crosslinking, then washing obtains double cross-linked chitosan water
Gel.The moisture content of the double cross connection chitosan gel rubber prepared under the conditions of this is 95%, and compressive strength is 4MPa, and compression strain is
92%。
Embodiment 24
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 76g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 1g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.Solution is fitted into bottle and is sealed, be put into during setting temperature is 60 DEG C of convection oven, heating 12h makes it
Gelation and deacetylated.Deacetylated chitosan gel rubber is placed in 72h in deionized water, shitosan crystallization is formed, then
Washing obtains aquagel.Aquagel is replaced with absolute ethyl alcohol, by supercritical CO2Dry（38 DEG C of temperature,
Pressure 1300psi）Shitosan aeroge is obtained.Nitrogen adsorption-desorption test obtains shitosan aeroge specific surface area and is
339m2/ g, density is 0.10g/cm3.
Embodiment 25
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 76g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 2g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.Solution is fitted into bottle and is sealed, be put into during setting temperature is 60 DEG C of convection oven, heating 12h makes it
Gelation and deacetylated.Deacetylated chitosan gel rubber is placed in 72h in deionized water, shitosan crystallization is formed, then
Washing obtains aquagel.Aquagel is replaced with absolute ethyl alcohol, by supercritical CO2Dry（38 DEG C of temperature,
Pressure 1300psi）Shitosan aeroge is obtained.Nitrogen adsorption-desorption test obtains shitosan aeroge specific surface area and is
372m2/ g, density is 0.14g/cm3。
Embodiment 26
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 76g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 4g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.Solution sealing is put into during setting temperature is 60 DEG C of convection oven, heating 12h makes its gelation and de-
Acetylation.Deacetylated chitosan gel rubber is placed in 72h in 50wt% ethanol solutions, then washing obtains aquagel.
Aquagel is replaced with absolute ethyl alcohol, by supercritical CO2Dry（38 DEG C of temperature, pressure 1300psi）Shell is obtained to gather
Sugared aeroge.Nitrogen adsorption-desorption test obtains shitosan aeroge specific surface area for 460m2/ g, density is 0.23g/cm3。
Embodiment 27
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 76g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 3g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.Solution is fitted into bottle and is sealed, be put into during setting temperature is 60 DEG C of convection oven, heating 12h makes it
Gelation and deacetylated.Deacetylated chitosan gel rubber is placed in 72h in deionized water, shitosan crystallization is formed, then
Washing obtains aquagel.Aquagel is replaced with absolute ethyl alcohol, by supercritical CO2Dry（38 DEG C of temperature,
Pressure 1300psi）Shitosan aeroge is obtained.Nitrogen adsorption-desorption test obtains shitosan aeroge specific surface area and is
425m2/ g, density is 0.18g/cm3。
Embodiment 28
By commercially available chitin 4wt% NaOH aqueous solution soaking 48h, after soaking 6h with 1wt% HCl/waters solution after filtering washing,
Filtering washing, obtains the chitin powder that acetyl degree is 93% after freeze-drying.By 20g potassium hydroxide, 4g urea, 76g water it is mixed
Bonding solvent is cooled to -20 DEG C in advance, adds 2g chitins to be cooled to -20 DEG C of holding 12h after pre-.Thaw at room temperature, that is, obtain transparent
Chitin solution.- 20 DEG C to chitin solution in add and 1g epoxychloropropane and stir 2h, solution is filled after evacuation and centrifugal degassing
Enter in bottle and seal, be put into during setting temperature is 60 DEG C of convection oven, heating 12h occurs chemical crosslinking and deacetylated anti-
Should.Reacted gel is placed in 72h in 75wt% ethanol solutions and forms physical crosslinking, then washing obtains double cross-linked chitosans
Hydrogel.The aquagel that double cross is joined is replaced with absolute ethyl alcohol, by supercritical CO2Dry（38 DEG C of temperature, pressure
1300psi）The shitosan aeroge of physical chemistry double cross connection is obtained.Nitrogen adsorption-desorption test obtains shitosan aeroge
Specific surface area is 339m2/ g, density is 0.25g/cm3。
Claims (9)
1. a kind of method of the aquagel that physical crosslinking is directly prepared from chitin, it is characterised in that：
The dicyandiamide solution for using is aqueous alkali, alkali-aqueous solution of urea, alkali-thiourea solution, or alkali-urea-thiocarbamide water
Solution；Dicyandiamide solution is mixed with chitin, and be refrigerated to it is below freezing, it is above freezing defrosting and obtain chitin solution；
Chitin solution is obtained into transparent partially deacetylated chitin basic hydrogel in 40 ~ 80 DEG C of heating half an hour；
Continue to heat, the deacetylation of chitin continues to increase, and chitin is changed into and is soluble in acidic aqueous solution after 2 hours
Alkaline chitosan hydrogel；By in the non-solvent of alkaline chitosan hydrogel immersion shitosan, regeneration obtains physics after washing
The aquagel of crosslinking.
2. method according to claim 1, it is characterised in that：The non-solvent of described shitosan is water, or added with
The water of monovalent cation, or organic solvent, or water and organic solvent mixed solution.
3. a kind of chemically and physically crosslinking double cross joins the preparation method of aquagel, it is characterised in that：
The dicyandiamide solution for using is aqueous alkali, alkali-aqueous solution of urea, alkali-thiourea solution, or alkali-urea-thiocarbamide water
Solution；Dicyandiamide solution is mixed with chitin, and be refrigerated to it is below freezing, it is above freezing defrosting and obtain chitin solution；
Under less than the gelling temperature of chitin solution, to adding crosslinking agent in the chitin solution of stabilization and stirring, control
Crosslinking agent is 0.1 with the mol ratio of chitin:1~2.5:1,2 hours portions formed above are then heated under conditions of 40 ~ 80 DEG C
Point chemical crosslinking it is deacetylated after chitosan gel rubber, the gel is then placed in the non-solvent of shitosan 30 minutes with enterprising
Row physical crosslinking, then joins aquagel with the double cross that pure water is chemically and physically crosslinked.
4. method according to claim 3, it is characterised in that described crosslinking agent is epoxide and/or aldehydes
Compound.
5. a kind of preparation method of shitosan organogel, it is characterised in that：
Water in the aquagel that will be prepared by claim 1 methods described is replaced into organic liquid, and to obtain shitosan organic
Water in gel, or the aquagel that will be prepared by claim 3 methods described is replaced into organic liquid and obtains shell and gathers
Sugared organogel.
6. method according to claim 5, it is characterised in that described organic liquid is alkanes, alcohols or ketone chemical combination
Thing.
7. a kind of preparation method of shitosan aeroge, it is characterised in that：The shitosan that will be prepared by claim 1 methods described
Hydrogel, or the aquagel that will be prepared by claim 3 methods described, or will be by claim 5 methods described
The shitosan organogel of preparation, dries removing liquid and obtains shitosan aeroge.
8. method according to claim 7, it is characterised in that described dries link using supercritical drying, constant pressure and dry
Or freeze-drying removes liquid medium.
9. a kind of chitosan gel rubber material prepared from chitin, is the physical crosslinking of the method preparation as described in claim 1
Aquagel, by claim 3 methods described prepare physical chemistry double cross join aquagel or right will
The shitosan aeroge for asking 7 methods describeds to prepare.
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