CN104387597A - Chemical and physical double-cross-linking high-strength chitin gel material and preparation method thereof - Google Patents
Chemical and physical double-cross-linking high-strength chitin gel material and preparation method thereof Download PDFInfo
- Publication number
- CN104387597A CN104387597A CN201410704260.7A CN201410704260A CN104387597A CN 104387597 A CN104387597 A CN 104387597A CN 201410704260 A CN201410704260 A CN 201410704260A CN 104387597 A CN104387597 A CN 104387597A
- Authority
- CN
- China
- Prior art keywords
- chitin
- double cross
- hydrogel
- cross connection
- cross
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Materials For Medical Uses (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a chemical and physical double-cross-linking high-strength chitin gel material and a preparation method thereof. The preparation method comprises the following steps: adding a cross-linking agent for partial chemical cross-linking at the gelatinization temperature lower than that of a chitin solution, subsequently soaking the chitin gel which is subjected to partial chemical cross-linking into a non-solvent for physical cross-linking, and washing with water, thereby obtaining double-cross-linking chitin hydrogel; replacing water in the double-cross-linking chitin hydrogel by an organic liquid, thereby obtaining chitin organic gel, and drying the double-cross-linking chitin hydrogel or the organic gel, thereby obtaining double-cross-linking chitin aerogel; and hot-rolling the double-cross-linking chitin hydrogel or the double-cross-linking chitin aerogel, thereby preparing double-cross-linking chitin biological plastic. The double-cross-linking chitin gel material disclosed by the invention is excellent in mechanical property, low density and high specific surface area, can be easily processed into finished products such as fiber, sheets, granules, films and columns, and is applicable to large-scale popularization and application.
Description
Technical field
The present invention relates to a class chitin material, particularly a kind of based on chemistry and the dual crosslinked high strength chitin hydrogel based material of physics and preparation method thereof, belong to macromolecular material, biomedical materials field.
Background technology
The three-dimensional space network that macromolecule hydrogel is made up of hydroaropic substance, its physicochemical property and biological vital tissue close, have a wide range of applications in biomedical and field of tissue engineering technology.Such as, there is the macromolecule hydrogel of the functions such as optics (CN102336995A), magnetic (CN102391603A), Thermo-sensitive (CN102690401A).But because the water content of hydrogel, porosity are higher, the macromolecular chain number on unit cross-sectional area is less, and cause its mechanical property lower, range of application is subject to a definite limitation.Chitin is only second to Mierocrystalline cellulose in the biosynthesizing amount of occurring in nature, is a kind of native amino polysaccharide, can prepares film forming, fiber and gel, be widely used in the fields such as food, biosensor, water treatment, pharmaceutical carrier and bio-medical material.
Chitin hydrogel has the wetting ability of nontoxic, biocompatibility, biodegradability and the hydrogel of chitin, water-retentivity and environmental sensitivity concurrently, has very large researching value.But because chitin is a kind of high crystalline polysaccharide, containing in a large amount of molecule and intermolecular hydrogen bonding, solubility property is very poor, water insoluble and most organic solvent, and the research about chitin material is less, and the material mechanical performance obtained is also very low.Patent of invention as publication number CN101857684A discloses a kind of chitin cross-linked hydrogel, due to the chitin strength of solution that can obtain very low (0.5 ~ 3 wt%), and hydrogel chemistry crosslinking degree too high (mol ratio of epoxy chloropropane/chitin is 9: 1 ~ 78: 1), hydroxyls all on chitin all participates in reaction and forms chemically crosslinked point, what therefore obtain is the chitin hydrogel of complete chemically crosslinked, compressive strength is only tens KPa, requirement (the J. Mater. Chem. as structured material and bio-medical material cannot be met, 2011, 21, 3865-3871).
Summary of the invention
Technical problem to be solved by this invention is the deficiency overcoming existing chitin hydrogel mechanical property, provides a kind of based on chemistry and the dual crosslinked high strength chitin hydrogel based material of physics and preparation method thereof.
The present invention is for solving the problems of the technologies described above, the chitin hydrogel that quantitative linking agent stirs rear forming section chemically crosslinked is added in chitin solution, then the non-solvent chitin hydrogel that partial chemical is cross-linked being placed in chitin carries out physical crosslinking further and forms double cross connection chitin hydrogel, obtains chemistry and physics dual crosslinked high strength double cross connection chitin hydrogel after washing; Water double cross joined in chitin hydrogel is replaced into organic liquid and obtains double cross connection chitin organogel; Double cross is joined chitin hydrogel or organogel drying removing liquid, obtain double cross connection chitin aerogel; Double cross is joined chitin aerogel 150
ocarbon aerogels is obtained after more than C carbonization; Double cross is joined chitin hydrogel or aerogel hot pressing double cross connection chitin biological plastics.
Described chitin solution is mixed with alkali/aqueous solution of urea, alkali/thiourea solution or alkali/urea/sulphur urea solution by chitin and is refrigerated to below freezing, obtain above freezing thawing, or alkali/aqueous solution of urea, alkali/thiourea solution or alkali/urea/sulphur urea solution is chilled to freezing point ~ 0 in advance
oc, then adds chitin stirring and dissolving and obtains.
In alkali/aqueous solution of urea, alkali/thiourea solution or alkali/urea/sulphur urea solution, described alkali can be one or more of KOH, NaOH, LiOH.
The solvent dissolving chitin is made up of the water of 2 ~ 50 wt% KOH, 0 ~ 10 wt% LiOH, 0 ~ 20 wt% NaOH, 0 ~ 20 wt% urea, 0 ~ 6 wt% thiocarbamide and surplus.
Described chitin source can be the cell of lower plant mushroom, algae, and the shell of crustacean shrimp, crab, insect, the cell walls etc. of higher plant, has no particular limits through the method purifying of known technology before using.As acid treatment removing calcium salt, alkali removing deproteinated, oxidation bleaching depigmentation etc.
The invention provides concrete preparative chemistry and the dual crosslinked chitin hydrogel process of physics:
Below the gelling temperature of chitin solution, in chitin solution, add linking agent stir, leave standstill more than 5 hours, the mol ratio of linking agent and chitin is 0.1:1 ~ 8:1, the chitin hydrogel of forming section chemically crosslinked, then the chitin hydrogel that partial chemical is cross-linked is placed in the non-solvent more than 2 hours of chitin, carries out physical crosslinking further and form double cross connection chitin hydrogel, after washing, obtain chemistry and the dual crosslinked chitin hydrogel of physics.
Described linking agent is epoxy compounds and/or aldehyde compound.Preferred as one, described linking agent is epoxy chloropropane and/or epoxy chlorobutane and/or glutaraldehyde.
Described non-solvent can be water or add cationic water, preferably containing monovalent cation such as H
+, NH
4 +, Li
+, Na
+or K
+the aqueous solution, such solution can such as by water-soluble and obtained to hydrochloric acid, sulfuric acid, nitric acid, acetic acid, ammonium sulfate, ammonium acetate, lithium chloride, sodium sulfate, potassium sulfate etc.
Described non-solvent can also be water content higher than 50 wt%, preferably higher than the non-polar organic liquid of 70 wt%.The example of this kind of suitable peptizer comprises alcohol, ketone, ester or its mixture.It is preferred for using methyl alcohol and ethanol to do peptizer.Lower boiling non-polar organic liquid has the low character of viscosity, is conducive to solidifying of chitin solution.In addition, be conducive to being separated in the process of peptizer recovery.
The method being prepared double cross connection chitin organogel by double cross connection chitin hydrogel is further:
Water double cross joined in chitin hydrogel is replaced into organic solvent and obtains double cross connection chitin organogel.
The method being prepared double cross connection chitin aerogel by double cross connection chitin hydrogel or organogel is further:
Double cross is joined chitin hydrogel or double cross connection chitin organogel drying removing liquid, obtain double cross connection chitin aerogel.
The method being prepared carbon aerogels by double cross connection chitin aerogel is further:
Double cross is joined chitin aerogel under inert atmosphere protection, 150
ocarbon aerogels is obtained after more than C carbonization.
Described is lower boiling, volatile alkanes, halogenated hydrocarbon, alcohols, phenols, ether and acetals, ketone, acid and anhydrides, ester class, itrogenous organic substance, the organic compound of sulfur-bearing for replacing the organic solvent of double cross connection chitin hydrogel, or the mixture of aforementioned all kinds of SOLVENTS.In above-named organic solvent, find in test, consider from the performance and cost angle improving double cross of the present invention connection chitin aerogel material, preferably use alkanes, alcohols and ketone compounds, more preferably use methyl alcohol, ethanol or acetone.
In the preparation process of described double cross connection chitin aerogel, described dry link can utilize conventional drying means, such as, carry out supercritical drying using carbonic acid gas, methyl alcohol, ethanol, acetone as supercutical fluid, or carry out constant pressure and dry and lyophilize removing liquid medium.
Double cross is joined chitin aerogel under inert atmosphere protection, 150
ocarbon aerogels is obtained after more than C carbonization.Inert atmosphere refers to and does not react with chitin, the gas preventing chitin material from high temperature burning or gaseous mixture.Following gas is especially applicable to being used as inert atmosphere: nitrogen, carbonic acid gas, helium, neon and argon gas.Also the mixture of these gases can be used.Appropriate sour gas, as HCl can the carbonization of catalysis chitin.
Double cross connection chitin biological plastics is obtained after double cross being joined chitin hydrogel, organogel or aerogel hot pressing.Consider working (machining) efficiency, the temperature of described hot-pressing processing is 50 ~ 150
oc, carries out under pressure 0.1 ~ 60 MPa.When containing water or volatile organic liquid, accelerating liquid volatilization can be operated at reduced pressure conditions.
The biological plastics that the present invention obtains after also providing and double cross being joined chitin hydrogel, double cross connection chitin organogel or the hot pressing of double cross connection chitin aerogel.
In double cross connection chitin hydrogel, aerogel and biological plastics of the present invention, under the prerequisite not damaging mechanical property, thermal characteristics, can various additive be contained, as softening agent, dyestuff, photostabilizer etc.; Filler can also be contained, as organic, mineral filler and fibrous reinforcement agent.Organic filler is as conducting polymer, hydrophilic high molecular material etc.Mineral filler is as Graphene, carbon nanotube, carbon black, silicon-dioxide, clay, titanium dioxide etc.Fibrous reinforcement agent comprises inorganic fibre as glass fibre, carbon fiber and organic fibre.One or more of these additives or filler can be added.
The present invention also provides the products formed be made up of double cross connection chitin hydrogel based material.Double cross connection chitin hydrogel, aerogel and biological plastics of the present invention can obtain the products formed of arbitrary form, as fiber, section bar, pipe, granular substance, flap and membranoid substance.The products formed that double cross connection chitin hydrogel material of the present invention obtains has excellent mechanical property, thermostability, high-specific surface area, thus may be used for various uses.Such as, the field such as weaving, water treatment, bio-medical material, tissue engineering material, packaging material for food.
The invention provides a kind of based on chemistry and the dual crosslinked high strength chitin hydrogel based material of physics and preparation method thereof.Feature of the present invention is the chitin hydrogel of first forming section chemically crosslinked, then carries out physical crosslinking further and obtains chemistry and physics dual crosslinked high strength chitin hydrogel, aerogel and biological plastics.In the present invention, partial chemical is cross-linked the synergy be cross-linked with part physical and makes dual network chitin hydrogel have more excellent mechanical property.The present invention be advantageous in that: the solvent adopted is KOH, NaOH, LiOH, urea (and/or thiocarbamide) and water, and relative to organic solvents such as ionic liquids, price is more cheap.The not only production technique environmental protection of this novel method, cost are low, and excellent product performance, are the important breakthroughs to prior art, are suitable for suitability for industrialized production and practical application, have broad application prospects.
Accompanying drawing explanation
Stress-strain curve under double cross connection chitin hydrogel compact model described in Fig. 1 embodiment 10-14.
Two cross-linked hydrogel stretching (a) of chitin described in Fig. 2 embodiment 12 and the photo in kind under (b) condition of torsion.
Stress-strain curve under double cross connection chitin hydrogel compact model described in Fig. 3 embodiment 16.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described further, but should remembers that protection scope of the present invention is not limited to limit by them.The mechanical property of dual network chitin hydrogel based material of the present invention adopts the stretch mode of universal material test machine and compact model to measure the tensile strength of material, Young's modulus, elongation at break, compressive strength, modulus of compression respectively, adopts specific surface area and the pore size distribution of gas adsorption-desorption instrument test material.
Embodiment 1
By commercially available chitin 0.1 mol/L rare HCl soaking at room temperature 12 h, to filter after distilled water wash with 0.1 mol/L NaOH aqueous solution soaking 12 h, refilter after distilled water wash with 0.3 wt% NaClO
2depigmentation purifying, dries and obtains the chitin powder that acetyl degree is 98%.Water containing 10 ~ 50 wt% KOH and surplus is prepared into solvent, adds chitin powder, stirs and is placed on freeze overnight below freezing, obtain the chitin solution that concentration is 5 wt% after thawing.5
obe that 0.1:1 adds epoxy chloropropane according to the mol ratio of linking agent and chitin under C, stir be placed in mould place 24h after obtain the crosslinked chitin hydrogel of partial chemical, then gel is placed in distilled water and proceeds physical crosslinking 24h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, compressive strength is 0.4 MPa.
Embodiment 2
The water of 2 ~ 30 wt% KOH, 0 ~ 10 wt% LiOH, 0 ~ 20 wt% urea and surplus is prepared into solvent, add the chitin powder that embodiment 1 obtains, stirring is placed on freeze overnight below freezing, obtains the chitin solution that concentration is 6 wt% after thawing.5
obe that 1:1 adds epoxy chloropropane according to the mol ratio of linking agent and chitin under C, stir be placed in mould place 24h after obtain the crosslinked chitin hydrogel of partial chemical, then gel is placed in ethanol and proceeds physical crosslinking 12h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, compressive strength reaches 1.2 MPa.
Embodiment 3
The water of 2 ~ 30 wt% KOH, 0 ~ 20 wt% NaOH, 0 ~ 20 wt% urea and surplus is prepared into solvent, add the chitin powder that embodiment 1 obtains, stirring is placed on freeze overnight below freezing, obtains the chitin solution that concentration is 4 wt% after thawing.5
obe that 3:1 adds epoxy chloropropane according to the mol ratio of linking agent and chitin under C, stir be placed in mould place 24h after obtain the crosslinked chitin hydrogel of partial chemical, then gel is placed in 80 wt% aqueous ethanolic solutions and proceeds physical crosslinking 12h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, compressive strength is 0.1 MPa.
Embodiment 4
The water of 2 ~ 30 wt% KOH, 0 ~ 10 wt% LiOH, 0 ~ 6 wt% thiocarbamide and surplus is prepared into solvent, add the chitin powder that embodiment 1 obtains, stirring is placed on freeze overnight below freezing, obtains the chitin solution that concentration is 6 wt% after thawing.5
obe that 5:1 adds epoxy chloropropane according to the mol ratio of linking agent and chitin under C, stir be placed in mould place 24h after obtain the crosslinked chitin hydrogel of partial chemical, then gel is placed in 80 wt% aqueous ethanolic solutions and proceeds physical crosslinking 5h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, compressive strength is 0.3 MPa.
Embodiment 5
The water of 2 ~ 30 wt% KOH, 0 ~ 6 wt% LiOH, 0 ~ 15 wt% NaOH, 0 ~ 6 wt% urea and surplus is prepared into solvent, add the chitin powder that embodiment 1 obtains, stirring is placed on freeze overnight below freezing, obtains the chitin solution that concentration is 7 wt% after thawing.5
obe that 8:1 adds epoxy chloropropane according to the mol ratio of linking agent and chitin under C, stir be placed in mould place 24h after obtain the crosslinked chitin hydrogel of partial chemical, then gel is placed in 60 wt% methanol aqueous solutions and proceeds physical crosslinking 2h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, compressive strength is 0.2 MPa.
Embodiment 6
The solvent that the water of 20 wt% KOH, 4 wt% urea and surplus is formed is chilled to-25 in advance
oc, adds chitin powder that embodiment 1 obtains and stirs 10min and dissolve obtain the chitin solution that concentration is 3 wt% completely.Continue under agitation in chitin solution according to linking agent: chitin mol ratio is that 1.5:1 dropwise adds epoxy chloropropane, pours into after mould 5
ounder C, crosslinked 5 h obtain the crosslinked chitin hydrogel of partial chemical, then gel are placed in 20 wt% aqueous ethanolic solutions and proceed physical crosslinking 12 h, are finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, its compressive strength is 0.1 MPa.
(comparative example 1)
Is added the commercially available chitin powder of 3 g in the solvent that the water of 97 g 8 wt% NaOH, 4 wt% urea and surplus is formed, after freeze-thaw, obtain the chitin solution that concentration is 3 wt%.Continue under agitation 15 ml epoxy chloropropane to be added drop-wise to (epoxy chloropropane: chitin mol ratio is 13:1) in chitin solution, be warming up to 40
oc, 8 h after washings are to the neutral chitin hydrogel obtaining complete chemically crosslinked.This hydrogel is jelly, and stretch, bending, folding and torsion condition issues raw fracture and broken, compressive strength is only 20 kPa.
(comparative example 2)
The solvent formed by the water of 97 g 20 wt% KOH, 4 wt% urea and surplus is met and is chilled to-25
oc, adds the commercially available chitin powder of 3 g, and stirring 10min dissolves obtain the chitin solution that concentration is 3 wt% completely.Continue under agitation 15 ml epoxy chloropropane to be added drop-wise to (epoxy chloropropane: chitin mol ratio is 13:1) in chitin solution, be warming up to 40
oc, 8 h after washings are to the neutral chitin hydrogel obtaining complete chemically crosslinked.This hydrogel is jelly, and stretch, bending, folding and torsion condition issues raw fracture and broken, compressive strength is only 30 kPa.
Embodiment 7
The solvent that the water of 20 wt% KOH, 4 wt% urea and surplus is formed is chilled to-25 in advance
oc, adds chitin powder that embodiment 1 obtains and stirs 10min and dissolve obtain the chitin solution that concentration is 5 wt% completely.Continue under agitation in chitin solution according to linking agent: chitin mol ratio is that 1:1 dropwise adds epoxy chloropropane, pours into after mould 5
ounder C, crosslinked 12 h obtain the crosslinked chitin hydrogel of partial chemical, then gel are placed in 90 wt% aqueous ethanolic solutions and proceed physical crosslinking 12 h, are finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, its compressive strength is 0.8 MPa.
Embodiment 8
The solvent that the water of 20 wt% KOH, 4 wt% urea and surplus is formed is chilled to-25 in advance
oc, adds chitin powder that embodiment 1 obtains and stirs 10min and dissolve obtain the chitin solution that concentration is 5 wt% completely.Continue under agitation in chitin solution according to linking agent: chitin mol ratio is that 1:1 dropwise adds epoxy chloropropane, pours into after mould 5
ounder C, crosslinked 12 h obtain the crosslinked chitin hydrogel of partial chemical, then gel are placed in 5 wt% H
2sO
4proceed physical crosslinking 12 h in the aqueous solution, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, its compressive strength is 0.1 MPa.
Embodiment 9
The solvent that the water of 20 wt% KOH, 4 wt% urea and surplus is formed is chilled to-25 in advance
oc, adds chitin powder that embodiment 1 obtains and stirs 10min and dissolve obtain the chitin solution that concentration is 5 wt% completely.Continue under agitation in chitin solution according to linking agent: chitin mol ratio is that 1:1 dropwise adds epoxy chloropropane, pours into after mould 5
ounder C, crosslinked 12 h obtain the crosslinked chitin hydrogel of partial chemical, then gel are placed in 5 wt% ammonia solns and proceed physical crosslinking 12 h, are finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, its compressive strength is 0.3 MPa.
Embodiment 10
The solvent that the water of 20 wt% KOH, 4 wt% urea and surplus is formed is chilled to-25 in advance
oc, adds chitin powder that embodiment 1 obtains and stirs 10min and dissolve obtain the chitin solution that concentration is 5 wt% completely.Continue under agitation in chitin solution according to linking agent: chitin mol ratio is that 1:3 dropwise adds epoxy chloropropane, pours into after mould 5
ounder C, crosslinked 12 h obtain the crosslinked chitin hydrogel of partial chemical, then gel are placed in 20 wt% aqueous ethanolic solutions and proceed physical crosslinking 12 h, are finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, its compressive strength is 0.1 MPa.Stress-strain curve under obtained double cross connection chitin hydrogel compact model is shown in Figure 1.
Embodiment 11
The solvent that the water of 20 wt% KOH, 4 wt% urea and surplus is formed is chilled to-25 in advance
oc, adds chitin powder that embodiment 1 obtains and stirs 10min and dissolve obtain the chitin solution that concentration is 5 wt% completely.Continue under agitation in chitin solution according to linking agent: chitin mol ratio is that 1:2 dropwise adds epoxy chloropropane, pours into after mould 5
ounder C, crosslinked 12 h obtain the crosslinked chitin hydrogel of partial chemical, then gel are placed in 20 wt% aqueous ethanolic solutions and proceed physical crosslinking 12 h, are finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, its compressive strength is 0.3 MPa.Stress-strain curve under obtained double cross connection chitin hydrogel compact model is shown in Figure 1.
Embodiment 12
The solvent that the water of 20 wt% KOH, 4 wt% urea and surplus is formed is chilled to-25 in advance
oc, adds chitin powder that embodiment 1 obtains and stirs 10min and dissolve obtain the chitin solution that concentration is 5 wt% completely.Continue under agitation in chitin solution according to linking agent: chitin mol ratio is that 1:1 dropwise adds epoxy chloropropane, pours into after mould 5
ounder C, crosslinked 12 h obtain the crosslinked chitin hydrogel of partial chemical, then gel are placed in 20 wt% aqueous ethanolic solutions and proceed physical crosslinking 12 h, are finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, its compressive strength is 0.6 MPa.Stress-strain curve under obtained double cross connection chitin hydrogel compact model is shown in Figure 1.Two cross-linked hydrogel stretching (a) of obtained chitin and the photo in kind under (b) condition of torsion are as shown in Figure 2.
Embodiment 13
The solvent that the water of 20 wt% KOH, 4 wt% urea and surplus is formed is chilled to-25 in advance
oc, adds chitin powder that embodiment 1 obtains and stirs 10min and dissolve obtain the chitin solution that concentration is 5 wt% completely.Continue under agitation in chitin solution according to linking agent: chitin mol ratio is that 2:1 dropwise adds epoxy chloropropane, pours into after mould 5
ounder C, crosslinked 12 h obtain the crosslinked chitin hydrogel of partial chemical, then gel are placed in 20 wt% aqueous ethanolic solutions and proceed physical crosslinking 12 h, are finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, its compressive strength is 0.2 MPa.Stress-strain curve under obtained double cross connection chitin hydrogel compact model is shown in Figure 1.
Embodiment 14
The solvent that the water of 20 wt% KOH, 4 wt% urea and surplus is formed is chilled to-25 in advance
oc, adds chitin powder that embodiment 1 obtains and stirs 10min and dissolve obtain the chitin solution that concentration is 5 wt% completely.Continue under agitation in chitin solution according to linking agent: chitin mol ratio is that 3:1 dropwise adds epoxy chloropropane, pours into after mould 5
ounder C, crosslinked 12 h obtain the crosslinked chitin hydrogel of partial chemical, then gel are placed in 20 wt% aqueous ethanolic solutions and proceed physical crosslinking 12 h, are finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, its compressive strength is 0.1 MPa.Stress-strain curve under obtained double cross connection chitin hydrogel compact model is shown in Figure 1.
Embodiment 15
The solvent that the water of 20 wt% KOH, 4 wt% urea and surplus is formed is chilled to-25 in advance
oc, adds chitin powder that embodiment 1 obtains and stirs 10min and dissolve obtain the chitin solution that concentration is 7 wt% completely.Continue under agitation in chitin solution according to linking agent: chitin mol ratio is that 1:1 dropwise adds epoxy chloropropane, pours into after mould 5
ounder C, crosslinked 12 h obtain the crosslinked chitin hydrogel of partial chemical, then gel are placed in 20 wt% aqueous ethanolic solutions and proceed physical crosslinking 12 h, are finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, its compressive strength is 1.6 MPa.
Embodiment 16
The solvent that the water of 20 wt% KOH, 4 wt% urea and surplus is formed is chilled to-25 in advance
oc, adds chitin powder that embodiment 1 obtains and stirs 10min and dissolve obtain the chitin solution that concentration is 9 wt% completely.Continue under agitation in chitin solution according to linking agent: chitin mol ratio is that 1:1 dropwise adds epoxy chloropropane, pours into after mould 5
ounder C, crosslinked 12 h obtain the crosslinked chitin hydrogel of partial chemical, then gel are placed in 20 wt% aqueous ethanolic solutions and proceed physical crosslinking 12 h, are finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can stretch, bends, folds, reverses and do not rupture, and have extraordinary toughness, its compressive strength is 2.4 MPa.Stress-strain curve under obtained double cross connection chitin hydrogel compact model is shown in Figure 3.
Embodiment 17
Double cross connection chitin hydrogel absolute ethanol washing embodiment 12 obtained is replaced, through supercritical CO
2dry obtained double cross connection chitin aerogel, its specific surface area is 404 m
2/ g, porosity 85%, density is 0.22 g/cm
3.This double cross joins chitin aerogel from room temperature with 10
oc/min is heated to 600
oc, nitrogen, as shielding gas, obtains black porous carbon aerogel, and its specific surface area is 680 m
2/ g.
Embodiment 18
Obtain double cross connection chitin aerogel through lyophilize after double cross connection chitin hydrogel trimethyl carbinol displacement embodiment 12 obtained, its specific surface area is 380 m
2/ g, porosity 84 %, density is 0.23 g/cm
3.Double cross joins chitin aerogel from room temperature with 10
oc/min is heated to 600
oc, nitrogen, as shielding gas, obtains black porous carbon aerogel.The specific surface area that nitrogen adsorption-desorption test obtains carbon aerogels is 600 m
2/ g.
Embodiment 19
After the double cross connection chitin hydrogel dehydrated alcohol displacement that embodiment 15 is obtained, through supercritical CO
2dry obtained double cross connection chitin aerogel.Gained chitin aerogel in HCl atmosphere, from room temperature with 10
oc/min is heated to 150
oc, nitrogen, as shielding gas, obtains black porous carbon aerogel, and its specific surface area is 420 m
2/ g.
Embodiment 20
After the double cross connection chitin hydrogel dehydrated alcohol displacement that embodiment 16 is obtained, through supercritical CO
2dry obtained double cross connection chitin aerogel.Gained chitin aerogel from room temperature with 10
oc/min is heated to 1200
oc, nitrogen, as shielding gas, obtains black porous carbon aerogel.Testing by nitrogen adsorption-desorption the specific surface area obtaining carbon aerogels is 1300 m
2/ g.
Embodiment 21
Double cross connection chitin hydrogel embodiment 12 obtained is 90
ounder C, pressure is progressively increased to 60 MPa by 0.1 MPa and obtains double cross connection chitin biological plastics, and its tensile strength is 120 MPa, and elongation at break is 30%.
Embodiment 22
Water in double cross connection chitin hydrogel embodiment 12 obtained is replaced into ethanol, obtains double cross connection chitin organogel.By this double cross connection chitin organogel 50
ounder C, pressure is progressively increased to 60 MPa by 0.1 MPa and obtains double cross connection chitin biological plastics, and its tensile strength is 95 MPa, and elongation at break is 26%.
Embodiment 23
Water in double cross connection chitin hydrogel embodiment 12 obtained is replaced into ethanol, obtains double cross connection chitin organogel, obtains double cross connection chitin aerogel further across supercritical co drying.By this double cross connection chitin aerogel 50
ounder C, pressure is progressively increased to 60 MPa by 0.1 MPa and obtains double cross connection chitin biological plastics, and its tensile strength is 110 MPa, and elongation at break is 30%.
Embodiment 24
Double cross connection chitin hydrogel embodiment 15 obtained is 110
ounder C, pressure is progressively increased to 60 MPa by 0.1 MPa and obtains double cross connection chitin biological plastics, and its tensile strength is 140 MPa, and elongation at break is 39%.
Embodiment 25
Double cross connection chitin hydrogel embodiment 16 obtained is 110
ounder C, pressure is progressively increased to 60 MPa by 0.1 MPa and obtains double cross connection chitin biological plastics, and its tensile strength is 170 MPa, and elongation at break is 28%.
Claims (13)
1. chemistry and the dual crosslinked chitin hydrogel preparation method of physics, is characterized in that:
Below the gelling temperature of chitin solution, in chitin solution, add linking agent stir, leave standstill more than 5 hours, the mol ratio of linking agent and chitin is 0.1:1 ~ 8:1, the chitin hydrogel of forming section chemically crosslinked, then the chitin hydrogel that partial chemical is cross-linked is placed in the non-solvent more than 2 hours of chitin, carries out physical crosslinking further and form double cross connection chitin hydrogel, after washing, obtain chemistry and the dual crosslinked chitin hydrogel of physics.
2. chitin hydrogel preparation method according to claim 1, is characterized in that: described linking agent is epoxy compounds and/or aldehyde compound.
3. chitin hydrogel preparation method according to claim 2, is characterized in that: described linking agent is epoxy chloropropane and/or epoxy chlorobutane and/or glutaraldehyde.
4. chitin hydrogel preparation method according to claim 1, it is characterized in that: the non-solvent of described chitin be water, the water adding monovalent cation or water content higher than 50 wt% non-polar organic liquid, described non-polar organic liquid is alcohol, ketone, ester or its mixture.
5. chitin hydrogel preparation method according to claim 1, it is characterized in that: described chitin solution is mixed with alkali/aqueous solution of urea, alkali/thiourea solution or alkali/urea/sulphur urea solution by chitin and is refrigerated to below freezing, obtain above freezing thawing, or alkali/aqueous solution of urea, alkali/thiourea solution or alkali/urea/sulphur urea solution is chilled to freezing point ~ 0 in advance
oc, then adds chitin stirring and dissolving and obtains.
6. chemistry and the dual crosslinked chitin organogel preparation method of physics, is characterized in that: the water in the double cross prepared by method described in claim 1 connection chitin hydrogel is replaced into organic solvent and obtains double cross connection chitin organogel.
7. preparation method according to claim 6, is characterized in that: described is alkanes, alcohols or ketone compounds for replacing the organic solvent of double cross connection chitin hydrogel.
8. preparation method according to claim 7, is characterized in that, described is methyl alcohol, ethanol or acetone for replacing the organic solvent of double cross connection chitin hydrogel.
9. prepare a method for double cross connection chitin aerogel, it is characterized in that:
By the double cross prepared by method described in claim 1 connection chitin hydrogel or by double cross connection chitin organogel drying removing liquid prepared by method described in claim 5, obtain double cross connection chitin aerogel.
10. method according to claim 9, is characterized in that: described dry link utilizes supercritical drying, or carries out constant pressure and dry and lyophilize removing liquid medium.
11. 1 kinds of methods preparing carbon aerogels, is characterized in that:
The double cross prepared by method described in claim 7 is joined chitin aerogel under inert atmosphere protection, 150
ocarbon aerogels is obtained after more than C carbonization.
The preparation method of 12. 1 kinds of double cross connection chitin biological plasticss, it is characterized in that, obtain biological plastics by after the double cross prepared by method described in claim 1 connection chitin hydrogel, the double cross connection chitin organogel prepared by method described in claim 5 or the double cross connection chitin aerogel hot pressing prepared by method described in claim 7, the temperature of described hot-pressing processing is 50 ~ 150
oc, pressure 0.1 ~ 60 MPa.
13. 1 kinds based on double cross connection chitin hydrogel material, it is characterized in that, it is the double cross connection chitin hydrogel prepared by method described in claim 1, the double cross connection chitin aerogel prepared by method described in claim 7 or the double cross connection chitin biological plastics prepared by method described in claim 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410704260.7A CN104387597B (en) | 2014-11-28 | 2014-11-28 | Chemical and physical double-cross-linking high-strength chitin gel material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410704260.7A CN104387597B (en) | 2014-11-28 | 2014-11-28 | Chemical and physical double-cross-linking high-strength chitin gel material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104387597A true CN104387597A (en) | 2015-03-04 |
| CN104387597B CN104387597B (en) | 2017-02-22 |
Family
ID=52605566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410704260.7A Active CN104387597B (en) | 2014-11-28 | 2014-11-28 | Chemical and physical double-cross-linking high-strength chitin gel material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104387597B (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461945A (en) * | 2015-12-29 | 2016-04-06 | 华南理工大学 | Ion-covalent double-network hydrogel and preparation method thereof |
| CN105837861A (en) * | 2016-04-03 | 2016-08-10 | 苏鑫 | Composite natural polymer gel material |
| CN106800662A (en) * | 2017-01-23 | 2017-06-06 | 武汉大学 | A kind of preparation method of chitosan gel rubber based material |
| CN107056318A (en) * | 2017-03-01 | 2017-08-18 | 山东省科学院新材料研究所 | A kind of CNT carbon aerogel composite material and preparation method thereof |
| CN107417934A (en) * | 2017-08-09 | 2017-12-01 | 武汉大学 | It is a kind of that there is power to cause the high-strength of optics anisotropic approach, high-ductility cellulose aquagel and preparation method thereof |
| CN107569722A (en) * | 2017-09-18 | 2018-01-12 | 盐城工学院 | A kind of chitin hydroxyapatite complex screw and preparation method thereof |
| CN107619482A (en) * | 2017-09-25 | 2018-01-23 | 武汉大学 | A kind of preparation method of anisotropy double cross connection cellulose aquagel and membrane material |
| CN108164744A (en) * | 2017-12-27 | 2018-06-15 | 武汉大学 | A kind of preparation method of elastomer element aeroge and its hydrophobic fibre element aeroge |
| CN108310460A (en) * | 2018-02-02 | 2018-07-24 | 武汉大学 | Injectable high intensity Thermo-sensitive modified chitin based aquagel and its preparation method and application |
| CN110368977A (en) * | 2019-07-25 | 2019-10-25 | 广西科学院 | The preparation method and application of a kind of calcium and magnesium double activity center catalyst |
| CN110408056A (en) * | 2019-07-08 | 2019-11-05 | 广西民族大学 | A kind of chitin hydrogel and preparation method thereof adulterating cellulose |
| CN110655675A (en) * | 2019-07-08 | 2020-01-07 | 广西民族大学 | In-situ doped nano calcium carbonate chitin hydrogel as well as preparation method and application thereof |
| CN111518284A (en) * | 2020-05-06 | 2020-08-11 | 盐城工学院 | Preparation method of chitin multilayer hydrogel material |
| CN112442196A (en) * | 2020-11-23 | 2021-03-05 | 武汉大学 | Preparation and application of degradable, biocompatible and high-strength chitin hydrogel |
| CN112574433A (en) * | 2019-09-30 | 2021-03-30 | 武汉大学 | Reversible processing and shaping method of natural polymer bioplastic |
| CN112574434A (en) * | 2019-09-30 | 2021-03-30 | 武汉大学 | Method for rapidly and continuously preparing high-toughness natural polymer bioplastic |
| CN113384740A (en) * | 2021-06-24 | 2021-09-14 | 长春工业大学 | Preparation method of ion/chemical double-crosslinking hemostatic antibacterial gel sponge |
| CN114907592A (en) * | 2021-02-07 | 2022-08-16 | 武汉大学 | Method for efficiently preparing chitin membrane material |
| CN115536896A (en) * | 2022-10-20 | 2022-12-30 | 南昌大学 | Chitin-chitosan-based double-crosslinked aerogel and preparation method thereof |
| CN116554538A (en) * | 2022-01-30 | 2023-08-08 | 武汉大学 | Preparation method of multifunctional natural high-molecular porous material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880410A (en) * | 2010-07-21 | 2010-11-10 | 武汉大学 | High-strength transparent cellulose material and preparation method thereof |
| CN102417606A (en) * | 2011-08-03 | 2012-04-18 | 武汉大学 | Preparation method of chitin aerogel |
-
2014
- 2014-11-28 CN CN201410704260.7A patent/CN104387597B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880410A (en) * | 2010-07-21 | 2010-11-10 | 武汉大学 | High-strength transparent cellulose material and preparation method thereof |
| CN102417606A (en) * | 2011-08-03 | 2012-04-18 | 武汉大学 | Preparation method of chitin aerogel |
Non-Patent Citations (2)
| Title |
|---|
| BO DUAN ET AL.: ""Structure and Properties of Films Fabricated from Chitin Solution by Coagulating with Heating"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| CHUNYU CHANG ET AL.: ""Novel hydrogels prepared via direct dissolution of chitin at low temperature:structure and biocompatibility"", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461945A (en) * | 2015-12-29 | 2016-04-06 | 华南理工大学 | Ion-covalent double-network hydrogel and preparation method thereof |
| CN105461945B (en) * | 2015-12-29 | 2018-04-13 | 华南理工大学 | A kind of covalent double-network hydrogel of ion and preparation method thereof |
| CN105837861B (en) * | 2016-04-03 | 2018-06-19 | 苏鑫 | A kind of composite natral high-molecular gel class material |
| CN105837861A (en) * | 2016-04-03 | 2016-08-10 | 苏鑫 | Composite natural polymer gel material |
| CN106800662A (en) * | 2017-01-23 | 2017-06-06 | 武汉大学 | A kind of preparation method of chitosan gel rubber based material |
| CN106800662B (en) * | 2017-01-23 | 2019-05-24 | 武汉大学 | A kind of preparation method of chitosan gel rubber based material |
| CN107056318A (en) * | 2017-03-01 | 2017-08-18 | 山东省科学院新材料研究所 | A kind of CNT carbon aerogel composite material and preparation method thereof |
| CN107056318B (en) * | 2017-03-01 | 2019-07-05 | 山东省科学院新材料研究所 | A kind of carbon nanotube-carbon aerogel composite material and preparation method thereof |
| CN107417934A (en) * | 2017-08-09 | 2017-12-01 | 武汉大学 | It is a kind of that there is power to cause the high-strength of optics anisotropic approach, high-ductility cellulose aquagel and preparation method thereof |
| CN107569722A (en) * | 2017-09-18 | 2018-01-12 | 盐城工学院 | A kind of chitin hydroxyapatite complex screw and preparation method thereof |
| CN107569722B (en) * | 2017-09-18 | 2021-02-09 | 盐城工学院 | Chitin-hydroxyapatite composite bone nail and preparation method thereof |
| CN107619482A (en) * | 2017-09-25 | 2018-01-23 | 武汉大学 | A kind of preparation method of anisotropy double cross connection cellulose aquagel and membrane material |
| CN107619482B (en) * | 2017-09-25 | 2019-12-10 | 武汉大学 | Preparation method of anisotropic double-crosslinked cellulose hydrogel and membrane material |
| CN108164744A (en) * | 2017-12-27 | 2018-06-15 | 武汉大学 | A kind of preparation method of elastomer element aeroge and its hydrophobic fibre element aeroge |
| CN108310460A (en) * | 2018-02-02 | 2018-07-24 | 武汉大学 | Injectable high intensity Thermo-sensitive modified chitin based aquagel and its preparation method and application |
| CN108310460B (en) * | 2018-02-02 | 2021-08-03 | 武汉大学 | Injectable high-strength temperature-sensitive modified chitin-based hydrogel and preparation method and application thereof |
| CN110655675A (en) * | 2019-07-08 | 2020-01-07 | 广西民族大学 | In-situ doped nano calcium carbonate chitin hydrogel as well as preparation method and application thereof |
| CN110408056A (en) * | 2019-07-08 | 2019-11-05 | 广西民族大学 | A kind of chitin hydrogel and preparation method thereof adulterating cellulose |
| CN110408056B (en) * | 2019-07-08 | 2022-08-09 | 广西民族大学 | Cellulose-doped chitin hydrogel and preparation method thereof |
| CN110655675B (en) * | 2019-07-08 | 2022-05-03 | 广西民族大学 | In-situ doped nano calcium carbonate chitin hydrogel as well as preparation method and application thereof |
| CN110368977A (en) * | 2019-07-25 | 2019-10-25 | 广西科学院 | The preparation method and application of a kind of calcium and magnesium double activity center catalyst |
| CN110368977B (en) * | 2019-07-25 | 2022-04-19 | 广西科学院 | Preparation method and application of calcium-magnesium double-active-center catalyst |
| CN112574434A (en) * | 2019-09-30 | 2021-03-30 | 武汉大学 | Method for rapidly and continuously preparing high-toughness natural polymer bioplastic |
| CN112574433A (en) * | 2019-09-30 | 2021-03-30 | 武汉大学 | Reversible processing and shaping method of natural polymer bioplastic |
| CN111518284A (en) * | 2020-05-06 | 2020-08-11 | 盐城工学院 | Preparation method of chitin multilayer hydrogel material |
| CN111518284B (en) * | 2020-05-06 | 2022-10-18 | 盐城工学院 | Preparation method of chitin multilayer hydrogel material |
| CN112442196B (en) * | 2020-11-23 | 2022-03-04 | 武汉大学 | Preparation and application of degradable, biocompatible and high-strength chitin hydrogel |
| CN112442196A (en) * | 2020-11-23 | 2021-03-05 | 武汉大学 | Preparation and application of degradable, biocompatible and high-strength chitin hydrogel |
| CN114907592A (en) * | 2021-02-07 | 2022-08-16 | 武汉大学 | Method for efficiently preparing chitin membrane material |
| CN114907592B (en) * | 2021-02-07 | 2023-08-22 | 武汉大学 | Method for efficiently preparing chitin membrane material |
| CN113384740A (en) * | 2021-06-24 | 2021-09-14 | 长春工业大学 | Preparation method of ion/chemical double-crosslinking hemostatic antibacterial gel sponge |
| CN116554538A (en) * | 2022-01-30 | 2023-08-08 | 武汉大学 | Preparation method of multifunctional natural high-molecular porous material |
| CN115536896A (en) * | 2022-10-20 | 2022-12-30 | 南昌大学 | Chitin-chitosan-based double-crosslinked aerogel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104387597B (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104387597A (en) | Chemical and physical double-cross-linking high-strength chitin gel material and preparation method thereof | |
| CN104448396A (en) | Chemical and physical crosslinking based dual-network cellulose gel system material | |
| Zainal et al. | Preparation of cellulose-based hydrogel: A review | |
| Cao et al. | Room temperature ionic liquids (RTILs): A new and versatile platform for cellulose processing and derivatization | |
| CN102417606B (en) | Preparation method of chitin aerogel | |
| CN101880410B (en) | High-strength transparent cellulose material and preparation method thereof | |
| CN104710629A (en) | Chitin film and preparation method thereof | |
| CN106800662A (en) | A kind of preparation method of chitosan gel rubber based material | |
| CN103059319B (en) | Preparation method of chitin nano fiber | |
| CN105837861A (en) | Composite natural polymer gel material | |
| CN105622780B (en) | A kind of homogeneous preparation method of quaternized chitin | |
| Liao et al. | A fungal chitin derived from Hericium erinaceus residue: Dissolution, gelation and characterization | |
| CN103834046B (en) | Alcoholic solvent is utilized to prepare the method for the zein mixture of including natural fibers element | |
| Liao et al. | Construction of hydrogels based on the homogeneous carboxymethylated chitin from Hericium erinaceus residue: Role of carboxymethylation degree | |
| CN105754011B (en) | A kind of preparation technology of water soluble algae acid | |
| CN111748106A (en) | Chitosan gel material prepared from chitosan solution with pH value of 6-8 and preparation method thereof | |
| Wang et al. | Thermostable and redispersible cellulose nanocrystals with thixotropic gelation behavior by a facile desulfation process | |
| Zhang et al. | Influences of cation valence on water absorbency of crosslinked carboxymethyl cellulose | |
| Mallik et al. | Fabrication of polysaccharide-based materials using ionic liquids and scope for biomedical use | |
| Wu et al. | Thermo-responsive behavior and gelation of curdlan alkyl-ethers prepared by homogeneous reaction | |
| Li et al. | High-tensile chitin films regenerated from cryogenic aqueous phosphoric acid | |
| Kawano et al. | Preparation of chitin nanofiber-reinforced xanthan gum hydrogels | |
| CN106496339A (en) | One kettle way prepares low viscosity, high intensity hydroxypropyl starch ether | |
| CN110483810A (en) | A kind of preparation method of nano-cellulose anti-bacterial hydrogel | |
| CN112574433A (en) | Reversible processing and shaping method of natural polymer bioplastic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |