CN104387597B - 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
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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 carapace cellulosic material, particularly to a kind of based on chemically and physically dual crosslinked high intensity first
Shell element gel based material and preparation method thereof, belongs 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.For example, there is optics（CN102336995A）、
Magnetic（CN102391603A）, Thermo-sensitive（CN102690401A）Macromolecule hydrogel etc. function.However, due to hydrogel
Water content, porosity are higher, and the macromolecular chain number on unit cross-sectional area is less, lead to its mechanical property relatively low, apply model
Enclose by a definite limitation.Biosynthesiss amount in nature for the chitin is only second to cellulose, is a kind of native amino polysaccharide, can
Preparation film forming, fiber and gel, are widely used in food, biosensor, water process, pharmaceutical carrier and bio-medical material etc.
Field.
Chitin hydrogel have concurrently nontoxic, biocompatibility, the biodegradability of chitin and the hydrophilic of hydrogel,
Water-retaining property and environmental sensitivity, have very big researching value.However, because chitin is a kind of high crystalline polysaccharide, containing a large amount of
Intramolecular and intermolecular hydrogen bonding, solubility property is very poor, and water insoluble and most organic solvent, with regard to grinding of carapace cellulosic material
Study carefully less, obtained material mechanical performance is also very low.Patent of invention as publication number CN101857684A discloses one kind
Chitin cross-linked hydrogel, the chitin solution concentration due to obtaining is very low（0.5~3 wt%）, and hydrogel chemistry friendship
Connection degree is too high（The mol ratio of epoxychloropropane/chitin is 9:1~78 :1）, on chitin, all of hydroxyl is involved in instead
Chemical crosslinking point should be formed, therefore obtain is the chitin hydrogel of chemical crosslinking completely, compressive strength is only tens KPa,
The requirement as structural material and bio-medical material cannot be met（J. Mater. Chem., 2011, 21, 3865-
3871）.
Content of the invention
The technical problem to be solved is to overcome the shortcomings of existing chitin hydrogel mechanical property, provides one
Plant based on chemically and physically dual crosslinked high intensity chitin hydrogel based material and preparation method thereof.
The present invention is to solve above-mentioned technical problem, forming part after adding quantitative cross-linking agent to stir in chitin solution
Then the chitin hydrogel of part chemical crosslinking is placed in the non-solvent of chitin further by the chitin hydrogel of chemical crosslinking
Carry out physical crosslinking and form double cross connection chitin hydrogel, obtain chemically and physically dual crosslinked high intensity double cross after washing
Connection chitin hydrogel；The water that double cross is joined in chitin hydrogel is replaced into organic liquid, and to obtain double cross connection chitin organic solidifying
Glue；Double cross is joined chitin hydrogel or organogel is dried and removes liquid, obtain double cross connection chitin aerogel；Double cross is joined
Chitin aerogel is 150oCarbon aerogels are obtained after more than C carbonization；Double cross is joined chitin hydrogel or aeroge hot pressing
Standby double cross joins chitin biological plasticss.
Described chitin solution is will be molten with alkali/aqueous solution of urea, alkali/thiourea solution or alkali/urea/sulphur urea for chitin
Liquid mixes and is refrigerated to below freezing, obtains in defrosting above freezing, or by alkali/aqueous solution of urea, alkali/thiourea solution or
Alkali/urea/sulphur urea solution is cooled to freezing point ~ 0 in advanceoC, is subsequently adding 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 KOH,
NaOH, LiOH one or more.
Dissolving chitin solvent by 2 ~ 50 wt% KOH, 0 ~ 10 wt% LiOH, 0 ~ 20 wt% NaOH, 0 ~
The water of 20 wt% carbamide, 0 ~ 6 wt% thiourea and surplus is constituted.
Described chitin source can be the cell of rudimentary plant mushroom, algae, crustacean shrimp, Eriocheir sinensiss, insecticide outer
Shell, cell wall of higher plant etc., limited without special using the front method purification through known technology.As acid treatment removes
Remove calcium salt, alkali removes deproteinization, oxidation bleaching depigmentation etc..
The present invention provides specific preparation chemically and physically dual crosslinked chitin hydrogel process：
Below the gelling temperature of chitin solution, cross-linking agent is added to stir in chitin solution, standing 5 is little
When more than, the mol ratio of cross-linking agent and chitin is 0.1：1 ~ 8：1, the chitin hydrogel of forming part chemical crosslinking, then
The chitin hydrogel of part chemical crosslinking is placed in more than 2 hours in the non-solvent of chitin, carries out further being physical crosslinking shape
Become double cross connection chitin hydrogel, obtain chemically and physically dual crosslinked chitin hydrogel after washing.
Described cross-linking agent is epoxide and/or aldehyde compound.It is ring as a kind of preferred, described cross-linking agent
Oxygen chloropropane and/or epoxy chlorobutane and/or glutaraldehyde.
Described non-solvent can be water or the water adding cation, preferably the such as H containing monovalent cation+、 NH4 +、Li+、Na+Or K+Aqueous solution, such solution can be for example by hydrochloric acid, sulphuric acid, nitric acid, acetic acid, ammonium sulfate, ammonium acetate, chlorination
Lithium, sodium sulfate, potassium sulfate etc. are dissolved in water and are obtained.
Described non-solvent can also be that water content is higher than 50 wt%, the non-polar organic liquid of preferably above 70 wt%.This
The example of the suitable coagulator of class includes alcohol, ketone, ester or its mixture.It is preferred for doing coagulator using methanol and ethanol.Low boiling
Point non-polar organic liquid has the low property of viscosity, is conducive to the solidification of chitin solution.In addition, the mistake reclaiming in coagulator
Be conducive in journey separating.
By the method that double cross connection chitin hydrogel prepares double cross connection chitin organogel further it is：
The water that double cross is joined in chitin hydrogel is replaced into organic solvent and obtains double cross connection chitin organogel.
By the method that double cross connection chitin hydrogel or organogel prepare double cross connection chitin aerogel further it is：
Double cross is joined chitin hydrogel or double cross connection chitin organogel is dried and removes liquid, obtain double cross connection carapace
Plain aeroge.
By the method that double cross connection chitin aerogel prepares carbon aerogels further it is：
By double cross connection chitin aerogel under inert atmosphere protection, 150oCarbon aerogels are obtained after more than C carbonization.
The described organic solvent joining chitin hydrogel for replacing double cross is low boiling, volatile alkanes, halo
Hydro carbons, alcohols, phenols, ether and acetals, ketone, acid and anhydrides, esters, itrogenous organic substance, the organic compound of sulfur-bearing, or
The mixture of aforementioned various solvent.In the organic solvent being enumerated above, find in test, join first from the double cross improving the present invention
The performance of shell element aerogel material and cost angle consider, and preferably use alkanes, alcohols and ketone compounds, more preferably make
With methanol, ethanol or acetone.
Described double cross joins in the preparation process of chitin aerogel, and the described link that is dried can be using conventional drying side
Method, for example, carries out supercritical drying using carbon dioxide, methanol, ethanol, acetone as supercritical fluid, or it is dry to carry out normal pressure
Dry and lyophilization removes liquid medium.
By double cross connection chitin aerogel under inert atmosphere protection, 150oCarbon aerogels are obtained after more than C carbonization.Lazy
Property atmosphere refers to not react with chitin, prevents gas or admixture of gas that carapace cellulosic material burns at high temperature.
Following gas is especially suitable for being used as inert atmosphere：Nitrogen, carbon dioxide, helium, neon and argon.Can also be used these
The mixture of gas.Appropriate sour gas, such as HCl can be catalyzed the carbonization of chitin.
Double cross is joined and after chitin hydrogel, organogel or aeroge hot pressing, obtains double cross connection chitin biological plasticss.
In view of working (machining) efficiency, the temperature of described hot-pressing processing is 50～150oC, is carried out under pressure 0.1～60 MPa.Containing water
Or in the case of volatile organic liquid, accelerating liquid can be operated at reduced pressure conditions to volatilize.
The present invention also provides and for double cross to join chitin hydrogel, double cross connection chitin organogel or double cross connection chitin gas
The biological plasticss obtaining after gel hot pressing.
Join chitin hydrogel in the double cross of the present invention, in aeroge and biological plasticss, do not damage mechanical property, hot
On the premise of energy, various additives can be contained, such as plasticizer, dyestuff, light stabilizer etc.；Filler can also be contained, such as organic,
Inorganic filler and fibrous reinforcement agent.Organic filler such as conducting polymer, hydrophilic high molecular material etc..Inorganic filler such as graphite
Alkene, CNT, carbon black, silicon dioxide, clay, titanium dioxide etc..Fibrous reinforcement agent includes inorfil such as glass fibre, carbon
Fiber and organic fiber.Can add these additives or filler one or more.
The present invention also provides and joins, by double cross, the products formed that chitin hydrogel based material is made.The double cross connection chitin of the present invention
Hydrogel, aeroge and biological plasticss can obtain any form of products formed, such as fiber, section bar, tube, granular substance,
Tablet and membranoid substance.The products formed that the double cross connection chitin hydrogel material of the present invention obtains has excellent mechanical property, heat
Stability, high-specific surface area, such that it is able to for various uses.For example, weaving, water process, bio-medical material, organizational project
The fields such as material, packaging material for food.
The present invention provide a kind of based on chemically and physically dual crosslinked high intensity chitin hydrogel based material and its preparation
Method.The method have the characteristics that being initially formed the chitin hydrogel of part chemical crosslinking, then it is physical crosslinking further
Obtain chemically and physically dual crosslinked high intensity chitin hydrogel, aeroge and biological plasticss.In the present invention, partly chemistry
Synergism crosslinked and that part physical is crosslinked makes dual network chitin hydrogel have more excellent mechanical property.This
Bright is also advantageous in that：The solvent being adopted is KOH, NaOH, LiOH, carbamide（And/or thiourea）And water, with respect to ionic liquid
Deng organic solvent, price is more cheap.This new method not only production technology environmental protection, low cost, and properties of product are excellent
Different, it is the important breakthrough to prior art, be suitable for industrialized production and practical application, have broad application prospects.
Brief description
Double cross described in Fig. 1 embodiment 10-14 joins the load-deformation curve under chitin hydrogel compact model.
The double cross-linked hydrogel stretching of chitin described in Fig. 2 embodiment 12（a）And torsion（b）Under the conditions of photo in kind.
Double cross described in Fig. 3 embodiment 16 joins the load-deformation curve under chitin hydrogel compact model.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is described further, but it should be remembered that the present invention
Protection domain is not limited to be limited by them.The mechanical property of the dual network chitin hydrogel based material of the present invention adopts universal material
The stretch mode of test machine and compact model respectively to the tensile strength of material, Young's moduluss, elongation at break, compressive strength,
Modulus of compressibility is measured, using specific surface area and the pore-size distribution of gas absorption-desorption instrument test material.
Embodiment 1
By commercially available chitin 0.1 mol/L dilute HCl soaking at room temperature 12 h, after filtering distilled water wash, use 0.1 mol/L
NaOH aqueous solution soaking 12 h, refilters after distilled water wash with 0.3 wt% NaClO2Depigmentation purification, dries and obtains acetyl
Spend the chitin powder for 98%.Water containing 10 ~ 50 wt% KOH and surplus is prepared into solvent, adds chitin powder, stirs
It is placed in freeze overnight below freezing after mixing, after defrosting, obtain the chitin solution that concentration is 5 wt%.5oAccording to cross-linking agent under C
Mol ratio with chitin is 0.1：1 addition epoxychloropropane, is placed in after stirring and obtains part after placing 24h in mould
Learn crosslinked chitin hydrogel, then gel is placed in distilled water and proceeds to be physical crosslinking 24h, be finally washed to neutral obtaining
Join chitin hydrogel to transparent double cross.Double cross connection chitin hydrogel stretchable, bending, fold, reverse and do not break
Split, there is extraordinary toughness, compressive strength is 0.4 MPa.
Embodiment 2
The water of 2 ~ 30 wt% KOH, 0 ~ 10 wt% LiOH, 0 ~ 20 wt% carbamide and surplus is prepared into solvent,
Chitin powder obtained by addition embodiment 1, is placed in freeze overnight below freezing after stirring, obtaining concentration after defrosting is 6
The chitin solution of wt%.5oUnder C, the mol ratio according to cross-linking agent and chitin is 1：1 addition epoxychloropropane, stirring is all
It is placed in the chitin hydrogel obtaining part chemical crosslinking after placing 24h in mould after even, then gel is placed in ethanol and continues
Carry out being physical crosslinking 12h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross joins chitin hydrogel
Stretchable, bending, fold, reverse and do not rupture, there is extraordinary toughness, compressive strength reaches 1.2 MPa.
Embodiment 3
The water of 2 ~ 30 wt% KOH, 0 ~ 20 wt% NaOH, 0 ~ 20 wt% carbamide and surplus is prepared into solvent,
Chitin powder obtained by addition embodiment 1, is placed in freeze overnight below freezing after stirring, obtaining concentration after defrosting is 4
The chitin solution of wt%.5oUnder C, the mol ratio according to cross-linking agent and chitin is 3：1 addition epoxychloropropane, stirring is all
It is placed in the chitin hydrogel obtaining part chemical crosslinking after placing 24h in mould after even, then gel is placed in 80 wt% ethanol
Proceed in aqueous solution to be physical crosslinking 12h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross joins
Chitin hydrogel is stretchable, bending, fold, reverse and do not rupture, and has extraordinary toughness, compressive strength is 0.1
MPa.
Embodiment 4
The water of 2 ~ 30 wt% KOH, 0 ~ 10 wt% LiOH, 0 ~ 6 wt% thiourea and surplus is prepared into solvent, plus
Enter the chitin powder obtained by embodiment 1, after stirring, be placed in freeze overnight below freezing, obtaining concentration after defrosting is 6 wt%
Chitin solution.5oUnder C, the mol ratio according to cross-linking agent and chitin is 5：1 addition epoxychloropropane, after stirring
It is placed in the chitin hydrogel obtaining part chemical crosslinking after placing 24h in mould, then gel is placed in 80 wt% ethanol water-soluble
Proceed in liquid to be physical crosslinking 5h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross joins carapace
Hydrogel is stretchable, bending, fold, reverse and do not rupture, and has extraordinary toughness, compressive strength is 0.3 MPa.
Embodiment 5
By 2 ~ 30 wt% KOH, 0 ~ 6 wt% LiOH, 0 ~ 15 wt% NaOH, 0 ~ 6 wt% carbamide and surplus
Water is prepared into solvent, adds the chitin powder obtained by embodiment 1, is placed in freeze overnight below freezing, after defrosting after stirring
Obtain the chitin solution that concentration is 7 wt%.5oUnder C, the mol ratio according to cross-linking agent and chitin is 8：1 addition epoxy chlorine
Propane, is placed in the chitin hydrogel obtaining part chemical crosslinking after placing 24h in mould, is then placed in gel after stirring
Proceed in 60 wt% methanol aqueous solutions to be physical crosslinking 2h, be finally washed to neutrality and obtain transparent double cross connection chitin water-setting
Glue.Double cross connection chitin hydrogel stretchable, bending, fold, reverse and do not rupture, there is extraordinary toughness, compression
Intensity is 0.2 MPa.
Embodiment 6
The solvent that the water of 20 wt% KOH, 4 wt% carbamide and surplus is constituted is cooled to -25 in advanceoC, adds embodiment 1 institute
The chitin powder stirring 10min obtaining is completely dissolved the chitin solution obtaining that concentration is 3 wt%.Continue under agitation to first
According to cross-linking agent in shell element solution：Chitin mol ratio is 1.5:1 is added dropwise over epoxychloropropane, pours into after mould 5oUnder C
Crosslinked 5 h obtain the chitin hydrogel of part chemical crosslinking, then gel are placed in 20 wt% ethanol waters and proceed
It is physical crosslinking 12 h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can
Stretch, bend, fold, reverse and do not rupture, there is extraordinary toughness, its compressive strength is 0.1 MPa.
（Comparative example 1）
3 g commercially available chitin powder is added in the solvent that the water of 97 g 8 wt% NaOH, 4 wt% carbamide and surplus is constituted
End, obtains the chitin solution that concentration is 3 wt% after freeze-thaw.Continue to be added drop-wise to 15 ml epoxychloropropane under agitation
In chitin solution（Epoxychloropropane：Chitin mol ratio is 13:1）, it is warming up to 40oC, is washed to neutrality after 8 h and has obtained
The crosslinked chitin hydrogel of full chemistry.This hydrogel is fruit jelly, stretching, bending, fold and torsion condition issue raw fracture and
Broken, compressive strength is only 20 kPa.
（Comparative example 2）
By the solvent of the water composition of 97 g 20 wt% KOH, 4 wt% carbamide and surplus to the cold to -25oC, adds 3 g
Commercially available chitin powder, stirring 10min is completely dissolved the chitin solution obtaining that concentration is 3 wt%.Continue under agitation by 15
Ml epoxychloropropane is added drop-wise in chitin solution（Epoxychloropropane：Chitin mol ratio is 13:1）, it is warming up to 40oC, 8 h
It is washed to the chitin hydrogel that neutrality obtains chemical crosslinking completely afterwards.This hydrogel is fruit jelly, stretching, bending, folding and torsion
There are fracture and broken, compressive strength only 30 kPa under the conditions of turning.
Embodiment 7
The solvent that the water of 20 wt% KOH, 4 wt% carbamide and surplus is constituted is cooled to -25 in advanceoC, adds embodiment 1 institute
The chitin powder stirring 10min obtaining is completely dissolved the chitin solution obtaining that concentration is 5 wt%.Continue under agitation to first
According to cross-linking agent in shell element solution：Chitin mol ratio is 1:1 is added dropwise over epoxychloropropane, pours into after mould 5oHand under C
Join the chitin hydrogel that 12 h obtain part chemical crosslinking, then gel is placed in 90 wt% ethanol waters and proceeds
It is physical crosslinking 12 h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can
Stretch, bend, fold, reverse and do not rupture, there is extraordinary toughness, its compressive strength is 0.8 MPa.
Embodiment 8
The solvent that the water of 20 wt% KOH, 4 wt% carbamide and surplus is constituted is cooled to -25 in advanceoC, adds embodiment 1 institute
The chitin powder stirring 10min obtaining is completely dissolved the chitin solution obtaining that concentration is 5 wt%.Continue under agitation to first
According to cross-linking agent in shell element solution：Chitin mol ratio is 1:1 is added dropwise over epoxychloropropane, pours into after mould 5oHand under C
Join the chitin hydrogel that 12 h obtain part chemical crosslinking, then gel is placed in 5 wt% H2SO4Proceed thing in aqueous solution
Manage crosslinked 12 h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can draw
Stretch, bend, fold, reverse and do not rupture, there is extraordinary toughness, its compressive strength is 0.1 MPa.
Embodiment 9
The solvent that the water of 20 wt% KOH, 4 wt% carbamide and surplus is constituted is cooled to -25 in advanceoC, adds embodiment 1 institute
The chitin powder stirring 10min obtaining is completely dissolved the chitin solution obtaining that concentration is 5 wt%.Continue under agitation to first
According to cross-linking agent in shell element solution：Chitin mol ratio is 1:1 is added dropwise over epoxychloropropane, pours into after mould 5oHand under C
Join the chitin hydrogel that 12 h obtain part chemical crosslinking, then gel is placed in 5 wt% ammonia spirits and proceeds physics
Crosslinked 12 h, are finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel stretchable,
Bend, fold, reverse and do not rupture, there is extraordinary toughness, its compressive strength is 0.3 MPa.
Embodiment 10
The solvent that the water of 20 wt% KOH, 4 wt% carbamide and surplus is constituted is cooled to -25 in advanceoC, adds embodiment 1 institute
The chitin powder stirring 10min obtaining is completely dissolved the chitin solution obtaining that concentration is 5 wt%.Continue under agitation to first
According to cross-linking agent in shell element solution：Chitin mol ratio is 1:3 are added dropwise over epoxychloropropane, pour into after mould 5oHand under C
Join the chitin hydrogel that 12 h obtain part chemical crosslinking, then gel is placed in 20 wt% ethanol waters and proceeds
It is physical crosslinking 12 h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can
Stretch, bend, fold, reverse and do not rupture, there is extraordinary toughness, its compressive strength is 0.1 MPa.Obtained
The load-deformation curve that double cross joins under chitin hydrogel compact model is shown in Figure 1.
Embodiment 11
The solvent that the water of 20 wt% KOH, 4 wt% carbamide and surplus is constituted is cooled to -25 in advanceoC, adds embodiment 1 institute
The chitin powder stirring 10min obtaining is completely dissolved the chitin solution obtaining that concentration is 5 wt%.Continue under agitation to first
According to cross-linking agent in shell element solution：Chitin mol ratio is 1:2 are added dropwise over epoxychloropropane, pour into after mould 5oHand under C
Join the chitin hydrogel that 12 h obtain part chemical crosslinking, then gel is placed in 20 wt% ethanol waters and proceeds
It is physical crosslinking 12 h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can
Stretch, bend, fold, reverse and do not rupture, there is extraordinary toughness, its compressive strength is 0.3 MPa.Obtained
The load-deformation curve that double cross joins under chitin hydrogel compact model is shown in Figure 1.
Embodiment 12
The solvent that the water of 20 wt% KOH, 4 wt% carbamide and surplus is constituted is cooled to -25 in advanceoC, adds embodiment 1 institute
The chitin powder stirring 10min obtaining is completely dissolved the chitin solution obtaining that concentration is 5 wt%.Continue under agitation to first
According to cross-linking agent in shell element solution：Chitin mol ratio is 1:1 is added dropwise over epoxychloropropane, pours into after mould 5oHand under C
Join the chitin hydrogel that 12 h obtain part chemical crosslinking, then gel is placed in 20 wt% ethanol waters and proceeds
It is physical crosslinking 12 h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can
Stretch, bend, fold, reverse and do not rupture, there is extraordinary toughness, its compressive strength is 0.6 MPa.Obtained
The load-deformation curve that double cross joins under chitin hydrogel compact model is shown in Figure 1.Obtained chitin double cross connection water-setting
Glue stretches（a）And torsion（b）Under the conditions of photo in kind as shown in Figure 2.
Embodiment 13
The solvent that the water of 20 wt% KOH, 4 wt% carbamide and surplus is constituted is cooled to -25 in advanceoC, adds embodiment 1 institute
The chitin powder stirring 10min obtaining is completely dissolved the chitin solution obtaining that concentration is 5 wt%.Continue under agitation to first
According to cross-linking agent in shell element solution：Chitin mol ratio is 2:1 is added dropwise over epoxychloropropane, pours into after mould 5oHand under C
Join the chitin hydrogel that 12 h obtain part chemical crosslinking, then gel is placed in 20 wt% ethanol waters and proceeds
It is physical crosslinking 12 h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can
Stretch, bend, fold, reverse and do not rupture, there is extraordinary toughness, its compressive strength is 0.2 MPa.Obtained
The load-deformation curve that double cross joins under chitin hydrogel compact model is shown in Figure 1.
Embodiment 14
The solvent that the water of 20 wt% KOH, 4 wt% carbamide and surplus is constituted is cooled to -25 in advanceoC, adds embodiment 1 institute
The chitin powder stirring 10min obtaining is completely dissolved the chitin solution obtaining that concentration is 5 wt%.Continue under agitation to first
According to cross-linking agent in shell element solution：Chitin mol ratio is 3:1 is added dropwise over epoxychloropropane, pours into after mould 5oHand under C
Join the chitin hydrogel that 12 h obtain part chemical crosslinking, then gel is placed in 20 wt% ethanol waters and proceeds
It is physical crosslinking 12 h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can
Stretch, bend, fold, reverse and do not rupture, there is extraordinary toughness, its compressive strength is 0.1 MPa.Obtained
The load-deformation curve that double cross joins under chitin hydrogel compact model is shown in Figure 1.
Embodiment 15
The solvent that the water of 20 wt% KOH, 4 wt% carbamide and surplus is constituted is cooled to -25 in advanceoC, adds embodiment 1 institute
The chitin powder stirring 10min obtaining is completely dissolved the chitin solution obtaining that concentration is 7 wt%.Continue under agitation to first
According to cross-linking agent in shell element solution：Chitin mol ratio is 1:1 is added dropwise over epoxychloropropane, pours into after mould 5oHand under C
Join the chitin hydrogel that 12 h obtain part chemical crosslinking, then gel is placed in 20 wt% ethanol waters and proceeds
It is physical crosslinking 12 h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can
Stretch, bend, fold, reverse and do not rupture, there is extraordinary toughness, its compressive strength is 1.6 MPa.
Embodiment 16
The solvent that the water of 20 wt% KOH, 4 wt% carbamide and surplus is constituted is cooled to -25 in advanceoC, adds embodiment 1 institute
The chitin powder stirring 10min obtaining is completely dissolved the chitin solution obtaining that concentration is 9 wt%.Continue under agitation to first
According to cross-linking agent in shell element solution：Chitin mol ratio is 1:1 is added dropwise over epoxychloropropane, pours into after mould 5oHand under C
Join the chitin hydrogel that 12 h obtain part chemical crosslinking, then gel is placed in 20 wt% ethanol waters and proceeds
It is physical crosslinking 12 h, be finally washed to neutrality and obtain transparent double cross connection chitin hydrogel.Double cross connection chitin hydrogel can
Stretch, bend, fold, reverse and do not rupture, there is extraordinary toughness, its compressive strength is 2.4 MPa.Obtained
The load-deformation curve that double cross joins under chitin hydrogel compact model is shown in Figure 3.
Embodiment 17
The double cross that embodiment 12 is obtained joins the displacement of chitin hydrogel absolute ethanol washing, through supercritical CO2It is dried
Prepared double cross joins chitin aerogel, and its specific surface area is 404 m2/ g, porosity 85%, density is 0.22 g/cm3.This double cross
Connection chitin aerogel is from room temperature with 10oC/min is heated to 600oC, nitrogen, as protective gas, obtains black porous carbon airsetting
Glue, its specific surface area is 680 m2/g.
Embodiment 18
The double cross that embodiment 12 is obtained is obtained double cross through lyophilization after joining the displacement of the chitin hydrogel tert-butyl alcohol
Connection chitin aerogel, its specific surface area is 380 m2/ g, porosity 84 %, density is 0.23 g/cm3.Double cross joins chitin gas
Gel is from room temperature with 10oC/min is heated to 600oC, nitrogen, as protective gas, obtains black porous carbon aerogels.Nitrogen is inhaled
The specific surface area that attached-desorption test obtains carbon aerogels is 600 m2/g.
Embodiment 19
After the double cross that embodiment 15 is obtained joins the displacement of chitin hydrogel dehydrated alcohol, through supercritical CO2System is dried
Obtain double cross connection chitin aerogel.Gained chitin aerogel in HCl atmosphere, from room temperature with 10oC/min is heated to 150oC,
Nitrogen, as protective gas, obtains black porous carbon aerogels, and its specific surface area is 420 m2/g.
Embodiment 20
After the double cross that embodiment 16 is obtained joins the displacement of chitin hydrogel dehydrated alcohol, through supercritical CO2System is dried
Obtain double cross connection chitin aerogel.Gained chitin aerogel is from room temperature with 10oC/min is heated to 1200oC, nitrogen is as protection
Gas, obtains black porous carbon aerogels.It is 1300 by the specific surface area that nitrogen adsorption-desorption test obtains carbon aerogels
m2/g.
Embodiment 21
The double cross that embodiment 12 is obtained joins chitin hydrogel 90oUnder C, pressure is stepped up 60 by 0.1 MPa
MPa is obtained double cross connection chitin biological plasticss, and its tensile strength is 120 MPa, and elongation at break is 30%.
Embodiment 22
The double cross that embodiment 12 is obtained joins the water in chitin hydrogel and is replaced into ethanol, obtains double cross connection carapace and have
Machine gel.By this double cross connection chitin organogel 50oUnder C, it is prepared double that pressure is stepped up 60 MPa by 0.1 MPa
Crosslinked chitin biological plasticss, its tensile strength is 95 MPa, and elongation at break is 26%.
Embodiment 23
The double cross that embodiment 12 is obtained joins the water in chitin hydrogel and is replaced into ethanol, obtains double cross connection carapace and have
Machine gel, is dried to obtain double cross connection chitin aerogel further across supercritical carbon dioxide.This double cross is joined chitin gas
Gel is 50oUnder C, pressure is stepped up 60 MPa by 0.1 MPa and double cross connection chitin biological plasticss is obtained, and its stretching is strong
Spend for 110 MPa, elongation at break is 30%.
Embodiment 24
The double cross that embodiment 15 is obtained joins chitin hydrogel 110oUnder C, pressure is stepped up by 0.1 MPa
60 MPa are obtained double cross connection chitin biological plasticss, and its tensile strength is 140 MPa, and elongation at break is 39%.
Embodiment 25
The double cross that embodiment 16 is obtained joins chitin hydrogel 110oUnder C, pressure is stepped up by 0.1 MPa
60 MPa are obtained double cross connection chitin biological plasticss, and its tensile strength is 170 MPa, and elongation at break is 28%.
Claims (13)
1. a kind of chemically and physically dual crosslinked chitin hydrogel preparation method it is characterised in that：
Below the gelling temperature of chitin solution, in chitin solution add cross-linking agent stir, standing 5 hours with
On, cross-linking agent is 0.1 with the mol ratio of chitin：1 ~ 8：1, the chitin hydrogel of forming part chemical crosslinking, then by portion
The chitin hydrogel dividing chemical crosslinking is placed in more than 2 hours in the non-solvent of chitin, carries out physical crosslinking formation further double
Crosslinked chitin hydrogel, obtains chemically and physically dual crosslinked chitin hydrogel after washing.
2. chitin hydrogel preparation method according to claim 1 it is characterised in that：Described cross-linking agent is epoxidation
Compound and/or aldehyde compound.
3. chitin hydrogel preparation method according to claim 2 it is characterised in that：Described cross-linking agent is epoxy chlorine
Propane and/or epoxy chlorobutane and/or glutaraldehyde.
4. chitin hydrogel preparation method according to claim 1 it is characterised in that：The non-solvent of described chitin is
Water, add the water of monovalent cation or water content to be higher than 50 wt% non-polar organic liquid, described non-polar organic liquid be alcohol,
Ketone, ester or its mixture.
5. chitin hydrogel preparation method according to claim 1 it is characterised in that：Described chitin solution is by first
Shell element mixes and is refrigerated to below freezing with alkali/aqueous solution of urea, alkali/thiourea solution or alkali/urea/sulphur urea solution, in ice
The above defrosting of point obtains, or alkali/aqueous solution of urea, alkali/thiourea solution or alkali/urea/sulphur urea solution are cooled to freezing point ~ 0 in advance oC, is subsequently adding chitin stirring and dissolving and obtains.
6. a kind of chemically and physically dual crosslinked chitin organogel preparation method it is characterised in that：Will be by claim 1
The water that the double cross of methods described preparation joins in chitin hydrogel is replaced into organic solvent and obtains double cross connection chitin organogel.
7. preparation method according to claim 6 it is characterised in that：Described joins chitin hydrogel for replacing double cross
Organic solvent be alkanes, alcohols or ketone compounds.
8. preparation method according to claim 7 is it is characterised in that described joins chitin hydrogel for replacing double cross
Organic solvent be methanol, ethanol or acetone.
9. a kind of prepare double cross join chitin aerogel method it is characterised in that：
The double cross prepared by claim 1 methods described is joined chitin hydrogel or by the preparation of claim 5 methods described
Double cross connection chitin organogel is dried and removes liquid, obtains double cross connection chitin aerogel.
10. method according to claim 9 it is characterised in that：The described link that is dried utilizes supercritical drying, or enters
Row constant pressure and dry and lyophilization remove liquid medium.
A kind of 11. methods preparing carbon aerogels it is characterised in that：
By the double cross prepared by claim 7 methods described connection chitin aerogel under inert atmosphere protection, 150oMore than C carbon
Carbon aerogels are obtained after change.
A kind of 12. double crosses join the preparation methoies of chitin biological plasticss it is characterised in that will be by claim 1 methods described system
Standby double cross joins chitin hydrogel, the double cross connection chitin organogel by the preparation of claim 5 methods described or presses right
Biological plasticss are obtained, the temperature of described hot-pressing processing after the double cross connection chitin aerogel hot pressing requiring 7 methods describeds preparations
For 50～150oC, pressure 0.1～60 MPa.
13. a kind of based on double cross join chitin hydrogel material it is characterised in that its be by claim 1 methods described preparation
Double cross joins chitin hydrogel, the double cross connection chitin aerogel by the preparation of claim 7 methods described or presses claim 12
The double cross connection chitin biological plasticss of methods described preparation.
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| CN116554538A (en) * | 2022-01-30 | 2023-08-08 | 武汉大学 | Preparation method of multifunctional natural high-molecular porous material |
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