CN105199113B - A kind of preparation method of alternately stratiform chitosan/alginic acid compound hydrogel material - Google Patents

A kind of preparation method of alternately stratiform chitosan/alginic acid compound hydrogel material Download PDF

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CN105199113B
CN105199113B CN201510591607.6A CN201510591607A CN105199113B CN 105199113 B CN105199113 B CN 105199113B CN 201510591607 A CN201510591607 A CN 201510591607A CN 105199113 B CN105199113 B CN 105199113B
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chitosan
solution
agar
template
alginic acid
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CN105199113A (en
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贺盟
汪森
王成双
张新疆
丁亮
翟雪松
韦军
曹鸣晖
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Wuhan University WHU
Yangcheng Institute of Technology
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Wuhan University WHU
Yangcheng Institute of Technology
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Abstract

The invention discloses a kind of preparation method of alternately stratiform chitosan/alginic acid compound hydrogel material, comprise the following steps:(1) mass concentration chitosan, sodium hydroxide, marine alga acid solution and calcium chloride solution needed for configuring;(2) agar template is placed in sodium hydroxide solution and soaked, then agar template is put into immersion in chitosan solution, be then immersed in distilled water after a period of time and take out;Chitosan gel rubber layer surface moisture is drawn with filter paper, is placed into after agar template is immersed in calcium chloride solution in marine alga acid solution, is taken out after solidification, it is with distilled water flushing agar template and stand-by with filter paper wiped clean;(3) operation of step (2) is repeated in, until the number of plies needed.The obtained alternately stratiform chitosan/marine alga acid gel of the method for the present invention has good solvent resistance, shape and thickness controllability, regular sandwich construction and biodegradability, and technical process is simply pollution-free, it is easy to industrialize.

Description

A kind of preparation method of alternately stratiform chitosan/alginic acid compound hydrogel material
Technical field
The present invention relates to the preparation method of alternately stratiform chitosan/alginic acid compound hydrogel material, belong to natural polymer Sub- material and renewable resource field.
Background technology
Blood vessel has obvious sandwich construction, and different cells are contained in different tube layer, and this give good tough of blood vessel Property and feature [Adv.Mater.2012,24,890].In recent years, constructed by the sandwich construction of simulated blood vessel with not Congruent gel layer material has caused very big attention, and obtains greater advance.Chitosan and alginic acid are two kinds of rich contents Renewable biomass resources, they are two kinds of typical polyelectrolyte, wherein, chitosan positively charged, alginic acid is negatively charged.Base In both electrostatic interactions, people prepare a series of chitosans/alginic acid composite using layer assembly method.But So far, alternately stratiform chitosan/alginic acid compound hydrogel material does not have any report.
The content of the invention
Goal of the invention:In order to overcome the deficiencies in the prior art, the present invention provides a kind of alternately stratiform chitosan/sea The preparation method of alginic acid compound hydrogel material, with good solvent resistance, shape and thickness controllability, regular multilayer knot Structure and biodegradability.
Technical scheme:In order to solve the above technical problems, a kind of alternately stratiform chitosan/alginic acid compound water congealing of the present invention The preparation method of glue material, comprises the following steps:
(1) configuration quality concentration is 1-2% chitosans, 5-10% sodium hydroxides and 1-2% marine algas acid solution and quality Concentration is 0.005-0.01mol/L calcium chloride solution, selects bar-shaped or spherical agar to be used as template;
(2) agar template is placed in sodium hydroxide solution and soaked, taken out, then agar template is put into chitosan solution Immersion, is then immersed in the agar template with chitosan gel rubber layer in distilled water after a period of time and takes out;Drawn with filter paper Agar template, is then immersed in calcium chloride solution after certain time that to place into alginic acid molten by chitosan gel rubber layer surface moisture In liquid, taken out after solidification, it is with distilled water flushing agar template and stand-by with filter paper wiped clean;
(3) operation of step (2) is repeated in, until the number of plies needed.
Preferably, it is 1-2 minutes, fine jade that agar template, which is placed in soak time in sodium hydroxide solution, in the step (2) It is 1-2 minutes that fat template, which is put into soak time in chitosan solution, and agar template is 1-2 points in calcium chloride solution soak time Clock.
Preferably, the agar template is spherical shape, a diameter of 3mm.
Preferably, the agar template is bar-shaped, a diameter of 5mm.
Preferably, the chitosan solution is obtained by 2wt% acetums dissolving chitosan, marine alga acid solution is by distilling Water dissolving alginic acid is obtained.
Preferably, the aqueous agar solution solidification forming in plastic tube at 5 DEG C is made in the agar template at 90 DEG C Or the dichloromethane solution dripped at room temperature under agitation is made.
In such scheme, selected chitosan and alginic acid concentration of polymer solution is 1-2%, when mass concentration is less than normal, institute Prepare gel thickness too small, it is more difficult to keep its regular sandwich construction and application is inconvenient;On the other hand, concentration of polymer solution is bigger than normal When, viscosity is relatively excessive, is easily adhered on gel layer, is unfavorable for forming regular multilayer gel structure.
Above-mentioned chitosan and alginic acid solution manufacturing method, can use known technology method, be not particularly limited.For example, The chitosan solution is obtained by the aqueous dissolution chitosan such as different quality concentration acetic acid and watery hydrochloric acid or sulfuric acid, and alginic acid can It is made with being dissolved by distilled water or the aqueous slkali of certain mass concentration.As a preferred embodiment, chitosan solution is molten by chitosan Solution is obtained in 2wt% aqueous acetic acids, and marine alga acid solution is dissolved in distilled water by alginic acid and is made.
Aqueous agar solution is made at 90 DEG C and is solidified at 5 DEG C in plastic tube for used bar-shaped agar template of the invention Aqueous agar solution is made at 90 DEG C and drips dichloromethane under agitation at room temperature at 5 DEG C for shaping, spherical agar template Alkane solution is made.
Gained chitosan solution regulates and controls to solidify and assemble through being loaded with the agar template of sodium hydroxide solution, prepares chitosan and coagulates Glue-line;Gained marine alga acid solution can prepare marine alga acid cure through being loaded with the agar template crosslinked and solidification forming of calcium chloride solution Glue-line.By changing chitosan and alginic acid concentration of polymer solution, and the mass concentration and soak time of regulation solidification liquid are come Control chitosan and alginic acid gel layer thickness.
The inventive method obtains chitosan and marine alga acid solution by the way that chitosan and marine alga acid starting material are dissolved respectively, profit Regulate and control the solidification and assembling of chitosan and marine alga acid solution as template with the agar for being loaded with solidification liquid.In chitosan gel rubber layer shape During, through sodium hydroxide inside and outside agar template and chitosan mass concentration gradient (sodium hydroxide quality in agar template Concentration is high, and chitosan mass concentration outside agar template is high) induce, chitosan molecule by sodium hydroxide due to going matter in solution Sonization, the amino of chitosan, which is exposed, to be come, thus its strand can be interacted by strong hydrogen bonding between amino and mutually tangled, and is entered And self aggregation and gelation form chitosan gel rubber layer.During alginic acid gel-forming, the agar of calcium chloride solution is loaded with The calcium ion that template is loaded can be crosslinked the carboxyl of alginic acid, and with agar template, the continuous of calcium ion moves into solution Move, marine alga acid molecule can be constantly crosslinked in solution, and then form the alginic acid gel layer with three-dimensional net structure.It is logical Cross regulation and control chitosan and marine alga acid solution, solidification liquid mass concentration and soak time regulate and control chitosan and alginic acid gel layer Thickness.We have prepared every layer of about the chitosan gel rubber layer of 36-166 μ m thicks and the marine alga acid cure of 63-212 μ m thicks Glue-line.
The obtained alternately stratiform chitosan/marine alga acid gel of the inventive method has good solvent resistance, shape and layer Thick controllability, regular sandwich construction and biodegradability.The inventive method technical process is simply pollution-free, it is easy to industry Change.
Brief description of the drawings
Fig. 1 is that the gained of bar-shaped agar template at different conditions replaces stratiform chitosan/alginic acid gel photograph and right The line chart of thickness is answered, figure (a) 1% chitosan and 1% alginic acid soak photo obtained by 1min, figure in correspondence solidification liquid successively (b) 1.5% chitosan and 1.5% alginic acid soak photo obtained by 1.5min in correspondence solidification liquid successively, and figure (c) 2% shell gathers Sugar and 2% the alginic acid photo obtained by immersion 2min in correspondence solidification liquid successively, scheme (d) a, b, obtained by the figure corresponding datas of c tri- Line chart;
Fig. 2 is alternating stratiform chitosan/marine alga acid gel of the spherical agar core under different chitosan mass concentration conditions The line chart of photo and correspondence thickness.Scheme (a) 1.5% marine alga acid soak 2 minutes, 1% chitosan soaks 1 minute gained alternately Stratiform chitosan/alginic acid gel photograph, figure (b) 1.5% marine alga acid soak 2 minutes, 1.5% chitosan soaks 1 minute institute Stratiform chitosan/alginic acid gel photograph must be replaced, figure (c) 1.5% marine alga acid soak 2 minutes, 2% chitosan soaks 1 point Alternating stratiform chitosan/alginic acid gel photograph, schemes (d) a, b, line chart obtained by the figure corresponding datas of c tri- obtained by clock;
Fig. 3 is alternating stratiform chitosan/sea of the spherical agar core under different solid interracial contact (immersion) time conditions The line chart of alginic acid gel photograph and correspondence thickness.Scheme (a) 1.5% chitosan to soak 1 minute, 2% institute of marine alga acid soak 1 minute Stratiform chitosan/alginic acid gel photograph must be replaced, figure (b) 1.5% chitosan soaks 1 minute, 2% 1.5 points of marine alga acid soak Alternating stratiform chitosan/alginic acid gel photograph obtained by clock, figure (c) 1.5% chitosan soaks 1 minute, 2% marine alga acid soak 2 Alternating stratiform chitosan/alginic acid gel photograph, schemes (d) a, b, line chart obtained by the figure corresponding datas of c tri- obtained by minute;
Fig. 4 is alternating stratiform chitosan/marine alga acid cure of the spherical agar core under different solid interracial contact time conditions The line chart of glue photo and correspondence thickness.Scheme (a) 1.5% marine alga acid soak 1 minute, 1% chitosan soaks 2 minutes gained alternately Stratiform chitosan/alginic acid gel photograph, figure (b) 1.5% marine alga acid soak 1 minute, 1.5% chitosan soaks 1.5 minutes institutes Stratiform chitosan/alginic acid gel photograph, figure (c) 1.5% marine alga acid soak 1 minute, 2% chitosan immersion 2 minutes must be replaced Gained alternating stratiform chitosan/alginic acid gel photograph, schemes (d) a, b, line chart obtained by the figure corresponding datas of c tri-;
Fig. 5 alternating stratiforms chitosan/marine alga acid gel soaks front and rear photo in different solvents, before (a) immersion 10wt% sodium hydroxide solution, the sodium hydroxide solution of the 10wt% after figure (b) immersion, the n-hexane before figure (c) immersion, figure (d) n-hexane after soaking, the hexamethylene before figure (e) immersion, the hexamethylene before figure (f) immersion.
Embodiment
Embodiment 1
Bar-shaped agar core is immersed in 1min in 5% mass concentration sodium hydroxide solution solidification liquid, then by bar-shaped agar The chitosan solution 1min of 1% mass concentration is immersed in, it is clean with distilled water flushing after taking-up, and carefully wiped with filter paper many Remaining moisture, is then sequentially placed into each 1min in the calcium chloride solution of 0.01mol/L mass concentrations and 1wt% marine alga acid solutions, then It is secondary to be cleaned with distilled water and wiped clean, 1min in 5% mass concentration sodium hydroxide solution is immersed in again, is repeated the above steps Alternating stratiform chitosan/alginic acid multilayer aquagel with tubular structure can be prepared.Wherein, the thickness of chitosan gel rubber layer Degree is followed successively by from inside to outside:36.5,38.8 and 53.3 microns, the thickness of alginic acid gel layer is followed successively by from inside to outside:71.1 Hes 125.3 microns, alternating stratiform chitosan/alginic acid gel photograph, shown in such as Fig. 1 (a).
Embodiment 2
Bar-shaped agar core is immersed in 1.5min in 5% mass concentration sodium hydroxide solution solidification liquid, then by bar-shaped fine jade Fat is immersed in the chitosan solution 1.5min of 1.5% mass concentration, after taking-up, clean with distilled water flushing and careful with filter paper Excessive moisture is wiped, is then sequentially placed into the calcium chloride solution of 0.01mol/L mass concentrations and 1.5wt% marine alga acid solutions each 1.5min, is cleaned and wiped clean with distilled water, 1.5min in 5% mass concentration sodium hydroxide solution is immersed in again again, Alternating stratiform chitosan/alginic acid multilayer aquagel with tubular structure can be prepared by repeating the above steps.Chitosan coagulates The thickness of glue-line is followed successively by from inside to outside:102.5,128.4 and 135.1 microns, the thickness of alginic acid gel layer from inside to outside according to It is secondary to be:124.3 and 132.7 microns, alternately shown in stratiform chitosan/alginic acid gel photograph such as Fig. 1 (b).
Embodiment 3
The chitosan solution for being loaded with the bar-shaped agar core of 5% sodium hydroxide solution solidification liquid and being immersed in 2% concentration 2min, it is clean with distilled water flushing after taking-up, and excessive moisture is carefully wiped with filter paper, then it is sequentially placed into 0.01mol/L's 2min in calcium chloride solution and 2wt% marine alga acid solutions, is cleaned and wiped clean with distilled water, 5% is immersed in again dense again 2min in sodium hydroxide solution is spent, repeat the above steps the alternating stratiform chitosan/marine alga that can be prepared with tubular structure Sour multilayer aquagel.The thickness of chitosan gel rubber layer is followed successively by from inside to outside:133.4,151.3 and 147.6 microns, marine alga acid cure The thickness of glue-line is followed successively by from inside to outside:144.0 and 193.9 microns, alternating stratiform chitosan/alginic acid gel photograph such as Fig. 1 (c) shown in.
Embodiment 4
The chitosan solution for being loaded with the bar-shaped agar core of 10% sodium hydroxide solution solidification liquid and being immersed in 2% concentration 2min, it is clean with distilled water flushing after taking-up, and excessive moisture is carefully wiped with filter paper, then it is sequentially placed into 0.01mol/L's 2min in calcium chloride solution and 2wt% marine alga acid solutions, is cleaned and wiped clean with distilled water, 10% is immersed in again dense again 2min in sodium hydroxide solution is spent, repeat the above steps the alternating stratiform chitosan/marine alga that can be prepared with tubular structure Sour multilayer aquagel.The thickness of chitosan gel rubber layer is followed successively by from inside to outside:147.2,158.7 and 165.8 microns, marine alga acid cure The thickness of glue-line is followed successively by from inside to outside:152.9 with 203.9 microns.
Embodiment 5
Spherical agar core is immersed in 1min in 5% mass concentration sodium hydroxide solution solidification liquid, then by spherical agar Core is immersed in the chitosan solution 1min of 1% mass concentration, after taking-up, clean with distilled water flushing, and is carefully wiped with filter paper Excessive moisture, is then sequentially placed into each 1min in 0.005mol/L calcium chloride solution and 1.5wt% marine alga acid solutions, uses again Distilled water is cleaned and wiped clean, and 2min in 5% mass concentration sodium hydroxide solution is immersed in again, is repeated the above steps Prepare alternating stratiform chitosan/alginic acid multilayer aquagel with onion structure.Chitosan gel rubber layer thickness from it is interior to It is followed successively by outside:43.4,55.7 and 93.0 microns, the thickness of alginic acid gel layer is followed successively by from inside to outside:83.2 and 81.1 microns, Alternately shown in stratiform chitosan/alginic acid gel photograph such as Fig. 2 (a).
Embodiment 6
Spherical agar core is immersed in 1min in 7.5% mass concentration sodium hydroxide solution solidification liquid, then by spherical fine jade Fat core is immersed in the chitosan solution 1min of 1.5% mass concentration, after taking-up, clean with distilled water flushing and careful with filter paper Excessive moisture is wiped, each 2min in 0.005mol/L calcium chloride solution and 1.5wt% marine alga acid solutions is then sequentially placed into, then It is secondary to be cleaned with distilled water and wiped clean, 1min in 7.5% mass concentration sodium hydroxide solution is immersed in again, repeats above-mentioned step Suddenly alternating stratiform chitosan/alginic acid multilayer aquagel with onion structure can be prepared.The thickness of chitosan gel rubber layer It is followed successively by from inside to outside:47.9,73.2 and 81.9 microns, the thickness of alginic acid gel layer is followed successively by from inside to outside:121.2 and 129.4 microns, alternately shown in stratiform chitosan/alginic acid gel photograph such as Fig. 2 (b).
Embodiment 7
Spherical agar core is immersed in 1min in 10% mass concentration sodium hydroxide solution solidification liquid, then by spherical agar Core is immersed in the chitosan solution 1min of 2% mass concentration, after taking-up, clean with distilled water flushing, and is carefully wiped with filter paper Excessive moisture, is then sequentially placed into each 2min in 0.005mol/L calcium chloride solution and 1.5wt% marine alga acid solutions, uses again Distilled water is cleaned and wiped clean, and 1min in 10% mass concentration sodium hydroxide solution is immersed in again, is repeated the above steps i.e. Alternating stratiform chitosan/alginic acid multilayer aquagel with onion structure can be prepared.The thickness of chitosan gel rubber layer is from interior To being followed successively by outside:68.4,85.6 and 98.0 microns, the thickness of alginic acid gel layer is followed successively by from inside to outside:119.5 and 173.2 Micron, alternately shown in stratiform chitosan/alginic acid gel photograph such as Fig. 2 (c).
Embodiment 8
Spherical agar core is immersed in 1min in 5% mass concentration sodium hydroxide solution solidification liquid, then by spherical agar Core is immersed in the chitosan solution 1min of 1.5% mass concentration, after taking-up, clean with distilled water flushing, and is carefully wiped with filter paper Excessive moisture is wiped, each 1min in 0.075mol/L calcium chloride solution and 2% marine alga acid solution is then sequentially placed into, again with steaming Distilled water is cleaned and wiped clean, 1min in 5% mass concentration sodium hydroxide solution is immersed in again, repeating the above steps to make It is standby go out alternating stratiform chitosan/alginic acid multilayer aquagel with onion structure.The thickness of chitosan gel rubber layer is from inside to outside It is followed successively by:48.6,65.6 and 84.3 microns, the thickness of alginic acid gel layer is followed successively by from inside to outside:96.4 and 149.4 microns, Alternately shown in stratiform chitosan/alginic acid gel photograph such as Fig. 3 (a).
Embodiment 9
Spherical agar core is immersed in 1min in 5% mass concentration sodium hydroxide solution solidification liquid, then by spherical agar Core is immersed in the chitosan solution 1min of 1.5% mass concentration, after taking-up, clean with distilled water flushing, and is carefully wiped with filter paper Excessive moisture is wiped, each 1.5min in 0.075mol/L calcium chloride solution and 2% marine alga acid solution is then sequentially placed into, uses again Distilled water is cleaned and wiped clean, and 1min in 5% mass concentration sodium hydroxide solution is immersed in again, is repeated the above steps Prepare alternating stratiform chitosan/alginic acid multilayer aquagel with onion structure.Chitosan gel rubber layer thickness from it is interior to It is followed successively by outside:55.7,88.3 and 98.2 microns, the thickness of alginic acid gel layer is followed successively by from inside to outside:117.8 it is micro- with 161.6 Rice, alternately shown in stratiform chitosan/alginic acid gel photograph such as Fig. 3 (b).
Embodiment 10
Spherical agar core is immersed in 1min in 10% mass concentration sodium hydroxide solution solidification liquid, then by spherical agar Core is immersed in the chitosan solution 1min of 1.5% mass concentration, after taking-up, clean with distilled water flushing, and is carefully wiped with filter paper Excessive moisture is wiped, each 2min in 0.075mol/L calcium chloride solution and 2% marine alga acid solution is then sequentially placed into, again with steaming Distilled water is cleaned and wiped clean, and 1min in 10% mass concentration sodium hydroxide solution is immersed in again, is repeated the above steps Prepare alternating stratiform chitosan/alginic acid multilayer aquagel with onion structure.Chitosan gel rubber layer thickness from it is interior to It is followed successively by outside:81.3,83.7 and 113.0 microns, the thickness of alginic acid gel layer is followed successively by from inside to outside:127.3 it is micro- with 189.4 Rice, alternately shown in stratiform chitosan/alginic acid gel photograph such as Fig. 3 (c).
Embodiment 11
Spherical agar core is immersed in 2min in 10% mass concentration sodium hydroxide solution solidification liquid, then by spherical agar Core is immersed in the chitosan solution 2min of 1% mass concentration, after taking-up, clean with distilled water flushing, and is carefully wiped with filter paper Excessive moisture, is then sequentially placed into each 1min in 0.01mol/L calcium chloride solution and 1wt% marine alga acid solutions, again with steaming Distilled water is cleaned and wiped clean, and 2min in 10% mass concentration sodium hydroxide solution is immersed in again, is repeated the above steps Prepare alternating stratiform chitosan/alginic acid multilayer aquagel with onion structure.Chitosan gel rubber layer thickness from it is interior to It is followed successively by outside:74.5,100.0 and 111.8 microns, the thickness of alginic acid gel layer is followed successively by from inside to outside:62.8 and 147.3 is micro- Rice, alternately shown in stratiform chitosan/alginic acid gel photograph such as Fig. 4 (a).
Embodiment 12
Spherical agar core is immersed in 1.5min in 10% mass concentration sodium hydroxide solution solidification liquid, then by bar-shaped fine jade Fat is immersed in the chitosan solution 1.5min of 1.5% mass concentration, after taking-up, clean with distilled water flushing and careful with filter paper Excessive moisture is wiped, each 1min in 0.01mol/L calcium chloride solution and 1.5wt% marine alga acid solutions is then sequentially placed into, then It is secondary to be cleaned with distilled water and wiped clean, 1.5min in 10% mass concentration sodium hydroxide solution is immersed in again, is repeated above-mentioned Step can prepare alternating stratiform chitosan/alginic acid multilayer aquagel with onion structure.The thickness of chitosan gel rubber layer Degree is followed successively by from inside to outside:113.6,138.9 and 147.1 microns, the thickness of alginic acid gel layer is followed successively by from inside to outside: 102.8 and 201.1 microns, alternately shown in stratiform chitosan/alginic acid gel photograph such as Fig. 4 (b).
Embodiment 13
Spherical agar core is immersed in 2min in 10% mass concentration sodium hydroxide solution solidification liquid, then by bar-shaped agar The chitosan solution 2min of 2% mass concentration is immersed in, it is clean with distilled water flushing after taking-up, and carefully wiped with filter paper many Remaining moisture, is then sequentially placed into each 1min in 0.01mol/L calcium chloride solution and 1.5wt% marine alga acid solutions, again with steaming Distilled water is cleaned and wiped clean, and 2min in 10% mass concentration sodium hydroxide solution is immersed in again, is repeated the above steps Prepare alternating stratiform chitosan/alginic acid multilayer aquagel with onion structure.Chitosan gel rubber layer thickness from it is interior to It is followed successively by outside:117.2,139.7 and 155.0 microns, the thickness of alginic acid gel layer is followed successively by from inside to outside:160.8 and 212.0 Micron, alternately shown in stratiform chitosan/alginic acid gel photograph such as Fig. 4 (c).
Figure d in Fig. 1 is figure (a), (b), line chart obtained by (c) three figure corresponding data in Fig. 1.Fig. 2 (d) is in Fig. 2 Scheme (a), (b), line chart obtained by (c) three figure corresponding data.Fig. 3 (d) is figure (a), (b), (c) three figure corresponding data in Fig. 3 Obtained line chart.Fig. 4 (d) is figure (a), (b), line chart obtained by (c) three figure corresponding data in Fig. 4.By to above-mentioned reality Number of cases is applied according to being analyzed, research finds chitosan gel rubber thickness degree within the specific limits with naoh concentration, chitosan The increase of concentration, soak time and the number of plies and increase, while alginic acid gel layer thickness is with marine alga acid solutions, chlorination The increase of calcium solution concentration, soak time and the number of plies and increase, show good regularity, thus we can pass through and adjust The control of mould and the realization of specific experiment preparation condition to chitosan/alginic acid interlayer plural gel shape and thickness is controlled, according to Actual application requirement can prepare the interlayer hydrogel material of specific thicknesses.As shown in figure 5, three groups of alternating stratiform shells are gathered Sugar/marine alga acid gel is immersed in 10wt% sodium hydroxides, n-hexane, hexamethylene successively, is placed at 25 DEG C to soak and is observed after 24h It is swelled and solubility behavior, result of study shows that the multilayer pattern and size of alternately lamellar gel are held essentially constant, and shows good Good solvent resistance.
Described above is only the preferred embodiment of the present invention, it should be pointed out that:For the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (4)

1. a kind of preparation method of alternately stratiform chitosan/alginic acid compound hydrogel material, it is characterised in that including following step Suddenly:
(1) configuration quality concentration is 1-2% chitosans, and 5-10% sodium hydroxides and 1-2% marine algas acid solution and concentration are 0.005-0.01mol/L calcium chloride solution, selects bar-shaped or spherical agar to be used as template;
(2) agar template is placed in sodium hydroxide solution and soaked, taken out, then agar template is put into leaching in chitosan solution Bubble, is then immersed in the agar template with chitosan gel rubber layer in distilled water after a period of time and takes out;Shell is drawn with filter paper Agar template, is then immersed in calcium chloride solution after certain time and places into marine alga acid solution by polysaccharide gel layer surface moisture In, taken out after solidification, it is with distilled water flushing agar template and stand-by with filter paper wiped clean;
(3) operation of step (2) is repeated in, until the number of plies needed;
The chitosan solution is obtained by 2wt% acetums dissolving chitosan, and marine alga acid solution dissolves alginic acid by distilled water Obtain;The aqueous agar solution solidification forming in plastic tube, spherical agar at 5 DEG C is made in bar-shaped agar template at 90 DEG C The template dichloromethane solution that obtained aqueous agar solution is dripped under agitation at room temperature at 90 DEG C is made.
2. the preparation method of alternately stratiform chitosan/alginic acid compound hydrogel material according to claim 1, its feature It is:It is 1-2 minutes that agar template, which is placed in soak time in sodium hydroxide solution, in the step (2), and agar template is put into shell Soak time is 1-2 minutes in glycan solution, and agar template is 1-2 minutes in calcium chloride solution soak time.
3. the preparation method of alternately stratiform chitosan/alginic acid compound hydrogel material according to claim 1, its feature It is:The agar template is spherical, a diameter of 3mm.
4. the preparation method of alternately stratiform chitosan/alginic acid compound hydrogel material according to claim 1, its feature It is:The agar template is bar-shaped, a diameter of 5mm.
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