CN104785177A - Preparation method of alginate-graphene compound double-network gel beads - Google Patents
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Abstract
The invention relates to a preparation method of alginate-graphene compound double-network gel beads. The preparation method comprises the following steps: (1) adding graphene oxide into an aqueous solution and carrying out ultrasonic treatment to prepare a uniform graphene oxide aqueous solution; (2) adding alginate into the graphene oxide aqueous solution and mechanically stirring to prepare a uniform mixed solution; (3) preparing a bivalent salt ion solution with a certain concentration and dropwise adding a peristaltic pump mixed solution into the bivalent salt ion solution at 0-100 DEG C to prepare alginate single-network gel beads loaded with the graphene oxide; (4) adding the single-network gel beads into an aqueous solution containing a reducing agent and carrying out water bath heat treatment to prepare the alginate-graphene compound double-network gel beads. Compared with the prior art, the preparation method is simple in process and liable to popularize; the prepared alginate-graphene compound double-network gel beads are excellent in resistance to salt and alkali, large in specific surface area and high in adsorbability.
Description
Technical field
The invention belongs to gel studying technological domain, relate to a kind of preparation method of dual network gel ball, especially relate to the preparation method of a kind of alginate-Graphene composite double network gel ball.
Background technology
Sodium alginate is a kind of natural polysaccharide carbohydrate extracted from the sea-tangle or sargassum of brown algae.Sodium alginate has the advantages such as thickening property is good, good film-forming property, gel strength are high, ropiness is good, sodium alginate can be cross-linked to form gel in divalent salts solion, this process is reversible reaction, therefore, alginate ball can in monovalent salt ion unstability again.In addition, alginate ball has height swellability, and swellability increases with pH and increases, and thus easily bursts at a high ph.
In order to overcome above-mentioned shortcoming, much research to carrying inorganic particle on alginate ball, in order to reduce the swellability of alginate ball.Such as, application number be 201110137410.7 Chinese invention patent disclose a kind of preparation method of absorptive gel ball, comprise and a) use the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA) to carry out carboxylated process to CNT, obtain carboxy-modified CNT, the weight ratio of the described concentrated sulfuric acid, red fuming nitric acid (RFNA) and CNT is 40-90:30-5:30-5; B) described carboxy-modified CNT is mixed with water soluble algae hydrochlorate in water, obtain the mixture of alginate and CNT; C) in described mixture, add calcium chloride solution, obtain absorptive gel ball.The technical scheme of above-mentioned patent disclosure is exactly by alginate and carbon nano-tube material compound, to improve the absorption property of alginate to organic dyestuff.
In gel research field, for improving the mechanical performance of gel, now occurred the concept of dual network gel, namely two kinds of gels are by non-covalent bond compound, and can independently in same system exist.Relative to dual network gel, tradition all concentrates on single network gel aspect to the modification of alginate, the research of dual network gel is less, secondly, the research of dual network gel also mainly concentrates on field of polymer technology, as polyacrylamide, polyacrylic acid, macrogol ester etc., what have need by crosslinking agent, initator.At present, report Graphene gel being formed in natural polymer to dual network gel is not yet had.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and provide a kind of process conditions simple, the preparation method of economical and practical alginate-Graphene composite double network gel ball, in order to prepare Salt-resistant alkali-resistant, and there is the gel ball of high-specific surface area.
Object of the present invention can be achieved through the following technical solutions:
A preparation method for alginate-Graphene composite double network gel ball, the method specifically comprises the following steps:
(1) graphene oxide is added in the aqueous solution, through ultrasonic process, obtained uniform graphene oxide water solution;
(2) in the obtained graphene oxide water solution of step (1), add alginate, through mechanical agitation, form uniform mixed solution;
(3) certain density divalent salts solion is prepared, under 0-100 DEG C of condition, adopt peristaltic pump by the divalent salts solion described in mixed solution instillation obtained for step (2), obtained load has the alginate list network gel ball of graphene oxide;
(4) single network gel ball that step (3) is obtained is joined in the aqueous solution containing reducing agent, after heating water bath process, i.e. obtained alginate-Graphene composite double network gel ball.
In graphene oxide water solution described in step (1), the concentration of graphene oxide is 0.1-20mg/mL.
Graphite oxide described in step (1) is the graphite oxide adopting Hummers method to be prepared from.
In mixed solution described in step (2), the concentration of alginate is 1-20mg/mL.
Described alginate is the one in sodium alginate, potassium alginate or ammonium alginate.
The preferred sodium alginate of described alginate.
The sodium salt of the polyanionic polysaccharide (alginic acid) that sodium alginate is made up of 3-D-mannuronic acid and α-L-guluronic acid, there is good biocompatibility, owing to containing abundant hydroxyl and carboxyl, there is the hydrophily of height, cheap, than being easier to derivatization, it is a kind of desirable adsorbing medium framework material.
Due to Mg
2+can not make sodium alginate generation cross-linking reaction, the divalent salts solion described in step (3) is except Mg
2+all divalent salts solions in addition.
The described preferred CaCl of divalent salts solion
2solution.
Reducing agent described in step (4) comprises the one in hydrazine hydrate, sodium borohydride, sodium acid carbonate, lithium aluminium hydride reduction, formaldehyde, saccharide compound, ascorbic acid, glutathione or amino acid.
One in the preferred sodium acid carbonate of described reducing agent, ascorbic acid or glutathione.
Mass ratio≤1 of the reducing agent described in step (4) and the graphene oxide described in step (1).
The temperature of the heating water bath process described in step (4) is 50-100 DEG C, and the time is 5-48h.
The present invention is in the process preparing alginate-Graphene composite double network gel ball, the Graphene adopted has excellent mechanical performance, high chemical stability and high-specific surface area, Graphene and alginate compound can be made up alginate as the deficiency of large biological molecule on physical and chemical performance, improve mechanical performance and chemical stability; And Graphene as nano material time, it has easy reunion, bio-toxicity and causes the shortcoming being difficult to reclaim because of undersized, Graphene and alginate compound can be improved the agglomeration of Graphene, and reduce toxicity, be prepared as gel form and also solve the problem being difficult to reclaim; In addition, gel reaction is become by the substep of dual network, Graphene and alginate form respectively Graphene gel network and alginate network, and two networks are separate but support each other, and the basis of single network gel increases again performance further that improve material.
Compared with prior art, the present invention has following characteristics:
1) present invention process simple, be easy to promote, obtained dual network gel ball, has better salt alkaline stability and adsorption capacity than the single network gel in tradition research being only load relationship;
2) the dual network gel ball that the present invention obtains more can suppress the reunion of Graphene than single network gel, specific area improves a lot.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of dual network gel ball in graphene oxide, single network gel ball and embodiment 1.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1:
Get five beakers, 40mg, 80mg, 160mg graphite oxide and 20mL distilled water is added respectively in five groups of beakers, ultrasonic 6h is to dissolution homogeneity, obtain 2mg/mL, 4mg/mL, 8mg/mL graphene oxide solution, dissolve 20mg sodium alginate respectively in each solution, mechanical agitation 1h is to forming homogeneous solution.Separately get five groups of beakers, all configure the CaCl of 10mg/mL
2solution, with peristaltic pump by graphene oxide/sodium alginate soln instillation CaCl
2solution, obtains the alginate ball (single network gel) of load graphene oxide.Separately get five beakers, take with the ascorbic acid of graphite oxide mass ratio 1:1 and molten after, single network gel ball is put into ascorbic acid solution and heats 8h, obtain the dual network gel ball of different Graphene content, pure zirconia Graphene, single network gel, dual network gel are carried out X diffraction analysis, as shown in Figure 1.
As seen from Figure 1,2 θ of pure zirconia Graphene and single network gel have characteristic peak at 10.6 ° and 12.5 ° of places respectively, show that graphene oxide sheet interlayer spacing is for being respectively in these two samples
with
as can be seen here, when there is sodium alginate in system, graphene oxide sheet interlayer spacing reduces, and this is owing to becoming in the process of gel at sodium alginate, divalent metal Ca
2+to Graphene, also there is faint crosslinked action.In addition, from the contrast of single dual network, in dual network, many peaks disappear, this is due to after graphene oxide becomes gel, direct effect between graphene sheet layer or ordered stacks disappear, and further demonstrate that alginate passes through bonding graphene oxide lamella and becomes gel also to serve facilitation to it.
Through BET test, single network gel ball specific area is 3.4m
2/ g, dual network gel ball specific area is 37.2m
2/ g.
Embodiment 2:
Get five beakers, 40mg, 80mg, 160mg graphite oxide and 20mL distilled water is added respectively in five groups of beakers, ultrasonic 6h is to dissolution homogeneity, obtain 2mg/mL, 4mg/mL, 8mg/mL graphene oxide solution, dissolve 20mg sodium alginate respectively in each solution, mechanical agitation 1h is to forming homogeneous solution.Separately get five groups of beakers, all configure the CaCl of 10mg/mL
2solution, with peristaltic pump by graphene oxide/sodium alginate soln instillation CaCl
2solution, obtains the alginate ball (single network gel) of load graphene oxide.Separately get five beakers, take with the glutathione of graphite oxide mass ratio 1:1 and after dissolving, single network gel ball put into glutathione solution at 60 DEG C of heating 8h, obtain the dual network gel ball of different Graphene content.
Embodiment 3:
Get five beakers, 40mg, 80mg, 160mg graphite oxide and 20mL distilled water is added respectively in five groups of beakers, ultrasonic 6h is to dissolution homogeneity, obtain 2mg/mL, 4mg/mL, 8mg/mL graphene oxide solution, dissolve 20mg sodium alginate respectively in each solution, mechanical agitation 1h is to forming homogeneous solution.Separately get five groups of beakers, all configure the CaCl of 10mg/mL
2solution, with peristaltic pump by graphene oxide/sodium alginate soln instillation CaCl
2solution, obtains the alginate ball (single network gel) of load graphene oxide.Separately get five beakers, take with the sodium acid carbonate of graphite oxide mass ratio 1:1 and dissolve, single network gel ball is put into sodium bicarbonate solution at 80 DEG C of heating 8h, obtain the dual network gel ball of different Graphene content.
Embodiment 4:
In the present embodiment, a kind of alginate-Graphene composite double network gel ball adopts following steps to be prepared from:
(1) graphene oxide is added in the aqueous solution, through ultrasonic process, obtained uniform graphene oxide water solution;
(2) in the obtained graphene oxide water solution of step (1), add alginate, through mechanical agitation, form uniform mixed solution;
(3) certain density divalent salts solion is prepared, under 0 DEG C of condition, adopt peristaltic pump by the divalent salts solion described in mixed solution instillation obtained for step (2), obtained load has the alginate list network gel ball of graphene oxide;
(4) single network gel ball that step (3) is obtained is joined in the aqueous solution containing reducing agent, after heating water bath process, i.e. obtained alginate-Graphene composite double network gel ball.
Wherein, in the graphene oxide water solution described in step (1), the concentration of graphene oxide is 0.1mg/mL.
In mixed solution described in step (2), the concentration of alginate is 1mg/mL.Described alginate is sodium alginate.
Divalent salts solion described in step (3) is liquor zinci chloridi.
Reducing agent described in step (4) is hydrazine hydrate, and the mass ratio of itself and the graphene oxide described in step (1) is 0.8.
The temperature of the heating water bath process described in step (4) is 50 DEG C, and the time is 48h.
Embodiment 5:
In the present embodiment, a kind of alginate-Graphene composite double network gel ball adopts following steps to be prepared from:
(1) graphene oxide is added in the aqueous solution, through ultrasonic process, obtained uniform graphene oxide water solution;
(2) in the obtained graphene oxide water solution of step (1), add alginate, through mechanical agitation, form uniform mixed solution;
(3) certain density divalent salts solion is prepared, under 25 DEG C of conditions, adopt peristaltic pump by the divalent salts solion described in mixed solution instillation obtained for step (2), obtained load has the alginate list network gel ball of graphene oxide;
(4) single network gel ball that step (3) is obtained is joined in the aqueous solution containing reducing agent, after heating water bath process, i.e. obtained alginate-Graphene composite double network gel ball.
Wherein, in the graphene oxide water solution described in step (1), the concentration of graphene oxide is 10mg/mL.
In mixed solution described in step (2), the concentration of alginate is 12mg/mL.Described alginate is potassium alginate.
Divalent salts solion described in step (3) is solution of zinc sulfate.
Reducing agent described in step (4) is sodium borohydride, and the mass ratio of itself and the graphene oxide described in step (1) is 0.6.
The temperature of the heating water bath process described in step (4) is 60 DEG C, and the time is 36h.
Embodiment 6:
In the present embodiment, a kind of alginate-Graphene composite double network gel ball adopts following steps to be prepared from:
(1) graphene oxide is added in the aqueous solution, through ultrasonic process, obtained uniform graphene oxide water solution;
(2) in the obtained graphene oxide water solution of step (1), add alginate, through mechanical agitation, form uniform mixed solution;
(3) certain density divalent salts solion is prepared, under 60 DEG C of conditions, adopt peristaltic pump by the divalent salts solion described in mixed solution instillation obtained for step (2), obtained load has the alginate list network gel ball of graphene oxide;
(4) single network gel ball that step (3) is obtained is joined in the aqueous solution containing reducing agent, after heating water bath process, i.e. obtained alginate-Graphene composite double network gel ball.
Wherein, in the graphene oxide water solution described in step (1), the concentration of graphene oxide is 20mg/mL.
In mixed solution described in step (2), the concentration of alginate is 20mg/mL.Described alginate is potassium alginate.
Divalent salts solion described in step (3) is calcium sulphate soln.
Reducing agent described in step (4) is lithium aluminium hydride reduction, and the mass ratio of itself and the graphene oxide described in step (1) is 1.
The temperature of the heating water bath process described in step (4) is 80 DEG C, and the time is 24h.
Embodiment 7:
In the present embodiment, a kind of alginate-Graphene composite double network gel ball adopts following steps to be prepared from:
(1) graphene oxide is added in the aqueous solution, through ultrasonic process, obtained uniform graphene oxide water solution;
(2) in the obtained graphene oxide water solution of step (1), add alginate, through mechanical agitation, form uniform mixed solution;
(3) certain density divalent salts solion is prepared, under 80 DEG C of conditions, adopt peristaltic pump by the divalent salts solion described in mixed solution instillation obtained for step (2), obtained load has the alginate list network gel ball of graphene oxide;
(4) single network gel ball that step (3) is obtained is joined in the aqueous solution containing reducing agent, after heating water bath process, i.e. obtained alginate-Graphene composite double network gel ball.
Wherein, in the graphene oxide water solution described in step (1), the concentration of graphene oxide is 8mg/mL.
In mixed solution described in step (2), the concentration of alginate is 16mg/mL.Described alginate is ammonium alginate.
Divalent salts solion described in step (3) is solution of zinc sulfate.
Reducing agent described in step (4) is amino acid, and the mass ratio of itself and the graphene oxide described in step (1) is 0.7.
The temperature of the heating water bath process described in step (4) is 100 DEG C, and the time is 5h.
Embodiment 8:
In the present embodiment, a kind of alginate-Graphene composite double network gel ball adopts following steps to be prepared from:
(1) graphene oxide is added in the aqueous solution, through ultrasonic process, obtained uniform graphene oxide water solution;
(2) in the obtained graphene oxide water solution of step (1), add alginate, through mechanical agitation, form uniform mixed solution;
(3) certain density divalent salts solion is prepared, under 100 DEG C of conditions, adopt peristaltic pump by the divalent salts solion described in mixed solution instillation obtained for step (2), obtained load has the alginate list network gel ball of graphene oxide;
(4) single network gel ball that step (3) is obtained is joined in the aqueous solution containing reducing agent, after heating water bath process, i.e. obtained alginate-Graphene composite double network gel ball.
Wherein, in the graphene oxide water solution described in step (1), the concentration of graphene oxide is 16mg/mL.
In mixed solution described in step (2), the concentration of alginate is 18mg/mL.Described alginate is sodium alginate.
Divalent salts solion described in step (3) is calcium nitrate solution.
Reducing agent described in step (4) is saccharide compound, and the mass ratio of itself and the graphene oxide described in step (1) is 0.85.
The temperature of the heating water bath process described in step (4) is 90 DEG C, and the time is 15h.
Embodiment 9:
In the present embodiment, a kind of alginate-Graphene composite double network gel ball adopts following steps to be prepared from:
(1) graphene oxide is added in the aqueous solution, through ultrasonic process, obtained uniform graphene oxide water solution;
(2) in the obtained graphene oxide water solution of step (1), add alginate, through mechanical agitation, form uniform mixed solution;
(3) certain density divalent salts solion is prepared, under 65 DEG C of conditions, adopt peristaltic pump by the divalent salts solion described in mixed solution instillation obtained for step (2), obtained load has the alginate list network gel ball of graphene oxide;
(4) single network gel ball that step (3) is obtained is joined in the aqueous solution containing reducing agent, after heating water bath process, i.e. obtained alginate-Graphene composite double network gel ball.
Wherein, in the graphene oxide water solution described in step (1), the concentration of graphene oxide is 6mg/mL.
In mixed solution described in step (2), the concentration of alginate is 2mg/mL.Described alginate is sodium alginate.
Divalent salts solion described in step (3) is calcium chloride solution.
Reducing agent described in step (4) is formaldehyde, and the mass ratio of itself and the graphene oxide described in step (1) is 0.5.
The temperature of the heating water bath process described in step (4) is 70 DEG C, and the time is 20h.
Claims (9)
1. a preparation method for alginate-Graphene composite double network gel ball, it is characterized in that, the method specifically comprises the following steps:
(1) graphite oxide is added in the aqueous solution, through ultrasonic process, obtained uniform graphene oxide water solution;
(2) in the obtained graphene oxide water solution of step (1), add alginate, through mechanical agitation, form uniform mixed solution;
(3) certain density divalent salts solion is prepared, under 0-100 DEG C of condition, adopt peristaltic pump by the divalent salts solion described in mixed solution instillation obtained for step (2), obtained load has the alginate list network gel ball of graphene oxide;
(4) single network gel ball that step (3) is obtained is joined in the aqueous solution containing reducing agent, after heating water bath process, i.e. obtained alginate-Graphene composite double network gel ball.
2. the preparation method of a kind of alginate according to claim 1-Graphene composite double network gel ball, is characterized in that, in the graphene oxide water solution described in step (1), the concentration of graphene oxide is 0.1-20mg/mL.
3. the preparation method of a kind of alginate according to claim 1-Graphene composite double network gel ball, is characterized in that, in the mixed solution described in step (2), the concentration of alginate is 1-20mg/mL.
4. the preparation method of a kind of alginate according to claim 1-Graphene composite double network gel ball, is characterized in that, described alginate is the one in sodium alginate, potassium alginate or ammonium alginate.
5. the preparation method of a kind of alginate according to claim 4-Graphene composite double network gel ball, is characterized in that, the preferred sodium alginate of described alginate.
6. the preparation method of a kind of alginate according to claim 1-Graphene composite double network gel ball, is characterized in that, the divalent salts solion described in step (3) is except Mg
2+all divalent salts solions in addition.
7. the preparation method of a kind of alginate according to claim 1-Graphene composite double network gel ball, it is characterized in that, the reducing agent described in step (4) comprises the one in hydrazine hydrate, sodium borohydride, sodium acid carbonate, lithium aluminium hydride reduction, formaldehyde, saccharide compound, ascorbic acid, glutathione or amino acid.
8. the preparation method of a kind of alginate according to claim 1-Graphene composite double network gel ball, is characterized in that, mass ratio≤1 of the reducing agent described in step (4) and the graphene oxide described in step (1).
9. the preparation method of a kind of alginate according to claim 1-Graphene composite double network gel ball, is characterized in that, the temperature of the heating water bath process described in step (4) is 50-100 DEG C, and the time is 5-48h.
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