CN102321190B - Photocatalytic oxidation process for preparing multi-aldehyde sodium alginate - Google Patents
Photocatalytic oxidation process for preparing multi-aldehyde sodium alginate Download PDFInfo
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Abstract
The invention discloses a photocatalytic oxidation process for preparing multi-aldehyde sodium alginate, which is characterized by comprising the following steps of: preparing an active carbon-supported TiO2 catalyst by using a sol-gel method; adding the catalyst into the prepared solution of sodium alginate, ensuring that adsorption balance is reached under the dark-state condition, introducing air or oxygen at a certain flow rate, turning on an ultraviolet lamp, performing clock reaction, filtering after the reaction is finished, adding a proper amount of sodium chloride into the filtrate, fully dissolving the sodium chloride, adding excessive ethanol to separate out a product, and performing suction filtration and drying to obtain an initial product; and performing dialysis and freeze-drying to obtain the multi-aldehyde sodium alginate product. In the process, an expensive oxidant of sodium periodate is avoided, so the production cost is reduced and the pollution is lightened. The process is more reasonable and high in operability, and is a feasible green method for preparing the multi-aldehyde sodium alginate.
Description
Technical field
The present invention relates to a kind of preparation method of sodium alginate, particularly a kind of photocatalytic oxidation process for preparing multi-aldehyde sodium alginate.
Background technology
Sodium alginate is a kind of sodium salt of the polyanionic polysaccharide carbohydrate (Lalgine) that extracts from natural brown alga, a kind of shape block copolymer that is formed by beta-D-mannuronic acid (M sugar) and α-L-guluronic acid (G is sugared), nontoxic, physiological compatibility good, can slow degradation be to discharge with urine after seminose and the gulose in vivo, be widely used in the fields such as pharmaceutical preparation, organizational project, cell cultures.But sodium alginate is used for medical material and pharmaceutical excipient has it significantly not enough: under at physiological condition, the gel matrix of its formation has unsettled mechanical property owing to the monovalent cation in its divalent cation and the internal milieu exchanges mutually; Formed gel lacks the recognition capability to specific cells, and wetting ability is strong, and the gel aperture is large, and release rate is very fast and prominent releasing easily occurs, and especially during the coated water-soluble small-molecule drug, often leaks, and causes entrapment efficiency lower, and time of releasing is too short; In addition, sodium alginate degradation rate in vivo is very low.The modification of physics or chemistry can overcome the above shortcoming of alginates to a certain extent.Preparing many aldehyde sodium alginates by partial oxidation is one of common chemical modification methods.
Contain two adjacent hydroxyls on the monomeric unit of sodium alginate, can be partially oxidized for having many aldehyde sodium alginates of high reaction activity.Many aldehyde sodium alginates can be hydrophobic modified to carry out with substance reactions such as alkylamines; Can be used as the bio-active substance qualitative responses such as nontoxic, water-soluble, cheap linking agent and albumen, polypeptide, special amino acid series, make up biocompatibility well, tissue engineering material safely and effectively.Therefore, the preparation of many aldehyde sodium alginates has important effect in biomedicine and pharmaceutical field.
The method of the common many aldehyde sodium alginates of preparation is that to adopt sodium periodate be that oxygenant lucifuge stoichiometric number in alcohol/aqueous systems hour makes.Sodium periodate is the adjacent diol type compound of oxicracking at ambient temperature, is the important reaction in the carbohydrate chemistry.Can realize partial oxidation to sodium alginate by sodium periodate, but the method is difficult for to the control of oxidisability, and the sodium periodate price is high, consumption is large, is unsuitable for applying.The another kind of method for oxidation of bibliographical information is take metal oxygen-containing acid such as potassium permanganate as oxygenant, realizes the partial oxidation of sodium alginate, but the oxidisability of its oxidation products is difficult to control, and selectivity of product is on the low side, and easily over oxidation is carboxylic acid.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, and the photocatalytic oxidation process for preparing multi-aldehyde sodium alginate that a kind of technique is more reasonable, cost is low is provided.
Technical problem to be solved by this invention is to realize by following technical scheme.The present invention is a kind of photocatalytic oxidation process for preparing multi-aldehyde sodium alginate, is characterized in, its step is as follows:
(1) with the gac mass concentration is the acidic solution immersion treatment of 3-30% after 20-120 minute, fully washs through deionized water, the gac of 100-150 ℃ of dry activated processing; Get butyl (tetra) titanate, successively to wherein adding Virahol and nitric acid, stirring at room, and the gac of activated processing added wherein, then slowly add distilled water, the volume ratio of nitric acid, butyl (tetra) titanate, Virahol and distilled water is 1:6-7:20-30:0.5-2.0, continues to stir, and makes black colloidal sol; With black colloidal sol sonic oscillation, ultrasonic power is 10-40KHZ, and the sound intensity is 0.5-2.0W/cm
2, being ground to 0.2-2.0mm after the ultrasonic rear drying, 400-500 ℃ of calcining namely gets activated carbon supported TiO
2Catalyzer;
(2) in quartz container, add sodium alginate, and add water and make the sodium alginate soln that mass volume ratio concentration is 0.3-2.5%, then add an amount of activated carbon supported TiO
2Catalyzer stirs and is issued to adsorption equilibrium in dark attitude condition; In quartz container, pass into the air or oxygen that flow is 6-20ml/min again; Open the ultraviolet lamp that places the quartz container top, the power of ultraviolet lamp is 100-300W, and centre wavelength is 365nm, and stirring at room was reacted 2-20 hour;
(3) after reaction finished, filtering recovering catalyst added an amount of sodium-chlor in filtrate, fully adds excessive ethanol after the dissolving product is separated out, suction filtration, dry crude product; The crude product molecular weight cut-off of packing into after with the abundant swelling of distilled water is at least 3500 dialysis tubing, and impurity is removed in dialysis, the dialysis postlyophilization, many aldehyde sodium alginates product.
The preferred nitric acid of the described acidic solution of the step of above-described photocatalytic oxidation process for preparing multi-aldehyde sodium alginate technical scheme (1), sulfuric acid, HF acid or hydrochloric acid.
The inventive method is to add an amount of light-sensitive semiconductor material TiO in reaction system
2, the wavelength by having certain energy is less than the irradiation of the UV-light of 387nm, TiO
2Namely gone out electron-hole pair by optical excitation, have the electron-hole pair of longer life by spreading and being adsorbed on TiO
2The materials such as the oxygen on surface, water react and form hydroxyl radical free radical and superoxide ion free radical, and these active groups with stronger oxidation capacity will be adsorbed on the sodium alginate oxidation of catalyst surface.Under the mild conditions, under the effect of UV-light and catalyzer, the C-C key fracture on the suitable diol structure in the partial monosomy unit of sodium alginate on 2,3, and glycol is oxidized to dialdehyde.
Structural changes before and after the sodium alginate oxidation of the present invention is as follows:
Compared with prior art, the present invention is owing to avoiding using expensive oxygenant sodium periodate, thereby reduced production cost, also reduced pollution simultaneously.Technique of the present invention is more reasonable, and is workable, for the preparation of many aldehyde sodium alginates provides a kind of feasible environment-friendly preparation method thereof.
Description of drawings
Fig. 1 is the infrared spectrogram by the prepared many aldehyde sodium alginates product of the inventive method.
Embodiment
Referring to accompanying drawing, further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not consist of its Copyright law.
(1) with the gac mass concentration is 3% acidic solution immersion treatment after 20 minutes, fully washs through deionized water, the gacs of 100 ℃ of dry activated processing; Get butyl (tetra) titanate, successively to wherein adding Virahol and nitric acid, stirring at room, and the gac of activated processing added wherein, then slowly adding distilled water, the volume ratio of nitric acid, butyl (tetra) titanate, Virahol and distilled water is 1:6:20:0.5, continue to stir, make black colloidal sol; With black colloidal sol sonic oscillation, ultrasonic power is 10-KHZ, and the sound intensity is 0.5W/cm
2, being ground to 0.2mm after the ultrasonic rear drying, 400 ℃ of calcinings namely get activated carbon supported TiO
2Catalyzer; Described acidic solution is hydrochloric acid soln;
(2) in quartz container, add sodium alginate, and adding water, to make mass volume ratio concentration be 0.3% sodium alginate soln, then adds an amount of activated carbon supported TiO
2Catalyzer stirs and is issued to adsorption equilibrium in dark attitude condition; In quartz container, pass into the air or oxygen that flow is 6ml/min again; Open the ultraviolet lamp that places the quartz container top, the power of ultraviolet lamp is 100W, and centre wavelength is 365nm, and stirring at room was reacted 2 hours;
(3) after reaction finished, filtering recovering catalyst added an amount of sodium-chlor in filtrate, fully adds excessive ethanol after the dissolving product is separated out, suction filtration, dry crude product; The crude product molecular weight cut-off of packing into after with the abundant swelling of distilled water is at least 3500 dialysis tubing, and impurity is removed in dialysis, the dialysis postlyophilization, many aldehyde sodium alginates product.
Embodiment 2, with reference to Fig. 1, and a kind of photocatalytic oxidation process for preparing multi-aldehyde sodium alginate, its step is as follows:
(1) with the gac mass concentration is 30% acidic solution immersion treatment after 120 minutes, fully washs through deionized water, the gacs of 150 ℃ of dry activated processing; Get butyl (tetra) titanate, successively to wherein adding Virahol and nitric acid, stirring at room, and the gac of activated processing added wherein, then slowly adding distilled water, the volume ratio of nitric acid, butyl (tetra) titanate, Virahol and distilled water is 1:7:30:2.0, continue to stir, make black colloidal sol; With black colloidal sol sonic oscillation, ultrasonic power is 40KHZ, and the sound intensity is 2.0W/cm
2, being ground to 2.0mm after the ultrasonic rear drying, 500 ℃ of calcinings namely get activated carbon supported TiO
2Catalyzer; Described acidic solution is sulphuric acid soln;
(2) in quartz container, add sodium alginate, and adding water, to make mass volume ratio concentration be 2.5% sodium alginate soln, then adds an amount of activated carbon supported TiO
2Catalyzer stirs and is issued to adsorption equilibrium in dark attitude condition; In quartz container, pass into the air or oxygen that flow is 20ml/min again; Open the ultraviolet lamp that places the quartz container top, the power of ultraviolet lamp is 300W, and centre wavelength is 365nm, and stirring at room was reacted 20 hours;
(3) after reaction finished, filtering recovering catalyst added an amount of sodium-chlor in filtrate, fully adds excessive ethanol after the dissolving product is separated out, suction filtration, dry crude product; The crude product molecular weight cut-off of packing into after with the abundant swelling of distilled water is at least 3500 dialysis tubing, and impurity is removed in dialysis, the dialysis postlyophilization, many aldehyde sodium alginates product.
Embodiment 3, with reference to Fig. 1, and a kind of photocatalytic oxidation process for preparing multi-aldehyde sodium alginate, its step is as follows:
(1) with the gac mass concentration is 15% acidic solution immersion treatment after 60 minutes, fully washs through deionized water, the gacs of 120 ℃ of dry activated processing; Get butyl (tetra) titanate, successively to wherein adding Virahol and nitric acid, stirring at room, and the gac of activated processing added wherein, then slowly adding distilled water, the volume ratio of nitric acid, butyl (tetra) titanate, Virahol and distilled water is 1:6.5:25:1.0, continue to stir, make black colloidal sol; With black colloidal sol sonic oscillation, ultrasonic power is 30KHZ, and the sound intensity is 1.0W/cm
2, being ground to 1.0mm after the ultrasonic rear drying, 450 ℃ of calcinings namely get activated carbon supported TiO
2Catalyzer; Described acidic solution is the HF acid solution;
(2) in quartz container, add sodium alginate, and adding water, to make mass volume ratio concentration be 1.5% sodium alginate soln, then adds an amount of activated carbon supported TiO
2Catalyzer stirs and is issued to adsorption equilibrium in dark attitude condition; In quartz container, pass into the air or oxygen that flow is 12ml/min again; Open the ultraviolet lamp that places the quartz container top, the power of ultraviolet lamp is 200W, and centre wavelength is 365nm, and stirring at room was reacted 10 hours;
(3) after reaction finished, filtering recovering catalyst added an amount of sodium-chlor in filtrate, fully adds excessive ethanol after the dissolving product is separated out, suction filtration, dry crude product; The crude product molecular weight cut-off of packing into after with the abundant swelling of distilled water is at least 3500 dialysis tubing, and impurity is removed in dialysis, the dialysis postlyophilization, many aldehyde sodium alginates product.
Embodiment 4, with reference to Fig. 1, and a kind of photocatalytic oxidation process for preparing multi-aldehyde sodium alginate experiment, its step is as follows:
(1) makes activated carbon supported TiO by oneself
2Catalyzer:
1. the activation of gac: take by weighing gac 5g and put into reactor, add 100 ml mass concentrations and be 15% salpeter solution, place water bath with thermostatic control reflow treatment 6h.Sample after the processing fully washs through deionized water, puts into baking oven in ll0 ℃ of dry 10h again, gets the activation modification gac.
2. activated carbon supported TiO
2The preparation of catalyzer: get the butyl (tetra) titanate of 6.5mL, add successively the Virahol of 24mL and the nitric acid of 1mL, behind the stirring at room 15min, 1. activated gac is added, then slowly add distilled water 1mL, continue to stir 1 hour, get black colloidal sol.With colloidal sol sonic oscillation 30min, vacuum-drying 24h under 80 ℃ condition slowly grinds Virahol wherein after the volatilization again, and 450 ℃ of calcining 4h obtain making by oneself activated carbon supported TiO in retort furnace
2Catalyzer;
(2) photocatalysis oxidation reaction: with the 2g sodium alginate with the moistening rear adding 250mL water of a small amount of ethanol, be mixed with solution after, pour in the quartz flask; In flask, add the activated carbon supported TiO2 catalyzer 0.8g of self-control, stir, catalyzer is suspended in the reaction system equably, and before the reaction beginning, be issued to adsorption equilibrium in dark attitude condition first; Pass into the air of certain flow in the flask, the flow of gas is 16ml/min again.Open the ultraviolet lamp (power 200W, centre wavelength 365nm) that places 20cm place, reactor top, stirring at room, clock reaction 5 hours.
(3) product is refining: after reaction finishes, and filtering recovering catalyst immediately.Add a small amount of sodium-chlor in the filtrate, fully add excessive ethanol after the dissolving product is separated out, suction filtration, dry head product.With the head product dialysis tubing (molecular weight cut-off 3500) of packing into after with the abundant swelling of distilled water, dialyse 24 hours to remove small molecular weight impurity.After dialysis is finished, the liquid freezing in the dialysis tubing is dry, many aldehyde sodium alginates product.The degree of oxidation of product is 78.6%.
Embodiment 5, with reference to Fig. 1, and a kind of photocatalytic oxidation process for preparing multi-aldehyde sodium alginate experiment, its step is as follows:
(1) makes activated carbon supported TiO by oneself
2Catalyzer:
1. the activation of gac: take by weighing gac 5g and put into reactor, add 100 ml mass concentrations and be 6% salpeter solution, place water bath with thermostatic control reflow treatment 3h.Sample after the processing fully washs through deionized water, puts into baking oven in l00 ℃ of dry 10h again, gets the activation modification gac.
2. activated carbon supported TiO
2The preparation of catalyzer: get the butyl (tetra) titanate of 6.5mL, add successively the Virahol of 20mL and the nitric acid of 1mL, behind the stirring at room 15min, 1. activated gac is added, then slowly add distilled water 1mL, continue to stir 1 hour, get black colloidal sol.With colloidal sol sonic oscillation 15min, again vacuum-drying 24h under 60 ℃ condition, and then grinding, 450 ℃ of calcining 4h obtain making by oneself activated carbon supported TiO in retort furnace
2Catalyzer;
(2) photocatalysis oxidation reaction: with the 2.5g sodium alginate with the moistening rear adding 250mL water of a small amount of ethanol, be mixed with solution after, pour in the quartz flask; In flask, add the activated carbon supported TiO2 catalyzer 0.2g of self-control, stir, catalyzer is suspended in the reaction system equably, and before the reaction beginning, be issued to adsorption equilibrium in dark attitude condition first; Pass into the air of certain flow in the flask, the flow of gas is 8ml/min again.Open the ultraviolet lamp (power 200W, centre wavelength 365nm) that places 20cm place, reactor top, stirring at room, clock reaction 2 hours.
(3) product is refining: after reaction finishes, and filtering recovering catalyst immediately.Add a small amount of sodium-chlor in the filtrate, fully add excessive ethanol after the dissolving product is separated out, suction filtration, dry head product.With the head product dialysis tubing (molecular weight cut-off 3500) of packing into after with the abundant swelling of distilled water, dialyse 24 hours to remove small molecular weight impurity.After dialysis is finished, the liquid freezing in the dialysis tubing is dry, many aldehyde sodium alginates product.The degree of oxidation of product is 23.5%.
Embodiment 6, with reference to Fig. 1, and a kind of photocatalytic oxidation process for preparing multi-aldehyde sodium alginate experiment, its step is as follows:
(1) makes activated carbon supported TiO by oneself
2Catalyzer:
1. the activation of gac: take by weighing gac 5g and put into reactor, add 100 ml mass concentrations and be 12% salpeter solution, place water bath with thermostatic control reflow treatment 8h.Sample after the processing fully washs through deionized water, puts into baking oven in l20 ℃ of dry 10h again, gets the activation modification gac.
2. activated carbon supported TiO
2The preparation of catalyzer: get the butyl (tetra) titanate of 6.5mL, add successively the Virahol of 28mL and the nitric acid of 1mL, behind the stirring at room 15min, 1. activated gac is added, then slowly add distilled water 1mL, continue to stir 1 hour, get black colloidal sol.With colloidal sol sonic oscillation 25min, vacuum-drying 24h under 70 ℃ condition slowly volatilizees Virahol wherein again, grinds again, and 450 ℃ of calcining 4h obtain making by oneself activated carbon supported TiO in retort furnace
2Catalyzer;
(2) photocatalysis oxidation reaction: with the 2.5g sodium alginate with the moistening rear adding 500mL water of a small amount of ethanol, be mixed with solution after, pour in the quartz flask; In flask, add the activated carbon supported TiO2 catalyzer 2g of self-control, stir, catalyzer is suspended in the reaction system equably, and before the reaction beginning, be issued to adsorption equilibrium in dark attitude condition first; Pass into the air of certain flow in the flask, the flow of gas is 13ml/min again.Open the ultraviolet lamp (power 200W, centre wavelength 365nm) that places 20cm place, reactor top, stirring at room, clock reaction 6 hours.
(3) product is refining: after reaction finishes, and filtering recovering catalyst immediately.Add a small amount of sodium-chlor in the filtrate, fully add excessive ethanol after the dissolving product is separated out, suction filtration, dry head product.With the head product dialysis tubing (molecular weight cut-off 3500) of packing into after with the abundant swelling of distilled water, dialyse 24 hours to remove small molecular weight impurity.After dialysis is finished, the liquid freezing in the dialysis tubing is dry, many aldehyde sodium alginates product.The degree of oxidation of product is 61.9%.
Claims (2)
1. the method for a photocatalytic oxidation process for preparing multi-aldehyde sodium alginate is characterized in that, its step is as follows:
(1) with the gac mass concentration is the acidic solution immersion treatment of 3-30% after 20-120 minute, fully washs through deionized water, the gac of 100-150 ℃ of dry activated processing; Get butyl (tetra) titanate, successively to wherein adding Virahol and nitric acid, stirring at room, and the gac of activated processing added wherein, then slowly add distilled water, the volume ratio of nitric acid, butyl (tetra) titanate, Virahol and distilled water is 1:6-7:20-30:0.5-2.0, continues to stir, and makes black colloidal sol; With black colloidal sol sonic oscillation, ultrasonic power is 10-40KHZ, and the sound intensity is 0.5-2.0W/cm
2, being ground to 0.2-2.0mm after the ultrasonic rear drying, 400-500 ℃ of calcining namely gets activated carbon supported TiO
2Catalyzer;
(2) in quartz container, add sodium alginate, and add water and make the sodium alginate soln that mass volume ratio concentration is 0.3-2.5%, then add an amount of activated carbon supported TiO
2Catalyzer stirs and is issued to adsorption equilibrium in dark attitude condition; In quartz container, pass into the air or oxygen that flow is 6-20ml/min again; Open the ultraviolet lamp that places the quartz container top, the power of ultraviolet lamp is 100-300W, and centre wavelength is 365nm, and stirring at room was reacted 2-20 hour;
(3) after reaction finished, filtering recovering catalyst added an amount of sodium-chlor in filtrate, fully adds excessive ethanol after the dissolving product is separated out, suction filtration, dry crude product; The crude product molecular weight cut-off of packing into after with the abundant swelling of distilled water is at least 3500 dialysis tubing, and impurity is removed in dialysis, the dialysis postlyophilization, many aldehyde sodium alginates product.
2. the method for photocatalytic oxidation process for preparing multi-aldehyde sodium alginate according to claim 1, it is characterized in that: the described acidic solution of step (1) is selected from nitric acid, sulfuric acid, HF acid or hydrochloric acid.
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| US6638917B1 (en) * | 2000-02-25 | 2003-10-28 | Scimed Life Systems, Inc. | Reducing adhesion |
| CN101301491A (en) * | 2008-07-07 | 2008-11-12 | 四川大学 | Composite bracket made of multialdehyde sodium alginate crosslinked calcium polyphosphate/chitosan and preparation and use thereof |
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| US6638917B1 (en) * | 2000-02-25 | 2003-10-28 | Scimed Life Systems, Inc. | Reducing adhesion |
| CN101301491A (en) * | 2008-07-07 | 2008-11-12 | 四川大学 | Composite bracket made of multialdehyde sodium alginate crosslinked calcium polyphosphate/chitosan and preparation and use thereof |
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| Title |
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| 多醛基海藻酸钠交联剂的制备及性能;王琴梅等;《应用化学》;20100210;第27卷(第2期);第155-158页 * |
| 王琴梅等.多醛基海藻酸钠交联剂的制备及性能.《应用化学》.2010,第27卷(第2期),第155-158页. |
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