CN107057085A - A kind of preparation method of calcium alginate sub-micron gel particles - Google Patents
A kind of preparation method of calcium alginate sub-micron gel particles Download PDFInfo
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- CN107057085A CN107057085A CN201710220222.8A CN201710220222A CN107057085A CN 107057085 A CN107057085 A CN 107057085A CN 201710220222 A CN201710220222 A CN 201710220222A CN 107057085 A CN107057085 A CN 107057085A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
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Abstract
A kind of preparation method of calcium alginate sub-micron gel particles, sodium alginate prepares the technical field of calcium alginate sub-micron gel particles.The present invention is used as calcium source by the use of calcium phosphate, it is not necessary to add oil phase material, by stirring, freshly prepd calcium phosphate granules is dispersed in sodium alginate soln, slowly discharges calcium ion, with sodium alginate cross-linking, obtain calcium alginate sub-micron gel particles.Calcium phosphate in the present invention is that the method for mixing calcium chloride solution with sodium radio-phosphate,P-32 solution is made, and newly-generated calcium phosphate crystal particle avoids Ostwald ripening, makes it have higher activity, and reduce cost.
Description
Technical field
Sodium alginate of the present invention prepares the technical field of calcium alginate sub-micron gel particles.
Background technology
Sodium alginate（Na Alg）Be a kind of connected by beta-D-mannuronic acid (M) and α-L- guluronic acids (G) and
Into natural polymer, from marine alga extract and obtain, nontoxic, non-immunogenicity, can with good biocompatibility and biology
Degradability.Sodium alginate energy and Ca in the aqueous solution2+、Ba2+、Sr2+Hydrogel is cross-linked to form Deng bivalent cation.
There are some reports that gel particles or gel micro-ball are formed on sodium alginate and calcium ion crosslinking at present, generally
Using certain density calcium chloride solution is directly added dropwise into sodium alginate soln, particle diameter distribution is cross-linked to form in millimetre-sized sea
Calcium alginate gel particle, the calcium alginate gel particle of micro/nano level can not be prepared using the method.Paques et al. with 1% sea
Solution of sodium alginate is aqueous phase, and the fatty acid triglycercide of medium chain is oil phase, and polyglycerol polyricinoleate is stabilizer, and oil is made
Bag aqueous emulsion, then the oil suspension of calcium chloride nano-particle is added in emulsion, calcium alginate sub-micron gel particles are made,
But the method adds organic oil phase in preparation process, post processing is difficult, and product is difficult purification.
The content of the invention
The present invention seeks to propose a kind of preparation for the calcium alginate sub-micron gel particles that can overcome prior art defect
Method.
The present invention comprises the following steps：
1）By calcium chloride water and sodium phosphate aqueous solution hybrid reaction, calcium phosphate crystal particle suspension liquid is made；
2）Under stirring condition, calcium phosphate crystal particle suspension liquid is slowly added in sodium alginate aqueous solution, calcium alginate is made
Sub-micron gel particles solution；
3）The pH value of calcium alginate sub-micron gel particles solution is adjusted to 5.5, faintly acid gel particles solution is obtained；
4）Dialysis is carried out to faintly acid gel particles solution and removes foreign ion, then concentrated, freeze-drying, calcium alginate is produced
Sub-micron gel particles.
The present invention is used as calcium source by the use of calcium phosphate, it is not necessary to add oil phase material, by stirring, makes freshly prepd calcium phosphate
Even particulate dispersion slowly discharges calcium ion in sodium alginate soln, with sodium alginate cross-linking, obtains calcium alginate sub-micron
Gel particles.
Calcium phosphate in the present invention is that the method for mixing calcium chloride solution with sodium radio-phosphate,P-32 solution is made, newly-generated phosphoric acid
Calcium crystal grain avoids Ostwald ripening, makes it have higher activity, and reduce cost.
The significant difference point of the present invention and prior art are as follows：
1st, calcium source is different：
Prior art discharges calcium ion with calcium chloride soluble in water or slightly solubility calcium carbonate through acidolysis mostly, and the present invention is logical
Calcium phosphate crystal particle suspension liquid is made in the superchlorination calcium aqueous solution and sodium phosphate aqueous solution hybrid reaction, then by calcium phosphate crystal
Particle discharges calcium ion, and its rate of release and concentration are more beneficial for the generation of calcium alginate sub-micron gel particles.
2nd, the difference of preparation method：
Calcium chloride is added directly into Na-alginate solution by prior art, it is difficult to prepare the calcium alginate gel of submicron order
Particle, prior art prepares the calcium alginate gel particle of submicron order using emulsion method, but the method needs to add oil phase material
And emulsifying agent, this purifying to calcium alginate gel particle makes troubles.
And the present invention is directly mixed using calcium phosphate crystal particle suspension liquid with sodium alginate aqueous solution, it is sufficiently stirred for down,
So that calcium ion slowly discharges, with sodium alginate cross-linking, calcium alginate sub-micron gel particles are obtained.Operating method letter of the present invention
It is single, it is to avoid expensive raw material and complicated process, without organic oil phase material, environmental protection in preparation.
Further, step 1 of the present invention）In, in the calcium chloride water in calcium chloride and sodium phosphate aqueous solution
The mixing mol ratio of sodium phosphate is 3: 2.1.The present invention using being reacted by the way of phosphate radical excess, with reduce in solution calcium from
The concentration of son, is more beneficial for the generation of calcium alginate sub-micron gel particles.
The concentration of the sodium alginate aqueous solution is 0.1~1.0wt%.When the concentration of sodium alginate aqueous solution is less than
0.1wt% or during higher than 1.0wt%, is difficult to prepare sub-micron gel particles.Also, the present invention can be by changing sodium alginate
Concentration adjust the particle diameter of submicron particle, make gel particles particle diameter distribution between 100~1000nm.
The pH value of calcium alginate sub-micron gel particles solution is adjusted to 5.5 with 0.5 mol/L aqueous acetic acid, with molten
The calcium phosphate crystal particle remained in enzymatic hydrolysis system.
Brief description of the drawings
The grain size distribution for the calcium alginate gel particle that Fig. 1 is prepared for the present invention.
Embodiment
Below in conjunction with example, the present invention is described in more detail, but the invention is not limited in this.
Embodiment 1：
By calcium chloride water（0.3mol/L）10mL and sodium phosphate aqueous solution（0.21 mol/L）10mL is mixed, and is stirred at room temperature
Reaction 10min is mixed, calcium phosphate crystal particle suspension liquid is obtained.
The sodium alginate for weighing 1g is dissolved in the sodium alginate soln that 1.0wt % are configured in 100mL deionized water.
Obtained calcium phosphate crystal particle suspension liquid is added drop-wise in sodium alginate soln, 4h is persistently stirred under normal temperature, so
Acetic acid to the pH value of solution that 0.5 mol/L is added dropwise in backward above-mentioned system is 5.5, to dissolve the calcium phosphate crystal of residual
Grain；Finally, obtained faintly acid gel solution is transferred in bag filter and dialysed with deionized water, changed water every 4h and survey
Its electrical conductivity is measured, until the front and rear conductivity values measured twice are consistent, bag filter inner gel suspension is taken out, it is concentrated, cold
Freeze drying to obtain calcium alginate sub-micron gel particles.
Embodiment 2：
By calcium chloride water（0.3mol/L）10mL and sodium phosphate aqueous solution（0.21 mol/L）10mL is mixed, and is stirred at room temperature
Reaction 10min is mixed, calcium phosphate crystal particle suspension liquid is obtained.
The sodium alginate for weighing 0.6g is dissolved in the sodium alginate soln that 0.6wt % are configured in 100mL deionized water.
Obtained calcium phosphate crystal particle suspension liquid is added drop-wise in sodium alginate soln, 4h is persistently stirred under normal temperature；So
The pH value that 0.5 mol/L acetic acid to solution are added dropwise in backward above-mentioned system is 5.5, to dissolve the calcium phosphate crystal of residual
Grain；Finally, obtained faintly acid gel solution is transferred in bag filter and dialysed with deionized water, changed water every 4h and survey
Its electrical conductivity is measured, until the front and rear conductivity values measured twice are consistent, bag filter inner gel suspension is taken out, it is concentrated, cold
Freeze drying to obtain calcium alginate sub-micron gel particles.
Embodiment 3
By calcium chloride water（0.3mol/L）10mL and sodium phosphate aqueous solution（0.21 mol/L）10mL is mixed, and is stirred at room temperature
Reaction 10min is mixed, calcium phosphate crystal particle suspension liquid is obtained.
The sodium alginate for weighing 0.6g is dissolved in the sodium alginate soln that 0.2wt % are configured in 300mL deionized water.
Obtained calcium phosphate crystal particle suspension liquid is added drop-wise in sodium alginate soln, 4h is persistently stirred under normal temperature；So
The pH value that 0.5 mol/L acetic acid to solution are added dropwise in backward above-mentioned system is 5.5, to dissolve the calcium phosphate crystal of residual
Grain；Finally, obtained faintly acid gel solution is transferred in bag filter and dialysed with deionized water, changed water every 4h and survey
Its electrical conductivity is measured, until the front and rear conductivity values measured twice are consistent, bag filter inner gel suspension is taken out, it is concentrated, cold
Freeze drying to obtain calcium alginate sub-micron gel particles.
Embodiment 4
Take the calcium alginate gel particle suspension in 1mL embodiments 1, embodiment 2 and embodiment 3 to be injected separately into sample cell, adopt
The particle diameter distribution of gel particles is determined with laser particle analyzer, as a result as shown in figure 1, show can be by changing the concentration of sodium alginate
To adjust the particle diameter of submicron particle, make gel particles particle diameter distribution between 100~1000nm.
Claims (4)
1. a kind of preparation method of calcium alginate sub-micron gel particles, it is characterised in that comprise the following steps：
1）By calcium chloride water and sodium phosphate aqueous solution hybrid reaction, calcium phosphate crystal particle suspension liquid is made；
2）Under stirring condition, calcium phosphate crystal particle suspension liquid is slowly added in sodium alginate aqueous solution, calcium alginate is made
Sub-micron gel particles solution；
3）The pH value of calcium alginate sub-micron gel particles solution is adjusted to 5.5, faintly acid gel particles solution is obtained；
4）Dialysis is carried out to faintly acid gel particles solution and removes foreign ion, then concentrated, freeze-drying, calcium alginate is produced
Sub-micron gel particles.
2. the preparation method of calcium alginate sub-micron gel particles according to claim 1, it is characterised in that：The step 1）
In, the mixing mol ratio of sodium phosphate is 3: 2.1 in calcium chloride and sodium phosphate aqueous solution in the calcium chloride water.
3. the preparation method of calcium alginate sub-micron gel particles according to claim 1, it is characterised in that：The alginic acid
The concentration of sodium water solution is 0.1~1.0wt%.
4. the preparation method of calcium alginate sub-micron gel particles according to claim 1, it is characterised in that：With 0.5 mol/
L aqueous acetic acid is adjusted to the pH value of calcium alginate sub-micron gel particles solution.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109464989A (en) * | 2018-11-23 | 2019-03-15 | 上海海洋大学 | A kind of preparation method of sodium alginate gel ball |
| CN109836594A (en) * | 2017-11-24 | 2019-06-04 | 杭州德柯医疗科技有限公司 | A kind of preparation method and applications of hydrogel, hydrogel |
| CN111235921A (en) * | 2020-01-21 | 2020-06-05 | 湖北工业大学 | Sodium alginate solution capable of effectively improving viscosity and thickening property and preparation method and application thereof |
| CN112515981A (en) * | 2020-11-24 | 2021-03-19 | 湖南御家化妆品制造有限公司 | Light absorption core-shell structure particle and preparation method and application thereof |
| CN115286828A (en) * | 2022-10-08 | 2022-11-04 | 潍坊潍森纤维新材料有限公司 | Preparation method of cellulose membrane for filling enteric-coated fabric |
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| CN1628861A (en) * | 2003-12-18 | 2005-06-22 | 中国科学院大连化学物理研究所 | Chitosan-calcium alginate gel microsphere soft tissue reinforced material and its preparation method and application |
| CN101081911A (en) * | 2007-06-15 | 2007-12-05 | 天津大学 | Big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon and method for preparing the same |
| CN104829779A (en) * | 2015-05-07 | 2015-08-12 | 宁波大学 | Light-response polymer microgel particle and preparation method thereof |
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| CN1628861A (en) * | 2003-12-18 | 2005-06-22 | 中国科学院大连化学物理研究所 | Chitosan-calcium alginate gel microsphere soft tissue reinforced material and its preparation method and application |
| CN101081911A (en) * | 2007-06-15 | 2007-12-05 | 天津大学 | Big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon and method for preparing the same |
| CN104829779A (en) * | 2015-05-07 | 2015-08-12 | 宁波大学 | Light-response polymer microgel particle and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836594A (en) * | 2017-11-24 | 2019-06-04 | 杭州德柯医疗科技有限公司 | A kind of preparation method and applications of hydrogel, hydrogel |
| CN114015073A (en) * | 2017-11-24 | 2022-02-08 | 杭州德柯医疗科技有限公司 | Hydrogel for injecting organisms and application thereof |
| CN114015073B (en) * | 2017-11-24 | 2024-03-22 | 杭州德柯医疗科技有限公司 | Hydrogel for injecting organisms and application thereof |
| CN109464989A (en) * | 2018-11-23 | 2019-03-15 | 上海海洋大学 | A kind of preparation method of sodium alginate gel ball |
| CN111235921A (en) * | 2020-01-21 | 2020-06-05 | 湖北工业大学 | Sodium alginate solution capable of effectively improving viscosity and thickening property and preparation method and application thereof |
| CN112515981A (en) * | 2020-11-24 | 2021-03-19 | 湖南御家化妆品制造有限公司 | Light absorption core-shell structure particle and preparation method and application thereof |
| CN112515981B (en) * | 2020-11-24 | 2021-07-30 | 湖南御家化妆品制造有限公司 | Light absorption core-shell structure particle and preparation method and application thereof |
| CN115286828A (en) * | 2022-10-08 | 2022-11-04 | 潍坊潍森纤维新材料有限公司 | Preparation method of cellulose membrane for filling enteric-coated fabric |
| CN115286828B (en) * | 2022-10-08 | 2023-01-17 | 潍坊潍森纤维新材料有限公司 | Preparation method of cellulose membrane for filling enteric-coated fabric |
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