CN109821470B - Preparation method of concentration switch type composite emulsifier - Google Patents
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Abstract
The invention relates to a preparation method of a concentration switch type composite emulsifier, which comprises the steps of firstly mixing a hydroxyapatite solution and a norleucine solution which are composite emulsifiers, adjusting the pH value of a water phase, then adding an oil phase with a certain proportion, and emulsifying the obtained solution in a high-speed stirrer to obtain a stable Pickering emulsion. After a certain amount of deionized water is added into the stable emulsion, rapid and complete emulsion breaking can be realized. The raw materials of the invention are nontoxic and green, the biological safety is excellent, the sources are rich and easy to obtain, the cost is low, the synthesis process is simple and easy to implement, the product quality is stable, the process repeatability is good, especially the Pickering emulsion has the on-off property to the concentration of the emulsifier, namely the stable emulsion and the complete emulsion breaking of the emulsion can be realized by controlling the amount of the added deionized water.
Description
Technical Field
The invention belongs to the field of colloid and interface chemistry, and particularly relates to a preparation method of a concentration switch type composite emulsifier.
Background
The Pickering emulsion is an indispensable method for preparing stable emulsion due to the unique particle membrane stabilizing mechanism and continuous phase rheological property, and has important application value in the fields of food, cosmetics, medicine and the like. However, in the course of actual production and living, people often need to regulate and control the stability of the emulsion according to their own needs, for example, the stability of the emulsion needs to be destroyed under specific time or condition, so the environmental response type emulsion has attracted attention in recent years.
For example, CN108440770A discloses a switching type Pickering emulsion with dual pH and temperature control functions and a switching type Pickering emulsion thereofThe preparation method is an oil-in-water Pickering emulsion consisting of an emulsifier, an oil phase and a water phase, wherein the emulsifier comprises nano silicon dioxide particles and a block polyether copolymer containing an oxyethylene chain (EO chain) and an oxypropylene chain (PO chain). CN106582431A discloses a carbon dioxide switch type composite emulsifier at room temperature, which is composed of commercial nano silicon dioxide particles without any modification and CO2/N2 switch type surfactant, the emulsion stabilized by the emulsifier belongs to Pickering emulsion, N2 or air is introduced into the emulsion to cause the inactivation of the emulsifier and the emulsion breaking, CO is introduced into the system2The emulsifier can be reactivated and a stable Pickering emulsion can be recovered. CN106943949B discloses a method for preparing a temperature-sensitive Pickering emulsifier, which comprises the steps of respectively dissolving poly (N-isopropylacrylamide) and cellulose acetate in acetone; performing electric spraying to prepare microspheres by taking an acetone solution of poly (N-isopropylacrylamide) as a shell layer solution of coaxial electric spraying and taking an acetone solution of cellulose acetate as a core layer solution of coaxial electric spraying; curing the microspheres through ultraviolet irradiation of a needle point outlet, and collecting the microspheres; and (3) carrying out freeze-drying treatment on the aqueous solution containing the microspheres to obtain the temperature-sensitive Pickering emulsifier.
Although some methods are developed to realize the preparation of the switch type emulsion, the methods still have the defects that a surfactant with poor biocompatibility is required for compounding, harsh equipment requirements are required, the cost of the added trigger is higher or the cost of the realized trigger conditions is higher.
Disclosure of Invention
The invention aims to provide a preparation method of a concentration switch type composite emulsifier which has the advantages of abundant and easily obtained raw material sources, low cost, simple synthesis process, good process repeatability, easy implementation, excellent biological safety, stable product quality, higher emulsion stability and sensitivity to the concentration of the emulsifier.
The invention aims to realize a preparation method of a concentration switch type composite emulsifier, which comprises the following specific steps:
1) dissolving 0.01mol of calcium nitrate in 10g of deionized water to form a solution A;
2) dissolving 0.01mol of sodium citrate in 10g of deionized water to form a solution B;
3) dissolving 0.006mol of sodium phosphate in 10g of deionized water to form a solution C;
4) dropwise adding the solution B obtained in the step 2) into the solution A obtained in the step 1) at room temperature, and fully stirring for 5min to form a mixed solution I;
5) dropwise adding the solution C obtained in the step 3) into the mixed solution I obtained in the step 4) at room temperature, continuously stirring in the dropwise adding process, and continuously stirring for 10min after the dropwise adding is finished to form a mixed solution II;
6) transferring the mixed solution II obtained in the step 5) to a closed hydrothermal reactor, reacting for 6 hours at 180 ℃, and naturally cooling to room temperature to obtain a reaction solution;
7) centrifuging the reaction solution obtained in the step 6) by using a high-speed centrifuge to obtain a precipitate, alternately centrifuging and washing the precipitate for three times by using deionized water and absolute ethyl alcohol to remove excessive electrolyte in the system, then re-dispersing the precipitate in the deionized water, and adjusting the pH to 9.5 by using 0.1M sodium hydroxide solution to obtain a solution D, namely hydroxyapatite dispersion liquid;
8) dissolving norleucine in deionized water to form a solution E;
9) compounding the solution D obtained in the step 7) and the solution E obtained in the step 8) to obtain 10mL of water phase, and fully stirring for 10min, wherein the mass fraction of hydroxyapatite is 0.5-5%, and the concentration of norleucine is 5-50 mmol/L; then, adjusting the pH to 4.0-10.0 by using 0.1M sodium hydroxide solution or 0.1M hydrochloric acid solution, adding 25-30mL of oil phase, and fully stirring for 10min to form a mixed solution III;
the oil phase is paraffin oil or biodiesel;
10) emulsifying the mixed solution III obtained in the step 9) for 2min in a high-speed stirrer to form stable emulsion;
11) adding 15-120mL of deionized water into the stable emulsion obtained in the step 10), and quickly demulsifying the originally stable emulsion to obtain the concentration switch type composite emulsifier.
The invention has the advantages that: the used medicine has good biocompatibility and bioactivity, meets the requirement of green chemistry, and has low cost. In addition, the emulsion prepared from the hydroxyapatite is sensitive to the concentration of an emulsifier, and demulsification can be realized by adding a certain amount of deionized water, so that the process repeatability is good.
The invention provides a preparation method of a switch type composite emulsifier based on compounding of hydroxyapatite nanoparticles and leucine. The invention does not relate to any toxic additive, and can add water in a simple original emulsion system to realize rapid and complete emulsion breaking. The invention can be widely applied to the fields of food, cosmetics, medicines and the like.
Drawings
Fig. 1 is an X-ray diffraction pattern of the water-soluble hydroxyapatite nanocrystal prepared in example 1.
Fig. 2 is a transmission electron micrograph of the water-soluble hydroxyapatite nanocrystal prepared in example 1.
FIG. 3 is a photograph of the emulsion prepared in example 1 (left to stand for 24 hours).
Detailed Description
Firstly, mixing a hydroxyapatite solution as a composite emulsifier with a norleucine solution, adjusting the pH value of a water phase, then adding an oil phase in a certain proportion, and emulsifying the obtained solution in a high-speed stirrer to obtain a stable Pickering emulsion. After a certain amount of deionized water is added into the stable emulsion, rapid and complete emulsion breaking can be realized. The stability of the emulsion is controlled by adjusting the concentration of the emulsifier.
The present invention is described in detail below with reference to specific examples.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1:
1) dissolving 0.01mol of calcium nitrate in 10g of deionized water to form a solution A;
2) dissolving 0.01mol of sodium citrate in 10g of deionized water to form a solution B;
3) dissolving 0.006mol of sodium phosphate in 10g of deionized water to form a solution C;
4) dropwise adding the solution B obtained in the step 2) into the solution A obtained in the step 1) at room temperature, and fully stirring for 5min to form a mixed solution I;
5) dropwise adding the solution C obtained in the step 3) into the mixed solution I obtained in the step 4) at room temperature, continuously stirring in the dropwise adding process, and continuously stirring for 10min after the dropwise adding is finished to form a mixed solution II;
6) transferring the mixed solution II obtained in the step 5) to a closed hydrothermal reactor, reacting for 6 hours at 180 ℃, and naturally cooling to room temperature to obtain a reaction solution;
7) centrifuging the reaction solution obtained in the step 6) by using a high-speed centrifuge to obtain a precipitate, alternately centrifuging and washing the precipitate for three times by using deionized water and absolute ethyl alcohol to remove excessive electrolyte in the system, then re-dispersing the precipitate in the deionized water, and adjusting the pH to 9.5 by using 0.1M sodium hydroxide solution to obtain a solution D, namely a hydroxyapatite solution.
8) Dissolving norleucine in deionized water to form a solution E;
9) compounding the hydroxyapatite solution obtained in the step 7) with the solution E obtained in the step 8) to obtain 10mL of water phase, fully stirring for 10min, wherein the mass fraction of the hydroxyapatite is 1%, the concentration of the norleucine is 5mmol/L, adjusting the pH to 4.5 by using a 0.1M hydrochloric acid solution, adding 5mL of paraffin oil, and fully stirring for 10min to form a mixed solution III;
10) emulsifying the mixed solution III obtained in the step 9) for 2min in a high-speed stirrer to form stable emulsion;
11) adding 15mL of deionized water into the stable emulsion obtained in the step 10), and quickly demulsifying the originally stable emulsion to obtain the concentration switch type composite emulsifier.
X-ray diffraction pattern of water-soluble hydroxyapatite nanocrystal in concentration switch type composite emulsifier prepared in example is shown in figure 1, which shows that the product is pure hydroxyapatite and has good crystallinity. The transmission electron micrograph of the water-soluble hydroxyapatite nanocrystal is shown in figure 2, which shows that the product is in a nanometer rod-shaped shape and has uniform particle size.
the form of the compound emulsifier with switch concentration prepared in example after standing for 24 hours is shown in FIG. 3, which shows that the compound emulsifier with switch concentration prepared is very stable.
Example 2: in the same manner as in example 1, except that,
9) compounding the hydroxyapatite solution obtained in the step 7) with the solution E obtained in the step 8) to obtain 10mL of water phase, fully stirring for 10min, wherein the mass fraction of the hydroxyapatite is 0.5%, the concentration of the norleucine is 10mmol/L, adjusting the pH to 4.0 by using a 0.1M hydrochloric acid solution, adding 5mL of paraffin oil, and fully stirring for 10min to form a mixed solution III;
11) adding 40mL of deionized water into the stable emulsion obtained in the step 10), and quickly demulsifying the originally stable emulsion to obtain the concentration switch type composite emulsifier.
Example 3: in the same manner as in example 1, except that,
9) compounding the hydroxyapatite solution obtained in the step 7) and the solution E obtained in the step 8) to obtain 10mL of water phase, fully stirring for 10min, wherein the mass fraction of the hydroxyapatite is 1.5%, the concentration of the norleucine is 15mmol/L, adjusting the pH to 5.0 by using a 0.1M hydrochloric acid solution, adding 5mL of biodiesel, and fully stirring for 10min to form a mixed solution III;
11) adding 50mL of deionized water into the stable emulsion obtained in the step 10), and quickly demulsifying the originally stable emulsion to obtain the concentration switch type composite emulsifier.
Example 4: in the same manner as in example 1, except that,
9) compounding the hydroxyapatite solution obtained in the step 7) with the solution E obtained in the step 8) to obtain 10mL of water phase, fully stirring for 10min, wherein the mass fraction of the hydroxyapatite is 2%, the concentration of the norleucine is 20mmol/L, adjusting the pH to 5.5 by using a 0.1M hydrochloric acid solution, adding 5mL of biodiesel, and fully stirring for 10min to form a mixed solution III;
11) adding 45mL of deionized water into the stable emulsion obtained in the step 10), and quickly demulsifying the originally stable emulsion to obtain the concentration switch type composite emulsifier.
Example 5: in the same manner as in example 1, except that,
9) compounding the hydroxyapatite solution obtained in the step 7) with the solution E obtained in the step 8) to obtain 10mL of water phase, fully stirring for 10min, wherein the mass fraction of the hydroxyapatite is 2.5%, the concentration of the norleucine is 25mmol/L, then adjusting the pH to 10.0 by using 0.1M sodium hydroxide solution, adding 5mL of paraffin oil, and fully stirring for 10min to form a mixed solution III;
11) adding 90mL of deionized water into the stable emulsion obtained in the step 10), and quickly demulsifying the originally stable emulsion to obtain the concentration switch type composite emulsifier.
Example 6: in the same manner as in example 1, except that,
9) compounding the hydroxyapatite solution obtained in the step 7) with the solution E obtained in the step 8) to obtain 10mL of water phase, fully stirring for 10min, wherein the mass fraction of the hydroxyapatite is 3%, the concentration of the norleucine is 30mmol/L, adjusting the pH to 9.0 by using 0.1M sodium hydroxide solution, adding 5mL of paraffin oil, and fully stirring for 10min to form a mixed solution III;
11) and (3) adding 100mL of deionized water into the stable emulsion obtained in the step 10), and quickly demulsifying the originally stable emulsion to obtain the concentration switch type composite emulsifier.
Example 7: in the same manner as in example 1, except that,
9) compounding the hydroxyapatite solution obtained in the step 7) with the solution E obtained in the step 8) to obtain 10mL of water phase, fully stirring for 10min, wherein the mass fraction of the hydroxyapatite is 4%, the concentration of the norleucine is 20mmol/L, adjusting the pH to 7.0 by using 0.1M sodium hydroxide solution, adding 5mL of biodiesel, and fully stirring for 10min to form a mixed solution III;
11) adding 95mL of deionized water into the stable emulsion obtained in the step 10), and quickly demulsifying the originally stable emulsion to obtain the concentration switch type composite emulsifier.
Example 8: in the same manner as in example 1, except that,
9) compounding the hydroxyapatite solution obtained in the step 7) with the solution E obtained in the step 8) to obtain 10mL of water phase, fully stirring for 10min, wherein the mass fraction of the hydroxyapatite is 5%, the concentration of the norleucine is 50mmol/L, adjusting the pH to 6.0 by using a 0.1M hydrochloric acid solution, adding 12mL of biodiesel, and fully stirring for 10min to form a mixed solution III;
11) adding 120mL of deionized water into the stable emulsion obtained in the step 10), and quickly demulsifying the originally stable emulsion to obtain the concentration switch type composite emulsifier.
Comparative example 1:
1) dissolving 0.01mol of calcium nitrate in 10g of deionized water to form a solution A;
2) dissolving 0.01mol of sodium citrate in 10g of deionized water to form a solution B;
3) dissolving 0.006mol of sodium phosphate in 10g of deionized water to form a solution C;
4) dropwise adding the solution B obtained in the step 2) into the solution A obtained in the step 1) at room temperature, and fully stirring for 5min to form a mixed solution I;
5) dropwise adding the solution C obtained in the step 3) into the mixed solution I obtained in the step 4) at room temperature, continuously stirring in the dropwise adding process, and continuously stirring for 10min after the dropwise adding is finished to form a mixed solution II;
6) transferring the mixed solution II obtained in the step 5) to a closed hydrothermal reactor, reacting for 6 hours at 180 ℃, and naturally cooling to room temperature to obtain a reaction solution;
7) centrifuging the reaction solution obtained in the step 6) by using a high-speed centrifuge to obtain a precipitate, alternately centrifuging and washing the precipitate for three times by using deionized water and absolute ethyl alcohol to remove excessive electrolyte in the system, then re-dispersing the precipitate in the deionized water, and adjusting the pH to 9.5 by using 0.1M sodium hydroxide solution to obtain a solution D;
9) compounding the hydroxyapatite solution obtained in the step 7) with the solution E obtained in the step 8) to obtain 10mL of water phase, fully stirring for 10min, wherein the mass fraction of the hydroxyapatite is 1%, the concentration of the norleucine is 0mmol/L, adjusting the pH to 7.5 by using 0.1M sodium hydroxide solution, adding 15mL of biodiesel, and fully stirring for 10min to form a mixed solution III;
10) emulsifying the mixed solution III obtained in the step 9) for 2min in a high-speed stirrer, and forming stable emulsion without switching on or off. Mainly because no norleucine with proper amount is added in the step 8), carboxyl on citrate molecules adsorbed on the surfaces of the particles cannot be combined with amino on the norleucine, and lipophilicity is improved.
Claims (2)
1. A preparation method of a concentration switch type composite emulsifier is characterized by comprising the following steps: the method comprises the following specific steps:
1) dissolving 0.01mol of calcium nitrate in 10g of deionized water to form a solution A;
2) dissolving 0.01mol of sodium citrate in 10g of deionized water to form a solution B;
3) dissolving 0.006mol of sodium phosphate in 10g of deionized water to form a solution C;
4) dropwise adding the solution B obtained in the step 2) into the solution A obtained in the step 1) at room temperature, and fully stirring for 5min to form a mixed solution I;
5) dropwise adding the solution C obtained in the step 3) into the mixed solution I obtained in the step 4) at room temperature, continuously stirring in the dropwise adding process, and continuously stirring for 10min after the dropwise adding is finished to form a mixed solution II;
6) transferring the mixed solution II obtained in the step 5) to a closed hydrothermal reactor, reacting for 6 hours at 180 ℃, and naturally cooling to room temperature to obtain a reaction solution;
7) centrifuging the reaction solution obtained in the step 6) by using a high-speed centrifuge to obtain a precipitate, alternately centrifuging and washing the precipitate for three times by using deionized water and absolute ethyl alcohol to remove excessive electrolyte in the system, then re-dispersing the precipitate in the deionized water, and adjusting the pH to 9.5 by using 0.1M sodium hydroxide solution to obtain a solution D, namely hydroxyapatite dispersion liquid;
8) dissolving norleucine in deionized water to form a solution E;
9) compounding the solution D obtained in the step 7) and the solution E obtained in the step 8) to obtain 10mL of water phase, and fully stirring for 10min, wherein the mass fraction of hydroxyapatite is 0.5-5%, and the concentration of norleucine is 5-50 mmol/L; then, adjusting the pH to 4.0-10.0 by using 0.1M sodium hydroxide solution or 0.1M hydrochloric acid solution, adding 25-30mL of oil phase, and fully stirring for 10min to form a mixed solution III;
the oil phase is paraffin oil or biodiesel;
10) emulsifying the mixed solution III obtained in the step 9) for 2min in a high-speed stirrer to form stable emulsion;
11) adding 15-120mL of deionized water into the stable emulsion obtained in the step 10), and quickly demulsifying the originally stable emulsion to obtain the concentration switch type composite emulsifier.
2. The method for preparing the concentration switch type composite emulsifier according to claim 1, wherein the method comprises the following steps: the stability of the emulsion is controlled by adjusting the concentration of the emulsifier.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105431133A (en) * | 2013-06-18 | 2016-03-23 | 路博润高级材料公司 | Colloidally stable dispersions based on modified galactomannans |
| CN105935455A (en) * | 2016-04-18 | 2016-09-14 | 北京林业大学 | Cellulose/hydroxyapatite nano composite material and preparation method thereof |
| CN105944581A (en) * | 2016-05-16 | 2016-09-21 | 辽宁大学 | Anion responsive Pickering emulsion as well as preparation method and application thereof |
| CN107555406A (en) * | 2016-07-01 | 2018-01-09 | 北京化工大学 | A kind of nanometer hydroxyapatite dispersion and its preparation technology |
| CN107758638A (en) * | 2017-11-14 | 2018-03-06 | 湖北工业大学 | A kind of nanocrystalline preparation method of water soluble hydroxy apatite fluorescent |
| CN108383201A (en) * | 2018-03-14 | 2018-08-10 | 江南大学 | A kind of fast emulsion breaking of oil-in-water emulsion and again antihunt means |
| CN108699192A (en) * | 2015-12-23 | 2018-10-23 | 路博润先进材料公司 | The alkali swellability emulsion polymer of hydrophobically modified |
-
2018
- 2018-12-21 CN CN201811573095.0A patent/CN109821470B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105431133A (en) * | 2013-06-18 | 2016-03-23 | 路博润高级材料公司 | Colloidally stable dispersions based on modified galactomannans |
| CN108699192A (en) * | 2015-12-23 | 2018-10-23 | 路博润先进材料公司 | The alkali swellability emulsion polymer of hydrophobically modified |
| CN105935455A (en) * | 2016-04-18 | 2016-09-14 | 北京林业大学 | Cellulose/hydroxyapatite nano composite material and preparation method thereof |
| CN105944581A (en) * | 2016-05-16 | 2016-09-21 | 辽宁大学 | Anion responsive Pickering emulsion as well as preparation method and application thereof |
| CN107555406A (en) * | 2016-07-01 | 2018-01-09 | 北京化工大学 | A kind of nanometer hydroxyapatite dispersion and its preparation technology |
| CN107758638A (en) * | 2017-11-14 | 2018-03-06 | 湖北工业大学 | A kind of nanocrystalline preparation method of water soluble hydroxy apatite fluorescent |
| CN108383201A (en) * | 2018-03-14 | 2018-08-10 | 江南大学 | A kind of fast emulsion breaking of oil-in-water emulsion and again antihunt means |
Non-Patent Citations (2)
| Title |
|---|
| W/O/W型多重乳状液的稳定性及其在食品加工中的研究应用进展;刘妍等;《农产品加工·学刊》;20130228(第307期);第35-38页 * |
| 白油W/O/W型多重乳状液的稳定性研究;刘华杰等;《日用化学工业》;20070430;第37卷(第2期);第88-91页 * |
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