CN115304782B - High internal phase Pickering emulsion stabilizer for 3D printing and preparation method and application thereof - Google Patents
High internal phase Pickering emulsion stabilizer for 3D printing and preparation method and application thereof Download PDFInfo
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims description 16
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- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 29
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- -1 alkenyl succinic anhydride Chemical compound 0.000 claims abstract description 11
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- KAYAKFYASWYOEB-UHFFFAOYSA-N 3-octadec-1-enyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCCC=CC1CC(=O)OC1=O KAYAKFYASWYOEB-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
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- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 3
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- GQNPFQQRWMSYAC-UHFFFAOYSA-N 3-icos-19-enyloxolane-2,5-dione Chemical compound C=CCCCCCCCCCCCCCCCCCCC1CC(=O)OC1=O GQNPFQQRWMSYAC-UHFFFAOYSA-N 0.000 description 2
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- 229920001661 Chitosan Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- 150000008065 acid anhydrides Chemical class 0.000 description 1
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- 125000001165 hydrophobic group Chemical group 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G83/008—Supramolecular polymers
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/30—Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
- A23P10/00—Shaping or working of foodstuffs characterised by the products
- A23P10/30—Encapsulation of particles, e.g. foodstuff additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
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- 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
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Abstract
The invention belongs to the technical field of material chemistry, and discloses a high internal phase Pickering emulsion stabilizer, which comprises the following steps: (1) Dispersing cyclodextrin in deionized water, adjusting the pH value of the aqueous solution, then dropwise adding alkenyl succinic anhydride until the pH value is constant, and freeze-drying the obtained aqueous solution, washing and drying to obtain ASA-CD; (2) Dissolving ASA-CD and KOH in water, adding methanol, heating in water bath, adding hexadecyl trimethyl ammonium bromide, continuously heating, carrying out solid-liquid separation on a reaction system, washing solids, and drying to obtain the ASA-CD-MOFs. The ASA-CD-MOFs can be used for preparing high internal phase Pickering emulsion of edible oil and used for 3D printing. The prepared emulsion has excellent coalescence resistance and freezing resistance, can stabilize the precipitation of an anhydrous phase and an oil phase for months, and does not need to add any surfactant.
Description
Technical Field
The invention belongs to the technical field of material chemistry, and particularly relates to a high internal phase Pickering emulsion stabilizer and application thereof.
Background
The emulsion is a dispersion system formed by dispersing a liquid in another liquid immiscible with the liquid, is mostly formed by mixing a water-insoluble oil phase and a water phase, and is widely applied to industries of papermaking, food, cosmetics, medicines and the like. Emulsions are thermodynamically unstable systems and emulsifiers or stabilizers must be added during the emulsion preparation in order to maintain the relative stability of the emulsion (kinetic stability). Most of the traditional emulsifiers or stabilizers are surfactants and high molecular polymers with surface activity, and the stability of the emulsion is maintained by reducing the interfacial tension between oil-water two-phase liquid, providing a stable interfacial film and improving the viscosity of a continuous phase. In recent years, solid particles have been receiving more and more attention because they can avoid adverse effects of surfactants on the environment, stabilize highly concentrated dispersed phase emulsions, and are less affected by changes in pH, salt concentration, temperature, and oil phase composition. For example, in the paper industry, water-insoluble sizing agents for papermaking need to be emulsified into an oil-in-water emulsion to be compatible with the papermaking system using water as a medium, and the purpose of sizing for papermaking is to increase the water resistance of paper, and the presence of surfactants generally reduces the water resistance of paper in addition to causing adverse effects on the environment, which can be avoided by using solid particle stabilized sizing agent emulsions.
The Pickering emulsion is also called solid (particle) stable emulsion, which is stable emulsion emulsified by only solid particles without adding traditional macromolecular organic surfactant, and the solid particles adsorbed on the oil-water interface have extremely high adsorption energyEThe emulsion is not easy to separate from the oil-water interface, the mode of emulsifying and stabilizing the emulsion by the solid particles is considered to be irreversible, the Pickering emulsion has very strong stability, and the emulsification technology and research are widely used in various industries and fields at present. The Pickering emulsion can reduce the complexity of an emulsification process, improve the stability of the emulsion and reduce the environmental pollution and other defects caused by the emulsifier due to avoiding using a high-molecular organic emulsifier, and is a novel emulsion with potential application value. Pickering milkThe emulsifier of the liquid is a stable system mainly comprising amphiphilic solid particles (organic and inorganic) and a small amount of surfactant as auxiliary. Pickering emulsion has potential application in food science as a nano-structured lipid carrier or fat substitute, and comes from the most common food-grade particles with abundant natural resources and low price, such as cellulose, chitosan or starch, however, the emulsion obtained by the natural substances has poor stability due to poor hydrophobicity.
Disclosure of Invention
Aiming at the problem of poor stability of Pickering emulsion formed by the existing natural substances, the invention provides an alkenyl succinic anhydride modified gamma-cyclodextrin metal-organic framework (CD-MOFs), which can form high internal phase Pickering emulsion without adding a surfactant and has good stability.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of an alkenyl succinic anhydride modified cyclodextrin metal-organic framework comprises the following steps:
(1) Dispersing Cyclodextrin (CD) in deionized water, uniformly stirring to obtain a CD aqueous solution, adjusting the pH value of the CD aqueous solution, then dropwise adding Alkenyl Succinic Anhydride (ASA), freeze-drying the obtained aqueous solution, washing and drying to obtain ASA-CD;
(2) Dissolving ASA-CD and KOH in water, adding methanol, heating in water bath, adding hexadecyl trimethyl ammonium bromide, continuously heating, carrying out solid-liquid separation on a reaction system, washing solids, and drying to obtain the ASA-CD-MOFs.
The cyclodextrin is beta-cyclodextrin or gamma-cyclodextrin, and more preferably gamma-cyclodextrin. The concentration of the CD aqueous solution is 9-15% w/w.
In the step (1), the pH of the CD aqueous solution is adjusted to 7.5-10.
The ASA is one of dodeca-eicosenyl succinic anhydride; the mass fraction of ASA relative to water is 0.1-1.0%.
In the step (2), the heating temperature is 50-60 ℃.
The concentration of ASA-CD in step (2) is 55-80% w/w; potassium hydroxide concentration 10-25% w/w; methanol concentration of 10-20% w/w; cetyl trimethylammonium bromide concentration of 5-12% w/w.
The alkenyl succinic anhydride modified cyclodextrin metal-organic framework obtained by the preparation method is cubic in shape, and the average particle size of the framework is 300-500 nm.
The alkenyl succinic anhydride modified cyclodextrin metal-organic framework can be used as a stabilizer of Pickering emulsion.
A preparation method of a high internal phase Pickering emulsion comprises the following steps:
(i) Dispersing ASA-CD-MOFs into water to prepare ASA-CD-MOFs aqueous dispersion;
(ii) Shearing and emulsifying the ASA-CD-MOFs aqueous dispersion and the oil phase to obtain the high internal phase Pickering emulsion.
The concentration of the ASA-CD-MOFs aqueous dispersion is 0.5-5%w/w; the mass fraction of the oil phase in the Pickering emulsion is 75-85%.
The oil phase is sunflower oil, soybean oil and fish oil.
The speed of the shearing emulsification is 5000-30000rpm, preferably 10000-22000rpm; the shearing emulsification time is 20-80s.
The high internal phase Pickering emulsion has an average particle diameter of 2-10 μm.
The high internal phase Pickering emulsion can be used as an additive for 3D printing.
The mechanism of the invention is as follows:
the preparation method comprises the steps of utilizing ASA modified cyclodextrin to graft hydrophobic groups onto the cyclodextrin to obtain modified cyclodextrin ASA-CD, then adding potassium hydroxide, methanol and hexadecyl trimethyl ammonium bromide to prepare organic metal framework nano particles, wherein the potassium hydroxide provides potassium ions for the CD, the hexadecyl trimethyl ammonium bromide serves as a catalyst when the organic metal framework nano particles are synthesized, the proportion of materials is moderate, otherwise ASA-CD with proper hydrophobicity and ASA-CD-MOFs particles with uniform and regular particle sizes cannot be obtained, and therefore the preparation and performance of the high internal phase Pickering emulsion can be directly influenced. ASA-CD-MOFs has very moderate wettability (the three-phase contact angle is close to 90 degrees), so that the particles can be effectively emulsified to prepare Pickering emulsion, meanwhile, a mutually-crosslinked compact particle film can be formed at the oil-water interface of the ASA-CD-MOFs, and a 3D network particle film is formed in a continuous phase, so that powerful conditions are provided for the construction and the stability of high internal phase Pickering emulsion, and the prepared Pickering emulsion has good viscoelastic rheological property and creates conditions for 3D printing application.
The invention has the following advantages:
the organic metal framework obtained by the invention is food grade ASA-CD-MOFs nano-particles containing potassium element with moderate wettability (three-phase contact angle of 90 degrees), can be used as an excellent food grade Pickering emulsion emulsification stabilizer, can be used for preparing ultrahigh internal phase Pickering emulsion with high stability and high rheological property, has excellent coalescence resistance and frost resistance, can stabilize precipitation of anhydrous phase and oil phase for months, does not need to add any surfactant or other modifiers, has simple steps and easy operation, can be used as 3D printing food grade emulsion, and has potential application value.
Drawings
FIG. 1 is an infrared spectrum of CD and different concentrations of ODSA-CD;
FIG. 2 is an infrared spectrum of CD-MOFs and different concentrations of ODSA-CD-MOFs;
FIG. 3 is a scanning electron microscope photograph of the ODSA-CD-MOFs;
FIG. 4 is an appearance and emulsion micrograph of a high internal phase Pickering emulsion of ODSA-CD-MOFs stabilized sunflower oil;
FIG. 5 is a cryo-scanning electron micrograph of a high internal phase Pickering emulsion of ODSA-CD-MOFs stabilized sunflower oil;
FIG. 6 is a confocal laser micrograph of a high internal phase Pickering emulsion of ODSA-CD-MOFs stabilized sunflower oil;
FIG. 7 is a 3D printed product with high internal phase Pickering emulsion of ODSA-CD-MOFs stabilized sunflower seed oil as raw material;
FIG. 8 shows 3D printing products using fish oil high internal phase Pickering emulsion stabilized by ODSA-CD-MOFs as raw material.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the present invention is not limited to the following examples.
EXAMPLE 1 preparation of high internal phase Pickering emulsion stabilizers ODSA-CD-MOFs
(1) Dispersing 12 parts by weight of gamma-cyclodextrin (gamma-CD) in 88 parts by weight of deionized water, uniformly stirring to obtain a CD aqueous solution, adjusting the pH of the CD aqueous solution to 8.5 by using NaOH, then dropwise adding 0.5 part by weight of octadecenyl succinic anhydride (ODSA) under the stirring condition until the pH is constant, freeze-drying the obtained aqueous solution, then washing by using 10 parts by weight of hexane/isopropanol mixed solution as a cleaning agent, and drying to obtain ODSA-CD; the IR spectra of gamma-CD and different concentrations of ODSA-CD are shown in FIG. 1: 950-1200cm -1 The range is the "fingerprint" area of carbohydrates, 1633cm -1 Is the bound water existing in CD, and the stretching vibration of O-H, C-H is 3100-3600cm -1 And 2700-3000cm -1 ，1856cm -1 The new peak appeared at (D) is the ester carbonyl peak of ODSA, 1772cm -1 The asymmetric stretching vibration of carboxylate RCOO-is generated, which shows that ODSA and CD are chemically crosslinked and successfully connected on the CD;
(2) Dispersing 74.5 parts by weight of ODSA-CD into 25.5 parts by weight of deionized water to prepare 74.5% ODSA-CD aqueous dispersion, adding 15 parts by weight of potassium hydroxide and 20 parts by weight of methanol into the aqueous dispersion, heating the aqueous dispersion in a water bath at 50-60 ℃ for 0.5h, adding 7.5 parts by weight of hexadecyl trimethyl ammonium bromide, continuing to heat the aqueous dispersion for 2h, washing the centrifuged precipitate, and drying the precipitate to obtain ODSA-CD-MOFs powder. CD-MOFs powder was obtained by replacing ODSA-CD with gamma-CD according to the above method.
The obtained infrared spectrogram spectra of CD-MOFs and ODSA-CD-MOFs with different concentrations are shown in FIG. 2: at 2851cm -1 Is C-H telescopic vibration area, 1666cm -1 The characteristic peak of the lactone ring of ODSA shows that the acid anhydride of ODSA and the hydroxyl on the CD glucose unit (C2, C3 and C6) are subjected to esterification reaction, so that the introduction of ODSA long carbon chain is realized, and the aim of enhancing hydrophobicity is fulfilled. ODSA has a long carbon chain of 18C, can impart hydrophobicity to CD, and CD-MOF synthesized by hydrophobically modified CD and KOH has improved hydrophobicity compared with CD-MOF synthesized by unmodified CD, is easier to form oil-in-water emulsion, and is beneficial to CDThe MOF particles are stably adsorbed at an oil-water interface, steric hindrance is generated to prevent oil drops from aggregating, and stable emulsion is easily obtained.
Scanning electron microscopy pictures of the ODSA-CD-MOFs are shown in FIG. 3: the obtained particles are in the form of cubes, and have a particle size distribution of 50-330nm and an average particle size of about 200nm.
EXAMPLE 2 preparation of high internal phase Pickering emulsion
(1) 2.2 parts by weight of the ODSA-CD-MOFs prepared in example 1 was dispersed in 97.8 parts by weight of deionized water to prepare an aqueous dispersion of ODSA-CD-MOFs;
(2) Adding 400 parts by weight of edible sunflower seed oil into the ODSA-CD-MOFs aqueous dispersion, shearing and emulsifying at 10000rpm for 60s to obtain a high internal phase Pickering emulsion with 80% internal phase, wherein appearance and emulsion micrographs are shown in FIG. 4: the viscosity of the emulsion is 0.1 pas, and the average particle size of the emulsion droplets is 7.2 μm.
A cryo-scanning electron microscope picture of the obtained high internal phase Pickering emulsion is shown in fig. 5: the ODSA-CD-MOFs particle film is covered on the surface of the liquid drop and forms a 3d network in a continuous phase, the structure can effectively stabilize coalescence of the emulsion and improve stability of the emulsion, and the obtained high internal phase emulsion liquid drop is spherical. The emulsion droplets have a particle size distribution of 5.2-10.5 μm and an average particle size of about 6.5. Mu.m. Sample preparation parameters are as follows: each emulsion sample (1 mL) was stained with 10. Mu.L of Nile Red, nile blue solution (1 mg/mL). The stained sample was dropped onto a glass slide and all samples were observed at different fluorescence wavelengths with a 20-fold magnifier. The excitation and emission spectra of nile red are 488 and 539nm, respectively, and the excitation and emission wavelengths of nile blue are 561 and 630nm, respectively. The appearance of the prepared Pickering emulsion observed by a confocal laser scanning microscope (FV 3000, olympus, japan) in a fluorescence mode is shown in FIG. 6, the left image is the oil phase distribution diagram of Nile red staining, and the right image is the ODSA-CD-MOFs particle distribution diagram of Nile blue staining. From this figure, it can be seen that: the particle film formed by the ODSA-CD-MOFs particles and the 3D particle network structure in the continuous phase effectively obstruct coalescence of emulsion droplets, and a high internal phase Pickering emulsion is formed.
Freezing the emulsion at-30 deg.C, thawing at 50 deg.C, and circulating for 20 times to prevent phase separation; no phase body is separated out after the mixture is placed for 6 months at normal temperature (20-30 ℃); this indicates that the emulsion is good in coalescence resistance and freeze resistance and can maintain a stable state for a long period of time.
Application example 1 application of high internal phase Pickering emulsion in 3D printing
Printing a square cream: printing was performed using an extrusion 3D printer with a pneumatic printhead (model: bio-Architect SR., jie Nuo Fei). The high internal phase Pickering emulsion prepared in example 1 was filled into the syringe of a printer before printing, the nozzle tip size and nozzle height were both set to 0.5mm, and the extrusion speed was 20mm/s -1 The printing temperature was 25 ℃ and the extrusion pressure was 60kPa.
Printing star-shaped cream: the high internal phase Pickering emulsion prepared in example 1 was added to a 5cm diameter syringe with a 0.5mm needle bore, a hand-print feed rate of about 0.2 mL/s, a needle travel rate of 0.5cm/s, and a printing temperature of 25 ℃.
The results are shown in FIG. 7: the cubic cream printed by the 3D printer has good stability, no phase body precipitation and stable appearance and shape. The star-shaped cream printed by hand also has good stability and shaping property, no phase body is separated out from the cream, and the appearance shape is kept stable in the printing process.
EXAMPLE 3 preparation of high internal phase Fish oil Pickering emulsion
Modified cyclodextrin organometallic frameworks ASA- α -CD-MOFs and ASA- β -CD-MOFs were prepared with α -CD and β -CD, respectively, as in example 1. This was combined with ASA- γ -CD-MOFs prepared in example 1 to prepare a high internal phase fish oil Pickering emulsion with 80% internal phase using fish oil as internal phase according to the method of example 2. The properties of the emulsion after preparation and after standing at room temperature for 60 days were determined.
TABLE 1 Properties of different emulsifiers and high internal phase fish oil Pickering emulsions prepared therewith
The results are shown in table 1: the MOFs particles prepared by alpha-CD can not effectively emulsify and stabilize high internal phase Pickering emulsion, while the beta-CD and the gamma-CD can prepare stable high internal phase Pickering emulsion, which may be caused by poor grafting effect of the alpha-CD and ASA, so that the particle amphipathy is too poor (the contact angle is 15 degrees and the particles belong to hydrophilic particles), and the average particle size is too large, so that the prepared Pickering emulsion can not form a compact interface particle film, emulsion droplets can be converged, stable Pickering emulsion can not be effectively formed, demulsification is caused, and therefore, the alpha-CD is not suitable for preparing emulsion stabilizer.
EXAMPLE 4 preparation of high internal phase Pickering emulsion
(1) Dispersing 9 parts by weight of beta-cyclodextrin (beta-CD) in 91 parts by weight of deionized water, uniformly stirring to obtain a CD aqueous solution, adjusting the pH of the CD aqueous solution to 7.5 by using NaOH, then dropwise adding 0.1 part by weight of dodecenyl succinic anhydride (DDSA) under the stirring condition until the pH is constant, freeze-drying the obtained aqueous solution, then washing by using a hexane/isopropanol (15 parts by weight) mixed solution as a cleaning agent, and drying to obtain DDSA-CD;
(2) Dispersing 55 parts by weight of ODSA-CD into 45 parts by weight of deionized water to prepare DDSA-CD aqueous dispersion with the concentration of 55%, then adding 10 parts by weight of potassium hydroxide and 10 parts by weight of methanol, heating in water bath at 50 to 60 ℃ for 0.5h, then adding 5 parts by weight of hexadecyl trimethyl ammonium bromide, continuing heating for 3h, washing the centrifuged precipitate, and drying to obtain DDSA-CD-MOFs powder with the average particle size of about 70 nm;
(3) Dispersing 0.5 weight part of DDSA-CD-MOFs into 99.5 weight parts of deionized water to prepare DDSA-CD-MOFs aqueous dispersion;
(4) Adding 300 parts by weight of soybean oil into DDSA-CD-MOFs aqueous dispersion, shearing and emulsifying at the rotating speed of 5000rpm for 80s to obtain 75% internal phase high internal phase Pickering emulsion, wherein the average particle size of emulsion droplets is 12 micrometers, the emulsion droplets are repeatedly frozen and thawed at minus 30 ℃ and 50 ℃ and then are kept stable, and no phase body is separated out after the emulsion is placed for 6 months.
Application example 2 application of high internal phase Pickering emulsion in 3D printing
(1) Dispersing 15 parts by weight of gamma-cyclodextrin (gamma-CD) in 85 parts by weight of deionized water, uniformly stirring to obtain a CD aqueous solution, adjusting the pH of the CD aqueous solution to 10 by using NaOH, then dropwise adding 1 part by weight of Eicosenyl Succinic Anhydride (ESA) under the stirring condition until the pH is constant, freeze-drying the obtained aqueous solution, then washing by using a hexane/isopropanol (20 parts by weight) mixed solution as a cleaning agent, and drying to obtain ESA-CD;
(2) Dispersing 80 parts by weight of ESA-CD into 20 parts by weight of deionized water to prepare an 80% ESA-CD aqueous dispersion, adding 25 parts by weight of potassium hydroxide and 25 parts by weight of methanol into the aqueous dispersion, heating the aqueous dispersion in a water bath at 50 to 60 ℃ for 0.5h, adding 12 parts by weight of hexadecyl trimethyl ammonium bromide, continuing heating the aqueous dispersion for 4h, washing the centrifuged precipitate, and drying the precipitate to obtain ESA-CD-MOFs powder with the average particle size of about 60 nm;
(3) Dispersing 5 parts by weight of ESA-CD-MOFs into 95 parts by weight of deionized water to prepare an ESA-CD-MOFs aqueous dispersion;
(4) Adding 565 parts by weight of fish oil into ESA-CD-MOFs aqueous dispersion, shearing and emulsifying at 20000rpm for 20s to obtain 85% internal phase high internal phase Pickering emulsion, wherein the average particle size of emulsion droplets is 19 μm, the emulsion droplets are repeatedly frozen and thawed at-30 ℃ and 50 ℃ and then are kept stable, and no phase body is separated out after the emulsion is placed for 6 months.
3D printing is carried out on the high internal phase Pickering emulsion respectively as an additive, and a square cream is printed: the preparation method comprises the steps of printing by using an extrusion type 3D printer with a pneumatic printing head (model: bio-Architect SR., jienough), filling the prepared high internal phase fish oil Pickering emulsion into an injector of the printer before printing, wherein the size of the tip of the nozzle and the height of the nozzle are both set to be 0.5mm, the extrusion speed is 20mm/s, the printing temperature is 25 ℃, and the extrusion pressure is 60kPa. The results are shown in FIG. 8: 3D printing of cube food-grade small cakes is carried out by using the high internal phase fish oil Pickering emulsion with stable emulsification of the prepared ASA-CD-MOFs particles, so as to obtain the fish oil emulsifiable paste with stable form and viscoelasticity.
Claims (8)
1. A preparation method of an alkenyl succinic anhydride modified cyclodextrin metal-organic framework is characterized by comprising the following steps:
(1) Dispersing cyclodextrin in deionized water, uniformly stirring to obtain a CD aqueous solution, adjusting the pH value of the CD aqueous solution, then dropwise adding alkenyl succinic anhydride, and freeze-drying the obtained aqueous solution, washing and drying to obtain ASA-CD;
(2) Adding water to ASA-CD and KOH for dissolving, adding methanol, heating in a water bath, then adding hexadecyl trimethyl ammonium bromide, continuing to heat, after solid-liquid separation of a reaction system, washing and drying the solid to obtain ASA-CD-MOFs;
the cyclodextrin is beta-cyclodextrin or gamma-cyclodextrin;
CD aqueous solution concentration 9-15%; the ASA is one of dodeca-eicosenyl succinic anhydride; the mass fraction of ASA relative to water is 0.1-1.0%;
the concentration of ASA-CD in step (2) is 55-80% w/w; potassium hydroxide concentration 10-25% w/w; methanol concentration of 10-20% w/w; cetyl trimethylammonium bromide concentration 5-12%;
the shape of the alkenyl succinic anhydride modified cyclodextrin metal-organic framework is cube, and the average particle size is 300-500 nm.
2. The method according to claim 1, wherein in the step (1), the pH of the aqueous solution of CD is adjusted to 7.5 to 10; in the step (2), the heating temperature is 50-60 ℃.
3. An alkenylsuccinic anhydride-modified cyclodextrin metal-organic framework obtained by the production method as claimed in any one of claims 1 to 2.
4. Use of the alkenylsuccinic anhydride-modified cyclodextrin metal-organic framework of claim 3 as a Pickering emulsion stabilizer.
5. A method of preparing a high internal phase Pickering emulsion using an alkenyl succinic anhydride modified cyclodextrin metal organic framework of claim 3, comprising the steps of:
(i) Dispersing an alkenyl succinic anhydride modified cyclodextrin metal-organic framework into water to prepare ASA-CD-MOFs aqueous dispersion;
(ii) Shearing and emulsifying the ASA-CD-MOFs aqueous dispersion and the oil phase to obtain a high internal phase Pickering emulsion;
the concentration of the ASA-CD-MOFs aqueous dispersion is 0.5-5%w/w; the mass fraction of the oil phase in the Pickering emulsion is 75-85%.
6. The process according to claim 5, characterized in that the oily phase is selected from sunflower oil, soybean oil or fish oil; the speed of the shearing emulsification is 5000-30000rpm; the shearing and emulsifying time is 20-80s.
7. A high internal phase Pickering emulsion prepared according to the process of claim 5 or 6, wherein the droplets in the emulsion have an average particle size of 2 to 10 μm.
8. Use of the high internal phase Pickering emulsion of claim 7 as an additive for 3D printing.
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| CN107151329A (en) * | 2016-03-04 | 2017-09-12 | 中国科学院上海药物研究所 | The fast synthesis method of cyclodextrin-metal-organic framework materials |
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