CN106674555A - Calcium alginate composite microsphere for stabilizing water-in-oil Pickering emulsion and preparation method thereof - Google Patents
Calcium alginate composite microsphere for stabilizing water-in-oil Pickering emulsion and preparation method thereof Download PDFInfo
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- 239000000648 calcium alginate Substances 0.000 title claims abstract description 77
- 235000010410 calcium alginate Nutrition 0.000 title claims abstract description 77
- 229960002681 calcium alginate Drugs 0.000 title claims abstract description 77
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 title claims abstract description 76
- 239000004005 microsphere Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title abstract 5
- 230000000087 stabilizing effect Effects 0.000 title abstract 3
- 238000001484 Pickering emulsion method Methods 0.000 title 1
- 239000000839 emulsion Substances 0.000 claims abstract description 86
- 150000001343 alkyl silanes Chemical class 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000011258 core-shell material Substances 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000002105 nanoparticle Substances 0.000 claims description 41
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 39
- 235000015110 jellies Nutrition 0.000 claims description 35
- 239000008274 jelly Substances 0.000 claims description 35
- 206010001497 Agitation Diseases 0.000 claims description 28
- 238000013019 agitation Methods 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 24
- 235000010413 sodium alginate Nutrition 0.000 claims description 24
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 21
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 21
- 239000001110 calcium chloride Substances 0.000 claims description 21
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 21
- 239000000661 sodium alginate Substances 0.000 claims description 21
- 229940005550 sodium alginate Drugs 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 239000012467 final product Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 10
- 230000000640 hydroxylating effect Effects 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 5
- 235000010443 alginic acid Nutrition 0.000 claims description 5
- 229920000615 alginic acid Polymers 0.000 claims description 5
- 235000013339 cereals Nutrition 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 230000009466 transformation Effects 0.000 claims description 5
- 229960001126 alginic acid Drugs 0.000 claims description 4
- 239000000783 alginic acid Substances 0.000 claims description 4
- 150000004781 alginic acids Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- -1 alkyl carbon Chemical compound 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims description 2
- HVUMOYIDDBPOLL-XGKPLOKHSA-N [2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XGKPLOKHSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 15
- 229920001661 Chitosan Polymers 0.000 abstract description 7
- 238000007789 sealing Methods 0.000 abstract description 5
- 239000002537 cosmetic Substances 0.000 abstract description 4
- 235000013305 food Nutrition 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 102000004190 Enzymes Human genes 0.000 abstract description 2
- 108090000790 Enzymes Proteins 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000005538 encapsulation Methods 0.000 abstract description 2
- 102000004169 proteins and genes Human genes 0.000 abstract description 2
- 108090000623 proteins and genes Proteins 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 238000010556 emulsion polymerization method Methods 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 229940079593 drug Drugs 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003937 drug carrier Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000227 bioadhesive Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000005046 Chlorosilane Substances 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
Classifications
-
- 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
- C08J3/12—Powdering or granulating
- C08J3/16—Powdering or granulating by coagulating dispersions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/10—Dispersions; Emulsions
- A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
- C08J3/12—Powdering or granulating
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/10—General cosmetic use
-
- 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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- Health & Medical Sciences (AREA)
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- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
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- Dispersion Chemistry (AREA)
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- Pharmacology & Pharmacy (AREA)
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- Dermatology (AREA)
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Abstract
The invention discloses a calcium alginate composite microsphere for stabilizing water-in-oil Pickering emulsion and a preparation method thereof, and belongs to the technical field of material high-molecular polymers. Alkylsilane grafted inorganic nanometer particles coat the surface of a calcium alginate microsphere to form the calcium alginate composite microsphere; the particle diameter distribution of the microsphere is 2 to 8 mum; the microsphere is of a core-shell structure; the core is hollow; the shell has two layers; the total thickness of the two layers of the shell is 1 to 1.5mum; the calcium alginate is an inner layer shell; the inorganic nanometer particle is assembled into the outermost layer shell; the technical defects that chitosan coats the surface of the calcium alginate microsphere, can only be used for stabilizing the water-in-oil Pickering emulsion, can only be used for encapsulating and sealing the oil-soluble medicine through being used as a medicine carrier, and cannot be used for encapsulating and sealing oil-soluble medicine are overcome; the calcium alginate composite microsphere is prepared by using an improved emulsion polymerization method; meanwhile, the characteristics of biocompatibility, adhesiveness, protein type macromolecule encapsulation and sealing and the like of the calcium alginate can be realized; the water-in-oil Pickering emulsion can be well stabilized; the calcium alginate composite microsphere can widely expand the application of Pickering emulsion as the medicine carrier to the fields of biologic medicine, cosmetics industry, food industry, enzyme engineering and the like.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of alginic acid for stablizing water-in-oil type pickering emulsion
Calcium complex microsphere and preparation method thereof.
Background technology
Pickering emulsion（Pickering emulsions）The emulsion that i.e. solid particle is stablized is by water phase, oil phase and is consolidated
Body particle composition.Generally hydrophilic solid particle energy stabilised oil-in-water emulsion, hydrophobic solid particle can stablize Water-In-Oil
Type emulsion.Compared with the emulsion of conventional surfactant stabilization, pickering emulsion has stability high, small toxicity, environment-friendly
Etc. advantage, the fields such as drug delivery, cosmetics and food industry have been widely used in.
Solid particle for stablizing pickering emulsion is a lot, is broadly divided into inorganic particle and organic granular.In view of certainly
Body toxicity, biological degradability and compatibility etc. are limited, and many particles are not suitable as being applied to the pik of biomedicine field
The stabilizer of woods emulsion.Calcium alginate microsphere be sodium alginate at room temperature with Ca2+The natural polymerses that crosslinking is obtained,
With good biocompatibility and bioadhesive, the advantages of biodegradability, therefore become and can apply to biological doctor
The pickering emulsion particle emulsifying agents in medicine field are first-selected.For example, being to use membrane emulsification system closest to prior art of the invention
It is standby go out the uniform calcium alginate microsphere and Chitosan-coated using relative hydrophobic reduces the hydrophilic of calcium alginate microsphere
Property（Fangfang Nan, Jie Wu, Feng Qi, Yan Liu, To Ngai, Guanghui Ma,Uniform
chitosan-coated alginate particles as emulsifiers for preparation of stable
Pickering emulsions with stimulus dependence, Colloids and Surfaces A, 2014,
246-252）；Pharmaceutical carrier such that it is able to be used as biomedical sector encapsulates oil-soluble medicine.However, because calcium alginate is micro-
Ball is very hydrophilic, is typically only capable to stabilised oil-in-water pickering emulsion；Calcium alginate microsphere is so limited as pik woods
The application of emulsion particle emulsifying agent.Prior art by the Chitosan-coated of relative hydrophobic to reduce the hydrophily of calcium alginate,
Stabilised oil-in-water pickering emulsion is removed by the calcium alginate microsphere of Chitosan-coated, although can be encapsulated as pharmaceutical carrier
Oil-soluble medicine is in phase in emulsion, but the calcium alginate microsphere of Chitosan-coated can not stablize water-in-oil type pickering emulsion,
The carrier that thus cannot function as encapsulating water soluble drug is used.
Based on this, inventor prepares the inorganic nanoparticles bag that a kind of alkyl silane is grafted by improving emulsion polymerization
Overlay on the complex microsphere on calcium alginate surface.The complex microsphere not only possesses the biocompatibility of calcium alginate, bioadhesive
With the characteristic such as encapsulating protein class macromolecular, and the cladding for passing through inorganic nanoparticles, suitable lipophile is obtained, can be very well
Stable water-in-oil type pickering emulsion.Can widely develop pickering emulsion as pharmaceutical carrier in biologic medical, cosmetic conduct
The application in the fields such as industry, food service industry and enzyme engineering.
The content of the invention
The purpose of the present invention is that the inorganic nanoparticles being grafted by alkyl silane are coated on calcium alginate microsphere surface, is made
Calcium alginate microsphere obtains suitable lipophile, can be used for stablizing water-in-oil type pickering emulsion；So as to be applied to pik woods
Emulsion is carrier and drug encapsulation that water soluble drug is interior phase and conveying, and builds step slow release medicine system.The present invention
Another purpose be to provide the preparation method of the calcium alginate compounded microballoon for stablizing water-in-oil type pickering emulsion.
A kind of calcium alginate compounded microballoon for stablizing water-in-oil type pickering emulsion, it is inorganic that its alkyl silane is grafted
Nano particle is coated on calcium alginate microsphere surface and constitutes calcium alginate compounded microballoon, and microspherulite diameter is distributed as 2 ~ 8 m；Alginic acid
Calcium complex microsphere is core shell structure, and core is hollow, and shell has two-layer, and two-layer shell total thickness is 1 ~ 1.5 m, and calcium alginate is inner layer case,
The inorganic nanoparticles of alkyl silane grafting are assembled into outermost shell, and the calcium alginate microsphere is 90 degree of left sides with the contact angle of water
The right side, the contact angle with the oil phase such as atoleine, n-hexane is 0 degree, and the microballoon can stablize water-in-oil type pickering emulsion.
The inorganic nanoparticles of described alkyl silane grafting include TiO2、SiO2、Fe3O4In it is optional wherein any one
Kind.
A kind of preparation method for stablizing the calcium alginate compounded microballoon of water-in-oil type pickering emulsion, including following step
Suddenly：
First step：The preparation of the inorganic nanoparticles of alkyl silane grafting：
（1）It is the nano particle TiO of 20 ~ 30 nm by commercially available particle diameter2、SiO2、Fe3O4In optional any of which be added to 10
The percent by volume of ~ 15 mL is the H of 30 %2O2In solution, wherein the mass percent of nano particle is 5 ~ 10 %, ultrasonic disperse
5 ~ 10 min obtain dispersion liquid；
（2）Dark is placed in after dispersion liquid is sealed and sentences the h of 500 ~ 800 rpm magnetic agitations 2 ~ 6, depressurization and 40 ~ 60
Drying obtains the modified powder of nanometric particles of hydroxylating at DEG C；
（3）The modified powder of nanometric particles of hydroxylating after drying is added to the alkyl trichlorine silicon that percent by volume is 1 ~ 5 %
Alkane（Note：Wherein atomic number of alkyl carbon is 6 ~ 10）In the mixed liquor of n-hexane, it is ensured that the consumption of mixed liquor can be completely dispersed and receive
Rice grain, the min of ultrasonic disperse 5 ~ 10, the h of 500 ~ 800 rpm magnetic agitations 8 ~ 12, period supplement n-hexane remains initial
Liquid level；
（4）The dispersion liquid that previous step is obtained, with the rpm of rotating speed 12000 ~ 15000, is centrifuged 5 ~ 15 under the conditions of 0 ~ 5 DEG C
Min, takes the nano particle for being deposited in that drying is grafted to alkyl silane at 40 ~ 60 DEG C；
Second step：Prepare water-in-oil type sodium alginate pickering emulsion：
（1）Water phase：Sodium alginate is dissolved in deionized water, the solution that mass percent is 1 ~ 1.5 %, 500 ~ 800 is configured to
8 ~ 12 h deaerations are stood after the min of rpm magnetic agitations 30 ~ 40；
（2）Oil phase：Surfactant is selected any one alkane prepared with first step in Span40/Span60/Span80
The nano particle of base silane grafting is added in atoleine, and wherein the mass percent of surfactant is 3 ~ 9 %, alkyl silicon
The % of mass percent 0.5 ~ 1, the min of magnetic agitation 30 ~ 40 under 500 ~ 800 rpm of the nano particle of alkane grafting；
（3）By above-mentioned water phase and oil phase with volume ratio 2:After 3 mixing, disperseed with Portable high speed under 8000 ~ 10000 rpm
Device emulsifies 30 ~ 40 min and obtains final product water-in-oil type sodium alginate pickering emulsion；
Third step：Prepare water-in-oil type calcium chloride pickering emulsion：With the preparation method of second step, its reclaimed water phase transformation is：
Calcium chloride is dissolved in deionized water, the solution that mass percent is 5 ~ 10 % is configured to, 500 ~ 800 rpm magnetic agitations 30 ~
8 ~ 12 h deaerations are stood after 40 min；Other steps are constant, obtain final product water-in-oil type calcium chloride pickering emulsion；
Four steps：Prepare calcium alginate compounded microballoon：By water-in-oil type sodium alginate pickering emulsion and water-in-oil type chlorination
Calcium pickering emulsion is slowly mixed together, and two kinds of volume ratios of emulsion are 1:1；In 25 ~ 35 DEG C, 500 ~ 800 rpm magnetic agitation states
The lower h of crosslinking curing 0.5 ~ 1；
5th step：The separation of calcium alginate compounded microballoon：
（1）The jelly that crosslinking curing is obtained is scattered in absolute ethyl alcohol, it is ensured that the consumption of absolute ethyl alcohol can be completely dispersed glue
Shape thing, 5 ~ 10 min are centrifuged at 0 ~ 5 DEG C with 8000 ~ 10000 rpm；
（2）Remove a layer jelly to be scattered in absolute ethyl alcohol again, it is ensured that the consumption of absolute ethyl alcohol can be completely dispersed jelly i.e.
Can, it is subsequently placed in vortex concussion instrument and mixes 2 ~ 6 min of dispersion, and it is even with 8000 ~ 10000 rpm with Portable high speed disperser
Slurry 2 ~ 3 min of dispersion, 5 ~ 10 min, repeat step are centrifuged at 4 DEG C again with 8000 ~ 10000 rpm（2）3 ~ 5 times；
（3）By step（2）The jelly for obtaining is scattered in deionized water, it is ensured that the consumption of deionized water can be completely dispersed glue
Thing, 5 ~ 10 min are centrifuged at 0 ~ 5 DEG C with 8000 ~ 10000 rpm；Abandon supernatant, repeat step（3）2 ~ 3 times；
（4）By step（3）The jelly for obtaining is scattered in n-hexane, it is ensured that the consumption of n-hexane can be completely dispersed jelly i.e.
Can, 5 ~ 10 min are centrifuged with 8000 ~ 10000 rpm at 0 ~ 5 DEG C；Abandon supernatant, repeat step（4）2 ~ 3 times；
（5）By step（4）The jelly for obtaining dries 24 ~ 36h at 40 ~ 60 DEG C, obtains final product calcium alginate compounded microballoon.
Described water-in-oil type sodium alginate pickering emulsion, is mutually sodium alginate aqueous solution, Span series surface in it
The inorganic nanoparticles that activating agent is grafted with alkyl silane cooperate with stable emulsion.
Described water-in-oil type calcium chloride pickering emulsion, is mutually calcium chloride water, Span series surface-actives in it
The inorganic nanoparticles that agent is grafted with alkyl silane cooperate with stable emulsion.
The physicochemical property of calcium alginate compounded microballoon of the present invention is as follows：
Microspherulite diameter is distributed as 2 ~ 8 m；Micro-sphere structure is core shell structure, and core is hollow, shell point two-layer, two-layer shell total thickness is 1 ~
1.5µm；Calcium alginate is hypostracum, and the inorganic nanoparticles of alkyl silane grafting are assembled into outer shell；Contact of the microballoon with water
Angle is 90 degree or so, is 0 degree with the contact angle of the oil phase such as atoleine, n-hexane.The oil water contact angular data of microballoon shows, this
Invent the wellability requirement that the microballoon has reached stable water-in-oil type pickering emulsion.
The present invention compared with prior art, has the advantages that：
1st, complex microsphere of the present invention can stablize water-in-oil type pickering emulsion, and the bio-compatible with calcium alginate
The advantages of property, bioadhesive, by the cladding of inorganic nanoparticles, the mechanical strength of calcium alginate is improve, be difficult it
It is swelling.
2nd, solve using Chitosan-coated in calcium alginate microsphere surface-stable oil-in-water type pickering emulsion, can only wrap
Oil sealing soluble drug and cannot function as encapsulating the technological deficiency that uses of water soluble drug carrier；
3rd, the compound calcium alginate microballoon obtained using the inventive method overcomes single calcium alginate microsphere in application process
The problems such as easy swelling, bad mechanical strength and the big easy to leak in gel network space；
4th, the nano particle that alkyl silane is grafted is coated on calcium alginate microsphere by the improvement emulsion polymerisation process that the present invention is provided
Surface, makes calcium alginate microsphere be changed into lipophile from hydrophily, is the calcium alginate compounded microballoon of large-scale production and water-in-oil type
Pickering emulsion is practical, it is not necessary to the method for specific apparatus there is provided simple and convenient；
5th, the calcium alginate compounded microballoon of stabilization water-in-oil type pickering emulsion of the present invention is in biologic medical, cosmetic conduct
The fields such as industry, food service industry and chemical materials have broad application prospects；It is particularly applicable to the encapsulating of water soluble drug
And conveying, and build step slow releasing medicinal system.
Brief description of the drawings
With reference to accompanying drawing, the present invention will be further described with specific embodiment.
Fig. 1 a are calcium alginate compounded microballoon pattern photos of the present invention, it is seen that size uniform, particle diameter distribution is 2 ~ 8
µm。
Fig. 1 b are single calcium alginate compounded microballoon pattern photos of the present invention, it is seen that single calcium alginate compounded microballoon
Surface is smooth, good sphericity.
(1) in Fig. 1 c is the profile of single calcium alginate compounded microballoon of the present invention, it is seen that hollow core and outer
The core shell structure of shell.
(2) in Fig. 1 c are the partial enlarged drawings of single calcium alginate compounded microballoon of the present invention, it is seen that calcium alginate
The hollow structure of complex microsphere, calcium alginate is hypostracum, alkyl silane grafting TiO2Nano particle is assembled into outer shell.
Optical viewer：SEM, model：JSM-7001F, manufacturer：JEOL, the place of production：Tokyo.
Fig. 2 is common calcium alginate microsphere stabilised oil-in-water pickering emulsion compares figure.
Fig. 3 is calcium alginate compounded microballoon stabilization water-in-oil type pickering emulsion compares figure prepared by the present invention.
Optical viewer：Instrument biomicroscope, model：XSP-24, manufacturer：Phoenix Optics Holding Co., Ltd., produces
Ground：Jiangxi, China Shangrao.
Specific embodiment
A kind of calcium alginate compounded microballoon for stablizing water-in-oil type pickering emulsion, inorganic the receiving of alkyl silane grafting
Rice grain is coated on calcium alginate microsphere surface and constitutes calcium alginate compounded microballoon, and its physicochemical property is distributed as including microspherulite diameter
2~8µm；Calcium alginate compounded microballoon is core shell structure, and core is hollow, and shell has two-layer, and two-layer shell total thickness is 1 ~ 1.5 m, alginic acid
Calcium is hypostracum, and the inorganic nanoparticles of alkyl silane grafting are assembled into outer shell, the contact angle of the calcium alginate microsphere and water
It is 90 degree or so, is 0 degree with the contact angle of the oil phase such as atoleine, n-hexane.The inorganic nanoparticles of alkyl silane grafting lead to
Testing sieve is crossed to select including TiO2、SiO2、Fe3O4；Any one wherein may be selected as outer shell；Make compound micro- at present
Ball can stablize Water-In-Oil pickering emulsion, and the subsequently research at aspects such as insoluble drug releases is still continuing the exploratory stage.It was prepared
Journey includes following examples：
Embodiment 1
（One）The TiO of alkyl silane grafting2The preparation of nano particle：（1）It is the TiO of 25nm by the commercially available particle diameters of 1g2Nano particle
The percent by volume for being added to 15 mL is the H of 30 %2O2In solution, the min of ultrasonic disperse 5 obtains dispersion liquid；（2）By dispersion liquid
Dark is placed in after sealing and sentences the h of 500 rpm magnetic agitations 2, depressurization and at 40 DEG C drying to obtain hydroxylating modified
TiO2Powder of nanometric particles；（3）By the modified TiO of the hydroxylating after drying2Powder of nanometric particles is added to the alkyl three of 0.2 mL eight
In the mixed liquor of chlorosilane and 19.8 mL n-hexanes, the min of ultrasonic disperse 5, the h of 500 rpm magnetic agitations 8, period supplement just oneself
Alkane maintains initial level；（4）The dispersion liquid that previous step is obtained, with the rpm of rotating speed 12000, is centrifuged 5 under the conditions of 4 DEG C
Min, takes the TiO for being deposited in that drying is grafted to alkyl silane at 40 DEG C2Nano particle.
（Two）Prepare water-in-oil type sodium alginate pickering emulsion：（1）Water phase：0.35 g sodium alginates are dissolved in 30 mL
In deionized water, 8 h deaerations are stood after the min of 500 rpm magnetic agitations 30；（2）Oil phase：By the Span80 of 1.5 g and 0.2 g
's（One）The TiO of alkyl silane grafting prepared by step2Nano particle is added in 45 mL atoleines, magnetic under 500 rpm
Power stirs 30 min；（3）After above-mentioned water phase is mixed with oil phase, 30 are emulsified with Portable high speed disperser under 8000 rpm
Min obtains final product water-in-oil type sodium alginate pickering emulsion；
（Three）Prepare water-in-oil type calcium chloride pickering emulsion：With in embodiment 1（Two）The preparation method of step, its reclaimed water phase transformation
For：2 g calcium chloride are dissolved in deionized water, 8 h deaerations are stood after the min of 500 rpm magnetic agitations 30；Other steps are constant,
Obtain final product water-in-oil type calcium chloride pickering emulsion；
（Four）Prepare the calcium alginate compounded microballoon of alkyl silane grafting：By water-in-oil type sodium alginate pickering emulsion and You Bao
Water type calcium chloride pickering emulsion is slowly mixed together, and two kinds of volume ratios of emulsion are 1:1, in 25 DEG C, 500 rpm magnetic agitation shapes
The h of crosslinking curing 0.5 under state；
（Five）The separation of calcium alginate compounded microballoon：（1）The jelly that crosslinking curing is obtained is scattered in absolute ethyl alcohol, it is ensured that
The consumption of absolute ethyl alcohol can be completely dispersed jelly, and 5 min are centrifuged with 8000 rpm at 4 DEG C；（2）Remove layer gluey
Thing is scattered in absolute ethyl alcohol again, it is ensured that the consumption of absolute ethyl alcohol can be completely dispersed jelly, is subsequently placed at vortex shake
Swing on instrument mix dispersion 2 min, and with Portable high speed disperser with 8000 rpm be homogenized disperse 2 min, at 4 DEG C with
8000 rpm are centrifuged 5 min, repeat step again（2）3 times；（3）By step（2）The jelly for obtaining is scattered in deionized water
In, it is ensured that the consumption of deionized water can be completely dispersed jelly, and 5 min are centrifuged with 8000 rpm at 4 DEG C；Abandon supernatant
Liquid, repeat step（3）2 times；（4）By step（3）The jelly for obtaining is scattered in n-hexane, it is ensured that the consumption of n-hexane can be complete
Full dispersion jelly, 5 min are centrifuged at 4 DEG C with 8000 rpm；Abandon supernatant, repeat step（4）2 times；（5）Will step
Suddenly（4）The jelly for obtaining dries 24h at 40 DEG C, obtains final product calcium alginate compounded microballoon.
Embodiment 2
（One）The SiO of alkyl silane grafting2The preparation of nano particle：（1）It is the SiO of 25nm by the commercially available particle diameters of 1.8g2Nanometer
The percent by volume that grain is added to 15 mL is the H of 30 %2O2In solution, the min of ultrasonic disperse 10 obtains dispersion liquid；（2）Will dispersion
Liquid-tight being honored as a queen is placed in dark and sentences the h of 800 rpm magnetic agitations 6, depressurization and at 60 DEG C drying obtain hydroxylating and be modified
SiO2Powder of nanometric particles；（3）By the modified SiO of the hydroxylating after drying2Powder of nanometric particles is added to the alkyl three of 1 mL eight
In the mixed liquor of chlorosilane and 19 mL n-hexanes, the min of ultrasonic disperse 10, the h of 800 rpm magnetic agitations 12, period supplement just oneself
Alkane maintains initial level；（4）The dispersion liquid that previous step is obtained, with the rpm of rotating speed 15000, is centrifuged 15 under the conditions of 4 DEG C
Min, takes the SiO for being deposited in that drying is grafted to alkyl silane at 60 DEG C2Nano particle.
（Two）Prepare water-in-oil type sodium alginate pickering emulsion：（1）Water phase：0.45 g sodium alginates are dissolved in 30 mL
In deionized water, 12 h deaerations are stood after the min of 800 rpm magnetic agitations 40；（2）Oil phase：By the Span80 of 3.5 g and 0.35
G's（One）The SiO of alkyl silane grafting prepared by step2Nano particle is added in 45 mL atoleines, magnetic under 800 rpm
Power stirs 40 min；（3）After above-mentioned water phase is mixed with oil phase, 40 are emulsified with Portable high speed disperser under 10000 rpm
Min obtains final product water-in-oil type sodium alginate pickering emulsion；
（Three）Prepare water-in-oil type calcium chloride pickering emulsion：With in embodiment 1（Two）The preparation method of step, its reclaimed water phase transformation
For：3 g calcium chloride are dissolved in deionized water, 12 h deaerations are stood after the min of 800 rpm magnetic agitations 40；Other steps are not
Become, obtain final product water-in-oil type calcium chloride pickering emulsion；
（Four）Prepare calcium alginate compounded microballoon：By water-in-oil type sodium alginate pickering emulsion and water-in-oil type calcium chloride pik
Woods emulsion is slowly mixed together, and two kinds of volume ratios of emulsion are 1:1, the crosslinking curing 1 under 35 DEG C, 800 rpm magnetic agitation states
h；
（Five）The separation of calcium alginate compounded microballoon：（1）The jelly that crosslinking curing is obtained is scattered in a certain amount of anhydrous second
In alcohol, 10 min are centrifuged with 10000 rpm at 4 DEG C；（2）Remove layer jelly to be scattered in again in appropriate absolute ethyl alcohol, put
Disperse 6 min in mixing in vortex concussion instrument, and 3 min of dispersion are homogenized with 10000 rpm with Portable high speed disperser, 4
10 min, repeat step are centrifuged again with 10000 rpm at DEG C（2）5 times；（3）By step（2）The jelly for obtaining is scattered in suitable
In amount deionized water, 10 min are centrifuged with 10000 rpm at 4 DEG C；Abandon supernatant, repeat step（3）3 times；（4）By step
（3）The jelly for obtaining is scattered in appropriate n-hexane, and 10 min are centrifuged with 10000 rpm at 4 DEG C；Supernatant is abandoned, is repeated
Step（4）3 times；（5）By step（4）The jelly for obtaining dries 36h at 60 DEG C, obtains final product calcium alginate compounded microballoon.
Embodiment 3
（One）The Fe of alkyl silane grafting3O4The preparation of nano particle：（1）It is the Fe of 25nm by the commercially available particle diameters of 1.5g3O4Nanometer
The percent by volume that grain is added to 15 mL is the H of 30 %2O2In solution, the min of ultrasonic disperse 8 obtains dispersion liquid；（2）Will dispersion
Liquid-tight being honored as a queen is placed in dark and sentences the h of 700 rpm magnetic agitations 4, depressurization and at 50 DEG C drying obtain hydroxylating and be modified
Fe3O4Powder of nanometric particles；（3）By the modified Fe of the hydroxylating after drying3O4Powder of nanometric particles is added to the alkane of 0.5 mL eight
In the mixed liquor of base trichlorosilane and 19.5 mL n-hexanes, the min of ultrasonic disperse 8, the h of 700 rpm magnetic agitations 10, period mend
Fill n-hexane and maintain initial level；（4）The dispersion liquid that previous step is obtained under the conditions of 4 DEG C, with the rpm of rotating speed 13000, from
The min of the heart 10, takes the Fe for being deposited in that drying is grafted to alkyl silane at 50 DEG C3O4Nano particle.
（Two）Prepare water-in-oil type sodium alginate pickering emulsion：（1）Water phase：0.4 g sodium alginates are dissolved in 30 mL
In ionized water, 10 h deaerations are stood after the min of 700 rpm magnetic agitations 35；（2）Oil phase：By the Span80 of 2.5 g and 0.25 g
's（a）Lipophile Fe prepared by step3O4Nano particle is added in 45 mL atoleines, magnetic agitation 35 under 700 rpm
min；（3）After above-mentioned water phase is mixed with oil phase, oil is obtained final product with 35 min of Portable high speed disperser emulsification under 9000 rpm
Water-in type sodium alginate pickering emulsion；
（Three）Prepare water-in-oil type calcium chloride pickering emulsion：With in embodiment 1（Two）The preparation method of step, its reclaimed water phase transformation
For：2.5 g calcium chloride are dissolved in deionized water, 10 h deaerations are stood after the min of 700 rpm magnetic agitations 35；Other steps are not
Become, obtain final product water-in-oil type calcium chloride pickering emulsion；
（Four）Prepare the calcium alginate compounded microballoon of lipophile：By water-in-oil type sodium alginate pickering emulsion and water-in-oil type chlorination
Calcium pickering emulsion is slowly mixed together, and two kinds of volume ratios of emulsion are 1:1；It is crosslinked under 30 DEG C, 700 rpm magnetic agitation states
Solidify 0.8 h；
（Five）The separation of calcium alginate compounded microballoon：（1）The jelly that crosslinking curing is obtained is scattered in absolute ethyl alcohol, it is ensured that
The consumption of absolute ethyl alcohol can be completely dispersed jelly, and 8 min are centrifuged with 9000 rpm at 4 DEG C；（2）Remove layer gluey
Thing is scattered in absolute ethyl alcohol again, it is ensured that the consumption of absolute ethyl alcohol can be completely dispersed jelly, is subsequently placed at vortex shake
Swing on instrument mix dispersion 4 min, and with Portable high speed disperser with 9000 rpm be homogenized disperse 2 min, at 4 DEG C with
9000 rpm are centrifuged 8 min, repeat step again（2）4 times；（3）By step（2）The jelly for obtaining is scattered in deionized water
In, it is ensured that the consumption of deionized water can be completely dispersed jelly, and 8 min are centrifuged with 9000 rpm at 4 DEG C；Abandon supernatant
Liquid, repeat step（3）2 times；（4）By step（3）The jelly for obtaining is scattered in n-hexane, it is ensured that the consumption of n-hexane can be complete
Full dispersion jelly, 8 min are centrifuged at 4 DEG C with 9000 rpm；Abandon supernatant, repeat step（4）2 times；（5）Will step
Suddenly（4）The jelly for obtaining dries 30h at 50 DEG C, obtains final product calcium alginate compounded microballoon.
Claims (5)
1. a kind of calcium alginate compounded microballoon for stablizing water-in-oil type pickering emulsion, it is characterised in that alkyl silane connects
The inorganic nanoparticles of branch are coated on calcium alginate microsphere surface and constitute calcium alginate compounded microballoon, and microspherulite diameter is distributed as 2 ~ 8
m；Calcium alginate compounded microballoon is core shell structure, and core is hollow, and shell has two-layer, and two-layer shell total thickness is 1 ~ 1.5 m, and calcium alginate is
Inner layer case, the inorganic nanoparticles of alkyl silane grafting are assembled into outer shell, and the calcium alginate microsphere is 90 with the contact angle of water
Degree left and right, the contact angle with the oil phase such as atoleine, n-hexane is 0 degree, and the microballoon can stablize water-in-oil type pickering emulsion.
2. the calcium alginate compounded microballoon for stablizing water-in-oil type pickering emulsion according to claim 1, its feature
It is that the inorganic nanoparticles of described alkyl silane grafting include TiO2、SiO2、Fe3O4In optional any of which.
3. a kind of preparation method for stablizing the calcium alginate compounded microballoon of water-in-oil type pickering emulsion, it is characterised in that
Comprise the following steps：
First step：The preparation of the inorganic nanoparticles of alkyl silane grafting：
（1）It is the nano particle TiO of 20 ~ 30 nm by commercially available particle diameter2、SiO2、Fe3O4In optional any of which be added to 10 ~
The percent by volume of 15 mL is the H of 30 %2O2In solution, wherein the mass percent of nano particle is 5 ~ 10 %, ultrasonic disperse 5
~ 10 min obtain dispersion liquid；
（2）Dark is placed in after dispersion liquid is sealed and sentences the h of 500 ~ 800 rpm magnetic agitations 2 ~ 6, depressurization and 40 ~ 60oC
Lower drying obtains the modified powder of nanometric particles of hydroxylating；
（3）The modified powder of nanometric particles of hydroxylating after drying is added to the alkyl trichlorine silicon that percent by volume is 1 ~ 5 %
Alkane（Note：Wherein atomic number of alkyl carbon is 6 ~ 10）In the mixed liquor of n-hexane, it is ensured that the consumption of mixed liquor can be completely dispersed and receive
Rice grain, the min of ultrasonic disperse 5 ~ 10, the h of 500 ~ 800 rpm magnetic agitations 8 ~ 12, period supplement n-hexane remains initial
Liquid level；
（4）The dispersion liquid that previous step is obtained is 0 ~ 5oUnder the conditions of C, with the rpm of rotating speed 12000 ~ 15000, centrifugation 5 ~ 15
Min, takes and is deposited in 40 ~ 60oThe nano particle that drying is grafted to alkyl silane under C；
Second step：Prepare water-in-oil type sodium alginate pickering emulsion：
（1）Water phase：Sodium alginate is dissolved in deionized water, the solution that mass percent is 1 ~ 1.5 %, 500 ~ 800 is configured to
8 ~ 12 h deaerations are stood after the min of rpm magnetic agitations 30 ~ 40；
（2）Oil phase：Surfactant is selected any one alkane prepared with first step in Span40/Span60/Span80
The nano particle of base silane grafting is added in atoleine, and wherein the mass percent of surfactant is 3 ~ 9 %, alkyl silicon
The % of mass percent 0.5 ~ 1, the min of magnetic agitation 30 ~ 40 under 500 ~ 800 rpm of the nano particle of alkane grafting；
（3）By above-mentioned water phase and oil phase with volume ratio 2:After 3 mixing, disperseed with Portable high speed under 8000 ~ 10000 rpm
Device emulsifies 30 ~ 40 min and obtains final product water-in-oil type sodium alginate pickering emulsion；
Third step：Prepare water-in-oil type calcium chloride pickering emulsion：With the preparation method of second step, its reclaimed water phase transformation is：
Calcium chloride is dissolved in deionized water, the solution that mass percent is 5 ~ 10 % is configured to, 500 ~ 800 rpm magnetic agitations 30 ~
8 ~ 12 h deaerations are stood after 40 min；Other steps are constant, obtain final product water-in-oil type calcium chloride pickering emulsion；
Four steps：Prepare calcium alginate compounded microballoon：By water-in-oil type sodium alginate pickering emulsion and water-in-oil type chlorination
Calcium pickering emulsion is slowly mixed together, and two kinds of volume ratios of emulsion are 1:1；In 25 ~ 35 °C, 500 ~ 800 rpm magnetic agitation states
The lower h of crosslinking curing 0.5 ~ 1；
5th step：The separation of calcium alginate compounded microballoon：
（1）The jelly that crosslinking curing is obtained is scattered in absolute ethyl alcohol, it is ensured that the consumption of absolute ethyl alcohol can be completely dispersed glue
Shape thing, 5 ~ 10 min are centrifuged under 0 ~ 5 °C with 8000 ~ 10000 rpm；
（2）Remove a layer jelly to be scattered in absolute ethyl alcohol again, it is ensured that the consumption of absolute ethyl alcohol can be completely dispersed jelly i.e.
Can, it is subsequently placed in vortex concussion instrument and mixes 2 ~ 6 min of dispersion, and it is even with 8000 ~ 10000 rpm with Portable high speed disperser
Slurry 2 ~ 3 min of dispersion, 5 ~ 10 min, repeat step are centrifuged under 4 °C again with 8000 ~ 10000 rpm（2）3 ~ 5 times；
（3）By step（2）The jelly for obtaining is scattered in deionized water, it is ensured that the consumption of deionized water can be completely dispersed glue
Thing, 5 ~ 10 min are centrifuged under 0 ~ 5 °C with 8000 ~ 10000 rpm；Abandon supernatant, repeat step（3）2 ~ 3 times；
（4）By step（3）The jelly for obtaining is scattered in n-hexane, it is ensured that the consumption of n-hexane can be completely dispersed jelly i.e.
Can, 5 ~ 10 min are centrifuged with 8000 ~ 10000 rpm under 0 ~ 5 °C；Abandon supernatant, repeat step（4）2 ~ 3 times；
（5）By step（4）The jelly for obtaining dries 24 ~ 36h under 40 ~ 60 °C, obtains final product calcium alginate compounded microballoon.
4. water-in-oil type sodium alginate pickering emulsion according to claim 3, it is characterised in that be mutually alginic acid in it
The inorganic nanoparticles that sodium water solution, Span series of surfactants are grafted with alkyl silane cooperate with stable emulsion.
5. water-in-oil type calcium chloride pickering emulsion according to claim 3, it is characterised in that be mutually calcium chloride water in it
The inorganic nanoparticles that solution, Span series of surfactants are grafted with alkyl silane cooperate with stable emulsion.
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