CN110379577A - Switching mode lotion based on magnetic-particle and preparation method thereof - Google Patents
Switching mode lotion based on magnetic-particle and preparation method thereof Download PDFInfo
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- CN110379577A CN110379577A CN201910613433.7A CN201910613433A CN110379577A CN 110379577 A CN110379577 A CN 110379577A CN 201910613433 A CN201910613433 A CN 201910613433A CN 110379577 A CN110379577 A CN 110379577A
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- 239000006249 magnetic particle Substances 0.000 title claims abstract description 46
- 239000006210 lotion Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 230000005291 magnetic effect Effects 0.000 claims abstract description 27
- 238000012986 modification Methods 0.000 claims abstract description 22
- 230000004048 modification Effects 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- 230000004044 response Effects 0.000 claims abstract description 7
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 238000004945 emulsification Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 229920003656 Daiamid® Polymers 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000412 dendrimer Substances 0.000 claims description 4
- 229920000736 dendritic polymer Polymers 0.000 claims description 4
- 239000004519 grease Substances 0.000 claims description 4
- SENLDUJVTGGYIH-UHFFFAOYSA-N n-(2-aminoethyl)-3-[[3-(2-aminoethylamino)-3-oxopropyl]-[2-[bis[3-(2-aminoethylamino)-3-oxopropyl]amino]ethyl]amino]propanamide Chemical compound NCCNC(=O)CCN(CCC(=O)NCCN)CCN(CCC(=O)NCCN)CCC(=O)NCCN SENLDUJVTGGYIH-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 229910018557 Si O Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940094933 n-dodecane Drugs 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 241000555268 Dendroides Species 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- -1 heptan Alkane Chemical class 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 15
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000002569 water oil cream Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000002907 paramagnetic material Substances 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/0018—Diamagnetic or paramagnetic materials, i.e. materials with low susceptibility and no hysteresis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Soft Magnetic Materials (AREA)
- Cosmetics (AREA)
- Compounds Of Iron (AREA)
Abstract
The lotion and preparation method thereof based on magnetic-particle that the invention discloses a kind of.The lotion is to carry out oil-water emulsion as emulsifier using the magnetic ferroferric oxide particle of dendritic macromole modification, prepares magnetic-particle lotion；And by introducing externally-applied magnetic field, fast emulsion breaking and circulating emulsion of the lotion under magnetic response, demulsification are realized.This method is easy to operate, and magnetic-particle dosage is few, at low cost, reusable, environmentally protective.
Description
Technical field
The invention belongs to surfactant fields, and in particular to a kind of switching mode lotion and its preparation based on magnetic-particle
Method.
Background technique
Several environment sensitive groups are introduced in surfactant molecule, when environmental factor changes, keep surface living
Property agent inner molecular structure changes under the stimulation of external environment (temperature, inorganic salts, magnetic field, pH value, carbon dioxide etc.),
And then by influencing the characteristics such as its polarity and electrostatic force, significant changes occur for table/interfacial characteristics of surfactant, thus
Realize that the activity of oil-water interfaces is controllable.
Magnetic response type surfactant is a kind of novel surfactant, and this surfactant is a kind of with superparamagnetic
The nano-scale particle of property.Superparamagnetism refers to the ferromagnetic material with one-domain structure when particle is less than critical dimension, low in temperature
In Curie temperature and while being higher than transition temperature, shows as paramagnetism feature, but its paramagnetic susceptibility is far high under external magnetic field
In the magnetic susceptibility of general paramagnetic material.The magnetization curve of superparamagnetic material is different from ferromagnet, without hysteresis.When removing outer magnetic
After, remanent magnetism disappears quickly.Being only limitted to it to the research of magnetic particle at present can be used as emulsion stabilizer preparation Pickering
Lotion (magnetic lotion), or lotion is made to be demulsified under the action of an external magnetic field by magnetic response, but to realize simultaneously with
The research of upper two kinds of functions is still lacking.
Summary of the invention
It is an object of the present invention to provide a kind of superparamagnetic iron oxide nanometers of dendritic macromole modification
Grain (Fe3O4@PAMAM magnetic-particle).
The superparamagnetic iron oxide nano particle of dendritic macromole modification provided by the present invention is core-shell structure,
Its core is the ferroferric oxide nano granules with superparamagnetism, and shell is daiamid (PAMAM) dendrimer；It is described
Core and shell are keyed by Si-O.
Wherein, daiamid (PAMAM) the dendrimer branching algebra can be 1-3 (algebra is integer generation).
The partial size of the ferroferric oxide nano granules with superparamagnetism is 10-20nm.
It is a further object to provide the superparamagnetic iron oxide nanometers of above-mentioned dendritic macromole modification
The preparation method of particle.
The preparation method of the superparamagnetic iron oxide nano particle of dendritic macromole modification provided by the present invention,
Include the following steps:
1) using toluene as solvent, 3- in ethanol by the ferroferric oxide nano granules dispersion with superparamagnetism, is added
Aminopropyl trimethoxysilane reagent is reacted, and black particle is obtained；
2) methyl acrylate is added using anhydrous methanol as solvent, in Xiang Suoshu black particle to be reacted, 0.5G is obtained
The magnetic-particle of PAMAM dendrimer modification；
3) using anhydrous methanol as solvent, second two is added in the magnetic-particle of Xiang Suoshu 0.5G PAMAM dendrimer modification
Amine reaction, obtains 1G Fe3O4@PAMAM magnetic-particle.
Above-mentioned steps 1) -3) reaction carried out in nitrogen atmosphere.
In above method step 1), the ferroferric oxide nano granules with superparamagnetism and 3- aminopropyl trimethoxy
The molar ratio of base silane reagent is 1:(1-3).
In above method step 1), the dispersion of the ferroferric oxide nano granules with superparamagnetism in ethanol is dense
Degree is mass percent 1~4%.
In above method step 1), the reaction temperature of the reaction is 90-130 DEG C, and the reaction time is 6-10 hours.
In above method step 2), the dosage of the methyl acrylate is 1-5mol.
In above method step 2), the reaction temperature of the reaction is 30-40 DEG C, and the reaction time is 38-45 hours.
In above method step 3), the dosage of the ethylenediamine is 3-10mol.
In above method step 3), the reaction temperature of the reaction is 40-50 DEG C, and the reaction time is 48-55 hours.
Further object of the present invention is to provide a kind of lotion based on above-mentioned magnetic-particle.
The lotion is prepared by the method comprising the following steps:
The superparamagnetic iron oxide nano particle that the dendritic macromole of above-mentioned preparation is modified is dispersed in appropriate oil
Xiang Zhong, then with grease volume ratio (2-0.5): 1 ratio is added oil and is mutually emulsified with water phase, obtains stable with Fe3O4@
PAMAM is the lotion of emulsifier.
Wherein, the oil mutually concretely n-dodecane, n-decane or normal heptane；The water phase is water (such as secondary water).
The mode of the dispersion is ultrasonic disperse.
The mode of the emulsification are as follows: 20-90s is emulsified with the speed of 2000-3000r/s on vortex mulser.
It is described with Fe3O4@PAMAM is Fe in the lotion of emulsifier3O4The concentration of@PAMAM is 0.1wt%-1wt%.
The superparamagnetic iron oxide particle that the present invention is modified by synthesis dendritic macromole, and utilize its magnetic
Grain is emulsified and is demulsified to lotion, realizes the switching mode of lotion.
The demulsification of lotion based on magnetic-particle:
Outer plus magnet is introduced in lotion bottom and is stirring at low speed lower progress magnetic response demulsification, and lotion can be in a short time
Demulsification.
Circulating emulsion, demulsification based on magnetic-particle lotion:
Select Fe3O4A concentration (0.4wt%) of@PAMAM, by above-mentioned emulsification and breaking method carry out circulating emulsion,
Demulsification recycles five times.
In some embodiments, Fe in switching mode lotion3O4The concentration of@PAMAM magnetic-particle be respectively 0.1wt%,
0.2wt% and 0.4wt%, emulsification times 30s, for oil mutually to analyze pure dodecane, water phase is secondary water.
In some embodiments, the big magnet that externally-applied magnetic field is 0.4T when demulsification, stirring at low speed speed is 30r/min.
Compared with prior art, the invention has the following beneficial effects:
1) present invention is successfully realized the quick emulsification of lotion and demulsification under magnetic response；
2) the lotion magnetic-particle dosage that the present invention is formed is few, can be recycled, emulsification times are short, good emulsion stability.
3) when lotion bottom introduces externally-applied magnetic field, magnetic-particle is acted on the present invention by magnetic field force, destroys original
Force balance state, magnetic-particle are moved to container bottom, realize lotion fast emulsion breaking.
Detailed description of the invention
Fig. 1 is Fe3O4@PAMAM magnetic-particle preparation process schematic diagram；
Fig. 2 is Fe3O4And Fe3O4@PAMAM magnetic-particle shape appearance figure；
Fig. 3 is Fe3O4And Fe3O4@PAMAM magnetic-particle magnetic property figure；
Fig. 4 is various concentration Fe3O4@PAMAM magnetic particle lotion effect picture and lotion micrograph；Wherein (A) is just prepared
Afterwards, (B) is placed 25 days, and (C) places various concentration Fe after 52 days and (D)-(F) just emulsification3O4@PAMAM magnetic particle lotion is micro-
Figure.
Fig. 5 is various concentration Fe3O4@PAMAM magnetic particle emulsion breaking effect picture；
Fig. 6 is Fe3O4@PAMAM magnetic particle lotion circulating emulsion, demulsification figure.
Specific embodiment
The present invention will be described below by way of specific embodiments, but the present invention is not limited thereto, all of the invention
Any modifications, equivalent replacements, and improvements etc. done within spirit and principle, should all be included in the protection scope of the present invention.
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Quantitative test in following embodiments, is respectively provided with three repeated experiments, and results are averaged.
Superparamagnetic Fe used in following embodiments3O4Nanoparticle is bought from Aladdin Reagent Company.
The superparamagnetic iron oxide particle Fe that embodiment 1, dendritic macromole are modified3O4The preparation of@PAMAM
Fe3O4The synthetic route of@PAMAM magnetic-particle is as shown in Figure 1.
The specific method is as follows: in nitrogen atmosphere, by 0.01mol Fe3O4Nano particle is dispersed in 100ml ethyl alcohol, with
200ml toluene is solvent, and 110 DEG C of reaction 8h of 0.0232mol 3- aminopropyl trimethoxysilane reagent are added, obtain black
Grain, then using anhydrous methanol as solvent, is slowly added to 0.05mol methyl acrylate, reacts 40h at 35 DEG C, obtain 0.5G
The magnetic-particle of PAMAM dendrimer modification is slowly added to 0.1mol ethylenediamine finally using 200ml anhydrous methanol as solvent,
50h is reacted at 45 DEG C, obtains 1G Fe3O4@PAMAM magnetic-particle.
To the superparamagnetic iron oxide particle Fe of the dendritic macromole modification of preparation3O4@PAMAM is characterized.Such as
Fe shown in Fig. 2, before modification3O4Magnetic-particle reunion is more serious, and after dendritic macromole modification, magnetic-particle has preferable
Dispersibility, the size of particle about 10-20nm, from Fe3O4It can be seen that core-shell structure copolymer knot in the biggish TEM figure of@PAMAM amplification factor
Structure (blue arrow instruction).
To the superparamagnetic iron oxide particle Fe of the dendritic macromole modification of preparation3O4The magnetic property of@PAMAM into
Row characterization.As shown in figure 3, the hysteresis loop of particle shows above-mentioned Fe without magnetic remanence and remanent magnetism3O4Particle and Fe3O4@PAMAM magnetic
Property particle all has superparamagnetism.From hysteresis loop it can also be seen that superparamagnetic Fe3O4Particle and Fe3O4The saturation magnetic of@PAMAM
Changing intensity is respectively 70emu/g and 56emu/g, due to Fe3O4The presence of the non magnetic organic layer of particle surface, makes the saturation of particle
The intensity of magnetization reduces.
The preparation of embodiment 2, lotion based on magnetic-particle
The Fe for various concentration embodiment 1 will be dispersed with preparing3O4The dodecane (oily phase) of@PAMAM magnetic particle: water is with 2:1
Volume ratio be added to the container, 30s is emulsified with the speed of 2500r/s on vortex mulser, obtains stable Fe3O4@PAMAM
For the lotion of emulsifier.
As shown in figure 4, with emulsifier Fe3O4The increase of@PAMAM content, the volume V of the stable emulsion of formationeIncrease,
And this state can maintain a very long time, and with emulsifier Fe3O4The increase of@PAMAM content, stable emulsion
Volume account for total system volume VtotalRatio (Ve/Vtotal) it is respectively 80%, 90% and 100%, place a period of time, lotion
Less, until placing 25 days, there is a small amount of demulsification in lotion, with emulsifier Fe for variation3O4Cream is stablized in the increase of@PAMAM content
The volume of liquid accounts for total system volume VtotalRatio (Ve/Vtotal) become 75%, 85% and 90%, it tends towards stability substantially later,
It is still varied less after by 52 days.As can be seen that Fe from microphoto3O4When@PAMAM magnetic particle content increases, lotion liquid
Drop partial size becomes smaller, this is primarily due to when emulsifier content is lower, and the emulsion droplet surface of formation does not have enough emulsifiers
Particle makes it stable, so group occur poly or poly simultaneously for drop, until stablizing, therefore size droplet diameter is larger, conversely, size droplet diameter compared with
It is small.
The demulsification of embodiment 3, lotion based on magnetic-particle
The various concentration Fe that will just have been prepared in embodiment 23O4@PAMAM magnetic particle lotion is placed on big magnet (0.4T)
On, and stir at low speed (mixing speed 30r/min) and carry out magnetic response demulsification, demulsification is as shown in Figure 5.As can be seen that not
With concentration Fe3O4@PAMAM magnetic particle emulsion breaking effect is fine, has reached grease and has been kept completely separate, can see in a liquid
Apparent oil-water interfaces are observed, with Fe3O4The increase of@PAMAM magnetic particle content, lotion reach complete demulsification institute's used time when
Between it is longer, demulsification is less susceptible to, demulsification the time be respectively 1min20s, 8min, 17min20s.
Embodiment 4, Fe3O4@PAMAM magnetic particle lotion circulating emulsion, demulsification
A Fe in selection example 23O4@PAMAM magnetic particles 0.4%, by embodiment 2 and embodiment 3
Emulsification and breaking method carry out circulating emulsion, demulsification, recycle five times, effect is as shown in Figure 6.From fig. 6, it can be seen that Fe3O4@
It is still able to maintain original property after the emulsification demulsification of PAMAM magnetic particle to be emulsified and be demulsified again, and the effect that emulsifies and be demulsified
Fruit is still fine, occurs apparent oil-water interfaces after demulsification, has reached grease and has been kept completely separate, Fe3O4@PAMAM magnetic particle is drawing
Demulsification can be reached by entering under externally-applied magnetic field physical action, not need that other medicaments are added, and can reuse.
Claims (10)
1. a kind of superparamagnetic iron oxide nano particle of dendritic macromole modification, it is characterised in that: the dendroid
The superparamagnetic iron oxide nano particle of macromolecular modification is core-shell structure, and core is four oxidations with superparamagnetism
Three iron nano-particles, shell are daiamid dendrimer；The core and shell are keyed by Si-O；The branch
The superparamagnetic iron oxide nano particle of shape macromolecular modification is expressed as Fe3O4@PAMAM magnetic-particle.
2. the superparamagnetic iron oxide nano particle of dendritic macromole modification according to claim 1, feature
Be: the daiamid dendrimer branching algebra is 1,2 or 3；
The partial size of the ferroferric oxide nano granules with superparamagnetism is 10-20nm.
3. the preparation side of the superparamagnetic iron oxide nano particle of dendritic macromole modification of any of claims 1 or 2
Method includes the following steps:
1) using toluene as solvent, 3- ammonia third in ethanol by the ferroferric oxide nano granules dispersion with superparamagnetism, is added
Base trimethoxy silane reagent is reacted, and black particle is obtained；
2) methyl acrylate is added using anhydrous methanol as solvent, in Xiang Suoshu black particle to be reacted, 0.5G PAMAM is obtained
The magnetic-particle of dendrimer modification；
3) it is anti-that ethylenediamine is added using anhydrous methanol as solvent, in the magnetic-particle of Xiang Suoshu 0.5G PAMAM dendrimer modification
It answers, obtains 1G Fe3O4@PAMAM magnetic-particle.
4. preparation method according to claim 3, it is characterised in that: the step 1) -3) described in react in nitrogen
It is carried out in atmosphere；
In the step 1), the ferroferric oxide nano granules with superparamagnetism and 3- aminopropyl trimethoxysilane are tried
The molar ratio of agent is 1:(1-3)；
In the step 1), the dispersion concentration of the ferroferric oxide nano granules with superparamagnetism in ethanol is quality
Percentage 1-4%；
In the step 1), the reaction temperature of the reaction is 90-130 DEG C, and the reaction time is 6-10 hours；
In the step 2), the dosage of the methyl acrylate is 1-5mol；
In the step 2), the reaction temperature of the reaction is 30-40 DEG C, and the reaction time is 38-45 hours；
In the step 3), the dosage of the ethylenediamine is 3-10mol；
In the step 3), the reaction temperature of the reaction is 40-50 DEG C, and the reaction time is 48-55 hours.
5. the superparamagnetic iron oxide nano particle of dendritic macromole modification of any of claims 1 or 2 is as emulsification
The application of agent.
6. a kind of superparamagnetic iron oxide nano particle based on dendritic macromole of any of claims 1 or 2 modification
Lotion preparation method, include the following steps:
By Fe of any of claims 1 or 23O4@PAMAM magnetic-particle is dispersed in appropriate oily phase, then according to grease volume ratio
(2-0.5): 1 ratio is added oil and is mutually emulsified with water phase, obtains with Fe3O4@PAMAM is the lotion of emulsifier.
7. preparation method according to claim 6, it is characterised in that: the oil is mutually n-dodecane, n-decane or positive heptan
Alkane；The water phase is water；
The mode of the dispersion is ultrasonic disperse；
The mode of the emulsification are as follows: 20-90s is emulsified with the speed of 2000-3000r/s on vortex mulser；
It is described with Fe3O4@PAMAM is Fe in the lotion of emulsifier3O4The concentration of@PAMAM is 0.1wt%-1wt%.
8. the lotion that claim 6 or 7 the methods are prepared.
9. the method that lotion described in pair claim 8 is demulsified includes the following steps: the bottom of the lotion described in claim 8
Portion introduces additional magnet and carries out magnetic response under stiring.
10. according to the method described in claim 9, it is characterized by: the externally-applied magnetic field is the magnet of 0.3-0.6T；It is described to stir
It mixes to stir at low speed, mixing speed 20-100r/min.
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| CN116119796A (en) * | 2023-03-03 | 2023-05-16 | 斯坦德技术工程(青岛)有限公司 | Ferroferric oxide nano-composite adsorption flocculant and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111693619A (en) * | 2020-05-18 | 2020-09-22 | 中国石油大学(北京) | P-mercaptobenzoic acid modified magnetic PAMAM dendritic polymer material |
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| CN112479323A (en) * | 2020-11-23 | 2021-03-12 | 上海安赐环保科技股份有限公司 | Emulsion for treating phenolic wastewater, preparation method thereof and wastewater treatment method |
| CN116119796A (en) * | 2023-03-03 | 2023-05-16 | 斯坦德技术工程(青岛)有限公司 | Ferroferric oxide nano-composite adsorption flocculant and preparation method thereof |
| CN116119796B (en) * | 2023-03-03 | 2023-07-14 | 斯坦德技术工程(青岛)有限公司 | Ferroferric oxide nano-composite adsorption flocculant and preparation method thereof |
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