CN100556961C - A kind of core-shell type complex particle and preparation method thereof - Google Patents
A kind of core-shell type complex particle and preparation method thereof Download PDFInfo
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- CN100556961C CN100556961C CNB2006101247261A CN200610124726A CN100556961C CN 100556961 C CN100556961 C CN 100556961C CN B2006101247261 A CNB2006101247261 A CN B2006101247261A CN 200610124726 A CN200610124726 A CN 200610124726A CN 100556961 C CN100556961 C CN 100556961C
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Abstract
A kind of core-shell type complex particle and preparation method thereof, the nuclear of core-shell type complex particle is metallics, or metal oxide particle, as carbonyl iron, iron powder, reduced iron powder, the ferric oxide particle, the Z 250 particle, zinc particles, the zinc oxide particle, gold particle, cobalt particle, the cobalt oxide particle, nickel particles, the nickel oxide particle, copper particle, copper oxide particle, the shell of core-shell type complex particle is a chelate surfactant, one end of tensio-active agent can with metallics, or the metal ion on metal oxide particle surface forms chelate bond, the other end is an organic group, give the affinity of core-shell type complex particle and oil or water, perhaps, make core-shell type complex particle become functional particle by connecing the various functional groups of skill.This method technology is simple, cost is low, efficient is high, and pollutes few.
Description
Technical field
The present invention relates to a kind of core-shell type complex particle and preparation method thereof, particularly a kind of chelate surfactant clad metal, or the core-shell type complex particle of metal oxide and preparation method thereof.
Background technology:
Core-shell type complex particle is a kind of organic-inorganic compoiste particle, examines to be inorganic particulate, and shell is organism or polymer, is the type material of development in recent years.This material gets up the inorganics nuclear protection by organic matter layer; reach and prevent the purpose that is corroded, can also give the functional of composite particles by the functional group of outer field organic molecule; or further grafting has the molecule of functional group, makes it to have various functional.For example, can be dispersed in the organism or in the macromolecular material in order to make micro-sized inorganic particles or nano inoganic particle, at micro-sized inorganic particles or lipophilic organism of nano inoganic particle surface-coated or polymer; After the superfine iron powder particle surface coats organism, can be dispersed in and make magnetic flow liquid in the organic solvent, be used for the vibration and noise reducing of automobile, aircraft, boats and ships, be used for the damping antidetonation of Highrise buildings, bridge; Can be dispersed in behind the nano ferriferrous oxide coating organism and make magnetic fluid in the organic solvent, be used for sealing etc.; After nano oxidized iron particle is coated with the machine thing, pass through the grafting functional group again,, can be used for Clinical Laboratory as antibody or antigen group.
Usually the preparation method of core-shell type complex particle is the sol-gel method preparation.But, coating porous, the compactness of sol-gel method preparation are poor, usually need just can obtain fine and close microtexture by high temperature sintering, yet this method also has problems to need to solve, do not match as thermal expansivity and to cause layering or be full of cracks owing to inorganic core and organic layer, also have inorganic layer and organic matter layer that the pyritous sensitivity is placed restrictions on this method, the reagent of this method consume expensive, cost is higher, and to use organic solvent, or even deleterious solvent such as toluene, do not meet green manufacturing.
The contriver discovers the principle of utilizing the chelation group of positively charged ion and chelate surfactant in the inorganics can form coordinate bond; earlier cleanup acid treatment is carried out on the inorganics surface with suitable acid; make the inorganic particulate surface produce suitable positively charged ion; then; with N-lauroyl ethylenediamine triacetic acid; or N-lauroyl ethylenediamine triacetic acid sodium salt; or N-two lauroyl ethylenediamine triacetic acid sodium salts; or N-hexadecyl ethylenediamine triacetic acid; or N-hexadecyl ethylenediamine triacetic acid sodium salt; or N-polyoxyethylene ether ethylenediamine triacetic acid; or the cationoid reaction on chelating type tensio-active agent such as N-polyoxytrimethylene ether ethylenediamine triacetic acid sodium and inorganic particulate surface, generate chelate bond, thereby organic molecule is combined in the surface of inorganic particulate; prepare inorganics and be nuclear, organic molecule is the core-shell type complex particle of shell.
The core-shell type complex particle of this method preparation can be protected inorganic core and organic original character easily, need not complicated technology, expensive reagent, is a kind of high efficiency, low cost, oligosaprobic environment-friendly preparation method thereof.
Summary of the invention
The object of the present invention is to provide a kind of not only efficient but also free of contamination quick method and the core-shell type complex particle thereof for preparing core-shell type complex particle.This kind core-shell type complex particle can be used for preparing magnetic flow liquid, magnetic fluid, magnetic micro-beads, inoganic particle modified macromolecular material etc.
A kind of core-shell type complex particle of the present invention, the nuclear of its core-shell type complex particle is metallics or metal oxide particle, shell is a chelate surfactant, described chelate surfactant is that the metal ion on an a kind of end and metallics or metal oxide particle surface forms chelate bond, the other end and oil or water have the organic group of affinity, or connect the organic group that skill has functional group.
Wherein said metallics is carbonyl iron, iron powder, reduced iron powder, zinc particles, gold particle, cobalt particle, nickel particles or copper particle.
Described metal oxide particle is ferric oxide particle, Z 250 particle, zinc oxide particle, cobalt oxide particle, nickel oxide particle or copper oxide particle.
Described chelate surfactant is N-alkyl ethylenediamine triacetic acid, N-alkyl ethylene diamine triacetate, N-acyl group ethylenediamine triacetic acid, N-acyl group ethylene diamine triacetate, N-polyether-based ethylenediamine triacetic acid or N-polyether-based ethylene diamine triacetate.
Wherein, described N-alkyl ethylenediamine triacetic acid is N-C
5-C
20The alkyl ethylenediamine triacetic acid is as N-heptane base ethylenediamine triacetic acid, N-octyl ethylenediamine triacetic acid, N-hexadecyl ethylenediamine triacetic acid or N-eicosyl ethylenediamine triacetic acid.
Described N-alkyl ethylene diamine triacetate is N-decyl ethylenediamine triacetic acid sodium salt, N-dodecyl ethylenediamine triacetic acid sodium salt, N-octadecyl ethylenediamine triacetic acid sodium salt or N-eicosyl ethylenediamine triacetic acid sodium salt.
Described N-acyl group ethylenediamine triacetic acid is N-C
5-C
20The acyl group ethylenediamine triacetic acid is as N-12 (bay) acyl group ethylenediamine triacetic acid or N-two lauroyl ethylenediamine triacetic acids
Described N-acyl group ethylene diamine triacetate is N-C
2-C
22The acyl group ethylene diamine triacetate is as N-acetylethylenediamine nitrilotriacetic sodium salt, N-12 (bay) acyl group ethylenediamine triacetic acid sylvite, N-lauroyl ethylenediamine triacetic acid sodium salt or N-two lauroyl ethylenediamine triacetic acid sodium salts.
Described N-polyether-based ethylenediamine triacetic acid is N-polyoxyethylene ether ethylenediamine triacetic acid or N-polyoxytrimethylene ether ethylenediamine triacetic acid.
Described N-polyether-based ethylene diamine triacetate is N-polyoxyethylene ether ethylenediamine triacetic acid sodium or N-polyoxytrimethylene ether ethylenediamine triacetic acid potassium.
The preparation method of core-shell type complex particle of the present invention comprises the steps:
Step 3, the filtering medium that step 2 is obtained change in the wide-mouth vessel, and put into vacuum drying oven in 60～80 ℃ of vacuum-dryings 2～8 hours, obtain exsiccant chelate surfactant clad metal, or the core-shell type complex particle of metal oxide;
Step 4, the chelate surfactant clad metal that step 3 is obtained, or the metal oxide core-shell type complex particle changes in the ball grinder, add steel ball by 1: 1 mass ratio, and with the air in the nitrogen replacement ball grinder, with 100～300 rev/mins rotating speed ball millings 5～10 hours, obtain core-shell type complex particle after will steel ball separating.
The preparation method of core-shell type complex particle of the present invention, technology is simple, and cost is low, the efficient height, and pollute few.
Description of drawings
Fig. 1, carbonyl iron dust and N-polyoxyethylene (5) ether ethylenediamine triacetic acid coat the magnetic hysteresis loop of the core-shell type complex particle of iron carbonyl.
Fig. 2, N-polyoxyethylene (5) ether ethylenediamine triacetic acid coat the transmission electron microscope photo figure of the core-shell type complex particle of iron carbonyl.
The differential thermal analysis curve of Fig. 3, carbonyl iron dust.
Fig. 4, N-polyoxyethylene (5) ether ethylenediamine triacetic acid coat the differential thermal analysis curve of the core-shell type complex particle of iron carbonyl.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Preparation N-polyoxyethylene (5) ether ethylenediamine triacetic acid coats the core-shell type complex particle of iron carbonyl.Its preparation process is:
It is 5% N-polyoxyethylene that step 2, the filtering medium that step 1 is obtained join 100 milliliters of mass concentrations
(5)In the aqueous solution of ether ethylenediamine triacetic acid sodium, stir after 2 hours, suction filtration gets filtering medium;
Step 3, the filtering medium that step 2 is obtained change in the watch-glass, and put into vacuum in dry case in 70 ℃ of vacuum in dry 6 hours, obtain exsiccant composite particles meal;
Step 4, the composite particles meal that step 3 is obtained change in the ball grinder, add steel ball by 1: 1 mass ratio, and with the air in the nitrogen replacement ball grinder, with 300 rev/mins rotating speeds ball milling 6 hours on the star ball mill, obtain core-shell type complex particle after will steel ball separating---N-polyoxyethylene (5) ether ethylenediamine triacetic acid coats the core-shell type complex particle of iron carbonyl.
Test the magnetic hysteresis loop that former carbonyl iron dust and N-polyoxyethylene (5) ether ethylenediamine triacetic acid coat the core-shell type complex particle of iron carbonyl respectively with U.S.'s ADE Model 4HF vibrating sample magnetometer (VSM), see accompanying drawing 1.Wherein 1# is the magnetic hysteresis loop of former carbonyl iron dust, 2# is the magnetic hysteresis loop that N-polyoxyethylene (5) ether ethylenediamine triacetic acid coats the core-shell type complex particle of iron carbonyl, article two, the line contrast is clear that both except saturation magnetization slightly changes (specific magnetising moment of the core-shell type complex particle of N-polyoxyethylene (5) ether ethylenediamine triacetic acid coating iron carbonyl is more smaller than the specific magnetising moment of former iron carbonyl), and other does not change; Illustrate that N-polyoxyethylene (5) ether ethylenediamine triacetic acid is coated to the outside surface of iron carbonyl, this non magnetic organism has reduced the percentage composition of magnetic thing iron carbonyl, and its content is directly proportional with specific magnetising moment reduction value, shows the N-polyoxyethylene
(5)The ether ethylenediamine triacetic acid is the skin that coats iron carbonyl, does not change the carbonyl iron internal structure.
Coat the shell pattern of the core-shell type complex particle of iron carbonyl with Japanese HITACHI H-8100 type TEM (transmission electron microscope) analysis instrument test N-polyoxyethylene (5) ether ethylenediamine triacetic acid, see Fig. 2, from figure, can clearly go out to see that the carbonyl iron surface has coated organic matter layer, change consistent with the magnetic property of particle.
(model: STA 449C) test carbonyl iron and N-polyoxyethylene (5) ether ethylenediamine triacetic acid coat the thermogravimetric analysis figure of the core-shell type complex particle of iron carbonyl with the anti-comprehensive thermal analyzer of speeding of Germany, Fig. 3 illustrates that untreated carbonyl iron begins obvious increase 200 ℃ of quality, and oxidation has promptly taken place.And Fig. 4 shows at 120-250 ℃ mass loss is arranged by the nucleocapsid composite particles after the processing, illustrates that particle has the casing layer, increases 300 ℃ of quality, and oxidation has taken place.The core-shell type complex particle antioxidant property that N-polyoxyethylene (5) ether ethylenediamine triacetic acid coating iron carbonyl is described has had tangible improvement, and the particle that proves preparation is the core-shell type complex particle that organism coats iron carbonyl.
With N-polyoxyethylene (5) ether ethylenediamine triacetic acid, perhaps N-polyoxyethylene (5) ether ethylenediamine triacetic acid potassio is for N-polyoxyethylene (5) ether ethylenediamine triacetic acid sodium, adopt the identical condition of embodiment 1, prepare-N-polyoxyethylene (5) ether ethylenediamine triacetic acid coats the core-shell type complex particle of iron carbonyl.
Preparation N-polyoxytrimethylene (8) ether ethylenediamine triacetic acid coats the core-shell type complex particle of reduced iron.Its preparation process is:
Step 3, the filtering medium that step 2 is obtained change in the watch-glass, and put into vacuum drying oven in 60 ℃ of vacuum-dryings 6 hours, obtain exsiccant composite particles meal;
Step 4, the composite particles meal that step 3 is obtained change in the ball grinder, add steel ball by 1: 1 mass ratio, and with the air in the nitrogen replacement ball grinder, with 300 rev/mins rotating speeds ball milling 8 hours on the star ball mill, obtain core-shell type complex particle after will steel ball separating---N-polyoxytrimethylene (8) ether ethylenediamine triacetic acid coats the core-shell type complex particle of reduced iron.
Embodiment 3
Preparation N-two lauroyl ethylenediamine triacetic acids coat the core-shell type complex particle of zinc.Its preparation process is:
Step 3, the filtering medium that step 2 is obtained change in the watch-glass, and put into vacuum drying oven in 60 ℃ of vacuum-dryings 4 hours, obtain exsiccant composite particles meal;
Step 4, the composite particles meal that step 3 is obtained change in the ball grinder; add steel ball by 1: 1 mass ratio; and with the air in the nitrogen replacement ball grinder; with 200 rev/mins rotating speeds ball milling 10 hours on the star ball mill, obtain core-shell type complex particle after will steel ball separating---N-two lauroyl ethylenediamine triacetic acids coat the core-shell type complex particle of zinc.
With N-C
5～C
20Acyl group ethylenediamine triacetic acid or N-C
2-C
21Acyl group ethylenediamine triacetic acid sodium salt or sylvite replace N-two lauroyl ethylenediamine triacetic acid sodium, adopt the identical preparation condition of embodiment 3, can prepare the core-shell type complex particle that corresponding N-acyl group ethylenediamine triacetic acid coats zinc.Replace zinc particles with other metallicss of the present invention or metal oxide particle, can prepare the corresponding metal particle of N-two lauroyl ethylenediamine triacetic acids coating or the core-shell type complex particle of metal oxide particle.
Embodiment 4
The core-shell type complex particle of preparation N-polyoxyethylene (10) ether ethylenediamine triacetic acid coated ferriferrous oxide.Its preparation process is:
Step 1,100 gram Z 250 powder are joined in the HCl aqueous solution that 100 ml concns are 0.1 mol, stirred 10 minutes, suction filtration gets filtering medium;
Step 3, the filtering medium that step 2 is obtained change in the watch-glass, and put into vacuum drying oven in 60 ℃ of vacuum-dryings 2 hours, obtain exsiccant composite particles meal;
Step 4, the composite particles meal that step 3 is obtained change in the ball grinder, add steel ball by 1: 1 mass ratio, and with the air in the nitrogen replacement ball grinder, with 100 rev/mins rotating speeds ball milling 5 hours on the star ball mill, obtain core-shell type complex particle after will steel ball separating---the core-shell type complex particle of N-polyoxyethylene (10) ether ethylenediamine triacetic acid coated ferriferrous oxide.
Embodiment 5
Preparation N-hexadecyl ethylenediamine triacetic acid coats the core-shell type complex particle of nickel.Its preparation process is:
Step 3, the filtering medium that step 2 is obtained change in the watch-glass, and put into vacuum drying oven in 80 ℃ of vacuum-dryings 8 hours, obtain exsiccant composite particles meal;
Step 4, the composite particles meal that step 3 is obtained change in the ball grinder, add steel ball by 1: 1 mass ratio, and with the air in the nitrogen replacement ball grinder, with 300 rev/mins rotating speeds ball milling 10 hours on the star ball mill, obtain core-shell type complex particle after will steel ball separating---N-hexadecyl ethylenediamine triacetic acid coats the core-shell type complex particle of nickel.
Use N-C
5-C
20Alkyl ethylenediamine triacetic acid, N-C
5-C
20Alkyl ethylenediamine triacetic acid potassium or N-C
5-C
20Other sodium salts of alkyl ethylenediamine triacetic acid replace N-hexadecyl ethylenediamine triacetic acid sodium, adopt present embodiment 5 similar methods, can prepare N-C
5-C
20The alkyl ethylenediamine triacetic acid coats the core-shell type complex particle of nickel.
Embodiment 6
Preparation N-lauroyl ethylenediamine triacetic acid coats the core-shell type complex particle of cobalt.Its preparation process is:
Step 3, the filtering medium that step 2 is obtained change in the watch-glass, and put into vacuum drying oven in 50 ℃ of vacuum-dryings 8 hours, obtain exsiccant composite particles meal;
Step 4, the composite particles meal that step 3 is obtained change in the ball grinder; add steel ball by 1: 1 mass ratio; and with the air in the nitrogen replacement ball grinder; with 250 rev/mins rotating speeds ball milling 9 hours on the star ball mill, obtain core-shell type complex particle after will steel ball separating---N-lauroyl ethylenediamine triacetic acid coats the core-shell type complex particle of cobalt.
Claims (8)
1, a kind of core-shell type complex particle, it is characterized in that: the nuclear of described core-shell type complex particle is metallics, shell is a chelate surfactant, and wherein, described metallics is carbonyl iron, iron powder, zinc particles, gold particle, cobalt particle, nickel particles or copper particle; Described chelate surfactant is that an a kind of end can form chelate bond with the atoms metal or the ion on metallics surface; the other end and oil or water have the organic group of affinity; or connecing the organic group that skill has functional group, described chelate surfactant specifically is N-alkyl ethylenediamine triacetic acid, N-alkyl ethylene diamine triacetate, N-acyl group ethylenediamine triacetic acid, N-acyl group ethylene diamine triacetate, N-polyether-based ethylenediamine triacetic acid or N-polyether-based ethylene diamine triacetate.
2, core-shell type complex particle according to claim 1 is characterized in that: described N-alkyl ethylenediamine triacetic acid is N-heptane base ethylenediamine triacetic acid, N-octyl ethylenediamine triacetic acid, N-hexadecyl ethylenediamine triacetic acid or N-eicosyl ethylenediamine triacetic acid.
3, core-shell type complex particle according to claim 1 is characterized in that: described N-alkyl ethylene diamine triacetate is N-decyl ethylenediamine triacetic acid sodium salt, N-dodecyl ethylenediamine triacetic acid sodium salt, N-octadecyl ethylenediamine triacetic acid sodium salt or N-eicosyl ethylenediamine triacetic acid sodium salt.
4, core-shell type complex particle according to claim 1 is characterized in that: described N-acyl group ethylenediamine triacetic acid is N-lauroyl ethylenediamine triacetic acid or N-two lauroyl ethylenediamine triacetic acids.
5, core-shell type complex particle according to claim 1 is characterized in that: described N-acyl group ethylene diamine triacetate is N-acetylethylenediamine nitrilotriacetic sodium salt, N-lauroyl ethylenediamine triacetic acid sylvite, N-lauroyl ethylenediamine triacetic acid sodium salt or N-two lauroyl ethylenediamine triacetic acid sodium salts.
6, core-shell type complex particle according to claim 1 is characterized in that: described N-polyether-based ethylenediamine triacetic acid is N-polyoxyethylene ether ethylenediamine triacetic acid or N-polyoxytrimethylene ether ethylenediamine triacetic acid.
7, core-shell type complex particle according to claim 1 is characterized in that: described N-polyether-based ethylene diamine triacetate is N-polyoxyethylene ether ethylenediamine triacetic acid sodium or N-polyoxytrimethylene ether ethylenediamine triacetic acid potassium.
8, the preparation method of the described core-shell type complex particle of claim 1 is characterized in that comprising the steps:
Step 1, metallics is joined in the aqueous solution of HCl that concentration is 0.05～1 mol or phosphoric acid or sulfuric acid or nitric acid or hydrofluoric acid, stirred 5～30 minutes, suction filtration gets filtering medium;
Step 2, the filtering medium that step 1 is obtained join in the aqueous solution that mass concentration is 1%～10% chelate surfactant, stir after 1～2 hour, and suction filtration gets filtering medium;
Step 3, the filtering medium that step 2 is obtained change in the wide-mouth vessel, and put into vacuum drying oven in 60～80 ℃ of vacuum-dryings 2～8 hours, obtain the core-shell type complex particle of exsiccant chelate surfactant clad metal particle;
The core-shell type complex particle of step 4, chelate surfactant clad metal particle that step 3 is obtained changes in the ball grinder, add steel ball by 1: 1 mass ratio, and with the air in the nitrogen replacement ball grinder, with 100～300 rev/mins rotating speed ball millings 5～10 hours, obtain core-shell type complex particle after will steel ball separating.
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| JP5879686B2 (en) * | 2009-10-15 | 2016-03-08 | 東レ株式会社 | Method for producing core-shell particles, core-shell particles, paste composition using the same, and sheet composition |
| CN102153930B (en) * | 2011-04-22 | 2014-09-03 | 大连市轻化工研究所 | Chelate type flashing erosion-resistant water-based metal anticorrosion coating and preparation method thereof |
| CN102881392A (en) * | 2011-07-15 | 2013-01-16 | 北京格加纳米技术有限公司 | Functionalized magnetic particle and synthetic method thereof |
| CN104008845B (en) * | 2014-06-10 | 2017-02-15 | 冯智勇 | Magneticfluid sealing material |
| CN104445439B (en) * | 2014-12-20 | 2016-10-05 | 姚阿连 | A kind of preparation method of the copper oxide of nucleocapsid structure-ferroso-ferric oxide composite magnetic |
| CN107262113B (en) * | 2017-06-29 | 2019-11-12 | 济南大学 | Core-shell structure NiO/Au/Fe2O3The preparation of nanocomposite |
| CN113611846B (en) * | 2021-07-29 | 2023-04-18 | 中汽创智科技有限公司 | Electrode material of lithium battery and preparation method and application thereof |
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| 聚乙二醇包裹羰基铁核壳粒子的制备及水基磁流变液的性能. 李立春等.物理化学学报，第21卷第7期. 2005 * |
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