CN107151205A - Erucic acid metal complex and preparation method thereof - Google Patents

Erucic acid metal complex and preparation method thereof Download PDF

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Publication number
CN107151205A
CN107151205A CN201610969355.0A CN201610969355A CN107151205A CN 107151205 A CN107151205 A CN 107151205A CN 201610969355 A CN201610969355 A CN 201610969355A CN 107151205 A CN107151205 A CN 107151205A
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erucic acid
preparation
metal complex
acid metal
metal
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CN107151205B (en
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樊海明
张欢
刘晓丽
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Northwest University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0072—Mixed oxides or hydroxides containing manganese
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

The invention discloses a kind of erucic acid metal complex and preparation method thereof.Structural formula（1）Shown erucic acid metal complex, M (eruciate)x （1）, wherein M=Fe, Mn, Co, Ni, Zn and Cu, eruciate are the erucic acid root for sloughing proton, X=2 or 3.This method realizes the preparation of complex by using metal and complexation reaction of the erucic acid in proton solvent, technological process is simple, and simple and efficient to handle, reaction condition is gentle, prepare cost low, stability is good, nontoxic, has universality in such erucic acid metal complex is prepared, it can prepare on a large scale, such complex overcomes the deficiency of existing predecessor, can be prepared as predecessor nontoxic, environmentally friendly, with low cost nanocrystalline, and being that preparation of industrialization is nanocrystalline lays the foundation.

Description

Erucic acid metal complex and preparation method thereof
Technical field
The present invention relates to a kind of erucic acid metal complex and preparation method thereof, belong to organic material preparing technical field.
Background technology
In recent years, continuing to develop with nano particle technology of preparing, especially along with high temperature thermal decomposition method at single point The important breakthrough in terms of nanocrystal preparation is dissipated, selects safe, simple, cheap, general, environment-friendly predecessor to be received to realize Rice grain size, pattern, the controllable preparation of component have turned into development trend and the technological challenge that current nanochemistry is synthesized.When Before, nanocrystal, which synthesizes relied on predecessor, includes levulinic ketone complex（Ferric acetyl acetonade etc.）, carbonyl class complex （Iron pentacarbonyl etc.）, metal organic complex（Zinc methide, dimethyl chromium etc.）Deng often toxicity compares these predecessors Greatly, expensive, unstable, explosive, the complex device as glove box is must be equipped with using such predecessor, and prepared Nanocrystal in quality and the advantage for not showing other style in nature.Therefore, select it is safe, simple, cheap, general, Environment-friendly predecessor prepares nano particle turns into the inexorable trend of current nanochemistry synthetic technology, and to receive later Meter Jing Ti industrialized productions establish good basis.
Erucic acid Chinese nickname water mustard oleic acid, overgrown with weeds acid, savoy acid, Erucic Acid, (Z) -13- docosenes Acid, erucic acid, 13- docosenoic acids, rape acid, cis-13-docosenoic acid is colourless needles knot Crystalline substance, molecular formula is C9H18=C13H24O2, belong to fatty acid compound, it is water insoluble, ethanol, methanol are dissolved in, ether is soluble in.
The content of the invention
It is an object of the invention to provide a kind of erucic acid metal complex and its preparation method and application.
The implementation process of the present invention is as follows：
Structural formula（1）Shown erucic acid metal complex,
M(eruciate)x （1）,
Wherein M=Fe, Mn, Co, Ni, Zn and Cu, eruciate are the erucic acid root for sloughing proton, X=2 or 3.
The preparation method of above-mentioned erucic acid metal complex, is comprised the following steps：
（1）Metal salt and erucic acid are dissolved in protonic solvent and obtain solution A, the metal in the metal salt be Fe, Mn, Co, Ni, Zn and Cu；
（2）Highly basic is dissolved in protonic solvent and obtains solution B；
（3）Solution B is added in solution A, question response terminates, after precipitation and separation is washed for several times with deionized water and protonic solvent Vacuum drying.
The metal salt is metal chloride, metal sulfate, metal nitrate and metal acetate salt etc..
The protonic solvent is water, methanol, ethanol, formic acid, acetic acid or ethamine etc..
The highly basic is sodium hydroxide, potassium hydroxide etc..
The metal salt, the concentration of erucic acid and highly basic dissolution/dispersion in protonic solvent are 0.01-100 mmol/mL.
Described metal salt and the mol ratio of erucic acid are 1:100~100:1, the mol ratio of highly basic and erucic acid is 1:100~ 100:1。
Step in preparation process（1）、（2）With（3）Temperature needed for dissolving, scattered and reaction is 20-80 DEG C.Preparation terminates It is 20-80 DEG C that product, which carries out vacuum drying temperature, afterwards, and vacuum drying time is 1-24 h.
The erucic acid metal complex in inorganic nano-crystal is prepared as predecessor application, particularly as solwution method Prepare the predecessor of inorganic nano-crystal.Inventor's discovery can be prepared extra small nanocrystalline using the predecessor.
Advantages of the present invention and good effect：This method is by using metal and complexation reaction of the erucic acid in proton solvent To realize the preparation of complex, technological process is simple, simple and efficient to handle, and reaction condition is gentle, and preparation cost is low, stability It is good, it is nontoxic, there is universality in such erucic acid metal complex is prepared, can prepare on a large scale, such complex overcomes The deficiency of existing predecessor, can prepare nanocrystalline, preparation of industrialization after being as predecessor nontoxic, environmentally friendly, with low cost It is nanocrystalline to lay the foundation.
Brief description of the drawings
Fig. 1 is the erucic acid iron pictorial diagram prepared by the present invention；
Fig. 2 is the erucic acid iron infrared spectrogram (FTIR) prepared by the present invention；
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of the erucic acid iron prepared by the present invention1HNMR；
Fig. 4 is the erucic acid irony spectrogram prepared by the present invention；
Fig. 5 (a) and (d) are 2 nm MnFe2O4Nanocrystalline transmission electron microscope (TEM) figure, Fig. 5 (b) and (e) are 3 nm MnFe2O4Nanocrystalline TEM figures, Fig. 5 (c) and (f) are 3.9 nm MnFe2O4Nanocrystalline TEM figures；
Prepared 2 nm, 3 nm and 3.9 nm MnFe in Fig. 6 embodiment of the present invention2O4Nanocrystalline X-ray powder diffraction (XRD) figure.
Embodiment
For the object, technical solution and advantage of invention are more clearly understood, the embodiment that develops simultaneously referring to the drawings is to hair It is bright to be further described.
Embodiment 1：The preparation of erucic acid iron
5 g Iron(III) chloride hexahydrates and 30 g erucic acid are dissolved in 200 mL methanol, after mixed solution is sufficiently stirred for, drip thereto Plus the 300 mL methanol solutions containing 4 g KOH, the precipitation methanol and ultra-pure water of generation lotion repeatedly, it is put into vacuum drying chamber 30 DEG C of dryings 4 hours, as shown in Figure 1.
By prepared erucic acid iron wax-like products and the uniform rear compressing tablet process of KBr grinding, infrared spectrum is then tested. Fig. 2 is the infrared spectrogram of prepared erucic acid iron, it can be seen that prepared erucic acid iron shows Carboxylates Eigen vibration peak, the eigen vibration peak of erucic acid iron is in 1590 cm-1, 1531 cm-1With 1445 cm-1, wherein 1590 cm-1With 1531 cm-1It is the nonsymmetrical vibration peak of carboxyl functional group in erucic acid iron；1445 cm-1It is the middle carboxyl functional group of erucic acid iron Symmetric vibration peak.
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of prepared erucic acid iron.A little erucic acid iron and manganese oleate are dissolved in deuterated chlorine In imitative, load nuclear magnetic tube and tested.The chemistry of hydrogen atom under the different chemical environments of erucic acid iron is can be seen that from Fig. 3 test results Displacement can be matched with analog result.
Fig. 4 is the mass spectrogram of prepared erucic acid iron, and a little erucic acid iron and manganese oleate are dispersed in methanol or acetonitrile Row mass spectral analysis.
Embodiment 2：The preparation of erucic acid zinc
7 g zinc acetates and 30 g erucic acid are dissolved in 200 mL ethanol, after mixed solution is sufficiently stirred for, and be added dropwise contain 4 g thereto KOH 300 mL ethanol solutions, the precipitation methanol and ultra-pure water of generation lotion repeatedly is put into vacuum drying chamber 30 DEG C and done Dry 4 hours.
Embodiment 3：The preparation of erucic acid nickel
6 g nickel nitrates and 30 g erucic acid are dissolved in 200 mL ethanol, after mixed solution is sufficiently stirred for, and be added dropwise contain 5 g thereto KOH 300 mL ethanol solutions, the precipitation methanol and ultra-pure water of generation lotion repeatedly is put into vacuum drying chamber 30 DEG C and done Dry 4 hours.
Embodiment 4：2 nm MnFe2O4Nanocrystalline preparation
(1) synthesis of presoma
Erucic acid iron：5 g Iron(III) chloride hexahydrates and 18 g erucic acid are dissolved in 200 mL methanol, after mixed solution is sufficiently stirred for, to The solution that 200 mL methanol contain 4 g NaOH is wherein added dropwise.The precipitation methanol and ultra-pure water of generation lotion repeatedly, are put into vacuum 30 DEG C of dryings 4 hours in drying box.
Manganese oleate：The chloride hydrate manganese of 4 g tetra- and 14 g oleic acid are dissolved in 150 mL methanol, after mixed solution is sufficiently stirred for, The solution that 200 mL methanol contain 4 g NaOH is added dropwise thereto.The precipitation methanol and ultra-pure water of generation lotion repeatedly, are put into true 30 DEG C of dryings 4 hours in empty drying box.
(2)2 nm MnFe2O4Nanocrystalline preparation
3 g erucic acid iron, 2 g manganese oleates and 0.5 g oleyl alcohol are weighed respectively, are dissolved into 8 g benzyl ether, are stirred under nitrogen atmosphere Mix and be sufficiently mixed uniformly；
Mixture is warming up to 245 DEG C with 15 DEG C/min speed, and flow back 45 min；
Mixture cools to room temperature, and 10 mL acetone are added to mixture, centrifuge sediment, sediment is scattered in into 10 mL first Benzene, is repeated 3 times.
Embodiment 5：3 nm MnFe2O4Nanocrystalline preparation
The synthesized reference embodiment 4 of predecessor erucic acid iron and manganese oleate.
4 g erucic acid iron, 3 g manganese oleates, 0.5 g oleyl alcohol and 1 g oleic acid are weighed respectively, are dissolved into 8 g dioctyl ethers, Stirring is sufficiently mixed uniform under nitrogen atmosphere；
Mixture is warming up to 245 DEG C with 15 DEG C/min speed, and flow back 45 min；
Mixture cools to room temperature, and 10 mL methanol are added to mixture, centrifuge sediment, sediment is being scattered in into 10 mL just Hexane, is repeated 3 times.
Embodiment 6：3.9 nm MnFe2O4Nanocrystalline preparation
The synthesized reference embodiment 4 of predecessor erucic acid iron and manganese oleate.
5 g erucic acid iron, 3 g manganese oleates, 1 g oleyl alcohol and 1 g oleic acid are weighed respectively, are dissolved into 8 g octadecylenes, nitrogen Atmosphere is enclosed lower stirring and is sufficiently mixed uniformly；
Mixture is warming up to 255 DEG C with 15 DEG C/min speed, and flow back 45 min；
Mixture cools to room temperature, and 10 mL ethanol are added to mixture, centrifuge sediment, sediment is scattered in into 10 mL chlorine It is imitative, it is repeated 3 times.
By 2 nm prepared by about 2 μ L, 3 nm and 3.9 nm MnFe2O4It is nanocrystalline drop in be coated with carbon film Cu it is online, After natural drying, transmission electron microscope is done.Fig. 5 is 2 nm, 3 nm and 3.9 nm MnFe prepared by embodiment 4,5,6 respectively2O4Receive Rice crystalline substance TEM figures.It can be seen that 2 prepared nm, 3 nm and 4 nm MnFe2O4Nanocrystalline uniform particle sizes, to nanometer Crystalline substance carries out Size Distribution statistics, and it is respectively 2 nm, 3 nm and 3.9 nm as a result to show average-size.
Fig. 6 is 2 nm, 3 nm and 3.9 nm MnFe prepared by embodiment 4,5,62O4Nanocrystalline XRD（Cu/Kα Target, the nm of λ=0.15418）.The MnFe of inverse spinel structure as can see from Figure 62O4Nanocrystalline（111）、（220）、 （311）、（400）、（511）、（440）With（622）Diffraction maximum, according to most strong（311）2 θ=34.980 ° of diffraction maximum, by Scherrer It is respectively 2.07 nm, 2.98 nm and 4.29 nm MnFe that formula, which calculates and obtains crystallite dimension,2O4It is nanocrystalline.
Above case study on implementation is served only for that the invention will be further described, it is impossible to be interpreted as the limit to the scope of the present invention System, some nonessential modifications and adaptations that those skilled in the art makes according to the above of the present invention belong to this hair Bright protection domain.

Claims (9)

1. structural formula（1）Shown erucic acid metal complex,
M(eruciate)x （1）,
Wherein M=Fe, Mn, Co, Ni, Zn and Cu, eruciate are the erucic acid root for sloughing proton, X=2 or 3.
2. the preparation method of the erucic acid metal complex described in claim 1, it is characterised in that comprise the following steps：
（1）Metal salt and erucic acid are dissolved in protonic solvent and obtain solution A, the metal in the metal salt be Fe, Mn, Co, Ni, Zn and Cu；
（2）Highly basic is dissolved in protonic solvent and obtains solution B；
（3）Solution B is added in solution A, question response terminates, after precipitation and separation is washed for several times with deionized water and protonic solvent Vacuum drying.
3. the preparation method of erucic acid metal complex according to claim 2, it is characterised in that：Described metal salt is selected from gold Belong to chloride, metal sulfate, metal nitrate and metal acetate salt.
4. the preparation method of erucic acid metal complex according to claim 2, it is characterised in that：The protonic solvent is Water, methanol, ethanol, formic acid, acetic acid or ethamine.
5. the preparation method of erucic acid metal complex according to claim 2, it is characterised in that：The highly basic is selected from hydroxide Sodium, potassium hydroxide.
6. the preparation method of erucic acid metal complex according to claim 2, it is characterised in that：Described metal salt and erucic acid Mol ratio be 1:100~100:1, the mol ratio of highly basic and erucic acid is 1:100~100:1.
7. the preparation method of erucic acid metal complex according to claim 2, it is characterised in that：The metal salt, erucic acid and The concentration that highly basic is dissolved in proton solvent is 0.01-100 mmol/mL.
8. the preparation method of erucic acid metal complex according to claim 2, it is characterised in that：Step（1）、（2）With（3）'s Reaction temperature is 20-80 DEG C.
9. erucic acid metal complex conduct in the inorganic nano-crystal for prepare Fe, Mn, Co, Ni, Zn and Cu described in claim 1 The application of predecessor.
CN201610969355.0A 2016-11-07 2016-11-07 Erucic acid metal complex and preparation method thereof Active CN107151205B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111635306A (en) * 2020-06-12 2020-09-08 上海海益环保科技有限公司 Erucic acid composite stabilizer and method for preparing stable erucic acid

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JP2000191923A (en) * 1998-12-24 2000-07-11 Japan Polychem Corp Metallic soap for thermoplastic resin
JP2006026481A (en) * 2004-07-13 2006-02-02 Fuji Photo Film Co Ltd Method for breaking metal salt or amide of fatty acid into fine particle
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111635306A (en) * 2020-06-12 2020-09-08 上海海益环保科技有限公司 Erucic acid composite stabilizer and method for preparing stable erucic acid
CN111635306B (en) * 2020-06-12 2022-09-27 上海海益环保科技有限公司 Erucic acid composite stabilizer and method for preparing stable erucic acid

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