CN111056982A - Dielectric switch material, preparation method and application - Google Patents
Dielectric switch material, preparation method and application Download PDFInfo
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- CN111056982A CN111056982A CN201911372207.0A CN201911372207A CN111056982A CN 111056982 A CN111056982 A CN 111056982A CN 201911372207 A CN201911372207 A CN 201911372207A CN 111056982 A CN111056982 A CN 111056982A
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- disodium
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- dimercaptomaleonitrile
- switching material
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/54—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and unsaturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention discloses a dielectric switch material, a preparation method and application thereof, and belongs to the field of new materials. Dissolving disodium dimercaptomaleinate, 1-butyl-3-methylimidazolium bromide and nickel chloride hexahydrate in water respectively, uniformly mixing, stirring for 1-2 hours after uniformly mixing to obtain a dark red precipitate, filtering and drying the precipitate, dissolving the dried product by using an organic solvent, and adding I into a dissolved system2And stirring the mixture after the addition is finished until the solution becomes black, standing the mixture for 2 to 3 days, and washing the generated crystals to obtain black strip-shaped crystals, namely the target product.
Description
Technical Field
The invention belongs to the field of new materials, and relates to a dielectric switch material, a preparation method and application thereof.
Background
With the rapid development of microelectronics, the research on electronic device materials at the molecular level is receiving more and more attention. More and more molecular-based switching materials (such as magnetic switching materials, fluorescent switching materials and the like) are used in the fields of temperature sensors, optical switches and the like, and the materials can be converted into two states at a certain temperature. The dielectric switch material is a special substance, generally the material contains easily polarized components, the most basic characteristic of the material is to transmit, store or record the action and influence of an electric field on the material in a polarization mode, and the material has very important application value in the fields of information memory, storage and the like. However, the dielectric switching materials reported so far are very rare.
Disclosure of Invention
The invention aims to provide a dielectric switch material, a preparation method and application thereof aiming at the technical problems.
The purpose of the invention can be realized by the following technical scheme:
a dielectric switching material is prepared by the following steps: dissolving disodium dimercaptomaleinate, 1-butyl-3-methylimidazolium bromide and nickel chloride hexahydrate in water respectively, uniformly mixing, stirring for 1-2 hours after uniformly mixing to obtain a dark red precipitate, filtering and drying the precipitate, dissolving the dried product by using an organic solvent, and adding I into a dissolved system2And stirring the mixture after the addition is finished until the solution becomes black, standing the mixture for 2 to 3 days, and washing the generated crystals to obtain black strip-shaped crystals, namely the target product.
A preparation method of a dielectric switch material comprises the steps of respectively dissolving disodium dimercaptomaleinate, 1-butyl-3-methylimidazolium bromide and nickel chloride hexahydrate in water, uniformly mixing, stirring for 1-2 hours after uniformly mixing to obtain a dark red precipitate, filtering and drying the precipitate, dissolving a dried product by using an organic solvent, and adding I into a dissolved system2And stirring the mixture after the addition is finished until the solution becomes black, standing the mixture for 2 to 3 days, and washing the generated crystals to obtain black strip-shaped crystals, namely the target product.
The technical scheme of the invention is as follows: the molar ratio of disodium dimercaptomaleonitrile, 1-butyl-3-methylimidazole bromine salt and nickel chloride hexahydrate is 1-5: 1-5: 1.
the technical scheme of the invention is as follows: the molar ratio of disodium dimercaptomaleonitrile, 1-butyl-3-methylimidazolium bromide and nickel chloride hexahydrate is 2: 2: 1,2: 3: 1 and 2: 4: 1.
the technical scheme of the invention is as follows: the organic solvent is acetonitrile, methanol, acetone and N, N, dimethyl formamide.
The technical scheme of the invention is as follows: i is2The molar ratio of the dimercaptomaleonitrile disodium to the dimercaptomaleonitrile disodium is 1: 1 to 2.
The technical scheme of the invention is as follows: the target product belongs to a monoclinic system, P21/c space group, and the crystal parameter is
In the order of 10.5716(7),
in the order of 7.2583(4),
26.5198(14), α/° 90, β/° 93.924(6), γ/° 90,
is 2030.1 (2).
In the technical scheme of the invention, the dielectric switch material is applied to the aspect of preparing a dielectric switch.
Drawings
FIG. 1 asymmetric units of the compound of example 1.
FIG. 2 interaction forces between adjacent anions and cations of the compound of example 1.
FIG. 3 is a graph showing the change of dielectric constant with temperature of the compound of example 1.
FIG. 4 thermogravimetric curves of the compound of example 1.
FIG. 5 differential thermal scanning curve of the compound of example 1.
Figure 6 temperature-variable XRD profile of the compound of example 1.
Has the advantages that:
the switch material provided by the invention is simple in preparation method and easy to realize industrial application, and has higher sensitivity when being used as a switch.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1
0.186g of disodium dimercaptomaleinate, 0.219g of 1-butyl-3-methylimidazolium bromide and 0.119g of nickel chloride hexahydrate in a mass ratio of about 2: 2: 1, dissolving in water, mixing, stirring at room temperature for 2h to obtain a dark red precipitate, filtering, and drying. The red, solid product was then dissolved in acetonitrile and 0.126g of I was added2Stirring at room temperature for 0.5h, the solution turned from red to black, then standing for 72h, crystallization occurred, and washing with methanol several times, to give black, long-striped crystals. Purity 95%, yield: 70 percent.
Example 2
0.186g of disodium dimercaptomaleinate, 0.328g of 1-butyl-3-methylimidazolium bromide and 0.119g of nickel chloride hexahydrate in a mass ratio of about 2: 3: 1 is dissolved in water and mixed, stirred for 1.5 hours at room temperature to obtain dark red precipitate, and then filtered and dried. The red, solid product was then dissolved in acetonitrile and 0.252g of I was added2After stirring at room temperature for 0.5h, the solution turned from red to black and then left to stand 48, crystals were produced and washed several times with methanol to give black, long-striped crystals. Purity 90%, yield: 70 percent.
Example 3
0.186g of disodium dimercaptomaleinate, 0.438g of 1-butyl-3-methylimidazolium bromide and 0.119g of nickel chloride hexahydrate in a mass ratio of about 2: 4: 1 is dissolved in water and mixed, stirred for 1 hour at room temperature to obtain dark red precipitate, and then filtered and dried. The red, solid product was then dissolved in N, N, dimethylformamide and 0.126g of I was added2Stirring at room temperature for 0.5h to turn the solution from red to black, standing for 60h to produce crystals, and washing with methanol several times to obtain black crystalsAnd (4) strip-shaped crystals. Purity 85%, yield: 65 percent.
Performance test crystal structure:
the crystal structure of this compound was resolved by X-ray single crystal diffraction, and the crystal structure parameters of this compound (example 1) are shown in Table 1. The crystal of the compound belongs to a monoclinic system, P21/c space group. FIG. 1 shows the smallest asymmetric unit of the crystal, which contains a maledicyanodiunderlene ([ Ni (mnt))2]-) Anion and a 1-butyl-3-methylimidazole [ bmin]+ cation. In this compound, the anion [ Ni (mnt) ]2]-The central atom Ni of the anion is coordinated with four S atoms to form a planar quadrilateral structure. [ bmin]+The cation is in chair configuration and comprises a cis-configured butyl chain. Around each anion, 7 oppositely charged cations are surrounded, and the cations and anions are connected by weak atypical hydrogen bond interactions (FIG. 2)
Table 1 structural refinement parameters of the compounds
Dielectric switching properties:
the curve of the change of dielectric constant with temperature of the compound (example 1) is shown in FIG. 3, at an electric field frequency of 104In Hz, the dielectric constant shows a slow rising trend along with the rise of temperature, the temperature reaches about 379K, and the dielectric constant shows an exponential sharp increase. During the subsequent cooling down, the dielectric constant decreases and two distinct thermally induced loops occur in the temperature interval studied. Thus, the compound can be used as a rare dielectric switching material.
And (3) thermogravimetry:
thermogravimetric analysis of this compound (example 1) was performed between 30 ℃ and 800 ℃ using a thermal analyzer under a nitrogen atmosphere.
The compound shown in FIG. 4 (example 1) has better thermal stability, and starts to decompose around 310 ℃.
Differential thermal scanning (DSC):
the compound (example 1) was subjected to thermodynamic analysis between-50 deg.C and 150 deg.C using differential scanning calorimetry under a nitrogen atmosphere, as shown in FIG. 5. Two endothermic peaks and one exothermic peak (endothermic peak: 106 ℃ C., 122 ℃ C.; exothermic peak: 80 ℃ C.) appeared during the temperature increase/decrease. The endothermic peak is assigned to the solid → solid phase transition.
Variable temperature X-ray powder diffraction (XRD):
the structural phase transition of the compound (example 1) was investigated by variable temperature XRD (fig. 6), and two new phases appeared at 120 ℃ and 135 ℃ with respect to the room temperature phase, and the diffraction peak positions thereof were significantly changed compared to the room temperature phase. This is consistent with the DSC results.
Claims (11)
1. A dielectric switching material, characterized by: the material is prepared by the following steps: dissolving disodium dimercaptomaleinate, 1-butyl-3-methylimidazolium bromide and nickel chloride hexahydrate in water respectively, uniformly mixing, stirring for 1-2 hours after uniformly mixing to obtain a dark red precipitate, filtering and drying the precipitate, dissolving the dried product by using an organic solvent, and adding I into a dissolved system2And stirring the mixture after the addition is finished until the solution becomes black, standing the mixture for 2 to 3 days, and washing the generated crystals to obtain black strip-shaped crystals, namely the target product.
2. A dielectric switching material as defined in claim 1, wherein: the molar ratio of disodium dimercaptomaleonitrile, 1-butyl-3-methylimidazole bromine salt and nickel chloride hexahydrate is 1-5: 1-5: 1.
3. a dielectric switching material as defined in claim 2, wherein: the molar ratio of disodium dimercaptomaleonitrile, 1-butyl-3-methylimidazole bromine salt and nickel chloride hexahydrate is 2: 2: 1,2: 4: 1 and 2: 3: 1.
4. a dielectric switching material as defined in claim 1, wherein: the organic solvent is acetonitrile, methanol, acetone and N, N, dimethylformamide.
5. A dielectric switching material as defined in claim 1, wherein: i is2The molar ratio of the dimercaptomaleonitrile disodium to the dimercaptomaleonitrile disodium is 1: 1 to 2.
6. A dielectric switching material as defined in claim 1, wherein: the target product belongs to a monoclinic system, P21/c space group, and the crystal parameter is
In the order of 10.5716(7),
in the order of 7.2583(4),
26.5198(14), α/° 90, β/° 93.924(6), γ/° 90,
is 2030.1 (2).
7. A method for preparing a dielectric switch material is characterized by comprising the following steps: dissolving disodium dimercaptomaleinate, 1-butyl-3-methylimidazolium bromide and nickel chloride hexahydrate in water respectively, uniformly mixing, stirring for 1-2 hours after uniformly mixing to obtain a dark red precipitate, filtering and drying the precipitate, dissolving the dried product by using an organic solvent, and adding I into a dissolved system2And stirring the mixture after the addition is finished until the solution becomes black, standing the mixture for 2 to 3 days, and washing the generated crystals to obtain black strip-shaped crystals, namely the target product.
8. A method of preparing a dielectric switching material according to claim 7, characterized in that: the molar ratio of disodium dimercaptomaleonitrile, 1-butyl-3-methylimidazole bromine salt and nickel chloride hexahydrate is 1-5: 1-5: 1; preferably: the molar ratio of disodium dimercaptomaleonitrile, 1-butyl-3-methylimidazole bromine salt and nickel chloride hexahydrate is 2: 2: 1,2: 4: 1 and 2: 3: 1.
9. a method of preparing a dielectric switching material according to claim 7, characterized in that: the organic solvent is acetonitrile, methanol, acetone and N, N, dimethylformamide.
10. A method of preparing a dielectric switching material according to claim 7, characterized in that: i is2The molar ratio of the dimercaptomaleonitrile disodium to the dimercaptomaleonitrile disodium is 1: 1 to 2.
11. Use of the dielectric switching material of claim 1 as a dielectric switch.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007055928A (en) * | 2005-08-24 | 2007-03-08 | Mitsui Chemicals Inc | Method for production of maleonitrile |
| CN107021918A (en) * | 2017-05-12 | 2017-08-08 | 南京晓庄学院 | It is a kind of to be coordinated balance cation salt and the magnet formed by metal dithionite alkene complex and preparation method thereof |
| CN107118158A (en) * | 2017-05-02 | 2017-09-01 | 南京晓庄学院 | A kind of magnetic switch material of near room temperature and preparation method thereof |
-
2019
- 2019-12-27 CN CN201911372207.0A patent/CN111056982A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007055928A (en) * | 2005-08-24 | 2007-03-08 | Mitsui Chemicals Inc | Method for production of maleonitrile |
| CN107118158A (en) * | 2017-05-02 | 2017-09-01 | 南京晓庄学院 | A kind of magnetic switch material of near room temperature and preparation method thereof |
| CN107021918A (en) * | 2017-05-12 | 2017-08-08 | 南京晓庄学院 | It is a kind of to be coordinated balance cation salt and the magnet formed by metal dithionite alkene complex and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HAI-BAO DUAN等: "Observation of novel dielectric bistability in a nickel-dithiolene ion-pair compound", 《SYNTHETIC METALS》 * |
| SHAN-SHAN YU: "3-Butyl-1-methyl-1H-imidazol-3-ium bis(1,2-dicyanoethene-1,2-dithiolato-κ2 S,S’)nickel(III)", 《ACTA CRYSTALLOGRAPHICA SECTION E》 * |
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