CN115819784A - Preparation method of porous liquid crystal composite material with molecular switch - Google Patents
Preparation method of porous liquid crystal composite material with molecular switch Download PDFInfo
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- CN115819784A CN115819784A CN202211228048.9A CN202211228048A CN115819784A CN 115819784 A CN115819784 A CN 115819784A CN 202211228048 A CN202211228048 A CN 202211228048A CN 115819784 A CN115819784 A CN 115819784A
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Abstract
The invention discloses a preparation method of a porous liquid crystal composite material with a molecular switch, which comprises the following steps: stirring a certain amount of molecular switch monomer and organic ligand unit in glacial acetic acid and heating for a period of time; the reaction mixture was cooled to room temperature and saturated NaHCO was slowly added 3 A solution, neutralizing the solution; extracting with chloroform for three times to obtain an organic phase; the organic phase is MgSO 4 Drying to obtain a crude product; removing chloroform from the crude product, and purifying by column chromatography to obtain 2- (phenyl diazanyl) terephthalic acid; and introducing the 2- (phenyl diazenyl) terephthalic acid into an MOF organic connecting agent by adopting a ligand exchange method to obtain the porous liquid crystal composite material with the molecular switch. The method can be used for preparing various porous liquid crystal composite materials with the molecular switch, wherein the porous liquid crystal composite materials with the molecular switch are used for manufacturing photosensitive liquid crystal screen equipment. UV molecular switch porous liquid crystal composite materialIt can be used for a photosensitive liquid crystal screen device.
Description
Technical Field
The invention belongs to the technical field of liquid crystal composite materials, and particularly relates to a preparation method of a porous liquid crystal composite material with a molecular switch.
Background
Liquid crystal, as a flowable anisotropic material, is easily stimulated by external forces such as an electric field, a magnetic field, heat, mechanical force, etc. to change the molecular alignment orientation, thereby realizing the adjustment of light. Among them, the liquid crystal material that realizes the transition by means of pressure, magnetic field, etc. can realize the fast response effect of high definition and high image capacity due to its excellent electro-optical effect, and has been widely used in the display field, forming the mature liquid crystal display industry. However, the conventional porous liquid crystal composite material is difficult to be transformed by means of external conditions such as heating, light irradiation and the like. The existing liquid crystal material which realizes the conversion by adopting the modes of heating, light irradiation and the like has weak electro-optic effect and not quick response effect. Therefore, it is necessary to develop a non-contact liquid crystal composite.
Disclosure of Invention
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a porous liquid crystal composite material with a molecular switch comprises the following steps: stirring a certain amount of molecular switch monomer and organic ligand unit in glacial acetic acid and heating for a period of time; the reaction mixture was cooled to room temperature and saturated NaHCO was slowly added 3 A solution, neutralizing the solution; extracting with chloroform for three times to obtain an organic phase; the organic phase is MgSO 4 Drying to obtain a crude product; removing chloroform from the crude product, and purifying by column chromatography to obtain 2- (phenyl diazanyl) terephthalic acid; introducing the 2- (phenyl diazenyl) terephthalic acid into an MOF organic connecting agent by adopting a ligand exchange method to obtain a porous liquid crystal composite material with a molecular switch, wherein a molecular switch monomer is
Wherein the organic ligand unit is 2-amino terephthalic acid.
Preferably, in the above technical solution, the molar ratio of the molecular switch monomer, 2-aminoterephthalic acid, and glacial acetic acid is 1:1:0.1.
preferably, the molecular switch monomer and the organic ligand unit are stirred and heated in glacial acetic acid, the heating temperature is 40 ℃, and the duration time is 24 hours.
Preferably, the chloroform extraction process comprises the following steps: the molecular switch monomer and the organic ligand unit were mixed in chloroform and stirred for 30 minutes, and then the solvent was separated to leave an organic phase.
Preferably, the organic phase is MgSO 4 The specific process of drying is as follows: adding magnesium sulfate into organic solution for dryingDrying with 40 deg.C drying agent in oven for 24 hr.
Preferably, the specific process for removing chloroform from the crude product comprises the following steps: performing rotary evaporation on the solution at 70 ℃, collecting the residual liquid for further use, and performing column chromatography purification specifically as follows: and (3) filling the column with normal hexane wet silica gel, selecting petroleum ether containing 1% of acetone as a mobile phase, and controlling the flow rate by using a constant flow pump to separate a crude product.
Preferably, in the above technical scheme, the MOF metal source is any one of copper nitrate, copper chloride, copper sulfate, copper acetate, chromium chloride, cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, ferric nitrate, ferric chloride, ferric sulfate, ferric acetate, aluminum nitrate, zinc acetate, zinc chloride, zinc sulfate, aluminum chloride, aluminum sulfate, aluminum acetate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, manganese nitrate, manganese chloride, manganese sulfate, manganese acetate, titanium nitrate, titanium chloride, titanium sulfate, silver nitrate, and chloroauric acid, and the COF organic linking agent is p-phenylenediamine or m-phenylenediamine.
Preferably, the 2- (phenyldiazenyl) terephthalic acid is introduced into the MOF metal source, and the specific process comprises the steps of putting the 2- (phenyldiazenyl) terephthalic acid and the MOF metal source into a reaction kettle, heating to 150 ℃ for reaction for three days, and washing with methanol and DMF solvent to remove impurities, thereby obtaining the photonic switch porous liquid crystal composite material.
Preferably, the 2- (phenyldiazenyl) terephthalic acid is introduced into the MOF organic connecting agent, and the specific process is that the 2- (phenyldiazenyl) terephthalic acid and an MOF metal source are put into a reaction kettle and heated to 150 ℃ for reaction for three days, and methanol and DMF solvent are used for washing to remove impurities, so as to obtain the PH molecular switch porous liquid crystal composite material.
Preferably, the 2- (phenyldiazenyl) dimethyl terephthalate is introduced into the COF organic connecting agent, and the specific process is that the 2- (phenyldiazenyl) terephthalic acid and the COF organic connecting agent are put into a reaction kettle and heated to 120 ℃ for reaction for three days, and methanol solvent is used for washing to remove impurities, so as to obtain the UV molecular switch porous liquid crystal composite material.
The synthesis equation of the porous liquid crystal composite material with the molecular switch is as follows:
the invention has the beneficial effects that: the porous liquid crystal composite material with the molecular switch can be used for reversible change in the fields of molecular adsorption, illumination absorption and the like. By photochemical or thermal treatment. An azobenzene functional group is incorporated into the MOF organic linker, which can change conformation under light or heat treatment conditions. After ultraviolet or heat treatment, the microstructure in the composite material is reversibly changed. The bistable transition can be excited by ultraviolet light through a molecular switch, so that writing can be realized in a non-contact manner.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a porous liquid crystal composite material with a molecular switch comprises the following steps: 0.5 mmol of nitrobenzene and 0.5 mmol of dimethyl-2-aminoterephthalate are heated to 40 ℃ in 10 ml of glacial acetic acid and stirred for 24 hours; the reaction mixture was cooled to room temperature and saturated NaHCO was slowly added 3 A solution, neutralizing the solution; extracting with chloroform for three times, specifically adding 10 ml chloroform solution into the above solution, slowly turning over with hands, mixing for 5min, separating the layered solution, and collecting the lower layer liquid to obtain organic phase; the organic phase is MgSO 4 Drying to obtain a crude product; removing chloroform from the crude product, and purifying by column chromatography, wherein the chloroform removing process comprises separating the solutionDistilling off chloroform at 65 deg.C, and purifying by column chromatography by using fine pipette to obtain solution, slowly adding along the inner wall of the column, adding petroleum ether containing 1% acetone when the solution completely enters the column, washing, and separating to obtain dimethyl 2- (phenyl diazenyl) terephthalate; reacting the 2- (phenyl diazenyl) dimethyl terephthalate with metal ions at 120 ℃ to form an MOF material, thereby obtaining the photonic switching porous liquid crystal composite material.
The optical switch test of the optical molecular switch porous liquid crystal composite material is carried out, and the test results are shown in the following table:
it can be seen that the conversion of the molecular configuration is achieved under the illumination condition of 530nm
The molecular configuration is recovered under the illumination condition of 400 nm. Therefore, the photonic switching porous liquid crystal composite material can be used for manufacturing photosensitive liquid crystal screen equipment.
Example 2
A preparation method of a porous liquid crystal composite material with a molecular switch comprises the following steps: 0.5 mmol of nitrobenzene and 0.5 mmol of dimethyl-2-aminoterephthalate are heated to 40 ℃ in 10 ml of glacial acetic acid and stirred for 24 hours; the reaction mixture was cooled to room temperature and saturated NaHCO was slowly added 3 A solution, neutralizing the solution; extracting with chloroform for three times, specifically adding 10 ml chloroform solution into the above solution, slowly reversing by hand and mixing for 5min, separating the layered solution, and taking the lower layer liquid to obtain organic phase; the organic phase is MgSO 4 Drying to obtain a crude product; removing chloroform from the crude product, purifying by column chromatography, wherein the chloroform removing process comprises fractionating the solution, distilling off chloroform at 65 deg.C, the column chromatography purification process comprises extracting the solution with a fine pipette, slowly adding the solution along the inner wall of the column, adding petroleum ether containing 1% acetone when the solution completely enters the column, and eluting with ethanolWashing to obtain 2- (phenyl diazanyl) dimethyl terephthalate; and reacting the dimethyl 2- (phenyldiazanyl) terephthalate with metal ions at 120 ℃ to form an MOF material, thereby obtaining the PH molecular switch porous liquid crystal composite material.
The PH switch porous liquid crystal composite material is subjected to a PH switch test, and the test results are shown in the following table:
| no acidity or alkalinity | PH＝7.4 | PH＝5.5 | Complete recovery of molecular configuration after heating | |
| Response value of ultraviolet-visible spectrophotometer | 1.1 | 0.5 | 1 | 1.1 |
It can be seen that a transition in molecular configuration is achieved at PH = 7.4. Molecular configuration was restored at PH = 5.5. The application of the PH molecular switch porous liquid crystal composite material needs further research.
Example 3
A preparation method of a porous liquid crystal composite material with a molecular switch comprises the following steps: 0.5 mmol of nitrobenzene and 0.5 mmol of dimethyl 2-amino-terephthalaldehyde were mixed at 10 mmolHeating to 40 ℃ in l of glacial acetic acid and stirring for 24 hours; the reaction mixture was cooled to room temperature and saturated NaHCO was slowly added 3 A solution, neutralizing the solution; extracting with chloroform for three times, specifically adding 10 ml chloroform solution into the above solution, slowly turning over with hands, mixing for 5min, separating the layered solution, and collecting the lower layer liquid to obtain organic phase; the organic phase is MgSO 4 Drying to obtain a crude product; removing chloroform from the crude product, and purifying by column chromatography, wherein the specific process for removing chloroform is to fractionate the solution, distilling off chloroform at 65 ℃, the specific process for purifying by column chromatography is to take the solution by a fine suction tube, slowly adding the solution along the inner wall of the column, and adding petroleum ether containing 1% acetone for washing when the solution completely enters the chromatographic column to obtain 2- (phenyldiazenyl) terephthalaldehyde dimethyl ester; and (3) reacting the 2- (phenyldiazyl) terephthalaldehyde dimethyl ester with COF precursors such as p-phenylenediamine and the like (adding 10 ml of acetic acid as a catalyst at 120 ℃ for reacting for 24 hours) to form a COF organic connecting agent, thereby obtaining the UV molecular switch porous liquid crystal composite material.
The UV molecular switch porous liquid crystal composite material is subjected to UV switch test, and the test results are shown in the following table:
it can be seen that the conversion of molecular configuration is realized under the ultraviolet illumination condition of UV-365nm
In Visile>The molecular configuration is recovered under the ultraviolet illumination condition of 400 nm. Therefore, it can be used for a photosensitive liquid crystal panel device.
It should be noted that the technical features of the reaction kettle and the like related to the present patent application should be regarded as the prior art, and the specific structure, the operation principle, the control mode and the spatial arrangement mode of the technical features may be selected conventionally in the field, and should not be regarded as the invention point of the present patent, and the present patent is not further detailed.
Having described preferred embodiments of the present invention in detail, it is to be understood that modifications and variations may be resorted to without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a porous liquid crystal composite material with a molecular switch is characterized by comprising the following steps: stirring a certain amount of molecular switch monomer and organic ligand unit in glacial acetic acid and heating for a period of time; the reaction mixture was cooled to room temperature and saturated NaHCO was slowly added 3 A solution, neutralizing the solution; extracting with chloroform for three times to obtain an organic phase; the organic phase is MgSO 4 Drying to obtain a crude product; removing chloroform from the crude product, and purifying by column chromatography to obtain 2- (phenyl diazanyl) terephthalic acid; introducing the 2- (phenyl diazenyl) terephthalic acid into an MOF organic connecting agent by adopting a ligand exchange method to obtain a porous liquid crystal composite material with a molecular switch, wherein a molecular switch monomer is
Wherein the organic ligand unit is 2-amino terephthalic acid.
2. The method for preparing porous liquid crystal composite material with molecular switch of claim 1, wherein the molar ratio of the molecular switch monomer, 2-aminoterephthalic acid and glacial acetic acid is 1:1:0.1.
3. the method for preparing porous liquid crystal composite with molecular switch of claim 2, wherein the molecular switch monomer and the organic ligand unit are stirred and heated in glacial acetic acid at 40 ℃ for 24 hours.
4. The method for preparing the porous liquid crystal composite material with the molecular switch as claimed in claim 3, wherein the specific process of chloroform extraction is as follows: the molecular switch monomer and the organic ligand unit were mixed in chloroform and stirred for 30 minutes, and then the solvent was separated to leave an organic phase.
5. The method for preparing porous liquid crystal composite with molecular switch as claimed in claim 4, wherein the organic phase is MgSO 4 The specific process of drying is as follows: the organic solution was dried by adding magnesium sulfate as a drying agent and further heating in an oven at 40 ℃ for 24 hours.
6. The method for preparing the porous liquid crystal composite material with the molecular switch as claimed in claim 5, wherein the specific process of removing chloroform from the crude product is as follows: performing rotary evaporation on the solution at 70 ℃, collecting the residual liquid for further use, and performing column chromatography purification specifically as follows: and (3) filling a silica gel column by using a normal hexane wet method, selecting petroleum ether containing 1% of acetone as a mobile phase, and controlling the flow rate by using a constant flow pump to separate a crude product.
7. The method for preparing the porous liquid crystal composite with the molecular switch according to claim 6, wherein the MOF metal source is any one of copper nitrate, copper chloride, copper sulfate, copper acetate, chromium chloride, cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, iron nitrate, iron chloride, iron sulfate, iron acetate, aluminum nitrate, zinc acetate, zinc chloride, zinc sulfate, aluminum chloride, aluminum sulfate, aluminum acetate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, manganese nitrate, manganese chloride, manganese sulfate, manganese acetate, titanium nitrate, titanium chloride, titanium sulfate, silver nitrate and chloroauric acid, and the COF organic connecting agent is p-phenylenediamine or m-phenylenediamine.
8. The method for preparing the porous liquid crystal composite material with the molecular switch of claim 7, wherein the 2- (phenyldiazanyl) terephthalic acid is introduced into the MOF metal source by placing the 2- (phenyldiazanyl) terephthalic acid and the MOF metal source into a reaction kettle, heating the mixture to 150 ℃ for reacting for three days, and washing the mixture with methanol and DMF solvent to remove impurities to obtain the porous liquid crystal composite material with the molecular switch.
9. The method for preparing the porous liquid crystal composite material with the molecular switch of claim 7, wherein the 2- (phenyldiazanyl) terephthalic acid is introduced into the MOF organic connecting agent, the specific process is that the 2- (phenyldiazanyl) terephthalic acid and an MOF metal source are put into a reaction kettle and heated to 150 ℃ for three days to react, and methanol and DMF solvent are used for washing to remove impurities, so as to obtain the PH molecular switch porous liquid crystal composite material.
10. The method for preparing a porous liquid crystal composite with a molecular switch according to claim 7, wherein the 2- (phenyldiazyl) dimethyl terephthalate is introduced into the COF organic linking agent by placing the 2- (phenyldiazyl) terephthalic acid and the COF organic linking agent into a reaction kettle, heating to 120 ℃ for reaction for three days, and washing with a methanol solvent to remove impurities to obtain the UV molecular switch porous liquid crystal composite.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110319604A1 (en) * | 2008-11-18 | 2011-12-29 | Universite De Versailles-Saint Quentin En Yvelines | Method for preparing metal-organic framework crystallised and porous aluminium aromatic azocarboxylates |
| CN110846050A (en) * | 2019-11-28 | 2020-02-28 | 武汉轻工大学 | Bent azo liquid crystal compound and preparation method and application thereof |
| WO2022132045A1 (en) * | 2020-12-14 | 2022-06-23 | National University Of Singapore | Polycrystalline iron-containing metal-organic framework membranes for organic solvent nanofiltration |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110319604A1 (en) * | 2008-11-18 | 2011-12-29 | Universite De Versailles-Saint Quentin En Yvelines | Method for preparing metal-organic framework crystallised and porous aluminium aromatic azocarboxylates |
| CN110846050A (en) * | 2019-11-28 | 2020-02-28 | 武汉轻工大学 | Bent azo liquid crystal compound and preparation method and application thereof |
| WO2022132045A1 (en) * | 2020-12-14 | 2022-06-23 | National University Of Singapore | Polycrystalline iron-containing metal-organic framework membranes for organic solvent nanofiltration |
Non-Patent Citations (2)
| Title |
|---|
| QI HUANG 等: "A steric hindrance alleviation strategy to enhance the photo-switching efficiency of azobenzene functionalized metal-organic frameworks toward tailorable carbon dioxide capture", 《JOURNAL OF MATERIALS CHEMISTRY A》, vol. 10, no. 15, pages 8303 - 8308 * |
| 李闪闪 等: "偶氮苯功能化的光响应共价有机框架材料", 《高等学校化学学报》, vol. 41, no. 6, pages 1384 - 1390 * |
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