CN113388384A - Photochromic material containing beta-cyclodextrin and viologen compound, preparation method and application thereof - Google Patents
Photochromic material containing beta-cyclodextrin and viologen compound, preparation method and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 71
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 45
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 title claims abstract description 44
- 235000011175 beta-cyclodextrine Nutrition 0.000 title claims abstract description 44
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- 238000001338 self-assembly Methods 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
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- 230000008859 change Effects 0.000 description 4
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 4
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
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- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 1
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
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- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/145—Heterocyclic containing oxygen as the only heteroatom
Abstract
The invention relates to the technical field of preparation of color-changing materials, in particular to a photochromic material containing beta-cyclodextrin and viologen compounds, a preparation method and application thereof; the photochromic material is formed by self-assembling a beta-cyclodextrin host and a viologen compound guest, wherein the molar ratio of the beta-cyclodextrin to the unilateral substituted viologen compound is 1:1, and the molar ratio of the bilaterally substituted viologen compound to the bilaterally substituted viologen compound is 2: 1. when the photochromic material is prepared, the beta-cyclodextrin host and the viologen compound guest are mixed and stirred at room temperature according to the corresponding molar ratio and dissolved in water; the two are self-assembled in the solution to form a supermolecule host-guest compound, and the photochromic material is obtained after concentration and drying; the photochromic mechanism of the photochromic material is that the charge transfer is caused by illumination to generate a developing free radical; the photochromic material has high sensitivity, high response speed, high stability and high fatigue resistance.
Description
Technical Field
The invention relates to the technical field of preparation of color-changing materials, in particular to a photochromic material containing beta-cyclodextrin and viologen compounds, a preparation method and application thereof.
Background
Cyclodextrins are the collective term for a series of cyclic oligosaccharides produced by amylose under the action of a cyclodextrin glucosyltransferase produced by Bacillus, and generally contain 6 to 12 glucose units. According to the results of X-ray crystal diffraction, infrared spectrum and nuclear magnetic resonance spectrum analysis, each glucose unit is combined into a ring by a 1, 4-glycosidic bond. Among them, the ones that have been studied more and are of great practical significance are molecules containing 6, 7, 8 glucose units, called α -cyclodextrin, β -cyclodextrin and γ -cyclodextrin, respectively. Beta-cyclodextrin is used in the present invention. Cyclodextrins are not cylindrical molecules but rather slightly conical rings, since the glycosidic bond linking the glucose units cannot rotate freely.
Cyclodextrin has the unique properties of 'internal hydrophobicity and external hydrophilicity', and in an aqueous solution, a hydrophobic cavity of the cyclodextrin can select guest molecules with proper inclusion shape and size to form a supermolecular host-guest complex, wherein the most common host-guest ratio is 1:1 and 2: 1. Cyclodextrin can also play a role in assisting dissolution as a macrocyclic compound, particularly when the object is an insoluble substance, the concentration of the object in a dissolution phase is obviously increased after the cyclodextrin is added, and the ionized or hydrogen bond compound object can also improve the solubility of the cyclodextrin. The cyclodextrin inclusion guest can also play a role in stabilizing the guest and reducing the volatility and degradability of the guest.
Photochromism refers to the reversible change of certain compounds between two physical or chemical states under the action of light of a certain wavelength and intensity, resulting in a corresponding change in the absorption peak, i.e., color, of the compound to the light. This can be expressed by the following equation:
wherein A and B represent two different color states of the same substance, respectively; lambda [ alpha ]1And λ2Respectively, representing two different wavelengths.
Photochromic materials include both inorganic and organic photo-reversible photochromic materials. The photochromism of organic systems is often accompanied by processes associated with photochemical reactions, leading to some modification of the structure of the compound, in a way that mainly consists of: valence bond isomerism, cis-trans isomerism, bond cleavage (including heterolytic and homolytic), polymerisation, oxidation-reduction, peri-reactions, etc. Organic photochromism has more researches on compounds including viologen, fulgide, spiropyran, spirooxazine, azobenzene and the like, and has wide application. The viologen compound has potential photochromic performance, and the research thereof is receiving more and more attention from material workers at home and abroad. However, the viologen compounds generally have the defects of poor thermal stability and oxidation resistance, low fatigue resistance and the like.
At present, the synthesis of beta-cyclodextrin is very mature, the beta-cyclodextrin is sold in the market, and the price is relatively cheap. Various viologen compounds can be synthesized by 4, 4' -bipyridyl and corresponding bromo-or chloro-compounds through substitution reaction, which provides convenience for the synthesis of applicable photochromic materials containing beta-cyclodextrin and viologen compounds.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
The invention aims to solve the problems of poor thermal stability and oxidation resistance, low fatigue resistance and the like of the existing photochromic material, and provides a photochromic material containing beta-cyclodextrin and a viologen compound, a preparation method and application thereof.
In order to achieve the purpose, the invention discloses a photochromic material containing beta-cyclodextrin and a viologen compound, which comprises a host beta-cyclodextrin and a guest viologen compound, wherein the molar ratio of the host beta-cyclodextrin to a unilateral substituted guest is 1:1, and the molar ratio of the host beta-cyclodextrin to a bilateral substituted guest is 2: 1.
The general formula of the viologen compound is
Wherein, X-Is F-,Cl-,Br-,I-,PF6 -R and R' are aromatic ring radical or substituent containing carboxyl.
Preferably, R is any one of phenyl, benzyl, naphthyl, furyl, thienyl and 4-carboxy-benzylidene, and R' is any one of phenyl, benzyl, naphthyl, furyl, thienyl and 4-carboxy-benzylidene.
The viologen compound is chloro-1- (4-carboxyl-benzylidene) -4, 4' -bipyridine.
The viologen compound is dichloro-1, 1 '-di (4-carboxyl-benzylidene) -4, 4' -bipyridine.
The viologen compound is bromo-1- (thiophene methylene) -4, 4' -bipyridine.
The invention also discloses a preparation method of the photochromic material containing the beta-cyclodextrin and the viologen compound, which comprises the following steps:
s1: dissolving beta-cyclodextrin and viologen compounds in distilled water according to a corresponding molar ratio, mixing and stirring uniformly at room temperature to obtain a clear solution, wherein the solution contains a supermolecule host-guest compound formed by self-assembly of the beta-cyclodextrin and the viologen compounds;
s2: and (4) concentrating and drying the solution of the host-guest compound formed by self-assembly in the step S1 at the temperature of 50 ℃ by using a rotary evaporator to obtain the photo-reversible photochromic material.
The invention also discloses the application of the photochromic material containing the beta-cyclodextrin and the viologen compound in the fields of optical information storage, decoration, protection, anti-counterfeiting and national defense.
The invention provides a photochromic material based on a supermolecule host-guest inclusion compound and a preparation method thereof by utilizing the inclusion effect of macrocyclic compound beta-cyclodextrin on viologens, wherein the color change mechanism of the photochromic material is as follows: under the light induction condition, charge transfer is generated between the electron-rich beta-cyclodextrin host and the electron-deficient viologen compound guest to generate chromogenic free radicals, so that the change of color is realized. When the viologen compound is encapsulated into the cavity of the beta-cyclodextrin to form a host-guest inclusion complex, the beta-cyclodextrin plays a role of a charge donor on one hand and plays a role of stabilizing the structure of the viologen compound on the other hand.
Compared with the prior art, the invention has the beneficial effects that:
1) the method is simple, the operation is simple and convenient, the required working procedures are less, and the required raw materials are simple and easy to obtain;
2) the obtained photo-reversible color-changing material has excellent performance, and has the characteristics of high sensitivity, high response speed, high stability, high fatigue resistance and the like;
3) the obtained photochromic material has the most outstanding advantages of high recovery speed and capability of recovering to the original color in the shade within about 5 to 10 minutes.
Drawings
FIG. 1 is a schematic diagram of the structure of a host-guest compound obtained in example 1;
FIG. 2 is a schematic diagram of the structure of the host-guest compound obtained in example 2;
FIG. 3 is a schematic diagram showing the structure of the host-guest compound obtained in example 3;
FIG. 4 is a solid UV diffuse reflectance chart before and after photochromic of the host-guest compound obtained in example 1;
FIG. 5 is a solid UV diffuse reflectance chart before and after photochromic of the host-guest compound obtained in example 2;
FIG. 6 is a solid UV diffuse reflectance chart before and after photochromism of the host and guest compounds obtained in example 3.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
Example 1
1) Weighing 0.1g of beta-cyclodextrin and 0.0283g of chloro-1- (4-carboxy-benzylidene) -4, 4' -bipyridine respectively, mixing and dissolving in about 30mL of aqueous solution at room temperature; the two can form a supermolecular host-guest compound in an aqueous solution in a self-assembly mode. The structure of the obtained host-guest compound is schematically shown in fig. 1, and half of the 4, 4' -bipyridyl group in the guest molecule is encapsulated in the cavity of the beta-cyclodextrin.
2) And (3) completely drying the solution of the host-guest compound by using a rotary evaporator at 50 ℃ to obtain the photochromic material based on beta-cyclodextrin and chlorinated-1- (4-carboxyl-benzylidene) -4, 4' -bipyridine.
3) The photochromic material can be changed from white to dark blue in a short time (about 2 minutes) under the illumination of a xenon lamp with full wavelength. The light was stopped and the discolored material was placed in the shade and the dark blue quickly faded to white (about 10 minutes). The obtained solid ultraviolet diffuse reflection patterns of the host-guest compound before and after photochromism by illumination are shown in figure 4, and the absorbance of the host-guest compound in the visible light range after illumination is obviously enhanced.
Example 2
1) 0.1g of beta-cyclodextrin and 0.0431g of dichloro-1, 1 '-bis (4-carboxy-benzylidene) -4, 4' -bipyridine are respectively weighed out and mixed and dissolved in 30mL of aqueous solution at room temperature; the two can form a supermolecular host-guest compound in an aqueous solution in a self-assembly mode. The structure of the obtained host-guest compound is schematically shown in fig. 2, and carboxyl groups at two ends of a guest molecule are encapsulated in cavities of two beta-cyclodextrins.
2) And (3) spin-drying the solution of the host-guest compound by using a rotary evaporator at 50 ℃, and completely drying to obtain the photochromic material based on beta-cyclodextrin and dichloro-1, 1 '-di (4-carboxyl-benzylidene) -4, 4' -bipyridine.
3) The photochromic material can be changed from white to blue-green within a short time (about 2 minutes) under the illumination of a full-wavelength xenon lamp. The illumination was stopped and the discolored material was placed in the shade and the blue-green color faded to white faster (about 8 minutes). The obtained solid ultraviolet diffuse reflection patterns of the host-guest compound before and after photochromism by illumination are shown in figure 5, and the absorbance of the host-guest compound in the visible light range after illumination is obviously enhanced.
Example 3
1) 0.1g of beta-cyclodextrin and 0.0431g of dichloro-1, 1 '-bis (4-carboxy-benzylidene) -4, 4' -bipyridine are respectively weighed out and mixed and dissolved in 30mL of aqueous solution at room temperature; the two can form a supermolecular host-guest compound in an aqueous solution in a self-assembly mode. The structure of the obtained host-guest compound is schematically shown in fig. 3, and half of the 4, 4' -bipyridyl group in the guest molecule is encapsulated in the cavity of the beta-cyclodextrin.
2) And (3) spin-drying the solution of the host-guest compound by using a rotary evaporator at 50 ℃, and completely drying to obtain the photochromic material based on beta-cyclodextrin and dichloro-1, 1 '-di (4-carboxyl-benzylidene) -4, 4' -bipyridine.
3) The photochromic material can be changed from white to blue-green within a short time (about 2 minutes) under the illumination of a full-wavelength xenon lamp. The illumination was stopped and the discolored material was placed in the shade and the blue-green color faded to white faster (about 8 minutes). The obtained solid ultraviolet diffuse reflection patterns of the host-guest compound before and after photochromism by illumination are shown in figure 6, and the absorbance of the host-guest compound in the visible light range after illumination is enhanced.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The photochromic material containing the beta-cyclodextrin and the viologen compound is characterized by comprising a host beta-cyclodextrin and a guest viologen compound, wherein the molar ratio of the host beta-cyclodextrin to a unilateral substituted guest is 1:1, and the molar ratio of the host beta-cyclodextrin to the bilateral substituted guest is 2: 1.
2. The photochromic material of claim 1 wherein the viologen compound has the formula
Wherein, X-Is F-,Cl-,Br-,I-,PF6 -R, R' is an aromatic ring group or a substituent group containing a carboxyl group.
3. The photochromic material of claim 2 wherein R is any one of phenyl, benzyl, naphthyl, furyl, thienyl, and 4-carboxy-benzylidene, and R' is any one of phenyl, benzyl, naphthyl, furyl, thienyl, and 4-carboxy-benzylidene.
4. The photochromic material of claim 1 wherein the viologen compound is chloro-1- (4-carboxy-benzylidene) -4, 4' -bipyridine.
5. The photochromic material of claim 1 wherein the viologen compound is 1,1 '-bis (4-carboxy-benzylidene) -4, 4' -bipyridine dichloride.
6. The photochromic material of claim 1 wherein the viologen compound is bromo-1- (thienylmethylene) -4, 4' -bipyridine.
7. A method for preparing the photochromic material containing the beta-cyclodextrin and the viologen compound according to any one of claims 1 to 6, comprising the following steps:
s1: dissolving beta-cyclodextrin and viologen compounds in distilled water according to a corresponding molar ratio, mixing and stirring uniformly at room temperature to obtain a clear solution, wherein the solution contains a supermolecule host-guest compound formed by self-assembly of the beta-cyclodextrin and the viologen compounds;
s2: and (4) concentrating and drying the solution of the host-guest compound formed by self-assembly in the step S1 at the temperature of 50 ℃ by using a rotary evaporator to obtain the photo-reversible photochromic material.
8. Use of a photochromic material comprising a β -cyclodextrin and a viologen compound as defined in any one of claims 1 to 6 in the field of optical information storage.
9. Use of a photochromic material comprising a β -cyclodextrin and a viologen compound as defined in any one of claims 1 to 6 in the field of decorative protection.
10. The application of the photochromic material containing the beta-cyclodextrin and the viologen compound as defined in any one of claims 1 to 6 in the fields of anti-counterfeiting and national defense.
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| CN109423272A (en) * | 2017-08-22 | 2019-03-05 | 鸿富锦精密工业（深圳）有限公司 | Photochromic compound-cyclodextrin inclusion compound and preparation method thereof |
| CN110650977A (en) * | 2017-03-16 | 2020-01-03 | 奥伦·A·谢尔曼 | Deep eutectic solvent composition |
| CN110799573A (en) * | 2017-06-20 | 2020-02-14 | 株式会社德山 | Photochromic polyrotaxane compound, and curable composition comprising same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110650977A (en) * | 2017-03-16 | 2020-01-03 | 奥伦·A·谢尔曼 | Deep eutectic solvent composition |
| CN110799573A (en) * | 2017-06-20 | 2020-02-14 | 株式会社德山 | Photochromic polyrotaxane compound, and curable composition comprising same |
| CN109423272A (en) * | 2017-08-22 | 2019-03-05 | 鸿富锦精密工业（深圳）有限公司 | Photochromic compound-cyclodextrin inclusion compound and preparation method thereof |
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