CN109161385A - A kind of liquid crystal material of cholesteric phase of visible light regulation color - Google Patents
A kind of liquid crystal material of cholesteric phase of visible light regulation color Download PDFInfo
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- CN109161385A CN109161385A CN201810820897.0A CN201810820897A CN109161385A CN 109161385 A CN109161385 A CN 109161385A CN 201810820897 A CN201810820897 A CN 201810820897A CN 109161385 A CN109161385 A CN 109161385A
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- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/10—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems
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Abstract
The invention belongs to light responsive material technical fields, more particularly, to a kind of liquid crystal material of cholesteric phase of visible light regulation color.The invention discloses a kind of liquid crystal material of cholesteric phase of visible light regulation color, in parts by weight, including 30-99 parts of nematic liquid crystals, 0.9-50 parts of unsubstituted type azobenzene derivatives and 0.1-50 parts of substituted type chirality azobenzene derivatives, the color of the liquid crystal material of cholesteric phase has visible light-responded property, and after stopping illumination, the color of the liquid crystal material being capable of long-time stable holding.
Description
Technical field
The invention belongs to light responsive material technical fields, more particularly, to a kind of cholesteric phase of visible light regulation color
Liquid crystal material.
Background technique
Most directly and most effective anti-counterfeiting technology be not need by the i.e. distinguishable true and false of any tool, for example, giving one
Fixed light stimulus, observer can identify material, hardness, lines, picture and text, color etc. by changing angle or directly touching
Security information.The visual color change obtained using the ordered structure of liquid crystal and its polymer, photoetching grating and multistep polarization polymerization
Anti-counterfeiting technology belongs to such.Since the color of this kind of anti-fake material is easily differentiated, and under space-time accurately light stimulus, color
Variation is obvious, therefore, is difficult to forge by product prepared by such material.Conventional light stimulus must often use ultraviolet light,
But ultraviolet light causes its penetration capacity weaker due to factors such as light scattering and the absorptions of endogenous chromophore.Simultaneously as color
Unstability, in a short time i.e. generate variation so that the antifalse effect of material is bad, it is difficult to meet application requirement.In order to
Anti-fake utilizability, safety and monopoly are improved, realizes that the regulation of color and long-time stability are compeled using visible light
The eyebrows and eyelashes.
The color of liquid crystal material of cholesteric phase and its variation are the important development directions of anti-counterfeiting technology.However, existing pass through
To regulate and control cholesteric liquid crystal color technology, mainly there are two defects for the isomerization of ultraviolet light response group: first is that UV energy
Height easily damages organism, while the penetration capacity of ultraviolet light is weaker, seriously limits its application；Second is that cholesteric liquid crystal
Dozens of minutes of the color generally after illumination termination even just changed in shorter time, it is difficult to remain steady in a long-term,
It is unfavorable for required design.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of gallbladders of visible light regulation color
Steroid phase liquid crystal material passes through controlledly synthesis first and obtains that there is chiral and visible light-responded substituted type chirality azobenzene to spread out
Biology is added in nematic liquid crystal in conjunction with unsubstituted type azobenzene derivatives, pours into the internal liquid crystal with orientation texture
In box, under visible light illumination, color can not only become the liquid crystal material of cholesteric phase being prepared with visible light-responded property
Change, and be able to maintain prolonged stabilization, thus solves prior art cholesteric liquid crystal and be only capable of realizing color tune by ultraviolet light
Control and color the technical issues of being difficult to long-time stable.
To achieve the above object, according to one aspect of the present invention, a kind of cholesteric phase of visible light regulation color is provided
Liquid crystal material, in parts by weight, the unsubstituted type azobenzene derivatives including 30-99 parts of nematic liquid crystals, 0.9-50 parts
And 0.1-50 parts of substituted type chirality azobenzene derivatives, the color of the liquid crystal material of cholesteric phase have visible light-responded property.
Preferably, the wavelength of the visible light is 400nm~650nm, intensity of illumination 1mW/cm2~80mW/cm2, shine
Penetrating the time is 0.5s~300s.
Preferably, the structural formula of the nematic liquid crystal isWherein, R11For cyano, nitro or
Methoxyl group, R12For the alkyl of C1~C3 or the hydroxy alkyl of C1~C3, R13For the alkyl of C1~C9 or the hydroxyl alkane of C1~C9
Base, n1For 1~4 integer.
Preferably, the unsubstituted type azobenzene derivatives are derivative for the unsubstituted type dinaphthalene molecule of S configuration or R configuration
Object.
Preferably, the structural formula of the unsubstituted type azobenzene derivatives isWherein,
R21For the alkyl of C1~C10 or the alkoxy of C1~C10, R22For ester group or oxygen, R23For the alkyl or C1~C8 of C1~C8
Hydroxy alkyl, R241And R242It is each independentlyThe alkene or C1 of C1~C6
The alkyl of~C10, n2For 1~3 integer；R2411For the alkyl of C1~C8 or the hydroxy alkyl of C1~C8.
Preferably, the substituted type chirality azobenzene derivatives include in 1~4-N=N-and 1~3 chirality
The heart, and at least 1 on described-phenyl ring of N=N-connection two at replaced by other groups in addition to H atom.
Preferably, the substituted type chirality azobenzene derivatives are the dinaphthalene molecule derivant of S configuration or R configuration, knot
Structure formula isWherein R31And R32Be each independently amino orAnd amino number
Amount not more than 1；R301、R302、R303And R304It is each independently hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine, and the number of hydrogen atom
Amount not more than 3；R305ForThe alkoxy of C1~C8 or
The hydroxy alkoxy base of C1~C8；R401、R402、R403、R404、R405、R406、R407And R408Be each independently hydrogen, methoxyl group,
Fluorine, chlorine, bromine or iodine, and the quantity of hydrogen atom is not more than 7；R2411For the alkyl of C1~C8 or the hydroxy alkyl of C1~C8；
R2521For cyano or nitro, n3For 1~3 integer.
Other side according to the invention provides the preparation method of liquid crystal material of cholesteric phase described in one kind, will
The substituted type chirality azobenzene of the unsubstituted type azobenzene derivatives of 0.9~50 parts by weight, 0.1~50 parts by weight
After derivative is mixed with 30~99 parts of the nematic liquid crystal, it is fitted into the internal liquid crystal cell with orientation texture and forms gallbladder
Steroid phase liquid crystal material.
Other side according to the invention provides a kind of preparation method of substituted type chirality azobenzene derivatives, packet
Include following steps:
(1) it will be dissolved in solvent AIt mixes with the aqueous solution of inorganic salts, is separated after reaction
To the first intermediate；
(2) by first intermediate being dissolved in solvent B and S configuration or R configurationReaction,
Isolated second intermediate；
(3) by second intermediate being dissolved in solvent C with It is mixed with the alcohol of C1~C8, isolated substituted type chirality azobenzene derivatives after reaction；
Wherein, R301、R302、R303And R304It is each independently hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine, and the number of hydrogen atom
Amount not more than 3；R401、R402、R403、R404、R405、R406、 R407And R408Be each independently hydrogen, methoxyl group, fluorine, chlorine, bromine or
Iodine, and the quantity of hydrogen atom is not more than 7；R2411For the alkyl of C1~C8 or the hydroxy alkyl of C1~C8；R2521For cyano or
Nitro, n3For 1~3 integer.
Preferably, step (1) solvent A is tetrahydrofuran, acetonitrile, ethyl acetate, methylene chloride, chloroform, first
One or more of benzene, acetic acid and pyridine；The inorganic salts are sodium nitrite, ammonium persulfate-sodium bisulfate, sodium chloride, carbon
One or more of sour potassium, cesium carbonate and potassium iodide；The reaction condition are as follows: 20 DEG C~90 DEG C, air or inert gas atmosphere
It encloses, stirs 2~36h；The isolated method are as follows: one or more of extraction, recrystallization, column chromatography and filtering.
Preferably, step (2) the solvent B is n,N-Dimethylformamide, dimethyl sulfoxide, methanol, ethyl alcohol, four chlorinations
One or more of carbon, the concentrated sulfuric acid, acetonitrile, tetrahydrofuran, n-hexane and petroleum ether；The reaction condition are as follows: 40 DEG C~
150 DEG C, air or atmosphere of inert gases stir 0.5h~120h；The isolated method are as follows: extraction, recrystallization, column chromatography
With filtering one or more of.
Preferably, step (3) solvent C is tetrahydrofuran, acetonitrile, ethyl acetate, acetone, methylene chloride, three chloromethanes
One or more of alkane, N,N-dimethylformamide, toluene, acetic acid and dimethyl sulfoxide；The reaction condition are as follows: 25 DEG C~
160 DEG C, air or atmosphere of inert gases stir 4.0~72.0h；The separation method are as follows: extraction, recrystallization, column chromatography and
One or more of filtering.
Preferably, step (1) reaction time is 2~12h, and step (2) uses dimethyl sulfoxide, methanol, ethyl alcohol, tetrahydro furan
It mutters, when one or more of acetonitrile and petroleum ether are as solvent, according to above-mentioned synthetic method, S configuration or R configurationTwo amino only one participate in reaction formed an azobenzene, be prepared containing a nitrogen nitrogen
The substituted type chirality azobenzene derivatives of double bond.
It as a preferred option, is 14~36h when step (1) reaction time, step (2) uses N, N- dimethyl formyl
When amine, carbon tetrachloride, the concentrated sulfuric acid, n-hexane and petroleum ether one or more are as solvent, according to above-mentioned synthetic method, S type or
R typeTwo amino can all participate in reaction and form two azobenzenes, be prepared containing there are two nitrogen nitrogen
The substituted type chirality azobenzene derivatives of double bond.
Other side according to the invention, provides a kind of substituted type chirality azobenzene derivatives, and structural formula isWherein R31And R32Be each independently amino orAnd amino amount is few
In 1；R301、R302、R303And R304It is each independently hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine, and the quantity of hydrogen atom is few
In 3；R305ForThe alkoxy or C1~C8 of C1~C8
Hydroxy alkoxy base；R401、R402、R403、R404、R405、R406、R407And R408It is each independently hydrogen, methoxyl group, fluorine, chlorine, bromine
Or iodine, and the quantity of hydrogen atom is not more than 7；R2411For alkyl or the hydroxy alkyl of C1~C8；R2521For cyano or nitro, n3
For 1~3 integer.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) present invention by by unsubstituted type azobenzene derivatives and substituted type chirality azobenzene derivatives simultaneously with to
The mixing of column phase liquid crystal, is prepared ternary liquid crystal material of cholesteric phase, compared with existing binary liquid crystal material of cholesteric phase, this hair
Bright ternary liquid crystal material of cholesteric phase can regulate and control color by visible light, according to the wavelength of the visible light of selection, light intensity and light
The control accurate of color is realized according to the time, it is even more important that after illumination terminates, corresponding color can also be for a long time
Holding.
(2) the present invention provides a kind of preparation method of substituted type chirality azobenzene derivatives, this method can be by changing
Become reaction condition, such as solvent and reaction time, it is final to realize that substituted type is chiral to realize the selective reaction of intermediate product
The controlledly synthesis of azobenzene derivatives, the structures of the substituted type chirality azobenzene derivatives being prepared have controllability and more
Sample.
(3) present invention is using the radius of substituent group in substituted type chirality azobenzene derivatives is small and sucting electronic effect etc.
Advantage makes it can be realized the reversible regulation of the cis and trans structure of azobenzene under the visible light of different wave length, and nothing
Substituted type azobenzene derivatives play the role of that three is promoted to dissolve each other in mixed system, so that the interaction force of three is more
By force, and then as the variation of helical structure occurs for liquid crystal material of cholesteric phase, the color for realizing the ternary material has visible light
Responsiveness and long-time stability.
(4) present invention realizes reaction choosing in substituted type chirality azobenzene derivatives synthesis process by changing synthesis condition
Selecting property has respectively obtained the substituted type chirality azobenzene derivatives with a nitrogen nitrogen double bond or two nitrogen nitrogen double bonds, experiment hair
Now containing there are two nitrogen nitrogen double bond substituted type chirality azobenzene derivatives be used as synthesis material, with only contain a nitrogen nitrogen double bond
Substituted type chirality azobenzene derivatives compare, under similarity condition, the color of the liquid crystal material that the former is prepared has more preferable
Thermal stability, can remain unchanged for a long time.
(5) preparation process of liquid crystal material of cholesteric phase of the present invention is simple, can technology；Compared with ultraviolet light, it is seen that light is worn
Saturating ability is stronger, and energy is low to damage organism, is suitble to the color of regulation liquid crystal material of cholesteric phase.
Detailed description of the invention
Fig. 1 is the structural formula and nuclear magnetic resonance spectroscopy for the substituted type chirality azobenzene derivatives that embodiment 1 is prepared；
Fig. 2 is the structural formula and nuclear magnetic resonance spectroscopy for the substituted type chirality azobenzene derivatives that embodiment 3 is prepared；
Fig. 3 is the liquid crystal material of cholesteric phase that is prepared of embodiment 3 wavelength corresponding to color after radiation of visible light；
Fig. 4 is the liquid crystal material of cholesteric phase that is prepared of comparative example 2 wavelength corresponding to color after ultraviolet light.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments,
The present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain this hair
It is bright, it is not intended to limit the present invention.In addition, technology involved in the various embodiments of the present invention described below is special
Sign can be combined with each other as long as they do not conflict with each other.
A kind of liquid crystal material of cholesteric phase of visible light regulation color, in parts by weight, including 30-99 parts of nematic phase
Liquid crystal, 0.9-50 parts of unsubstituted type azobenzene derivatives and 0.1-50 parts of substituted type chirality azobenzene derivatives, can
Under light-exposed irradiation, the color of the liquid crystal material of cholesteric phase has visible light-responded property.
Wherein unsubstituted type azobenzene derivatives refer to the azobenzene derivatives-N=N-connection two phenyl ring
Ortho position and meta position are not replaced by other groups other than H atom, can be chiral or achiral common azo of unsubstituted type
Benzene derivative；And the substituted type chirality azobenzene derivatives are for the above-mentioned unsubstituted common azobenzene derivatives of type,
Its-two phenyl ring of N=N-connection on replaced at least 1 by other groups in addition to H atom.
The nematic liquid crystal can be the various nematic liquid crystals with liquid crystal structure, the nematic phase that the present invention uses
The general structure of liquid crystal isWherein, R11For cyano, nitro or methoxyl group, R12For the alkyl of C1~C3
Or the hydroxy alkyl of C1~C3, R13For the alkyl of C1~C9 or the hydroxy alkyl of C1~C9, n1It is 1~4.It can be on the market
One of commercialization liquid crystal SLC1717, SLC9023,5CB, P0616A, SLC7011 of purchase, also including other synthesis
Nematic liquid crystal.
The present invention is by by unsubstituted type azobenzene derivatives, substituted type chirality azobenzene derivatives and nematic liquid crystal
It is mixed with to obtain ternary liquid crystal material of cholesteric phase, realizes the visible light-responded property of the color of liquid crystal material, i.e. the liquid crystal material
The color of material changes with the wavelength change of visible light, and is able to maintain long-time stable.Wavelength be 400nm~
650nm, intensity of illumination 1mW/cm2~80mW/cm2, irradiation time is the liquid under the conditions of the radiation of visible light of 0.5s~300s
Brilliant material color has visible light-responded property, after illumination stopping, still keeping colour stable for a long time.
As a preferred option, the structure of unsubstituted type azobenzene derivatives is the unsubstituted type connection of S configuration or R configuration
Naphthalene molecule derivant, structural formula are preferably Wherein, R21For the alkyl of C1~C10 or the alkane of C1~C10
Oxygroup, R22For ester group or oxygen, R23For the alkyl of C1~C8 or the hydroxy alkyl of C1~C8, R241And R242It is each independentlyThe alkene of C1~C6 or the alkyl of C1~C10, n2For 1~3 integer；
R2411For the alkyl of C1~C8 or the hydroxy alkyl of C1~C8.
As a preferred option, substituted type chirality azobenzene derivatives include 1~4-N=N-and 1~3 hand
Property center, and at least 1 on described-phenyl ring of N=N-connection two at replaced by other groups in addition to H atom.
It is further preferred that the structure of the substituted type chirality azobenzene derivatives is the dinaphthalene point of S configuration or R configuration
Sub- derivative, structural formula areWherein R31And R32Be each independently amino orAnd when being amino, amino amount is not more than 1；R301、 R302、R303And R304It is each independently
Hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine, and the quantity of hydrogen atom is not more than 3；R305ForThe alkoxy of C1~C8 or the hydroxy alkoxy of C1~C8
Base；R401、R402、R403、R404、R405、R406、R407And R408It is each independently hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine, and hydrogen is former
The quantity of son is not more than 7；R2411For the alkyl of C1~C8 or the hydroxy alkyl of C1~C8；R2521For cyano or nitro, n3For
1~3 integer.
Liquid crystal material of cholesteric phase of the present invention the preparation method comprises the following steps: by the unsubstituted type of 0.9~50 parts by weight
Azobenzene derivatives, the substituted type chirality azobenzene derivatives of 0.1~50 parts by weight and 30~99 parts of the nematic phase
After liquid crystal mixing, it is fitted into the internal liquid crystal cell with orientation texture and forms liquid crystal material of cholesteric phase.
The present invention also provides a kind of preparation method of substituted type chirality azobenzene derivatives, the substituted type chirality azos
The preparation of benzene derivative can realize the selectivity of intermediate product by changing reaction condition such as reaction time and solvent type
Reaction, and then the substituted type chirality azobenzene derivatives of different structure are controllably obtained, include the following steps:
(1) it will be dissolved in solvent AIt mixes with the aqueous solution B of inorganic salts, is separated after reaction
Obtain the first intermediate；Preferably, solvent A be tetrahydrofuran, acetonitrile, ethyl acetate, methylene chloride, chloroform, toluene,
One or more of acetic acid and pyridine；The inorganic salts are sodium nitrite, ammonium persulfate-sodium bisulfate, sodium chloride, carbonic acid
One or more of potassium, cesium carbonate and potassium iodide；The reaction condition are as follows: 20 DEG C~90 DEG C, air or inert gas atmosphere
It encloses, stirs 2~36h；The isolated method are as follows: one or more of extraction, recrystallization, column chromatography and filtering.
(2) by first intermediate being dissolved in solvent B and S configuration or R configurationReaction,
Isolated second intermediate；Preferably, solvent B is n,N-Dimethylformamide, dimethyl sulfoxide, methanol, ethyl alcohol, four chlorinations
One or more of carbon, the concentrated sulfuric acid, acetonitrile, tetrahydrofuran, n-hexane and petroleum ether；The reaction condition are as follows: 40 DEG C~
150 DEG C, air or atmosphere of inert gases stir 0.5h~120h；The isolated method are as follows: extraction, recrystallization, column chromatography
With filtering one or more of.
(3) by second intermediate being dissolved in solvent C with It is mixed with the alcohol of C1~C8, isolated substituted type chirality azobenzene derivatives after reaction；Preferably,
Solvent C be tetrahydrofuran, acetonitrile, ethyl acetate, acetone, methylene chloride, chloroform, N,N-dimethylformamide, toluene,
One or more of acetic acid and dimethyl sulfoxide；The reaction condition are as follows: 25 DEG C~160 DEG C, air or atmosphere of inert gases,
Stir 4.0~72.0h；The separation method are as follows: one or more of extraction, recrystallization, column chromatography and filtering.
Wherein, R301、R302、R303And R304It is each independently hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine, and the number of hydrogen atom
Amount not more than 3；R401、R402、R403、R404、R405、R406、 R407And R408Be each independently hydrogen, methoxyl group, fluorine, chlorine, bromine or
Iodine, and the quantity of hydrogen atom is not more than 7；R2411For the alkyl of C1~C8 or the hydroxy alkyl of C1~C8；R2521For cyano or
Nitro, n3For 1~3 integer.
It is 2~12h when step (1) reaction time as preferred preparation method, step (2) uses dimethyl sulfoxide, first
When one or more of alcohol, ethyl alcohol, tetrahydrofuran, acetonitrile and petroleum ether are as solvent, according to above-mentioned synthetic method, S configuration
Or R configurationTwo amino only one participate in reaction formed an azobenzene, be prepared containing
The substituted type chirality azobenzene derivatives of one nitrogen nitrogen double bond.
It as a preferred option, is 14~36h when step (1) reaction time, step (2) uses N, N- dimethyl formyl
When amine, carbon tetrachloride, the concentrated sulfuric acid, n-hexane and petroleum ether one or more are as solvent, according to above-mentioned synthetic method, S type or
R typeTwo amino can all participate in reaction and form two azobenzenes, be prepared containing there are two nitrogen nitrogen
The substituted type chirality azobenzene derivatives of double bond.
It is further preferable that when control synthesis condition makes S type or R typeTwo amino both participate in
Reaction, when obtained substituted type chirality azobenzene derivatives are used for the synthesis of liquid crystal material of cholesteric phase of the present invention, when with visible light
When irradiation certain time makes liquid crystal material of cholesteric phase reach particular color, after stopping illumination, at room temperature, color has very long
Stability.
As a preferred option, the present invention provides a kind of substituted type chirality azobenzene derivatives, structural formula isWherein R31And R32Be each independently amino orAnd amino amount is not more than 1
It is a；R301、R302、R303And R304It is each independently hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine, and the quantity of hydrogen atom is not more than 3
It is a；R305ForThe alkoxy of C1~C8 or C1~C8's
Hydroxy alkoxy base；R401、R402、R403、R404、R405、R406、R407And R408Be each independently hydrogen, methoxyl group, fluorine, chlorine, bromine or
Iodine, and the quantity of hydrogen atom is not more than 7；R2411For the alkyl of C1~C8 or the hydroxy alkyl of C1~C8；R2521For cyano or
Nitro, n3For 1~3 integer.
The ternary liquid crystal material of cholesteric phase that the present invention is prepared is under the conditions of radiation of visible light, according to the wave of visible light
Long, light intensity and irradiation time etc. realize the controllable of color, and after radiation of visible light stops, substituted type chirality azobenzene
Cis-isomer has longer thermostabilization half-life period, and cis-isomer can keep stablizing without to trans- for a long time
Isomers transformation, the color of display can at least be kept 52 hours, or even be 100 hours or more, have good application
Prospect.
The following are embodiments:
Embodiment 1
(1) the 2- fluoroaniline of 0.28g is dissolved in the tetrahydrofuran of 10ml and obtains A, A with the rate of 1 μ l be added dissolved with
It in the sodium nitrite in aqueous solution B of 3.22g, is reacted under 20 DEG C of air atmospheres, magneton is stirred to react 4.0h, product water and dichloro
Methane extraction, methylene chloride obtain reaction intermediate 1 after being mutually spin-dried for；
(2) be dissolved in the reaction intermediate of 0.26g 1 in the acetonitrile of 10ml and the in the mixed solvent of petroleum ether (volume ratio 1:
1) (S)-(-) -1,1 of 0.35g, is added’In connection-dinaphthylamine, under 25 DEG C of argon atmospheres, magneton stirs 0.5h, through filtering
Substituted type chirality azobenzene derivatives, structural formula are obtained with after column chromatography are as follows:
(3) by the above-mentioned substituted type chirality azobenzene derivatives of 0.3g, the unsubstituted type azobenzene derivatives of 0.36gWith 0.3g nematic liquid crystalAfter (5CB) mixing, it is fitted into the internal liquid crystal cell with orientation texture and forms cholesteric phase
Liquid crystal material；
It (4) is 50mW/cm with light intensity2580nm light irradiate 0.5s, obtain reflected light be green cholesteric liquid crystal material
Material, corresponding wavelength 510nm, and green can be stabilized 52h.
The structural formula and its nuclear magnetic resonance spectroscopy for the substituted type chirality azobenzene derivatives that the present embodiment is prepared are shown in figure
1, it is peak corresponding to the H on amino at chemical shift 4.5, it was demonstrated that and with the presence of amino, while the product prepared is yellow,
Illustrate there is azobenzene generation, further confirms that (S)-(-) -1,1’Only one amino occurs on connection-dinaphthylamine raw molecule
Reaction, another amino, which is not engaged in, to be reacted and emerges from nuclear magnetic resonance spectroscopy.
In addition, the unsubstituted type azobenzene derivatives being calculated according to Group Contribution MethodSolubility parameter value be located at nematic liquid crystal 5CB and substitution
Type chirality azobenzeneBetween solubility parameter value, show that unsubstituted type azobenzene derivatives can be with
Promote the intermiscibility between three as function served as bridge well, further enhances the interaction force between three.
Embodiment 2
(1) 2, the 6- dibromo aniline of 0.51g is dissolved in the chloroform of 21ml and obtains A, A is added with the rate of 40 μ l
It dissolved in the potassium iodide aqueous solution B of 6.52g, is reacted under 60 DEG C of argon atmospheres, mechanic whirl-nett reaction 26h, product is through filtering and column
Reaction intermediate is obtained after chromatography；
(2) reaction intermediate of 0.25g is dissolved in the carbon tetrachloride of 10ml, adds (R)-(-) -1 of 0.58g,
In 1 '-connection-dinaphthylamine, under 60 DEG C of nitrogen atmospheres, mechanic whirl-nett reaction 120.0h is filtered and is obtained substituted type hand after column layer
Property azobenzene derivatives, structural formula are as follows:
(3) by 0.002g substituted type chirality azobenzene derivatives, the unsubstituted type azobenzene derivatives of 0.018gWith 1.98g nematic liquid crystalAfter mixing, it is fitted into the internal liquid crystal cell with orientation texture and forms cholesteric liquid crystal material
Material；
It (4) is 20mW/cm with light intensity2400nm light irradiate 10s, obtain reflected light be blue cholesteric liquid crystal material
Material, corresponding wavelength 460nm, and blue can be stabilized 56h.
Embodiment 3
(1) 2, the 6- difluoroaniline of 1.25g is dissolved in the tetrahydrofuran of 10ml and obtains A, A is added molten with the rate of 2 μ l
In the aqueous solution B for having 3.2g cesium carbonate and potassium carbonate (mass ratio 1:1), reacted under 45 DEG C of nitrogen atmospheres, magneton is stirred to react
36h obtains reaction intermediate after recrystallization；
(2) reaction intermediate of 0.2g is dissolved in 10mlN, the in the mixed solvent (body of dinethylformamide and the concentrated sulfuric acid
Product is than 1:1), add (S)-(-) -1 of 0.3g, in 1 '-connection-dinaphthylamine, under 42 DEG C of air atmospheres, mechanic whirl-nett reaction
72h is filtered and is obtained substituted type chirality azobenzene derivatives, structural formula with after column chromatography are as follows:
(3) the unsubstituted type azobenzene derivatives of 0.144g substituted type chirality azobenzene derivatives, 0.36gWith 0.216g nematic phase liquid
It is brilliantAfter mixing, it is fitted into the internal liquid crystal cell with orientation texture and forms gallbladder
Steroid phase liquid crystal material；
It (4) is 1mW/cm with light intensity2600nm light irradiate 120s, obtain reflected light be orange cholesteric liquid crystal material
Material, corresponding wavelength 610nm, and orange it is stabilized 87h.
The structural formula and its nuclear magnetic resonance spectroscopy for the substituted type chirality azobenzene that the present embodiment synthesizes are shown in Fig. 2, from figure
In as can be seen that be at 4.5 there is no peak corresponding to the H on amino in chemical shift, while the product yellowly prepared.
The above result shows that (S)-(-) -1, two amino on 1 '-connection-dinaphthylamine raw molecule have both participated in reaction, form 2
Substituted type azobenzene.Preparation-obtained liquid crystal material of cholesteric phase reflects the corresponding wavelength of light color can be according to light application time
Regulated and controled, from figure 3, it can be seen that reflection light color is corresponding after the light of 600nm irradiates 120s to liquid crystal material of cholesteric phase
Wavelength be 610nm.
Compared with Example 1, substituted type chirality azobenzene derivatives are obtained using identical raw material to the present embodiment,
Two amino on (S)-(-) -1,1 '-connection-dinaphthylamine are made to have selection simply by the conditions such as reaction time and solvent of change
Participation reaction, thus the substituted type chirality azobenzene derivatives being prepared have good comparability.In the present embodiment
Two connected amino of dinaphthalene both participate in reaction and generate two azobenzenes, and only one amino participates in reaction life in embodiment 1
At an azobenzene, the color of the finally obtained liquid crystal material of cholesteric phase of the present embodiment is allowed to stablize the longer time.?
It further illustrates, in the case where that can compare, S type or R typeTwo amino when both participating in reaction,
The color of preparation-obtained liquid crystal material of cholesteric phase has longer stability.
Embodiment 4
(1) by 4- amino -2,3 of 3.15g, 5,6- tetrafluorobenzoic aid amine, which are dissolved in the pyridine of 10ml, obtains A, and A is with 50 μ l
Rate be added dissolved in the aqueous solution B of the ammonium persulfate-sodium bisulfate of 4.2g, reacted under 90 DEG C of air atmospheres, magneton stirring
2h is reacted, product water and chloroform extraction, chloroform obtain reaction intermediate after being mutually spin-dried for；
(2) reaction intermediate of 0.1g is dissolved in the in the mixed solvent (volume ratio of 16ml dimethyl sulfoxide, methanol and ethyl alcohol
1:1:2), (S)-(-) -1 of 0.2g is added, in 1 '-connection-dinaphthylamine, under 56 DEG C of air atmospheres, magneton is stirred to react 4.0h,
It adds and obtains substituted type chirality azobenzene derivatives, structural formula after recrystallizing and column chromatographs are as follows:
(3) by 0.84g substituted type chirality azobenzene derivatives, the unsubstituted type azobenzene derivatives of 0.36gWith 1.2g nematic liquid crystalAfter mixing, it is fitted into the internal liquid crystal cell with orientation texture and forms cholesteric liquid crystal
Material；
It (4) is 50mW/cm with light intensity2650nm light irradiate 120s, obtaining reflected light is red cholesteric liquid crystal material
Material, corresponding wavelength 620nm, and red can be stabilized 102.0h.
Embodiment 5
(1) the 4- amino -2,3,5,6-4 fluobenzoic acid amine of 4.15g is dissolved in the in the mixed solvent of 16ml toluene and acetonitrile
(volume ratio 3:1) obtains A, and A is added with the rate of 18 μ l dissolved with 5.6g ammonium persulfate-sodium bisulfate and sodium hydroxide (mass ratio
In aqueous solution B 5:2), being reacted under 48 DEG C of air atmospheres, magneton is stirred to react 30h, after product is recrystallized and column chromatographs
To reaction intermediate 1；
(2) by the reaction intermediate of 0.36g 1 be dissolved in 32ml n-hexane and petroleum ether in the mixed solvent (volume ratio 3:
5) (S)-(-) -1,1 of 0.42g, is added’In connection-dinaphthylamine, under 120 DEG C of air atmospheres, magneton is stirred to react 42.0h,
Intermediate 2 is obtained with after column chromatography by extracting and recrystallizing；
(3) 0.22g intermediate 2 is dissolved in (body in the mixed solution of 16ml tetrahydrofuran, methylene chloride and chloroform
Product is than 1:2:1), it is added 0.35g'sUnder 25 DEG C of air atmospheres, magneton is stirred to react 40h, and product passes through
Substituted type chirality azobenzene derivatives, structural formula are obtained after extraction, recrystallization and column chromatography are as follows:
(4) by 0.50g substituted type chirality azobenzene derivatives, the unsubstituted type azobenzene derivatives of 0.18gWith 1.2g nematic liquid crystalAfter mixing, it is fitted into the internal liquid crystal cell with orientation texture and forms gallbladder
Steroid phase liquid crystal material；
It (5) is 80mW/cm with light intensity2520nm light irradiate 1.2s, obtain reflected light be yellow cholesteric liquid crystal material
Material, corresponding wavelength 580nm, and yellow can be stabilized 86h.
Embodiment 6
(1) mixing for the 4- amino -2,3,5,6-4 fluobenzoic acid amine of 3.75g being dissolved in 12ml methylene chloride and acetonitrile is molten
(volume ratio 1:2) obtains A in agent, and A is added with the rate of 41 μ l dissolved with 3.8g hydrogen persulfate sylvite and sodium nitrite (mass ratio
In aqueous solution B 1:3), under 60 DEG C of argon atmospheres, reaction intermediate 1 after filtering automatic reaction 28h；
(2) reaction intermediate of 0.11g 1 is dissolved in the petroleum ether of 23ml, adds (S)-(-) -1,1 of 0.36g’-
In connection-dinaphthylamine, under 150 DEG C of air atmospheres, magneton is stirred to react 10.0h, obtains intermediate 2 after extracting and column chromatographs；
(3) 0.22g intermediate 2 is dissolved in (volume in the mixed solution of acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide
Than 2:1:1), it is added 0.35g'sUnder 40 DEG C of nitrogen atmospheres, magneton stirring
72h is reacted, product obtains substituted type chirality azobenzene derivatives, structural formula after filtering and column chromatographs are as follows:
(4) by 0.32g substituted type chirality azobenzene derivatives, the unsubstituted type azobenzene derivatives of 0.50gWith 1.0g to
Column phase liquid crystalAfter (5CB) mixing, it is fitted into shape in the internal liquid crystal cell with orientation texture
At liquid crystal material of cholesteric phase；
It (5) is 45mW/cm with light intensity2460nm light irradiate 1.2s, obtaining reflected light is red cholesteric liquid crystal material
Material, corresponding wavelength 660nm, corresponding wavelength 650nm, and red can be stabilized 78h.
Embodiment 7
(1) the chloro- 4- formic acid-aniline of the 2- of 3.75g is dissolved in the in the mixed solvent (volume of 24ml ethyl acetate and acetic acid
Than 1:2) obtain A, A is added with the rate of 9 μ l dissolved in the aqueous solution B of 2.2g sodium chloride and sodium hydroxide (mass ratio 1:1),
Under 54 DEG C of air atmospheres, magneton is stirred to react 18h, the reaction intermediate 1 after extraction and recrystallization；
(2) reaction intermediate of 0.18g 1 is dissolved in 36mlN, the mixed solvent of dinethylformamide and carbon tetrachloride
In (volume ratio 3:2), add (R)-(-) -1,1 of 0.36g’In connection-dinaphthylamine, under 40 DEG C of argon atmospheres, magneton stirring
112.0h is reacted, obtains intermediate 2 after extraction, recrystallization and column chromatography；
(3) 0.14g intermediate 2 is dissolved in 30ml ethyl acetate, in acetone and toluene mixed solution (volume ratio 1:4:1),
It is added 0.26g'sUnder 60 DEG C of nitrogen atmospheres, mechanic whirl-nett reaction 25h, product warp
Substituted type chirality azobenzene derivatives, structural formula are obtained after crossing recrystallization and column chromatography are as follows:
(4) by 0.36g substituted type chirality azobenzene derivatives, the unsubstituted type azobenzene derivatives of 0.1gWith 1.0g nematic phase liquid
It is brilliantAfter mixing, it is fitted into the internal liquid crystal cell with orientation texture and forms cholesteric phase liquid
Brilliant material；
It (5) is 80mW/cm with light intensity2530nm light irradiate 300s, obtain reflected light be orange cholesteric liquid crystal material
Material, corresponding wavelength 600nm, and red can be stabilized 67h.
Embodiment 8
(1) the 4- amino -2,3,5,6-4 bromobenzoic acid amine of 2.54g is dissolved in the in the mixed solvent of 32ml toluene and pyridine
(volume ratio 1:2) obtains A, and the aqueous solution dissolved with 2.2g cesium carbonate and sodium hydroxide (mass ratio 6:1) is added with the rate of 3 μ l by A
In B, under 82 DEG C of argon atmospheres, magneton is stirred to react 22.0h, obtains reaction intermediate 1 after product is extracted and column chromatographs；
(2) by the reaction intermediate of 0.28g 1 be dissolved in 18ml carbon tetrachloride and n-hexane in the mixed solvent (volume ratio 5:
4) (S)-(-) -1 of 0.28g, is added, in 1 '-connection-dinaphthylamine, under 96 DEG C of air atmospheres, magneton is stirred to react 102.0h,
Intermediate 2 is obtained after extraction, recrystallization and column chromatography；
(3) be dissolved in 0.09g intermediate 2 in the mixed solution of 28ml tetrahydrofuran, toluene and acetic acid (volume ratio 2:2:
3), it is added 0.17g'sUnder 130 DEG C of air atmospheres, magnetic agitation reacts 9h, product
Substituted type chirality azobenzene derivatives, structural formula are obtained after filtering, recrystallization and column chromatography are as follows:
(4) by 0.28g substituted type chirality azobenzene derivatives, the unsubstituted type azobenzene derivatives of 0.23g and 1.0g nematic
Phase liquid crystalAfter (5CB) mixing, it is fitted into the internal liquid crystal cell with orientation texture and is formed
Liquid crystal material of cholesteric phase；
It (5) is 5mW/cm with light intensity2520nm light irradiate 12s, obtaining reflected light is red liquid crystal material of cholesteric phase,
Its corresponding wavelength is 660nm, and red can be stabilized 72h.
Comparative example 1
Other conditions prepare cholesteric phase with embodiment 3, only with substituted type chirality azobenzene derivatives and nematic liquid crystal
Liquid crystal material, the cholesteric liquid crystal being prepared with wavelength is 600nm, light intensity 1mW/cm2Radiation of visible light 10s when, and
The variation of liquid crystal material of cholesteric phase color is not observed.
Comparative example 2
Other conditions prepare cholesteric phase with comparative example 1, only with substituted type chirality azobenzene derivatives and nematic liquid crystal
Liquid crystal material, the cholesteric liquid crystal being prepared with wavelength is 365nm, light intensity 1mW/cm2Ultraviolet light 10s when, can
To observe that liquid crystal material of cholesteric phase color becomes red, after ultraviolet lighting stops, red is only capable of maintaining 30min, is not able to maintain
It is prolonged to stablize.
Preparation-obtained liquid crystal material of cholesteric phase reflection light color it is corresponding with wavelength as shown in figure 4, when 365nm's
After light irradiates 10s to liquid crystal material of cholesteric phase, obtaining reflected light is red liquid crystal material of cholesteric phase, and corresponding wavelength is
635nm, after ultraviolet lighting stops, red can only be stabilized 30min.
Comparative example 3
Other conditions prepare cholesteric with embodiment 3, only with unsubstituted type chirality azobenzene derivatives and nematic liquid crystal
Phase liquid crystal material, the cholesteric liquid crystal being prepared with wavelength is 600nm, light intensity 1mW/cm2Radiation of visible light 10s when,
The variation of liquid crystal material of cholesteric phase color is not observed.
Comparative example 4
Other conditions prepare cholesteric with comparative example 3, only with unsubstituted type chirality azobenzene derivatives and nematic liquid crystal
Phase liquid crystal material, the cholesteric liquid crystal being prepared with wavelength is 365nm, light intensity 1mW/cm2Ultraviolet light 10s when,
It can be observed that liquid crystal material of cholesteric phase color becomes yellow, after ultraviolet lighting stops, yellow is only capable of maintaining 10min, Bu Nengbao
Hold prolonged stabilization.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all wrap
Containing within protection scope of the present invention.
Claims (10)
1. a kind of liquid crystal material of cholesteric phase of visible light regulation color, which is characterized in that in parts by weight, including 30-99 parts
Nematic liquid crystal, 0.9-50 parts of unsubstituted type azobenzene derivatives and 0.1-50 parts of substituted type chirality azo benzenesulfonamide derivative
The color of object, the liquid crystal material of cholesteric phase has visible light-responded property.
2. liquid crystal material of cholesteric phase as described in claim 1, which is characterized in that the wavelength of the visible light be 400nm~
650nm, intensity of illumination 1mW/cm2~80mW/cm2, irradiation time is 0.5s~300s.
3. liquid crystal material of cholesteric phase as described in claim 1, which is characterized in that the structural formula of the nematic liquid crystal isWherein, R11For cyano, nitro or methoxyl group, R12For the alkyl of C1~C3 or the hydroxyl alkane of C1~C3
Base, R13For the alkyl of C1~C9 or the hydroxy alkyl of C1~C9, n1For 1~4 integer.
4. liquid crystal material of cholesteric phase as described in claim 1, which is characterized in that the unsubstituted type azobenzene derivatives are S
The unsubstituted type dinaphthalene molecule derivant of configuration or R configuration, structural formula are preferably Wherein, R21For the alkyl of C1~C10 or the alkane of C1~C10
Oxygroup, R22For ester group or oxygen, R23For the alkyl of C1~C8 or the hydroxy alkyl of C1~C8, R241And R242It is each independentlyThe alkene of C1~C6 or the alkyl of C1~C10, n2For 1~3 integer；R2411
For the alkyl of C1~C8 or the hydroxy alkyl of C1~C8.
5. liquid crystal material of cholesteric phase as described in claim 1, which is characterized in that the substituted type chirality azobenzene derivatives packet
Include 1~4-N=N-and 1~3 chiral centre, and at least 1 on described-phenyl ring of N=N-connection two at quilt
Other groups in addition to H atom replace；
Preferably, the substituted type chirality azobenzene derivatives are the dinaphthalene molecule derivant of S configuration or R configuration, structural formula
ForWherein R31And R32Be each independently amino orAnd amino amount is few
In 1；R301、R302、R303And R304It is each independently hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine, and the quantity of hydrogen atom is not more than
3；R305ForThe alkoxy of C1~C8 or C1~C8's
Hydroxy alkoxy base；R401、R402、R403、R404、R405、R406、R407And R408Be each independently hydrogen, methoxyl group, fluorine, chlorine, bromine or
Iodine, and the quantity of hydrogen atom is not more than 7；R2411For the alkyl of C1~C8 or the hydroxy alkyl of C1~C8；R2521For cyano or nitre
Base, n3For 1~3 integer.
6. a kind of preparation method of substituted type chirality azobenzene derivatives, which comprises the steps of:
(1) it will be dissolved in solvent AIt is mixed with the aqueous solution of inorganic salts, isolated after reaction
One intermediate；
(2) by first intermediate being dissolved in solvent B and S configuration or R configurationReaction, separation
Obtain the second intermediate；
(3) by second intermediate being dissolved in solvent C with It is mixed with the alcohol of C1~C8, isolated substituted type chirality azobenzene derivatives after reaction；
Wherein, R301、R302、R303And R304It is each independently hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine, and the quantity of hydrogen atom is not
More than 3；R401、R402、R403、R404、R405、R406、R407And R408It is each independently hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine, and
The quantity of hydrogen atom is not more than 7；R2411For the alkyl of C1~C8 or the hydroxy alkyl of C1~C8；R2521For cyano or nitro, n3
For 1~3 integer.
7. preparation method as claimed in claim 6, which is characterized in that step (1) solvent A is tetrahydrofuran, acetonitrile, second
One or more of acetoacetic ester, methylene chloride, chloroform, toluene, acetic acid and pyridine；The inorganic salts be sodium nitrite,
One or more of ammonium persulfate-sodium bisulfate, sodium chloride, potassium carbonate, cesium carbonate and potassium iodide；The reaction condition are as follows: 20
DEG C~90 DEG C, air or atmosphere of inert gases stir 2~36h；The isolated method are as follows: extraction, recrystallization, column chromatography and
One or more of filtering.
8. preparation method as claimed in claim 6, which is characterized in that step (2) the solvent B is N, N- dimethyl formyl
One of amine, dimethyl sulfoxide, methanol, ethyl alcohol, carbon tetrachloride, the concentrated sulfuric acid, acetonitrile, tetrahydrofuran, n-hexane and petroleum ether or
It is several；The reaction condition are as follows: 40 DEG C~150 DEG C, air or atmosphere of inert gases stir 0.5h~120h；The separation
Method are as follows: one or more of extraction, recrystallization, column chromatography and filtering.
9. preparation method as claimed in claim 6, which is characterized in that step (3) solvent C is tetrahydrofuran, acetonitrile, second
One of acetoacetic ester, acetone, methylene chloride, chloroform, N,N-dimethylformamide, toluene, acetic acid and dimethyl sulfoxide or
It is several；The reaction condition are as follows: 25 DEG C~160 DEG C, air or atmosphere of inert gases stir 4.0~72.0h；The separation side
Method are as follows: one or more of extraction, recrystallization, column chromatography and filtering.
10. a kind of substituted type chirality azobenzene derivatives, which is characterized in that its structural formula isWherein R31With
R32Be each independently amino orAnd amino amount is not more than 1；R301、R302、R303And R304Respectively
From independently being hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine, and the quantity of hydrogen atom is not more than 3；R305For The alkoxy of C1~C8 or the hydroxy alkoxy base of C1~C8；
R401、R402、R403、R404、R405、R406、R407And R408It is each independently hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine, and hydrogen atom
Quantity is not more than 7；R2411For alkyl or the hydroxy alkyl of C1~C8；R2521For cyano or nitro, n3For 1~3 integer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112596317A (en) * | 2020-12-16 | 2021-04-02 | 北京大学 | Preparation method and application of intelligent liquid crystal color changing device with ultraviolet light drive |
| CN112920813A (en) * | 2020-12-11 | 2021-06-08 | 湘潭大学 | Photo-thermal responsive chiral photosensitive liquid crystal dopant containing azobenzene binaphthalene |
| CN115806826A (en) * | 2021-09-14 | 2023-03-17 | 中国科学院理化技术研究所 | Cholesteric liquid crystal capable of realizing multi-wavelength light tuning guidance, and preparation and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070237906A1 (en) * | 2004-01-28 | 2007-10-11 | Kent Displays Incorporated | Chiral nematic photo displays |
| CN102010720A (en) * | 2010-11-11 | 2011-04-13 | 北京科技大学 | Method for regulating optical performance of liquid crystals by using azobenzene |
| WO2013081155A1 (en) * | 2011-12-01 | 2013-06-06 | 独立行政法人産業技術総合研究所 | Photosensitive azobenzene derivative |
| CN105489380A (en) * | 2014-10-01 | 2016-04-13 | 韩国科学技术研究院 | Photoreactive smart window |
| CN106496064A (en) * | 2016-10-13 | 2017-03-15 | 天津大学 | One class is used for the azobenzene derivatives of the ortho position of solar heat storage containing electron-withdrawing group and preparation method thereof |
| CN106833680A (en) * | 2017-01-03 | 2017-06-13 | 复旦大学 | A kind of photoresponse three-stable state chiral molecules material and its preparation method and application |
| CN104142587B (en) * | 2014-07-16 | 2017-07-04 | 北京大学 | Bireflectance band cholesteric liquid crystal with reversible response characteristics to light and preparation method thereof |
-
2018
- 2018-07-24 CN CN201810820897.0A patent/CN109161385A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070237906A1 (en) * | 2004-01-28 | 2007-10-11 | Kent Displays Incorporated | Chiral nematic photo displays |
| CN102010720A (en) * | 2010-11-11 | 2011-04-13 | 北京科技大学 | Method for regulating optical performance of liquid crystals by using azobenzene |
| WO2013081155A1 (en) * | 2011-12-01 | 2013-06-06 | 独立行政法人産業技術総合研究所 | Photosensitive azobenzene derivative |
| CN104142587B (en) * | 2014-07-16 | 2017-07-04 | 北京大学 | Bireflectance band cholesteric liquid crystal with reversible response characteristics to light and preparation method thereof |
| CN105489380A (en) * | 2014-10-01 | 2016-04-13 | 韩国科学技术研究院 | Photoreactive smart window |
| CN106496064A (en) * | 2016-10-13 | 2017-03-15 | 天津大学 | One class is used for the azobenzene derivatives of the ortho position of solar heat storage containing electron-withdrawing group and preparation method thereof |
| CN106833680A (en) * | 2017-01-03 | 2017-06-13 | 复旦大学 | A kind of photoresponse three-stable state chiral molecules material and its preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| DAVID BLÉGER等: "o-Fluoroazobenzenes as Readily Synthesized Photoswitches Offering Nearly Quantitative Two-Way Isomerization with Visible Light", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| DONGXU ZHAO等: "Precisely Tuning Helical Twisting Power via Photoisomerization Kinetics of Dopants in Chiral Nematic Liquid Crystals", 《LANGMUIR》 * |
| HE HUANG等: "Long-Lived Supramolecular Helices Promoted by Fluorinated Photoswitches", 《MACROMOLECULAR RAPID COMMUNICATIONS》 * |
| LANG QIN等: "Piecewise Phototuning of Self-Organized Helical Superstructures", 《ADVANCED MATERIALS》 * |
| 张伶莉: "光调谐的胆甾相液晶应用的发展", 《液晶与显示》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112920813A (en) * | 2020-12-11 | 2021-06-08 | 湘潭大学 | Photo-thermal responsive chiral photosensitive liquid crystal dopant containing azobenzene binaphthalene |
| CN112920813B (en) * | 2020-12-11 | 2023-08-22 | 湘潭大学 | Photo-thermal response chiral photosensitive liquid crystal dopant containing azobenzene binaphthyl |
| CN112596317A (en) * | 2020-12-16 | 2021-04-02 | 北京大学 | Preparation method and application of intelligent liquid crystal color changing device with ultraviolet light drive |
| CN115806826A (en) * | 2021-09-14 | 2023-03-17 | 中国科学院理化技术研究所 | Cholesteric liquid crystal capable of realizing multi-wavelength light tuning guidance, and preparation and application thereof |
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