CN107418593A - Double bond containing fullerene liquid-crystal compounds and its application - Google Patents
Double bond containing fullerene liquid-crystal compounds and its application Download PDFInfo
- Publication number
- CN107418593A CN107418593A CN201710783173.9A CN201710783173A CN107418593A CN 107418593 A CN107418593 A CN 107418593A CN 201710783173 A CN201710783173 A CN 201710783173A CN 107418593 A CN107418593 A CN 107418593A
- Authority
- CN
- China
- Prior art keywords
- acid
- crystal
- double bond
- fullerene
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
- C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/11—Compounds covalently bound to a solid support
Abstract
There is high index of refraction, the fullerene liquid-crystal compounds containing double bond functional group, its preparation method, as well as application of the packing material in photonic crystal field the invention discloses a kind of.The fullerene liquid crystal molecule structure is made up of three parts, is specially：Rigid fowler enoic acid moiety, the flexible gallic acid-derivate part containing double bond, and soft segment part connecting the two, the precursor of the soft segment is glycol；Wherein, the both ends of soft segment are connected with gallic acid-derivate part of the ester bond respectively with fowler enoic acid moiety, containing double bond.The high index of refraction that this fullerene liquid-crystal compounds has, the liquid crystal molecule of low-refraction can be substituted well as the packing material of photonic crystal, obtain contrast of refractive index height, the photonic crystal of excellent performance.
Description
Technical field
The present invention relates to a kind of application of liquid-crystal compounds and the liquid-crystal compounds in tunable photonic crystal is prepared.
Background technology
Photonic crystal be by two kinds and the two or more materials with differing dielectric constant in space according to certain cycle
Sequentially arrange the material with ordered structure formed.Electromagnetic wave it is this with the material of periodic structure in propagate when meeting
Modulated by the cycle potential field being made up of dielectric, so as to form the photonic band gap similar to semiconductor energy band structure.Photon
Between band if without overlapping, photon band gap or forbidden photon band (photonic bang gap, PBG) can will be formed.Liquid crystal has
There is very big optical anisotropy and external environment condition (electric field, magnetic field, temperature or polarised light etc.) is changed very sensitive
Property, so as to as one of packing material for preparing photonic crystal by very big concern.Biography can be prepared using liquid crystal property
The adjustable optical device such as sensor, photoswitch, wave filter.1999, nematic liquid crystal was filled into colloid by Busch and John first
In the space of crystal, and the movement of the photon band gap of counter opal structure is theoretically foretold, it is brilliant in photon to have started liquid crystal
The beginning applied in body.
Up to the present, the photonic crystal based on liquid crystal filling shows excellent performance.For example, it is based on phenylacetylene type liquid
Lens prepared by the regulatable type graded index photonic crystal of brilliant molecule filling, its focus effectively can be controlled and regulated and controled
Scope can expand to 680nm.The photonic crystal of the thermo-responsive counter opal structure prepared using liquid crystal elastic body has double
Weight structure color, forbidden photon band can realize reversible regulation and control by temperature change.And by liquid crystal elastic body and SiO2Colloidal crystal
The shape of the photon-driven device of preparation can be quick and reversible with the change of temperature generation bend accordingly, reply row
For.The photonic crystal filled by cholesteric liquid crystal can be used as DSSC (DSCs) back reflector, Neng Gouyou
Effect causes photoelectric current maximum to improve 21%, energy conversion efficiency maximum and can improve 17%.
In general, the property of photonic crystal is influenceed by medium refraction index, filling rate and lattice structure, therefore,
High performance photonic crystal can be obtained by improving medium refraction index in photonic crystal.However, currently used for preparing photonic crystal
Liquid crystal packing material, its refractive index is normally between 1.5-1.6；For example, in conventional colloidal crystal template, titanium dioxide
The refractive index of silicon is 1.45, and the refractive index of polystyrene is 1.59, therefore, the refraction of the photonic crystal obtained by above material
Rate contrast is not high.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of liquid-crystal compounds of high index of refraction, and utilize the liquid crystal
Compound prepares a kind of method of high refractive index contrast tunable photonic crystal.
Want to obtain the high photonic crystal of contrast of refractive index, the liquid crystal material of high index of refraction can be used to replace commonly using at present
Liquid crystal packing material.The refractive index of liquid crystal material is influenceed by the bulk density of material and polarizable degree, and polarizable degree
Mainly there are three types：Electronic polarization, atom polarization and dipole moment polarization.Generally, the liquid filled in photonic crystal
Brilliant material is in solid-state form.When material is in solid-state, electronic polarization plays a leading role, and strong influence the refractive index of material,
Therefore more pi-electrons are contained, its refractive index is bigger.[C60] the spherical caged knot that is made up of 60 carbon atoms of fullerene
Structure, big pi bond is formed, show high refractive index (n=2.2), high C60The refractive index of the fullerene polymer of content is also relatively high
(n>1.75), equally, high C60The fullerene liquid crystal of content also has high refractive index.
There is photon band gap and the high photonic crystal of contrast of refractive index in order to obtain in the range of ultraviolet-visible, protect
The high-performance of photonic crystal is demonstrate,proved, inventor designs and prepared a kind of double bond containing fullerene liquid-crystal compounds, combines this
Double bond containing fullerene liquid-crystal compounds has the cycle formed after the property of high index of refraction, and nano-scale microballoon self assembly
Property ordered structure, devise the tunable photonic crystal of high fullerene content liquid crystal filling, improve the refractive index pair of photonic crystal
Than degree, high performance tunable photonic crystal is obtained.
Described double bond containing fullerene liquid-crystal compounds, its molecular structure composition are：Rigid fowler enoic acid moiety, contains
There are the gallic acid-derivate part of double bond, and the soft segment part of connection the former two；The precursor of soft segment is glycol,
The both ends of soft segment are connected with gallic acid-derivate part of the ester bond respectively with fowler enoic acid moiety, containing double bond；It is described
Fowler olefin(e) acid is [60] fullerene acetic acid, [60] fullerene propionic acid or [60] fullerene malonic acid, and the structural formula of glycol is HO-
R1- OH, R1Structure is CmH2m, m 2-12, double bond containing gallic acid-derivate structural formula is
In structural formula, n=4-18
Above-mentioned double bond containing fullerene liquid-crystal compounds is with Cn-Cm-C60- ene is named.Wherein, CnIn n refer to and be connected to
The carbon number (totally 3) of each carbochain of the tail chain on gallic acid, CmIn m refer to the carbon of middle flexible interval carbochain
Number, last C60Refer to [C60] fullerene.
In above-mentioned double bond containing fullerene liquid-crystal compounds, fullerene content shared in liquid crystal molecule 40% with
On, maximum can be to 60% or so；And the temperature range of fullerene liquid crystalline phase broadens with the reduction of end alkyl chain length,
And its crystalline phase of most compounds is in room temperature even subzero to the transition temperature of liquid crystalline phase, belongs to room temperature type liquid crystal.For example,
C8-C8-C60- ene is below 98 DEG C all in liquid crystalline phase in DSC detectable scope.
In above-mentioned double bond containing fullerene liquid-crystal compounds, all more than 1.70, highest can reach the refractive index of its molecule
To 1.85 or so.The refractive index (as shown in table 1) of liquid crystal molecule is commonly used apparently higher than in document.
The refractive index of the compound of table 1.
a：Institute's labeled compound refractive index value, which comes from, has reported data in literature, b：Compound refractive index is according to ellipsometer
Test obtains, c：Δ n is liquid crystal molecule and SiO2The difference of molecular refractivity.
The present invention provides a kind of preparation method of above-mentioned double bond containing fullerene liquid-crystal compounds, mainly including following
Step：
(1) alkenyl halide is prepared first with two alkyl halides, wherein, the molecular structure of alkenyl halide isX is
Bromine or chlorine, n are carbon chain lengths, and its value is 4-18；
(2) using Gallic Acid methyl esters as raw material, reacted with alkenyl halide under weakly alkaline environment, obtain 3,
4,5- triolefin p-methoxybenzoic acid methyl esters；
(3) 3,4,5- triolefin p-methoxybenzoic acid methyl esters are hydrolyzed in acid condition, obtain 3,4,5- tri- alkenyloxy group benzene
Formic acid；
(4) 3,4,5- triolefin p-methoxybenzoic acids in the presence of catalyst, occur esterification, obtain 3,4,5- with glycol
Triolefin p-methoxybenzoic acid alcohol ester；Wherein, the chemical structural formula of glycol is HO-R1- OH, R1Structure is CmH2m, m 2-12；
(5) 3,4,5- triolefin p-methoxybenzoic acid alcohol esters under catalyst action, occur esterification and obtained with fowler olefin(e) acid
Final double bond containing fullerene liquid-crystal compounds；Wherein, the fowler olefin(e) acid is [60] fullerene acetic acid, [60] fullerene third
Acid or [60] fullerene malonic acid.
The present invention provides one kind by the use of above-mentioned double bond containing fullerene liquid-crystal compounds as packing material, to prepare one kind
The method of high refractive index contrast tunable photonic crystal, this method comprise the following steps：
(1) microsphere particle is synthesized；
(2) colloidal crystal template is prepared；
(3) double bond containing fullerene liquid-crystal compounds is filled in colloidal crystal space, that is, obtains tunable photonic crystal.
In the above-mentioned method for preparing photonic crystal, in step (1), the microsphere particle can be inorganic matter, such as be based on two
Modification or unmodified inorganic microspheres particle prepared by silica or titanium dioxide, or prepared based on polystyrene
Organic matter microsphere particles, such as PS (polystyrene), P (St-MMA-AA) (poly- (styrene methyl methacrylate-acrylic acid))
Or P (St-MMA-SPMAP) (poly- (Styrene-Methyl Methacrylate-Methacrylic Acid propyl sulfonic acid potassium)) etc.；Described is micro-
Spherolite footpath is located in the range of 150-450nm.
In above-mentioned preparation method step (2), the structure of the colloidal crystal template can be opal structural or
Counter opal structure.Specific operating procedure is as follows：
(1) opal structural colloidal crystal：Using ethanol as solvent, using vertical sedimentation method, under the conditions of room temperature (25 DEG C),
Prepare SiO2The template of opal structural, is then solidified in high temperature, improves the intensity of template.
(2) counter opal structure colloidal crystal：Using deionized water as solvent, using co-electrodeposition method, in 60 DEG C, 60% humidity
Under the conditions of, prepare polymer microballoon and SiO2Colloidal crystal, subsequent high temperature sintering, remove polymer microballoon, obtain SiO2Anti- egg
The template of white stone structure.
In above-mentioned preparation method step (3), the double bond containing fullerene liquid crystal molecule is dissolved in benign organic solvent,
Such as carbon disulfide, chloroform, dichloromethane, toluene equal solvent, preparation solution concentration is 5~10 mg/mls.In a manner of being added dropwise,
Sample is added dropwise in colloidal crystal template, and by being repeatedly added dropwise so that double bond containing fullerene liquid crystal molecule fills up Colloidal crystals
Body space, obtain the photonic crystal of double bond containing fullerene liquid crystal molecule filling.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1. the liquid-crystal compounds of fullerene containing double bond synthesized by the present invention has high fullerene (C60) content, 40% with
On, it might even be possible to reach 60% or so.For example, C4-C8-C60In-ene molecules, C60Content be about 59%；C8-C8-C60-ene
In molecule, C60Content be about 52%；C16-C8-C60In-ene molecules, C60Content be about 42%.
2. due to C in molecule60Content it is high, therefore the liquid-crystal compounds of fullerene containing double bond synthesized by the present invention have it is high
Refractive index.For example, C8-C8-C60Refractive index of-ene the molecules at 589nm is 1.794, its refractive index in visible-range
All it is above 1.74.The refraction for the conventional liquid-crystal compounds that the refractive index of the fullerene liquid-crystal compounds is both greater than reported at present
Rate.Therefore, the photonic crystal prepared using the liquid crystal of fullerene containing double bond as packing material, has high-index-contrast
Degree, excellent in optical properties.
Its liquid crystalline phase of 3. present invention uses the liquid-crystal compounds of fullerene containing double bond has the arrangement architecture of long-range order, C60
Long range ordered structure be advantageous to the transmission of photon.
Brief description of the drawings
Fig. 1 is 1- fullerene acetic acid 8- (3,4,5- tri- (octene epoxide) benzoic acid) ethohexadiol ester (C in embodiment one8-C8-
C60- ene) schematic arrangement.
Fig. 2 is 1- fullerene acetic acid 8- (3,4,5- tri- (octene epoxide) benzoic acid) ethohexadiol ester (C in embodiment one8-C8-
C60- ene) differential scanning calorimetric thermogram (DSC).
Fig. 3 is 1- fullerene acetic acid 8- (3,4,5- tri- (octene epoxide) benzoic acid) ethohexadiol ester (C in embodiment one8-C8-
C60- ene) X-ray diffraction pattern (XRD).
Fig. 4 is 1- fullerene acetic acid 8- (3,4,5- tri- (octene epoxide) benzoic acid) ethohexadiol ester (C in embodiment one8-C8-
C60- ene) petrographic microscope photo (POM).
Fig. 5 is 1- fullerene acetic acid 8- (3,4,5- tri- (octene epoxide) benzoic acid) ethohexadiol ester (C in embodiment one8-C8-
C60- ene) refractive index curve.
Fig. 6 is single dispersing SiO in embodiment two2Microballoon SEM spectrograms.
Fig. 7 is C in embodiment two8-C8-C60The front and rear SiO of-ene fillings2The reflectance spectrum of photonic crystal of opals structure
Figure and C8-C8-C60SiO after-ene fillings2The spectrogram that the reflection peak of photonic crystal of opals structure varies with temperature.
Fig. 8 is SiO in embodiment three2Counter opal structure colloidal crystal template SEM spectrograms.
Fig. 9 is C in embodiment three8-C8-C60SiO after-ene fillings2The reflection peak of photonic crystal with inverse opal structure with
The spectrogram of temperature change.
Embodiment
The 1- fullerene acetic acid 8- of embodiment one (3,4,5- tri- (octene epoxide) benzoic acid) ethohexadiol ester (C8-C8-C60-
Ene) the preparation of (molecular structure is as shown in figure)：
(1) synthesis of the bromo- 1- octenes of 8- and sign
In THF (100mL) solution containing potassium tert-butoxide (0.12mol), the THF of the bromooctanes of 1,8- bis- (0.1mol) is added
(50mL) solution, stir 1 hour under room temperature condition.Afterwards, reaction solution is poured into deionized water (200mL), extracted with ether
(3 × 60mL), collect organic phase.Organic phase uses 5%Na successively2CO3Solution wash 2 times, deionization wash 3 times, anhydrous sodium sulfate
Dry, filter, revolving.The crude product being collected into using distillation is evaporated under reduced pressure, clean product is obtained, is colourless liquid.It is above-mentioned anti-
Answer process as follows：
Nuclear-magnetism characterizes：1H NMR(400MHz):δ1.26-1.48(m,6H),1.78-1.92(m,2H),1.99-2.11(m,
2H),3.40(t,2H),4.89-5.05(m,2H),5.73-5.87(m,1H).Nuclear magnetic data coincide with molecular structure.
(2) synthesis of 3,4,5- tri- (octene epoxide) methyl benzoate and sign
In DMF (35mL) solution containing reactant Gallic Acid methyl esters (18mmol), the bromo- 1- of 8- are added
Octene (54mmol), K2CO3(54mmol), 80 DEG C of stirrings, back flow reaction 6 hours.Reaction solution is poured into toluene and deionized water afterwards
In the mixed liquor of (each 150mL), separate organic layer and water layer, and with toluene aqueous phase extracted 3 times, collect all organic phases, go from
Organic phase is washed to neutrality by sub- water, and anhydrous sodium sulfate is dried, filters, rotated, and crude product uses post separation (eluent：
Ethyl acetate：Petroleum ether=1:8) target product is collected, the product revolving being collected into, and recrystallized with acetone, obtain pure
Net white solid product, vacuum drying oven drying.Above-mentioned course of reaction is as follows：
Nuclear-magnetism characterizes：1H NMR(400MHz):δ1.18-1.57(m,18H),1.67-1.92(m,6H),1.96-2.15
(m,6H),3.89(s,3H),4.01(t,6H),4.84-5.12(m,6H),5.69-5.92(m,3H),7.25(s,2H).Nuclear-magnetism
Data are coincide with molecular structure.
(3) synthesis of 3,4,5- tri- (octene epoxide) benzoic acid and sign
Ethanol containing reactant 3,4,5- tri- (octene epoxide) methyl benzoate (1.5mmol), KOH (10.5mmol)
The stirring of (100mL) solution, back flow reaction 4 hours, add THF (20mL), and the hydrochloric acid (volume ratio of concentrated hydrochloric acid and deionized water is added dropwise
For 1：1) solution makes reaction solution pH ≈ 1, then pours into mixed liquor in 1L deionized water, filtering, collects solid, acetone is tied again
Crystalline substance, obtain pure white solid product, vacuum drying oven drying.Above-mentioned course of reaction is as follows：
Nuclear-magnetism characterizes：1H NMR(400MHz):δ1.11-1.59(m,18H),1.68-1.92(m,6H),1.95-2.18
(m,6H),4.02(t,6H),4.84-5.12(m,6H),5.70-5.92(m,3H),7.32(s,2H).Nuclear magnetic data and molecule knot
Structure coincide.
(3) synthesis of 3,4,5- tri- (octene epoxide) benzoic acid ethohexadiol monoesters and sign
In toluene (150mL) solution for containing 3,4,5- tri- (octene epoxide) benzoic acid (2.5mmol), ethohexadiol is added
(10mmol), PTSA (0.11g), stirring reaction 20h at a temperature of 140 DEG C.After reaction terminates, reaction solution is poured into 150mL first
In benzole soln, filtering, collect liquid, and successively with 5% Na2CO3Wash 2 times, deionization wash 3 times, anhydrous sodium sulfate drying,
Filtering, is spin-dried for, and carries out post separation (eluent：Petroleum ether：Ethyl acetate=8:1), acetone recrystallization, white solid is obtained,
Dried in vacuum drying oven.Above-mentioned course of reaction is as follows：
Nuclear-magnetism characterizes：1H NMR(400MHz):δ1.19-1.64(m,26H),1.67-1.91(m,8H),1.98-2.18
(m,6H),3.58-3.71(m,4H),4.01(t,6H),4.28(t,2H),4.87-5.15(m,6H),5.71-5.97(m,3H),
7.25(s,2H).Nuclear magnetic data coincide with molecular structure.
(4) 1- fullerenes acetic acid 8- (3,4,5- tri- (octene epoxide) benzoic acid) ethohexadiol ester (C8-C8-C60- ene) conjunction
Into with sign
In dichloro-benzenes and DMF mixed solutions containing fullerene acetic acid (0.26mmol), add dissolved with 8- hydroxyls -3,4,5-
Three (octene epoxide) octyl benzoate (0.26mmol) toluene (2mL) solution, sequentially add DMAP (0.25mmol), PTSA
(0.26mmol), DIPC (0.28mmol), stirring reaction 4 hours under room temperature condition.After reaction terminates, filter, be spin-dried for, thick production
Product carry out post separation (eluent：Toluene：Petroleum ether=3:1.Solution containing product is spin-dried for, methanol extraction.Place one day
Afterwards, brown product is filtrated to get, is dried in vacuum drying oven.Above-mentioned course of reaction is as follows：
Structural characterization：1H NMR(400MHz):δ1.28-1.64(m,26H),1.67-1.94(m,10H)1.97-2.12
(m,6H),4.01(t,6H),4.29(t,2H),4.47(t,2H),4.79(s,1H),4.88-5.06(m,6H),5.74-5.90
(m,3H),7.25(s,2H).MALDI-TOF,Cal.for C101H64O7:(M)+1388.465.Found:1387.885.More than
Characterize data proves to obtain target product.
To C8-C8-C60- ene the compounds have carried out DSC (Fig. 2) detections first, employ three kinds of different speed：20
DEG C/min, 10 DEG C/min, 5 DEG C/min, in scanning process, first with 20 DEG C/min speed, then it is followed successively by 10 DEG C/min, 5 DEG C/
Min order；In temperature-rise period, within the temperature range of -20-150 DEG C, it was observed that phase transition temperature：98 DEG C, with reference to XRD,
POM schemes, and can obtain the transition temperature that the phase transition temperature is the opposite isotropic phase liquid of liquid crystal.Fig. 3 is the XRD diffraction of sample
Figure, by being compared to the peak value of diffraction maximum, can obtain the diffraction maximum and proportionate relationship be present：1:2:3:5:6, this explanation should
The arrangement mode of compound is layered arrangement structure, and sample liquid crystal state in this is smectic liquid crystal；Fig. 4 is the compound by each
The polarized light microscopy photo photographed after 80 DEG C of constant temperature 1h is cooled to same condition, the texture of gained is a kind of granular texture.Fig. 5
It is the refractive index curve chart of the compound.Compound C8-C8-C60- ene has high refractive index, will in visible-range
Higher than 1.74.
The preparation and performance test of the photonic crystal of embodiment two
(1) silica (SiO2) microballoon preparation
UsingMethod prepares the monodispersed SiO of different-grain diameter2Particle.Specific operation process is as follows：250mL round bottoms burn
In bottle, 65.5mL ethanol, 20mL deionized waters, 10mL ammoniacal liquor, 4.5mL tetraethyl orthosilicates (TEOS) are added, is stirred vigorously 1min
Afterwards, mixing speed, room temperature reaction 3h are reduced.Reaction solution is centrifuged, then disperseed with absolute ethyl alcohol, is centrifuged again.Absolute ethyl alcohol point
Dissipate, centrifugally operated is carried out 2 times.Finally, the SiO of preparation2Particle preserves in absolute ethyl alcohol, obtains SiO2Particle dispersion.Pass through
The ratio for adjusting ammoniacal liquor/deionized water/TEOS obtains various sizes of SiO2Particle.As shown in Figure 6.
(2)SiO2The preparation of colloidal crystal template
The processing of slide substrate：The concentrated sulfuric acid is put into after sheet glass to be cut into certain size：Hydrogen peroxide=3:1 mixing
5h is soaked in solution.Rinsed afterwards with ionized water and remove mixed liquor, successively with each ultrasonic 2 times of deionized water, ethanol, nitrogen drying
Afterwards, 30min is dried at 60 DEG C.
The preparation of colloidal crystal：Treated slide is vertically put into equipped with SiO2In the 5mL containers of particle dispersion.Room
Under temperature, with the volatilization of solvent, SiO2Particle is assembled to surface of glass slide, in the presence of capillary force, in forming three on slide
Tie up orderly SiO2Colloidal crystal.After solvent completely volatilization, slide is taken out, is put in Muffle furnace, 5h is calcined at 500 DEG C.
SiO after being solidified2Colloidal crystal template.
(3)C8-C8-C60The preparation and test of the photonic crystal of opals structure of-ene fillings
Will be dissolved with C8-C8-C60- ene CS2Solution is added dropwise in SiO2On colloidal crystal surface, by the way that sample is repeatedly added dropwise
Product C8-C8-C60- ene enters SiO2In colloidal crystal space, the light of the opal structural of the liquid crystal of fullerene containing double bond filling is obtained
Sub- crystal.
Tested using fiber spectrometer.Before and after filling reflection spectrum curve and filling back reflection peak with temperature change
Change situation is as shown in Figure 7.Before filling, SiO2There is a reflection peak at 518nm in the photonic crystal formed with air, when in space
Fill C8-C8-C60After-ene, red shift occurs for reflection peak, to 595nm.It is due to C that red shift, which occurs, for reflection peak8-C8-C60- ene is replaced
After air (refraction index n=1), the effective refractive index numerical value of the photonic crystal formed becomes greatly so as to which Red Shift Phenomena occur.
For C8-C8-C60The photonic crystal of-ene fillings, its reflection peak be located at 595nm during room temperature, (the height when raising temperature to 115 DEG C
In the clearing point temperature of sample), reflection peak is blue shifted to 582nm, when being cooled to room temperature again, reflection peak again red shift to initial bit
Put, show repeatable property.Temperature raises, and blue shift occurs for reflection peak, and this reflects peak position and temperature with other liquid crystal molecules
Relation be consistent.
Embodiment three：The preparation and test of photonic crystal
(1) preparation of polymer (P (St-MMA-AA)) microballoon
In 250mL three neck round bottom flask, 100mL deionized waters and a certain amount of neopelex are first added
(SDBS) monomer styrene (19g, St), methylbenzene e pioic acid methyl ester (1g, MMA), acrylic acid (1.2g, AA), crosslinking agent two, are weighed
Vinyl benzene (0.9g, DVB) is well mixed, and then monomer mixed solution is added in the SDBS aqueous solution.It is passed through N2, timing
After 5min, system starts to warm up, and stirs simultaneously, mixing speed 350rpm.Prepare 0.5g ammonium persulfates (APS) 20mL go from
The sub- aqueous solution.After reacting liquid temperature is warming up to 90 DEG C, the 8mLAPS aqueous solution is added in reaction solution, starts timing.React 2h
After add the 6mL APS aqueous solution, continue react 2h after, the remaining 6mL APS aqueous solution is added in reaction solution.Continue anti-
Terminate reaction after answering 4h.Reaction solution is centrifuged, then disperseed with deionized water, is centrifuged again.Deionized water is scattered, centrifugally operated enters
Row 2 times.Finally, the polymer microballoon of preparation preserves in aqueous phase.
(2) preparation of polyalcohol colloid crystal template
The processing of slide substrate：The concentrated sulfuric acid is put into after sheet glass to be cut into certain size：Hydrogen peroxide=3:1 mixing
5h is soaked in solution.Rinsed afterwards with ionized water and remove mixed liquor, successively with each ultrasonic 2 times of deionized water, ethanol, nitrogen drying
Afterwards, 30min is dried at 60 DEG C.
The preparation of colloidal crystal：First, compound concentration is 0.1mol/L HCl solution, by TEOS, HCl solution, anhydrous second
Alcohol is 1 according to mass ratio:1:1.5 ratio is mixed to get TEOS mixed liquor.Then, it is 0.13% to prepare 20mL mass concentrations
Polymer emulsions, and add 200 μ L TEOS mixed liquor thereto.After magnetic agitation 6h, polymer and TEOS are blended
Mixed liquor be transferred in several 5mL containers, and be vertically put into processed good slide.Finally, the container for being placed with slide is put
(condition is set in climatic chamber：Temperature 60 C, humidity 60%) prepare template.After solvent in 5mL containers completely volatilization,
Slide is put into Muffle furnace, is warming up to 500 DEG C, 2h is with polymer microballoon of going out for calcining, obtains SiO2Counter opal result glue
Body crystal template.As shown in Figure 8.
(3)C8-C8-C60The preparation and test of the photonic crystal with inverse opal structure of-ene fillings
Will be dissolved with C8-C8-C60- ene CS2Solution is added dropwise in SiO2On anti-protein structure colloidal crystal template surface, pass through
Repeatedly it is added dropwise and causes sample C8-C8-C60- ene enters SiO2In the pore structure of anti-protein structure colloidal crystal template, Gao Fu is obtained
Strangle the SiO of alkene content liquid crystal filling2Photonic crystal with inverse opal structure.
Its optical property is tested using fiber spectrometer.Fig. 9 a are by P (St-MMA-AA) and SiO2The photonic crystal of preparation
The change curve of reflection peak before and after roasting.Before roasting, reflection peak is located at 634nm or so, after roasting, because air substitutes P
(St-MMA-AA), the effective refractive index of photonic crystal reduces, so as to which blue shift occurs for reflection peak, to 456nm or so.Fig. 9 b are to fill out
Fill C8-C8-C60Reflection peak position of the photonic crystal in room temperature and isotropism state after-ene.Fill C8-C8-C60After-ene,
Reflection peak red shift is to 677nm or so, and compared to the red shift that 220nm occurs when being not filled by, this is due to：One side sample C8-C8-
C60- ene dutycycle is big；Another aspect C8-C8-C60- ene has high refractive index, and the effective refractive index of photonic crystal occurs
Very big raising, so as to which big red shift occurs in reflection peak.When rise temperature to sample is in isotropism state, reflection peak occurs blue
When moving phenomenon, and being cooled to room temperature, original state can be returned to.Show good repeatability.
Claims (9)
1. a kind of double bond containing fullerene liquid-crystal compounds, it is characterised in that the molecular structure of compounds, which forms, is：Rigid richness
Strangle enoic acid moiety, the gallic acid-derivate part containing double bond, and the soft segment part of connection the former two；Soft segment
Precursor be glycol, the both ends of soft segment with ester bond respectively with fowler enoic acid moiety, the gallic acid-derivate containing double bond
Part is connected；The fowler olefin(e) acid is [60] fullerene acetic acid, [60] fullerene propionic acid or [60] fullerene malonic acid, glycol
Structural formula is HO-R1- OH, R1Structure is CmH2m, m 2-12, double bond containing gallic acid-derivate structural formula is
In structure above, n=4-18.
2. the double bond containing fullerene liquid-crystal compounds described in claim 1, the refractive index of its molecule is more than 1.70.
3. one kind using double bond containing fullerene liquid-crystal compounds described in claim 1 or 2 as packing material, prepare it is ultraviolet can
See the method for tunable photonic crystal in optical range, comprise the following steps：
(1) microsphere particle is synthesized；
(2) colloidal crystal template is prepared；
(3) toward double bond containing fullerene liquid-crystal compounds is filled in colloidal crystal template space, that is, tunable photonic crystal is obtained.
4. the method according to claim 3 for preparing photonic crystal, it is characterised in that in step (1), for synthesizing microballoon
The material of particle, it is based on silica, the modification of titanium dioxide preparation or unmodified inorganic microspheres particle, or base
In organic matter microsphere particles prepared by polystyrene.
5. the method according to claim 4 for preparing photonic crystal, it is characterised in that described based on poly- in step (1)
Organic matter microsphere particles prepared by styrene are polystyrene, poly- (styrene methyl methacrylate-acrylic acid) or poly- (benzene
Ethylene methyl methacrylate-methacrylic acid propyl sulfonic acid potassium).
6. the method according to claim 3 for preparing photonic crystal, it is characterised in that in step (1), synthesized microballoon
Particle diameter be 150-450nm.
7. the method according to claim 3 for preparing photonic crystal, it is characterised in that in step (2), with sheet glass or silicon
Piece is substrate, and the colloidal crystal template of opal structural either counter opal structure is prepared using mono-dispersion microballoon.
8. the method according to claim 3 for preparing photonic crystal, it is characterised in that in step (3), double bond containing fowler
Alkene liquid-crystal compounds dissolves in organic solvent, is added dropwise on colloidal crystal template, prepares the tunable of double bond containing fullerene
Photonic crystal.
9. a kind of preparation method of the double bond containing fullerene liquid-crystal compounds described in claim 1, comprises the following steps：
(1) alkenyl halide is prepared first with two alkyl halides, the molecular structure of alkenyl halide isX is bromine or chlorine, and n is
Carbon chain lengths, its value are 4-18；
(2) using Gallic Acid methyl esters as raw material, reacted with alkenyl halide under weakly alkaline environment, obtain 3,4,5-
Triolefin p-methoxybenzoic acid methyl esters；
(3) 3,4,5- triolefin p-methoxybenzoic acid methyl esters are hydrolyzed in acid condition, obtain 3,4,5- triolefin p-methoxybenzoic acids；
(4) 3,4,5 triolefin p-methoxybenzoic acids in the presence of catalyst, occur esterification, obtain 3,4,5- triolefins with glycol
P-methoxybenzoic acid alcohol ester；Wherein, the chemical structural formula of glycol is HO-R1- OH, R1Structure is CmH2m, m 2-12；
(5) 3,4,5- triolefin p-methoxybenzoic acid alcohol esters under catalyst action, occur esterification and obtained containing double with fowler olefin(e) acid
The fullerene liquid-crystal compounds of key.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710783173.9A CN107418593B (en) | 2017-09-03 | 2017-09-03 | Fullerene liquid crystal compound containing double bonds and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710783173.9A CN107418593B (en) | 2017-09-03 | 2017-09-03 | Fullerene liquid crystal compound containing double bonds and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107418593A true CN107418593A (en) | 2017-12-01 |
| CN107418593B CN107418593B (en) | 2020-10-09 |
Family
ID=60434769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710783173.9A Active CN107418593B (en) | 2017-09-03 | 2017-09-03 | Fullerene liquid crystal compound containing double bonds and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107418593B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108403634A (en) * | 2018-04-04 | 2018-08-17 | 苏州大学 | Water-soluble micella and preparation method thereof based on Janus molecule nano particles |
| CN109438592A (en) * | 2018-08-01 | 2019-03-08 | 青岛大学 | A kind of polymer microballoon and its colloidal crystal of fullerene modification |
| CN116144374A (en) * | 2023-01-10 | 2023-05-23 | 青岛大学 | Preparation and application of fullerene liquid crystal compound based on alpha-ramine formic acid |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6538153B1 (en) * | 2001-09-25 | 2003-03-25 | C Sixty Inc. | Method of synthesis of water soluble fullerene polyacids using a macrocyclic malonate reactant |
| WO2004027078A2 (en) * | 2002-09-18 | 2004-04-01 | The Trustees Of The University Of Pennsylvania | Fluorinated dendrons and self-organizing ultrahigh density nanocylinder compositions |
| CN102295554A (en) * | 2011-05-30 | 2011-12-28 | 苏州大学 | Liquid crystal with high fullerene content and its preparation method |
| CN102585227A (en) * | 2011-12-31 | 2012-07-18 | 中国计量学院 | Preparation method of gel glass dispersed nano-liquid crystal micro-droplet thin film |
| CN102691106A (en) * | 2011-03-23 | 2012-09-26 | 中国科学院化学研究所 | Preparation method of flawless photonic crystal |
| CN102781951A (en) * | 2009-11-30 | 2012-11-14 | 第一雷恩大学 | Luminescent hybrid liquid crystal |
| CN106381520A (en) * | 2016-08-29 | 2017-02-08 | 浙江理工大学 | Method for preparing photonic crystal with inverse opal structure through ultraviolet radiation |
-
2017
- 2017-09-03 CN CN201710783173.9A patent/CN107418593B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6538153B1 (en) * | 2001-09-25 | 2003-03-25 | C Sixty Inc. | Method of synthesis of water soluble fullerene polyacids using a macrocyclic malonate reactant |
| WO2004027078A2 (en) * | 2002-09-18 | 2004-04-01 | The Trustees Of The University Of Pennsylvania | Fluorinated dendrons and self-organizing ultrahigh density nanocylinder compositions |
| CN102781951A (en) * | 2009-11-30 | 2012-11-14 | 第一雷恩大学 | Luminescent hybrid liquid crystal |
| CN102691106A (en) * | 2011-03-23 | 2012-09-26 | 中国科学院化学研究所 | Preparation method of flawless photonic crystal |
| CN102295554A (en) * | 2011-05-30 | 2011-12-28 | 苏州大学 | Liquid crystal with high fullerene content and its preparation method |
| CN102585227A (en) * | 2011-12-31 | 2012-07-18 | 中国计量学院 | Preparation method of gel glass dispersed nano-liquid crystal micro-droplet thin film |
| CN106381520A (en) * | 2016-08-29 | 2017-02-08 | 浙江理工大学 | Method for preparing photonic crystal with inverse opal structure through ultraviolet radiation |
Non-Patent Citations (3)
| Title |
|---|
| DEPARTMENT OF CHEMISTRY ET AL: "Organizing Carbon Nanotubes with Liquid Crystals", 《NANO LETTERS》 * |
| 张小艳: "基于二维晶体的富勒烯超分子液晶的设计、合成和表征", 《工程科技Ⅰ辑》 * |
| 高鸿锦等: "《液晶与平板显示技术》", 30 June 2007, 北京邮电大学出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108403634A (en) * | 2018-04-04 | 2018-08-17 | 苏州大学 | Water-soluble micella and preparation method thereof based on Janus molecule nano particles |
| CN108403634B (en) * | 2018-04-04 | 2019-11-22 | 苏州大学 | Water-soluble micella and preparation method thereof based on Janus molecule nano particle |
| CN109438592A (en) * | 2018-08-01 | 2019-03-08 | 青岛大学 | A kind of polymer microballoon and its colloidal crystal of fullerene modification |
| CN109438592B (en) * | 2018-08-01 | 2021-06-18 | 青岛大学 | Fullerene modified polymer microsphere and colloidal crystal thereof |
| CN116144374A (en) * | 2023-01-10 | 2023-05-23 | 青岛大学 | Preparation and application of fullerene liquid crystal compound based on alpha-ramine formic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107418593B (en) | 2020-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107418593A (en) | Double bond containing fullerene liquid-crystal compounds and its application | |
| CN103833872B (en) | A kind of two oxime ester lightlike initiating agent and its preparation method and application | |
| Song et al. | Supramolecular Nanofibers by Self‐Organization of Bola‐amphiphiles through a Combination of Hydrogen Bonding and π–π Stacking Interactions | |
| KR101601359B1 (en) | Mesogen containing compounds | |
| CN104558004B (en) | Organic second order non-linear optical chromophore and preparation method and use with D π A structures | |
| CN110330513A (en) | A kind of high stable shines by force the chiral nano silver clustered materials of high quantum production rate | |
| CN109021981B (en) | Bonding type fluorescent rare earth liquid crystal ionomer and preparation method thereof | |
| CN101058437A (en) | Liquid state preparation method for nano cadmium sulfide hollow sphere | |
| CN110256329A (en) | Containing α-cyano-containing talan structure fluorescent liquid crystal monomer, polymer and preparation method thereof | |
| CN109265353A (en) | Pentanediamine dodecanedioic acid salt and its crystal | |
| CN101511729B (en) | Templated metal oxide particles and methods of making | |
| JP7240187B2 (en) | Xanthene compound, coloring composition containing said compound, colorant for color filter and color filter | |
| EP1541614A1 (en) | Thermoplastic layered alkylsiloxanes and process for production thereof | |
| JP7079494B2 (en) | New compound and its synthesis method | |
| CN106279133A (en) | Organic second order non-linear optical chromophore and synthetic method and application | |
| CN113956889B (en) | Color polysilsesquioxane liquid crystal film and preparation method and application thereof | |
| CN113149839B (en) | Self-aligned liquid crystal medium compound and application thereof | |
| CN111196834B (en) | Compounds with circularly polarized luminescence | |
| KR20150140413A (en) | Mesogen containing compounds | |
| CN113511987B (en) | Chiral photosensitive doping agent and preparation method and application thereof | |
| CN109096188B (en) | Compound containing 4- (p-phenylethynyl) -1, 8-naphthalic anhydride, preparation method and application thereof | |
| CN116144374A (en) | Preparation and application of fullerene liquid crystal compound based on alpha-ramine formic acid | |
| CN109265355A (en) | Pentanediamine suberate and its crystal | |
| CN1183035C (en) | Prepn of low temp phase barium metaborate nano powder | |
| CN113896899B (en) | Supramolecular polymer material with aggregation-induced emission performance and stimulus responsiveness and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |