CN106519733A - 3-substituent benzanthrone liquid crystal dye, as well as preparation method and application thereof - Google Patents
3-substituent benzanthrone liquid crystal dye, as well as preparation method and application thereof Download PDFInfo
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- CN106519733A CN106519733A CN201610832268.0A CN201610832268A CN106519733A CN 106519733 A CN106519733 A CN 106519733A CN 201610832268 A CN201610832268 A CN 201610832268A CN 106519733 A CN106519733 A CN 106519733A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B3/00—Dyes with an anthracene nucleus condensed with one or more carbocyclic rings
- C09B3/02—Benzathrones
- C09B3/06—Preparation from starting materials already containing the benzanthrone nucleus
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13725—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on guest-host interaction
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Abstract
The invention discloses a 3-substituent benzanthrone liquid crystal dye, as well as a preparation method and application thereof. According to the preparation method, different acetenyl groups are introduced to the 3-bit of 3-bromobenzanthracen serving as a parent to improve the solubility of a molecule in a liquid crystal and reinforce the linear structure of the molecule, so that the dichroism of a liquid crystal compound can be improved; and highly delocalized electron and parent on a benzene ring are utilized to form a large conjugated system. The synthesized benzanthrone fluorescent bidirectional liquid crystal dye has a maximum absorption wavelength concentrated in a visible region and a transmission wavelength concentrated at about 500nm, and has the advantages of novel structure, easily available raw materials and simple synthesis method; and the dye has a better dichroic ratio and orderly parameters in the liquid crystal, can be used for manufacturing liquid crystal display products, and especially has high dichroism in guest-host liquid crystal displays.
Description
Technical field
The present invention relates to it is a kind of containing 3 different new benzanthrone class liquid crystalline dyes compounds for replacing and its application,
Belong to display material field.
Background technology
Informationalized high speed development has driven the development of liquid crystal flat-panel technology and industry, traditional cathode-ray tube (CRT)
Technology is replaced by FPD, and the life that flat-panel monitor gives people brings revolutionary change.
It is the new display pattern risen in the last few years that " guest-master " shows." guest-master " (GH) pattern is to show color change
Mode of operation, almost simultaneously put forward by G.Heilmeier etc. and DS patterns.Adulterate in nematic liquid crystal main material
Some dichroic dyes constitute a pair " guest-master " materials, apply electric field to which, and liquid crystal molecule occurs orientation and changes." guest-
It is main " (GH) pattern be exactly realizing showing using the dichroic dye light absorbs of molecularly oriented are changed.
Fluorescence " guest-master " escope is the improvement of traditional " guest-master " escope, and it is should by two tropism dyestuff of fluorescence
In for liquid crystal display, so not only light absorbing intensity, and the intensity of launching light can also be controlled by electric field, so as to
The characteristics of by the advantage and conventional liquid crystal of emissive display, is integrated in one, and makes more portable low power dissipation electron device
Part.Pure liquid crystal material can not meet the various characteristics of liquid crystal material, such as light, electricity, heat etc..Then utilize liquid-crystal compounds
Or dyestuff becomes an apparent trend so as to obtaining the more superior liquid crystal material of performance compounding liquid crystal material.Compounding
Liquid crystalline dyes can obtain higher more stable liquid crystal phase temperature range, higher clearing point and adjust the function of refractive index.
The content of the invention
For solving the problems, such as to lack fluorescence dichroic dye of good performance present in prior art, the present invention is provided
Liquid crystalline dyes, can as two tropism dyestuff of fluorescence be applied to liquid crystal display product.
One of technical purpose of the present invention is to provide a class new liquid crystalline dyes.
Another technical purpose of the present invention is the preparation method for providing above-mentioned liquid crystalline dyes compound, including following step
Suddenly：
Respectively by 4 '-acetenyl -4- alkyl biphenyls, align the positive decine of butyl phenyl ether acetylene, 1-, to acetylenylbenzene formic acid second
Ester is coupled with 3- bromines benzanthrone and obtains the liquid crystalline dyes compound；
The preparation method of 4 '-acetenyl -4- alkyl biphenyls is：4 '-bromo- 4- alkyl biphenyls and 2- methyl -3- butine -
2- alcohol is coupled, and obtains 4 '-acetenyl -4- alkyl biphenyls through alkali process；
Described 4 '-bromo- 4- alkyl biphenyls are selected from 4 '-bromo- 4- ethyl biphenyls, 4 '-bromo- 4- n-pentyls biphenyl.
Specific synthetic line is as follows：
Further, 4 '-bromo- 4- n-pentyls biphenyl or 4 '-bromo- 4- ethyl biphenyls are entered with 2- methyl -3- butyne-2-alcohols
During row reaction, the optimal mixing mol ratio of the two is 1:1, using dry triethylamine as reaction dissolvent, add the triphen of catalytic amount
Base phosphine palladium bichloride, triphenylphosphine and cuprous iodide catalyst, under nitrogen protective condition, magnetic agitation is heated to backflow.Reaction 8h
TLC tracking and monitorings are removed under reduced pressure excess of solvent completely to reaction afterwards, and solid product crosses silica gel column chromatography, obtains solid (compound 1).
Further, compound 1 is added add in bottle with two necks the heating of absolute ethyl alcohol magnetic agitation to be allowed to dissolve, and is added
The potassium hydroxide of amount, is heated to backflow, and potassium hydroxide gradually dissolves, and what tracking and monitoring reacted carries out degree, constantly adds KOH.
Persistently stop reaction after backflow a few hours, now reaction solution is brown.Room temperature is cooled to, product is poured in water, used
Hydrochloric acid solution adjusts pH value and separates out a large amount of yellow mercury oxides to neutral, suction filtration, wash after dry white-yellowish solid, crude product crosses silicon
Plastic column chromatography, obtains solid 4 '-acetenyl -4- ethyl biphenyls, 4 '-acetenyl -4- n-pentyl biphenyl (compound 2)
Further, respectively by 4 '-acetenyl -4- ethyl biphenyls, 4 '-acetenyl -4- n-pentyl biphenyl, to n-butoxy
The positive decine of phenylacetylene, 1-, when reacting to acetylenylbenzene Ethyl formate and 3- bromine benzanthrones, the optimal mixing mole of the two
Than for 1：1, using dry triethylamine as reaction dissolvent, add triphenylphosphine palladium chloride, triphenylphosphine and the iodate of catalytic amount sub-
Copper catalyst, under nitrogen protective condition, magnetic agitation is heated to backflow.After reaction 8h, TLC tracking and monitorings are reduced pressure completely to reaction
Excess of solvent is removed, solid product is crossed silica gel column chromatography, obtains orange/yellow solid (F) liquid crystalline dyes.
Another aspect of the present invention provides above-mentioned liquid crystalline dyes compound as fluorescence dichroic dye in manufacture liquid crystal
Show the application in product.Described liquid crystal display product is guest-host type liquid crystal display.Specifically being used as the brilliant dye of guest's body fluid
Material, is applied to prepare guest-host type liquid crystal display.
The present invention provides a class guest-host type liquid crystal display, and described liquid crystal display is with liquid crystalline dyes of the present invention
Compound is used as guest's body liquid crystalline dyes.
Additionally, the liquid-crystal compounds of the present invention also has liquid crystalline phase, described liquid crystal host is smectic liquid crystal, nematic phase
Liquid crystal or cholesteric liquid crystal.
The compound of the present invention has liquid crystalline phase, can mix with liquid crystal E7 and be applied to liquid crystal display.
Invention beneficial effect
Firstth, the present invention introduces the different acetenyls for replacing in 3- positions, strengthens the linear of molecule with benzanthrone as parent
Structure further improves the dichroism of dyestuff, and liquid-crystal compounds structure is novel, and raw material is easy to get, and synthetic method is simple；
Secondth, 5 two tropism liquid crystalline dyes maximum absorption wavelengths of benzanthrone class fluorescence of present invention synthesis concentrate on visible
Light area, launch wavelength concentrate on 500nm or so, launch bright-coloured yellow-green fluorescence, rub in dichloromethane and different solvents
That extinction coefficient is more than 104.Preferable dichroic ratio and order parameter is shown in liquid crystal E7, can be used to manufacture liquid crystal
Product, especially guest-host type liquid crystal display is shown, as guest's body liquid crystalline dyes；
3rd, liquid-crystal compounds of the invention also has liquid crystalline phase, additionally, it is also used as liquid crystal addO-on therapy, adds
The photoelectric properties of liquid crystal host are improved in adding to liquid crystal host.
Description of the drawings
Fig. 1 is the differential scanning calorimetric figure of F1 prepared by embodiment 1.
Specific embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Wherein, align the positive decine of butyl phenyl ether acetylene, 1-, be purchase gained to acetylenylbenzene Ethyl formate raw material.
Embodiment 1
The synthesis of liquid crystalline dyes F1
(1) synthesis of 2- methyl -4- (4 '-ethyl biphenyl) 3- crotonylenes-methyl alcohol (compound 1)
By 4 '-bromo- 4- ethyl biphenyls of 302mg (1mmol) and 100 μ L (1mmol) 2- methyl -3- butyne-2-alcohols and 7mg
Two triphenylphosphine palladiums, 15mg triphenylphosphines, 8mgCuI are separately added in 50mL twoport round-bottomed flasks as catalyst, are used
15mL dry triethylamines are used as acid binding agent and solvent.Stir under nitrogen protective condition, be heated to backflow and be allowed to reaction completely.Decompression
Triethylamine is removed, crude product crosses silica gel column chromatography (eluant, eluent：Dichloromethane), removal of solvent under reduced pressure obtains 281.7mg white solids,
Yield 92%.Fusing point：48.4-49.7℃.
1H-NMR(400MHz,CDCl3):δ=7.54 (s, 4H), 7.50 (d, J=8.0Hz, 2H), 7.25 (d, J=
3.2Hz,2H),3.12(s,1H),2.68-2.61(m,2H),1.69-1.60(m,2H),1.38-1.31(m,4H),0.90(t,J
=6.8Hz, 3H).
Fusing point：113.4-114.7℃.TOF MS EI+：Calculated value：[C19H20]+(m/z)=248.1565, measured value：
[C19H20]+(m/z)=248.1574.
The synthesis of (2) 4 '-acetenyl -4- ethyl biphenyls (compound 2)
The reaction of upper step obtained 281.7mg white solids is added and add in 50mL bottle with two necks 20mL absolute ethyl alcohol magnetic force
Agitating heating is allowed to dissolve, and adds excessive potassium hydroxide, is heated to backflow, and potassium hydroxide gradually dissolves, tracking and monitoring reaction
Carry out degree, constantly add KOH.Persistently stop reaction after backflow a few hours, now reaction solution is brown.It is cooled to room
Temperature, product is poured in 100mL water, is adjusted pH value with hydrochloric acid solution and is floatd wadding to a large amount of yellow of neutral precipitation, suction filtration, washing
Dry 187.1mg white-yellowish solids afterwards, crude product cross silica gel column chromatography, eluant, eluent PE, yield 82%.
(3) synthesis of target product F1
1mmol 3- bromine benzanthrones 309mg is added in two mouthfuls of flasks, respectively by 14mg triphenylphosphine palladium chlorides, 52mg
During triphenylphosphine, 16mg cuprous iodides, 20mL dry triethylamines add two mouthfuls of flasks, nitrogen protection is lower to add 4 '-second of 206mg
Alkynyl -4- ethyl biphenyls, under magnetic agitation, the reaction of back flow reaction 8h TLC tracking and monitorings is complete, mixture is cooled to room temperature and is subtracted
Pressure removes solvent, silica gel column chromatography purification, and eluant, eluent is dichloromethane and petroleum ether ratio is 1：1, collect orange-yellow fluorescence Spectra
Band, obtains orange/yellow solid 357.5mg, yield 82%.
1H NMR (500MHz, CDCl3) δ 8.83 (ddd, J=8.4,7.7,1.1Hz, 2H), 8.51 (dd, J=7.9,
1.2Hz, 1H), 8.42 (d, J=7.9Hz, 1H), 8.33 (d, J=8.1Hz, 1H), 7.93 (d, J=7.8Hz, 1H), 7.90
7.86 (m, 1H), 7.75 (dd, J=13.7,7.6Hz, 3H), 7.65 (d, J=8.3Hz, 2H), 7.60 7.54 (m, 3H), 7.31
(d, J=8.1Hz, 2H), 2.72 (q, J=7.6Hz, 2H), 1.30 (t, J=7.6Hz, 3H).
13C NMR (126MHz, CDCl3) δ 183.51 (d, J=45.0Hz), 144.14 (s), 141.64 (s), 137.54
(s), 135.74 (s), 135.59 (s), 134.26 (s), 133.64 (s), 133.56 (d, J=21.3Hz), 133.48 (s),
132.18 (s), 130.78 130.51 (m), 130.26 (s), 128.69 (s), 128.49 (s), 128.22 (d, J=3.0Hz),
127.73 (s), 127.01 (d, J=5.0Hz), 124.24 (s), 123.26 (s), 123.07 (s), 97.20 (s), 87.67 (s),
58.43(s),28.57(s),18.43(s).
Fusing point：253.5℃.TOF MS EI+(m/z)：Calculated value：[C33H22O]+(m/z)=434.5272, measured value：
[C33H22O]+(m/z)=434.1667.
Embodiment 2
The synthesis of liquid crystalline dyes F2
The same F1 of synthetic method, changes 4 '-bromo- 4- n-pentyls biphenyl into 4 ' in step (1)-bromo- 4- ethyl biphenyls.Step
Suddenly in (3), solvent is DCM：PE=2：1, obtain end-product yellow solid 406.3mg, yield 85%.
1H NMR (500MHz, CDCl3) δ 8.84 (dd, J=19.2,7.7Hz, 2H), 8.51 (d, J=7.9Hz, 1H),
8.43 (d, J=7.8Hz, 1H), 8.33 (d, J=8.1Hz, 1H), 7.96 7.84 (m, 2H), 7.75 (dd, J=15.9,
8.1Hz, 3H), 7.66 (d, J=8.3Hz, 2H), 7.57 (t, J=8.3Hz, 3H), 7.29 (d, J=8.1Hz, 2H), 2.70
2.63(m,2H),1.72–1.62(m,2H),1.42–1.32(m,4H),0.95–0.88(m,3H).
13C NMR(126MHz,CDCl3)δ153.46(s),144.11(s),141.40–141.13(m),137.51(s),
137.03(s),136.10(s),132.44(s),132.26(s),131.43(s),130.23(s),129.71(s),129.61
(d, J=5.4Hz), 129.43 (d, J=4.1Hz), 128.76 (s), 128.47 (s), 128.13 (s), 128.13 (s),
126.96 (s), 125.10 (s), 123.67 (s), 122.52 (s), 122.30 (d, J=5.7Hz), 97.13 (s), 87.39 (s),
58.41(s),29.71(s),28.56(s),18.46(s),15.56(s).
Fusing point：157.3-158.6℃.TOF MS EI+(m/z)：Calculated value：[C36H28O]+(m/z)=476.6069, it is real
Measured value：[C36H28O]+(m/z)=476.2149.
Embodiment 3
The synthesis of liquid crystalline dyes F3
Synthetic method is that the 4 '-acetenyl -4- ethyl biphenyls in step (3) are changed into step in F1 (3), difference
Align butyl phenyl ether acetylene.Solvent is DCM：PE=1：2, obtain orange-yellow end-product 313.6mg, yield 78%.
1H NMR (500MHz, CDCl3) δ 8.82 (dd, J=15.1,7.7Hz, 2H), 8.50 (d, J=7.9Hz, 1H),
8.41 (d, J=7.7Hz, 1H), 8.33 (d, J=8.1Hz, 1H), 7.88 (dd, J=16.2,8.0Hz, 2H), 7.75 (t, J=
7.6Hz, 1H), 7.64 7.52 (m, 3H), 6.94 (d, J=8.7Hz, 2H), 4.02 (t, J=6.5Hz, 2H), 1.84 1.76
(m, 2H), 1.57 1.48 (m, 2H), 1.00 (t, J=7.4Hz, 3H).
13C NMR(126MHz,CDCl3)δ183.61(s),159.79(s),135.75(s),133.47(s),133.35
(s),133.26(s),132.71(s),130.30(s),130.12(s),128.41(s),128.16(s),126.99(s),
126.56 (s), 123.86 (s), 123.52 (s), 123.15 (s), 114.70 (d, J=9.7Hz), 97.48 (s), 85.90 (s),
67.87(s),31.26(s),19.25(s),13.86(s).
Fusing point：150.1-151.2℃.TOF MS EI+(m/z)：Calculated value：[C29H22O2]+(m/z)=402.4838, it is real
Measured value：[C29H22O2]+(m/z)=402.1627.
Embodiment 4
The synthesis of liquid crystalline dyes F4
Synthetic method is that the 4 '-acetenyl -4- ethyl biphenyls in step (3) are changed into step in F1 (3), difference
The positive decine of 1-.Solvent is DCM：PE=1：1, obtain yellow solid end-product 263.5mg, yield 72%.
1H NMR (400MHz, CDCl3) δ 8.72 (dd, J=19.1,7.7Hz, 2H), 8.47 (d, J=7.1Hz, 1H),
8.28 (dd, J=21.7,8.0Hz, 2H), 7.80 (t, J=7.8Hz, 1H), 7.71 (dd, J=15.0,7.4Hz, 2H), 7.53
(t, J=7.4Hz, 1H), 2.60 (t, J=7.1Hz, 2H), 1.80 1.68 (m, 2H), 1.59 1.50 (m, 2H), 1.34 (d, J
=21.2Hz, 8H), 0.90 (t, J=6.7Hz, 3H).
13C NMR(126MHz,CDCl3)δ183.58(s),135.75(s),135.75(s),133.49(s),132.99
(s),130.77(s),130.34(s),129.96(s),128.58(s),128.26(s),128.04(s),127.64(s),
126.79(s),126.14(s),124.37(s),123.42(s),123.05(s),98.71(s),78.38(s),31.88(s),
29.27(s),29.17(s),29.12(s),28.82(s),22.70(s),19.91(s),14.14(s).
Fusing point：55.1-56.2℃.TOF MS EI+(m/z)：Calculated value：[C27H26O]+(m/z)=366.4947, actual measurement
Value：[C27H26O]+(m/z)=366.1913.
Embodiment 5
The synthesis of liquid crystalline dyes F5
Synthetic method with step in F1 (3), difference is, the 4 '-acetenyl -4- ethyl biphenyls in step (3) are changed into
To acetylenylbenzene Ethyl formate.Solvent is DCM：PE=4：1, obtain yellow solid 345.7mg, yield 86%.
1H NMR (400MHz, CDCl3) δ 8.84 8.74 (m, 2H), 8.50 (dd, J=7.9,1.2Hz, 1H), 8.39 (d,
J=7.9Hz, 1H), 8.30 (d, J=8.1Hz, 1H), 8.12 (d, J=8.4Hz, 2H), 7.89 (dd, J=16.2,8.0Hz,
2H), 7.79 7.70 (m, 3H), 7.57 (dd, J=14.6,7.4Hz, 1H), 4.44 (q, J=7.1Hz, 2H), 1.46 (t, J=
7.1Hz,3H).
13C NMR(126MHz,CDCl3)δ183.61(s),166.01(s),135.61(s),133.25(s),132.75
(s),131.62(s),131.12(s),130.33(s),129.67(s),128.80(s),128.25(s),127.65(s),
127.39(s),123.44(s),123.33(s),122.71(s),96.10(s),89.80(s),65.34(s),61.30(s),
58.45(s),18.44(s).
Fusing point：185.5-186.8℃.TOF MS EI+(m/z)：Calculated value：[C28H18O3]+(m/z)=402.4407, it is real
Measured value：[C28H18O3]+(m/z)=402.1262.
The property of the liquid crystalline dyes compound of the present invention is determined：
(1) spectral quality tests of the liquid crystalline dyes compound F in dichloromethane：
Test concentrations：Concentration of the liquid-crystal compounds in different solvents is 1.0 × 10-5mol/L.Accurately weigh respectively
1.0×10-2Liquid-crystal compounds (± 0.1mg) prepared by mmol, is put into volume for using CH after 10mL volumetric flasks2Cl2Constant volume, obtains
Concentration is 1.0 × 10-3Mol/L stock solutions.100 μ L of stock solution are pipetted in 10mL volumetric flasks, after solvent volatilization completely
With other solvent constant volumes to be measured, 1.0 × 10 are obtained-5The solution of mol/L, tests for UV absorption, fluorescence spectrum.
Liquid-crystal compounds fluorescence quantum yield ΦFThe measure of value：With concentration 1.0 × 10-5Mol/L, ΦFIt is worth the sulphur for 0.55
Sour quinoline is given repeated exhortations solution (5.0 × 10-2Mol/L aqueous sulfuric acids) on the basis of.For preventing liquid-crystal compounds fluorescence under a high concentration condition
Quenching, during test, the absorbance of liquid-crystal compounds solution is controlled in the range of 0.02-0.05.Desired parameters are in same test condition
Under measure, substitute into formula (1) calculate：
In formula：Φ(sample)、Φ(standard)Difference representative sample, the Φ of reference materialFValue；Abs(standard)、Abs(sample)
The absorbance of reference material under excitation wavelength, sample is represented respectively；Flu (sample) and Flu (standard) difference representative samples,
The fluorescence spectrum integral area of reference material.
The test result of F series liquid crystal dyestuffs is as follows：
Spectral qualities of the 1. liquid crystalline dyes F3 of table in different solvents
Table 2.F series dyes spectral signature in methylene chloride
Conclusion：The maximum absorption wavelength of benzanthrone derivative series dyes concentrates on 400nm or so, the maximum of F series
In 500nm or so, half-peak breadth is larger concentrates between 70-80 for the absorption half-peak breadth of F series and transmitting, and color is pure for launch wavelength
Just, it is more beneficial for realizing that pure color shows.
(2) polarization spectrum property tests of the liquid crystalline dyes F in liquid crystal E7：
Bulk liquid crystal：Liquid crystal E7 have wider, stable nematic phase range (- 10-60 DEG C), good chemical stability,
High positive dielectric anisotropy is used as bulk liquid crystal.
Liquid crystal cell：The orientation of the upper and lower two substrates of test liquid crystal cell is parallel to each other, and box thickness is 15 μm.
Dichroic ratio, the measure of order parameter：Ratio by liquid crystalline dyes F according to mass concentration for 0.5% (w/w) is mixed
To in liquid crystal, it is well mixed at room temperature, the mixture is loaded into parallel liquid crystal cell then, irrigation crystal mouth is sealed.Difference test fluid
Absorbance A on crystallization compound and liquid crystal cell alignment films parallel direction‖With the absorbance A in vertical direction⊥, in parallel direction
Fluorescence intensity F‖With fluorescence intensity F in vertical direction⊥；And (2), (3), (4), (5) calculate liquid-crystalization according to the following formula
Absorption order parameter Ss of the compound F in liquid crystalA, dichroic compare DAWith fluorescence order parameter SF, dichroic compare DF：
Liquid crystalline dyes compound F polarization spectrum test results are as follows：
Polarized UV and polarized fluorescence data of the 3. liquid-crystal compounds F of table in liquid crystal E7
The target product F of synthesis shows preferable dichroic ratio and order parameter in liquid crystal E7.The S of F1AAnd SFIt is
Maximum, it is with practical value to respectively reach 0.66 and 0.55.Dichroic ratio is 5.46.Meet host and guest and show practical application
Require.
(3) F series is in negative liquid crystal BHR28000-300 polarization spectrums and optical-electronic property
Liquid crystalline dyes F1, F2 and F3 the additional different voltages of negative liquid crystal BHR28000-300 tests (2,4,6,8,10V)
Ultraviolet polarization spectrum, spectrum test data are as shown in table 4..
Polarization spectrum properties of the 4. liquid crystalline dyes F of table in negative liquid crystal BHR28000-300
(4) liquid crystal behavior of liquid crystalline dyes compound F
Liquid crystalline dyes compound F1 to preparing carries out differential scanning, obtains its differential scanning calorimetric figure, as shown in Figure 1.
Claims (6)
1. new benzanthrone class liquid crystalline dyes containing 3 alkynyl substituted bases, it is characterised in that：The dyestuff has following
Chemical molecular general structure：
2. the preparation method of the liquid crystalline dyes compound described in claim 1, comprises the following steps：
Respectively by 4 '-acetenyl -4- alkyl biphenyls, align the positive decine of butyl phenyl ether acetylene, 1-, to acetylenylbenzene Ethyl formate with
3- bromines benzanthrone is coupled and obtains the liquid crystalline dyes compound；
The preparation method of 4 '-acetenyl -4- alkyl biphenyls is：4 '-bromo- 4- alkyl biphenyls and 2- methyl -3- butyne-2-alcohols
Be coupled, 4 '-acetenyl -4- alkyl biphenyls are obtained through alkali process；
Described 4 '-bromo- 4- alkyl biphenyls are selected from 4 '-bromo- 4- ethyl biphenyls, 4 '-bromo- 4- n-pentyls biphenyl.
3. the liquid crystalline dyes compound described in claim 1 is being manufactured in liquid crystal display product as two tropism liquid crystalline dyes of fluorescence
Application.
4. application according to claim 3, it is guest-host type liquid crystal display that its feature can apply to liquid crystal display.
5. a class guest-host type liquid crystal display, it is characterised in that using the liquid crystalline dyes compound described in claim 1 as guest's body
Liquid crystalline dyes.
6. the compound described in claim 1 has liquid crystalline phase, can mix with liquid crystal E7 and be applied to liquid crystal display.
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Citations (4)
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|---|---|---|---|---|
| US20070221884A1 (en) * | 2004-07-16 | 2007-09-27 | Holger Hoppe | Liminescent Silicon Oxide Flakes |
| CN101489961A (en) * | 2006-07-11 | 2009-07-22 | 默克专利有限公司 | Electroluminescent polymers and use thereof |
| WO2013187749A1 (en) * | 2012-06-11 | 2013-12-19 | Даугавпилсский Университет | Method for producing a novel luminescent polymer material |
| WO2016126423A2 (en) * | 2015-02-03 | 2016-08-11 | E I Du Pont De Nemours And Company | Electroactive materials |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070221884A1 (en) * | 2004-07-16 | 2007-09-27 | Holger Hoppe | Liminescent Silicon Oxide Flakes |
| CN101489961A (en) * | 2006-07-11 | 2009-07-22 | 默克专利有限公司 | Electroluminescent polymers and use thereof |
| WO2013187749A1 (en) * | 2012-06-11 | 2013-12-19 | Даугавпилсский Университет | Method for producing a novel luminescent polymer material |
| WO2016126423A2 (en) * | 2015-02-03 | 2016-08-11 | E I Du Pont De Nemours And Company | Electroactive materials |
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| Title |
|---|
| GIGUERE, JEAN-BENOIT ET AL: "4,10-Dibromoanthanthrone as a New Building Block for p-Type, n-Type, and Ambipolar p-Conjugated Materials", 《CHEMISTRY - A EUROPEAN JOURNAL》 * |
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