CN110343082A - A kind of dibenzofurans class can poly- property compound and its application - Google Patents
A kind of dibenzofurans class can poly- property compound and its application Download PDFInfo
- Publication number
- CN110343082A CN110343082A CN201810326676.8A CN201810326676A CN110343082A CN 110343082 A CN110343082 A CN 110343082A CN 201810326676 A CN201810326676 A CN 201810326676A CN 110343082 A CN110343082 A CN 110343082A
- Authority
- CN
- China
- Prior art keywords
- independently
- another
- compound
- nitrae
- isosorbide
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
-
- 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
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
-
- 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
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
- C09K19/3842—Polyvinyl derivatives
- C09K19/3852—Poly(meth)acrylate derivatives
- C09K19/3861—Poly(meth)acrylate derivatives containing condensed ring systems
-
- 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
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
- C09K19/3895—Polymers with mesogenic groups in the side chain containing two or more mesogenic groups per monomer unit, e.g. polyitaconates, polymaleates
-
- 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
-
- 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
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
- C09K2019/3408—Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems
Abstract
The invention belongs to liquid crystal material technical fields, and in particular to a kind of dibenzofurans class can poly- property compound and its application.Liquid-crystal compounds of the present invention has the structure as shown in general formula I.Invent the polymerizable liquid crystal compound compared to the prior art, more preferable with good dissolubility, orientation effect, faster, polymerization is more complete for rate of polymerization, and residual is lower, shows bad problem to largely improve.Liquid-crystal composition orientation effect containing the compound is more preferable, and polymerization is more complete, remains lower.And the compound is cheap, performance is stablized, and can be widely used for field of liquid crystal display, has important application value.
Description
Technical field
The invention belongs to liquid crystal material technical field, being related to a kind of dibenzofurans class can poly- property compound and its application.
Background technique
In recent years, liquid crystal display device is widely used in various electronic equipments, such as smart phone, tablet computer, automobile
Navigator, television set etc..Representative liquid crystal display mode has twisted-nematic (TN) type, super twisted nematic (STN) type, face inscribe
Change (IPS) type, fringing field switching (FFS) type and vertical orientation (VA) type.Wherein, when VA mode is due to having quickly decline
Between, the image of high contrast, wide viewing angle and high quality, and receive more and more attention.
However, liquid crystal media used in the display element of the active array addressing mode of VA mode etc., there is not for itself
Foot, if image retention level will be significantly worse than the display element of positive dielectric anisotropy, the response time is slow, and driving voltage is relatively high
Deng.To solve the above-mentioned problems, there are some novel VA display technologies.Such as MVA technology, PVA technology, PSVA technology.Its
In, PSVA technology had both realized the similar wide view angle display pattern of MVA/PVA, also simplified CF technique, and realizing reduces CF
While cost, aperture opening ratio is improved, higher brightness can also be obtained, and then obtain higher contrast.Further, since whole
The liquid crystal in face has pre-tilt angle, does not have domino delay phenomenon, can also obtain under the driving voltage maintained like faster
Response time, image retention level will not be affected.
The prior art has been found that the application aspect of LC mixture and RMs in PSA display still has the shortcomings that.It is first
It first, is not up to the present that each desired solvable RM is suitable for PSA display: simultaneously, if it is desired to by means of UV
Light is polymerize (this may be advantageous for certain applications) without adding photoinitiator, then selection becomes smaller: in addition,
LC mixture (hereinafter also referred to as " LC body mixture ") combines " material system " to be formed with selected polymerizable components and answers
With minimum rotary viscosity and best photoelectric properties, for increasing " voltage retention " (VHR) to reach effect.In PSVA
Aspect is very important using the high VHR after the irradiation of (UV) light, otherwise will lead to final display and the problems such as image retention occur.
Up to the present, due to there is no inclination angle to occur or occur deficiency after polymerizable unit is too short for UV sensibility wavelength or illumination
The poor problem of homogeneity after illumination of inclination angle or polymerizable components.Not all LC mixture with polymerizable group
The combination being grouped as is adapted to PSVA display.
Therefore, the synthesis and structure-performance relation of the new structural polymerizable compound with excellent properties are ground
Study carefully an important process as field of liquid crystals.
Summary of the invention
The first object of the present invention is to provide a kind of polymerizability compound for polymer stabilizing technology.Contain the change
The liquid-crystal composition orientation effect for closing object is more preferable, and polymerization is more complete, remains lower.And the compound is cheap, performance is stablized,
It can be widely used for field of liquid crystal display, there is important application value.
Liquid-crystal compounds of the present invention, has the following structure:
Wherein, the ring A and ring B indicates Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-Asia cyclohexene independently of one another
Isosorbide-5-Nitrae-phenylene that base or 1-4 hydrogen atom are replaced by F or Cl independently of one another；
The P1、P2、P3Acrylate-based, methacrylate, fluoropropenes acid ester group, chlorine are indicated independently of one another
For acrylate-based, ethyleneoxy, oxetanyl or epoxy group；
The Z1、Z4Singly-bound ,-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-O- ,-CH=are indicated independently of one another
N- ,-N=CH- ,-N=N- ,-C ≡ C-, C1-C12Alkylidene or alkenyl, wherein the C1-C12Alkylidene or alkenyl in
One or more hydrogen atoms can be replaced by F, Cl or CN independently of one another, and one or more non-conterminous-CH2Group can
Independently of one another by-O- ,-S- ,-NH- ,-CO-, COO- ,-OCO- ,-OCOO- ,-SCO- ,-COS- or ethylene linkage with mutually not straight
Connected mode is connect to replace；
The Z2、Z3Singly-bound ,-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-O- ,-CH=are indicated independently of one another
N- ,-N=CH- ,-N=N- ,-C ≡ C-, C1-C12Alkylidene or alkenyl, the C1-C12Alkylidene or alkenyl in one
Or multiple hydrogen atoms can be replaced by F, Cl or CN independently of one another, and one or more non-conterminous-CH2Group can be with that
This is not independently by-O- ,-S- ,-NH- ,-CO-, COO- ,-OCO- ,-OCOO- ,-SCO- or-COS- to be connected directly mutually
Mode replaces；
L1, L2Expression-F ,-Cl ,-CN ,-NO independently of one another2、-CH3、-C2H5、-C(CH3)3、-CH(CH3)2、-CH2CH
(CH3)C2H5、-OCH3、-OC2H5、-COCH3、-COC2H5、-COOCH3、-COOC2H5、-CF3、-OCF3、-OCHF2Or-OC2F5；
R, s indicates 0,1,2 or 3 independently of one another；
M, n indicates 0 or 1 independently of one another.
As a preferred solution of the present invention, in general formula I, about ring A and ring B:
Preferably, the ring A and ring B indicates Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene or 1-4 hydrogen atom independently of one another
The 1,4- phenylene replaced by F or Cl atom；
It is highly preferred that the ring A and ring B indicate Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene, the fluoro- Isosorbide-5-Nitrae-of 2- independently of one another
Phenylene, the fluoro- Isosorbide-5-Nitrae-phenylene of 2-.
About the P1、P2、P3: preferably, the P1、P2、P3Methacrylate or propylene are indicated independently of one another
Perester radical.
About the Z1、Z4: preferably, the Z1、Z4Singly-bound ,-O- or C are indicated independently of one another1-C5Alkylidene and alkane
Oxygroup.
About Z2、Z3: preferably, the Z2、Z3Singly-bound or-(CH are indicated independently of one another2)k, k expression 1-8, specifically,
K is 1,2,3,4,5,6,7 or 8；It is highly preferred that the Z2、Z3Singly-bound or-(CH are indicated independently of one another2)k, k indicate 1,2,3,
4 or 5；Further, the Z2、Z3Singly-bound or-(CH are indicated independently of one another2)k, wherein k indicates 1,2 or 3.
About L1, L2: preferably, the L1, L2Expression-F ,-Cl ,-CN, C independently of one another1-C3Alkyl or alkoxy；
It is highly preferred that the L1、L2It is identical or different, expression-F ,-Cl ,-CN ,-CH independently of one another3、-OCH3、-CF3、-OCF3Or-
OCHF2；Further, the L1、L2It is identical or different, expression-F ,-Cl independently of one another.
About r, s: preferably, described r, s indicate 0 or 1 independently of one another.
About m, n: preferably, described m, n indicate 0 or 1, and m+n≤1 independently of one another.
In compound formula I of the present invention:
Preferably, in general formula I, the ring A and ring B indicates Isosorbide-5-Nitrae-phenylene independently of one another, 1 or 4 cyclohexylidene or
The 1,4- phenylene that 1-4 hydrogen atom is replaced by F or Cl atom；The P1、P2、P3Methacrylate is indicated independently of one another
Base is acrylate-based；The Z1、Z4Singly-bound ,-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O- are respectively indicated independently of one another
CO-O- ,-CH=N- ,-N=CH- ,-N=N- ,-C ≡ C-, C1-C12Alkylidene or alkenyl, wherein the C1-C12Alkylidene or alkene
One or more hydrogen atoms of base kind can be replaced by F, Cl or CN independently of one another, and one or more non-conterminous-CH2-
Group can be respectively independently of one another by-O- ,-S- ,-NH- ,-CO- ,-COO- ,-OCO- ,-OCOO- ,-SCO- ,-COS- or alkene
Key is replaced in a manner of not being connected directly mutually；The Z2、Z3Singly-bound or-(CH are indicated independently of one another2)k, k indicate 1,2,3,
4 or 5；The L1, L2It is identical or different, expression-F ,-Cl ,-CH independently of one another3、-OCH3、-CF3、-OCF3Or-OCHF2；r,s
0,1,2 or 3 are indicated independently of one another；Described m, n indicate 0 or 1, and m+n≤1 independently of one another.
It is further preferred that in general formula I, the ring A and ring B indicate Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-Asia ring independently of one another
Hexyl, the fluoro- Isosorbide-5-Nitrae-phenylene of 2-, the fluoro- Isosorbide-5-Nitrae-phenylene of 2-；The P1、P2、P3Methacrylate is indicated independently of one another
Or it is acrylate-based；The Z1、Z4Singly-bound ,-O- or C are indicated independently of one another1-C5Alkylidene and alkoxy；The Z2、Z3That
This independently indicates singly-bound or-(CH2)k, wherein k indicates 1,2 or 3；The L1、L2It is identical or different, indicate independently of one another-
F、-Cl、-CN、-CH3、-OCH3、-CF3、-OCF3Or-OCHF2；Further, L1、L2It is identical or different, earth's surface independent of one another
Show-F ,-Cl；Described r, s indicate 0 or 1 independently of one another；Described m, n indicate 0 or 1, and m+n≤1 independently of one another.
As still more preferably technical solution of the invention:
In general formula I, the P1、P2、P3Methacrylate or acrylate-based is indicated independently of one another；The Z1、
Z4Singly-bound ,-O- or C are indicated independently of one another1-C5Alkylidene and alkoxy；Z2、Z3Independently of one another indicate singly-bound ,-F or-
(CH2)k, k expression 1,2 or 3；
Wherein,
M=n=0, L1And L2Expression-F, r and s are independently from each other 0 or 1；
Or, m=1, n=0, L1And L2It is former that expression-F, ring A are selected from Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene or 1-2 hydrogen
For son by one or more Isosorbide-5-Nitrae-phenylenes replaced in F or Cl atom, r and s are independently from each other 0 or 1；
Or, m=0, n=1, L1And L2It is former that expression-F, ring B are selected from Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene or 1-2 hydrogen
For son by one or more Isosorbide-5-Nitrae-phenylenes replaced in F or Cl atom, r and s are independently from each other 0 or 1；
R and s as described in the above technical scheme are independently from each other 0 or 1 and refer to r=s=1 or r=s=0 or r is
0 and s is that 1 or r is 1 and s is one of 0 four kinds of situations.
As still more preferably technical solution of the invention, the compound is selected from one of following compound:
It is above it is various in, P1、P2、P3Methacrylate or acrylate-based is indicated independently of one another；The Z1、Z4That
This independently indicates singly-bound ,-O- or C1-C5Alkylidene and alkoxy；Z2、Z3Singly-bound or-(CH are indicated independently of one another2)k, k
Indicate 1,2 or 3.
As preferred forms of the invention, the compound is selected from one of following compound:
Second purpose of invention is the composition that protection contains the liquid-crystal compounds.The compound is in the composition
Mass percent is 0.01~10%, preferably 0.01~5%, further preferably 0.1~3%.
The third object of the present invention is that the protection liquid-crystal compounds and the composition containing the liquid-crystal compounds exist
The application of field of liquid crystal display, the application preferably in liquid crystal display device.The liquid crystal display device includes but not
It is limited to TN, ADS, VA, PSVA, FFS or IPS liquid crystal display.
The negative dielectric anisotropic of the liquid-crystal compounds is high, and significantly improves clearing point simultaneously, relatively high optics
Anisotropy, moderate rotary viscosity and liquid crystal intersolubility, low-temperature working effect show outstanding, good thermal stability, chemistry
The performance of stability, optical stability and mechanics etc.；To which driving voltage be effectively reduced, liquid crystal display device is improved
Response speed, while having the characteristics that optical anisotropy numerical value is moderate, charge conservation rate is high.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention., all other without departing from the present invention
The lower equivalent change or modification completed of revealed spirit, should be included in the scope of the said claims.
Each liquid-crystal compounds used by below in an example unless otherwise instructed, can pass through well known method
Carry out synthesize or obtained from public commercial source, these synthetic technologys be it is conventional, acquired each liquid-crystal compounds accords with after tested
Close standard for electronic compounds.
According to the common detection methods of this field, the various performance parameters of liquid-crystal compounds are obtained by linear fit,
In, the concrete meaning of each performance parameter is as follows:
△ n represents optical anisotropy (25 DEG C)；△ ε represents dielectric anisotropy (25 DEG C, 1000Hz)；γ 1 represents rotation
Turn viscosity (mPa.s, 25 DEG C)；Cp represents clearing point.
Embodiment 1
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-01 is as follows:
Specific step is as follows:
(1) synthesis of compound BYLC-01-1:
By 100ml n,N-Dimethylformamide, 30gIt is anti-that 500ml is added in (0.087mol)
It answers in bottle, is slowly added to 4.2g sodium hydroxide, temperature control reacts 1h to 45~55 DEG C.Continue 45~55 DEG C of temperature control, 14.8g is added dropwise
Iodomethane, temperature control react 6h.Reaction solution is poured into water, is filtered, washing to neutrality obtains white solid (compound after dry
BYLC-01-1,0.079mol) 28.4g, GC:99.8%, yield: 90.8%.
(2) synthesis of compound BYLC-01-2:
Under nitrogen protection, 28.4g (0.079mol) compound BYLC-01-1,25.2g are added into 1000ml reaction flask
Diethyl malonate, 74.1g cesium carbonate, 1g cuprous iodide, 500ml tetrahydrofuran react at room temperature 48h.Reaction solution is poured into water
In, pH is adjusted to neutrality with dilute hydrochloric acid.Conventional post-processing is carried out, is extracted through ethyl acetate, chromatogram purification, n-hexane elution, second
Alcohol is recrystallized to give white solid (compound BYLC-01-2,0.072mol) 28.2g, GC:99.7%, yield: 91.1%.
(3) synthesis of compound BYLC-01-3:
Under nitrogen protection, 28.2g (0.072mol) compound BYLC-01-2,250ml are added into 500ml reaction flask
Methylene chloride, temperature control are added dropwise 6g Boron tribromide to -15 DEG C~-20 DEG C, react at room temperature 2h.Conventional post-processing is carried out, through acetic acid second
Ester extraction, column chromatograph to obtain white solid (compound BYLC-01-3,0.068mol) 25.7g, GC:99.8%, yield:
94.4%.
(4) synthesis of compound BYLC-01-4:
Under nitrogen protection, addition 10g lithium aluminium hydride reduction and 1000ml ether into 2000ml reaction flask, -10 DEG C of temperature control~-
15 DEG C, the diethyl ether solution of 25.7g compound BYLC-01-3 (0.068mol) is added dropwise, continues -10 DEG C~-15 DEG C of temperature control, reaction
1h；Then 6h is reacted at room temperature.Ethyl acetate is added into reaction solution, adjusts pH to faintly acid with dilute hydrochloric acid.Then it carries out conventional
Post-processing operation is extracted through ethyl acetate, chromatogram purification, and the mixed solution that the volume ratio of normal heptane and toluene is 3:1 carries out weight
Crystallization, obtains white solid (compound BYLC-01-4,0.062mol) 18.2g, GC:99.8%, yield: 91.2%.
(5) synthesis of compound BYLC-01:
Under nitrogen protection, 18.2g (0.062mol) compound BYLC-01-4,30g tri- is added into 1000ml reaction flask
Ethamine, 500ml methylene chloride -10 DEG C~-15 DEG C of temperature control, are added dropwise 28g methacrylic chloride, continue -10 DEG C~-15 DEG C of temperature control,
React 1h；Then 6h is reacted at room temperature.Reaction solution is poured into water, is neutralized to neutrality with sodium bicarbonate.Carry out conventional post-processing, stone
Oily ether is recrystallized to give white solid (compound BYLC-01,0.054mol) 26.9g, GC:99.9%, yield: 87.1%.
Gained white solid BYLC-01 is analyzed using GC-MS, the m/z of product is 498.1 (M+).
1H-NMR(300MHz,CDCl3):0.75-1.25(m,3H),1.95-2.65(m,3H),4.75-5.05(m,2H),
6.55-7.45(m,8H)。
Embodiment 2
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-02 is as follows:
Specific step is as follows:
The synthesis of compound BYLC-02:
Under nitrogen protection, 30.0g compound BYLC-01-3,37.6g triethylamine and 250mL dichloro are added into reaction flask
Methane is cooled to -10 DEG C, and 32.0g acryloyl chloride is added dropwise in -10 DEG C of temperature control~0 DEG C, is warmed to room temperature reaction 6h for reaction solution and pours into water
In, it is neutralized with bicarbonate uranium aqueous solution, carries out conventional post-processing, through chromatogram purification, n-hexane elution, ethyl alcohol recrystallization obtains white
Color solid (compound BYLC-02) 39.4g, LC:99.6%, yield: 84.3%.
Gained white solid BYLC-02 is analyzed using GC-MS, the m/z of product is 456.1 (M+).
1H-NMR(300MHz,CDCl3): 3.35-4.55 (m, 5H), 4.65-5.85 (m, 3H), 5.95-6.45 (m, 6H),
5.65-7.25(m,4H)。
Embodiment 3
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-03 is as follows:
Specific step is as follows:
(1) synthesis of compound BYLC-03-1:
Under nitrogen protection, bromo- 4, the 6- difluorodiphenyl of 40g 3- benzyloxy -7- and furans, 300ml tetrahydro are added in reaction flask
Furans is cooled to -70 DEG C~-80 DEG C, and 0.13mol n-BuLi is added dropwise, and 18.0g is added dropwise in -70 DEG C~-80 DEG C reaction 1h of temperature control
Trimethylborate is risen again naturally to -30 DEG C, and dilute hydrochloric acid acidification adjusts pH value less than 2, carries out conventional post-processing, is recrystallized to give
Light yellow solid (compound BYLC-03-1) 31.2g, LC:98.5%, yield 86.7%；
(2) synthesis of compound BYLC-03-2:
31.2g compound BYLC-03-1,17.5g para chlorobromobenzene, 18.0g Anhydrous potassium carbonate, 200ml are added in reaction flask
Toluene, 150ml ethyl alcohol, 150ml water, 0.3 4 triphenylphosphines close palladium, and heating reflux reaction 8h carries out conventional post-processing, obtains class
White solid (compound BYLC-03-2): 33.4g, LC:99.6%, yield: 83.2%；
Other steps are the same as embodiment 1
Compound BYLC-03: gained white solid BYLC-03 is analyzed using GC-MS, the m/z of product are as follows:
576.1(M+)。
1H-NMR(300MHz,CDCl3):1.35-2.20(m,9H),3.63-4.45(m,3H),4.55-5.65(m,2H),
5.75-7.25(m,6H),7.25-8.25(m,4H)。
Embodiment 4
The structural formula of liquid-crystal compounds are as follows:
Reaction condition is the same as embodiment 1,2.
Gained white solid BYLC-04 is analyzed using GC-MS, the m/z of product is 532.1 (M+).
1H-NMR(300MHz,CDCl3):3.35-4.55(m,5H),5.65-6.45(m,9H),6.45-7.45(m,8H)。
Embodiment 5
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-05 is as follows:
The bromo- 4,6- difluorodiphenyl of 3- benzyloxy -7- is replaced with 3- benzyloxy -7- bromomethyl -4,6- difluorodiphenyl and furans
And furans, other
Condition is the same as embodiment 1.
Gained white solid BYLC-05 is analyzed using GC-MS, the m/z of product is 512.1 (M+).
1H-NMR(300MHz,CDCl3): 1.55-2.55 (m, 8H), 3.05-4.25 (m, 5H), 5.45-6.25 (m, 6H),
6.65-7.25(m,4H)。
Embodiment 6
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-06 is as follows:
Specific step is as follows:
(1) synthesis of compound BYLC-06-1:
Addition 34.5g 3- benzyloxy -7- hydroxyl -4,6- difluorodiphenyl and furans in reaction flask, 20.5g Anhydrous potassium carbonate,
Reaction mixture is heated to 60 DEG C by 300mlN, dinethylformamide, and the bromo- 1- propyl alcohol of 20.4g 3-, temperature control is added dropwise to it
100 DEG C~110 DEG C reaction 6h are down to room temperature, carry out conventional post-processing, are recrystallized to give off-white color color solid (compound BYLC-
06-1) 33.5g, LC:99.7%, yield 81.5%；
(2) synthesis of compound BYLC-06-2:
Under nitrogen protection, 33.5g compound BYLC-06-1,31.5g triphenylphosphine, 200ml tetrahydro furan are added in reaction flask
It mutters, is cooled to -10 DEG C~0 DEG C, the solution of 18.8g bromine and 30ml tetrahydrofuran composition, 5 DEG C~10 DEG C of temperature control reactions are added dropwise
3h, aqueous solution of sodium bisulfite destroy hydrolysis, carry out conventional post-processing, are recrystallized to give light yellow solid (compound BYLC-
06-2) 32.1g, LC:98.8%, yield 83.4%；
Other steps are the same as embodiment 1
Compound BYLC-06: gained white solid BYLC-06 is analyzed using GC-MS, the m/z of product are as follows:
556.1(M+)。
1H-NMR(300MHz,CDCl3):1.15-2.25(m,10H),2.65-4.25(m,5H),4.35-5.65(m,3H),
5.65-6.65(m,4H),6.75-7.75(m,3H)。
Technical solution according to above embodiments 1-6, it is only necessary to which the corresponding raw material of simple replacement does not change any substance
Operation, can synthesize following liquid-crystal compounds.
Embodiment 7
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-07 is as follows:
(1) synthesis of compound BYLC-07-1:
By 100ml n,N-Dimethylformamide, 30gIt is added in 500ml reaction flask, slowly adds
Enter 4.2g sodium hydroxide, temperature control reacts 1h to 45~55 DEG C.Continue 45~55 DEG C of temperature control, 14.8g iodomethane is added dropwise, temperature control is anti-
Answer 6h.Reaction solution is poured into water, is filtered, washing to neutrality obtains white solid (compound BYLC-07-1) after dry
28.4g, GC:99.7%, yield: 89.2%.
(2) synthesis of compound BYLC-07-2:
Under nitrogen protection, 28.4g compound BYLC-07-1,25.2g malonic acid diethyl are added into 1000ml reaction flask
Ester, 74.1g cesium carbonate, 1g cuprous iodide, 500ml tetrahydrofuran react at room temperature 48h.Reaction solution is poured into water, dilute hydrochloric acid is used
PH is adjusted to neutrality.Conventional post-processing is carried out, is extracted through ethyl acetate, chromatogram purification, n-hexane elution, ethyl alcohol recrystallization obtains
White solid (compound BYLC-07-2) 29.3g, GC:99.7%, yield: 93.1%.
(3) synthesis of compound BYLC-07-3:
Under nitrogen protection, 29.3g compound BYLC-07-2,250ml methylene chloride, control are added into 500ml reaction flask
6g Boron tribromide is added dropwise to -15 DEG C~-20 DEG C in temperature, reacts at room temperature 2h.Conventional post-processing is carried out, is extracted through ethyl acetate, column layer
Analysis obtains white solid (compound BYLC-07-3) 24.3g, GC:99.8%, yield: 91.1%.
(4) synthesis of compound BYLC-07-4:
Under nitrogen protection, addition 10g lithium aluminium hydride reduction and 1000ml ether into 2000ml reaction flask, -10 DEG C of temperature control~-
15 DEG C, the diethyl ether solution of 24.3g compound BYLC-07-3 is added dropwise, continues -10 DEG C~-15 DEG C of temperature control, reacts 1h；Then room temperature
React 6h.Ethyl acetate is added into reaction solution, adjusts pH to faintly acid with dilute hydrochloric acid.Then conventional post-processing operation is carried out,
It is extracted through ethyl acetate, chromatogram purification, the mixed solution that the volume ratio of normal heptane and toluene is 3:1 is recrystallized, and is obtained white
Color solid (compound BYLC-07-4) 17.1g, GC:99.8%, yield: 87.2%.
(5) synthesis of compound BYLC-07:
Under nitrogen protection, 17.1g compound BYLC-07-4,30g triethylamine, 500ml are added into 1000ml reaction flask
Methylene chloride -10 DEG C~-15 DEG C of temperature control, is added dropwise 28g methacrylic chloride, continues -10 DEG C~-15 DEG C of temperature control, reacts 1h；So
After react at room temperature 6h.Reaction solution is poured into water, is neutralized to neutrality with sodium bicarbonate.Conventional post-processing is carried out, petroleum ether is tied again
Crystalline substance obtains white solid (compound BYLC-07) 24.3g, GC:99.9%, yield: 83.4%.
Gained white solid BYLC-07 is analyzed using GC-MS, the m/z of product is 462.1 (M+).
1H-NMR(300MHz,CDCl3):0.95-1.95(m,6H),3.05-4.05(m,3H),4.35-5.65(m,7H),
5.75-6.45 (m, 4H), 7.15-7.65 (m, 5H).
Embodiment 8
The structural formula of liquid-crystal compounds are as follows:
By raw materialBecomeOther reaction conditions are the same as embodiment 1.
Gained white solid BYLC-08 is analyzed using GC-MS, the m/z of product is 480.1 (M+).
1H-NMR(300MHz,CDCl3):0.95-1.95(m,6H),3.05-4.05(m,3H),4.35-5.65(m,7H),
5.75-6.45 (m, 4H), 7.15-7.65 (m, 4H).
Embodiment 9
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-09 is as follows:
Specific step is as follows:
The synthesis of compound BYLC-09:
Under nitrogen protection, 30.0g compound BYLC-07-3,37.6g triethylamine and 250mL dichloro are added into reaction flask
Methane is cooled to -10 DEG C, and 32.0g acryloyl chloride is added dropwise in -10 DEG C of temperature control~0 DEG C, is warmed to room temperature reaction 6h for reaction solution and pours into water
In, it is neutralized with bicarbonate uranium aqueous solution, carries out conventional post-processing, through chromatogram purification, n-hexane elution, ethyl alcohol recrystallization obtains white
Color solid (compound BYLC-09) 36.4g, LC:99.6%, yield: 81.1%.
Gained white solid BYLC-09 is analyzed using GC-MS, the m/z of product is 420.1 (M+).
1H-NMR(300MHz,CDCl3): 3.35-4.55 (m, 7H), 4.65-5.85 (m, 3H), 5.95-6.45 (m, 8H),
5.65-7.25(m,4H)。
Embodiment 10
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-10 is as follows:
Specific step is as follows:
(1) synthesis of compound BYLC-10-1:
Under nitrogen protection, 40g is added in reaction flask300ml tetrahydrofuran, drop
0.13mol n-BuLi is added dropwise to -70 DEG C~-80 DEG C in temperature, and 18.0g boric acid front three is added dropwise in -70 DEG C~-80 DEG C reaction 1h of temperature control
Ester is risen again naturally to -30 DEG C, and dilute hydrochloric acid acidification adjusts pH value less than 2, carries out conventional post-processing, is recrystallized to give light yellow solid
Body (compound BYLC-10-1) 31.4g, LC:98.7%, yield 86.2%；
(2) synthesis of compound BYLC-10-2:
31.4g compound BYLC-10-1,17.5g para chlorobromobenzene, 18.0g Anhydrous potassium carbonate, 200ml are added in reaction flask
Toluene, 150ml ethyl alcohol, 150ml water, 0.3 4 triphenylphosphines close palladium, and heating reflux reaction 8h carries out conventional post-processing, obtains class
White solid (compound BYLC-10-2): 32.1g, LC:99.6%, yield: 81.7%；
Other steps are the same as embodiment 1
Compound BYLC-10: gained white solid BYLC-10 is analyzed using GC-MS, the m/z of product are as follows:
538.1(M+)。
1H-NMR(300MHz,CDCl3):1.35-2.20(m,6H),3.63-4.45(m,6H),5.45-6.25(m,8H),
7.15-7.75(m,8H)。
Embodiment 11
The structural formula of liquid-crystal compounds are as follows:
By raw material byBecomeOther
Part is same
Embodiment 4.
Gained white solid BYLC-11 is analyzed using GC-MS, the m/z of product are as follows: 556.1 (M+).
1H-NMR(300MHz,CDCl3):1.35-2.20(m,6H),3.63-4.45(m,6H),5.45-6.25(m,7H),
7.15-7.75(m,8H)。
Embodiment 12
The structural formula of liquid-crystal compounds are as follows:
Reaction condition is the same as embodiment 1,3.
Gained white solid BYLC-12 is analyzed using GC-MS, the m/z of product is 496.1 (M+).
1H-NMR(300MHz,CDCl3):3.35-4.55(m,7H),5.65-6.45(m,11H),6.45-7.65(m,8H)。
Embodiment 13
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-13 is as follows:
WithInstead ofOther conditions are the same as embodiment 1.
Gained white solid BYLC-13 is analyzed using GC-MS, the m/z of product is 476.1 (M+).
1H-NMR(300MHz,CDCl3): 1.55-2.55 (m, 11H), 3.05-4.25 (m, 7H), 5.45-6.25 (m, 8H),
6.65-7.65(m,4H)。
Embodiment 14
The structural formula of liquid-crystal compounds are as follows:
WithInstead ofOther
Part is same
Embodiment 7.
Gained white solid BYLC-14 is analyzed using GC-MS, the m/z of product is 494.1 (M+).
1H-NMR(300MHz,CDCl3): 1.55-2.55 (m, 11H), 3.05-4.25 (m, 6H), 5.45-6.25 (m, 6H),
6.65-7.65(m,4H)。
Embodiment 15
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-15 is as follows:
Specific step is as follows:
(1) synthesis of compound BYLC-15-1:
40g is added in reaction flask23.5g Anhydrous potassium carbonate, 300mlN, N- bis-
Reaction mixture is heated to 60 DEG C by methylformamide, to its be added dropwise the bromo- 1- propyl alcohol of 20.4g 3-, 100 DEG C~110 DEG C of temperature control
6h is reacted, room temperature is down to, conventional post-processing is carried out, is recrystallized to give off-white color color solid (compound BYLC-15-1) 35.1,
LC:99.7%, yield 83.4%；
(2) synthesis of compound BYLC-15-2:
Under nitrogen protection, 35.1gBYLC-15-1,31.5g triphenylphosphine, 200ml tetrahydrofuran, drop are added in reaction flask
The solution of 18.8g bromine and 30ml tetrahydrofuran composition, 5 DEG C~10 DEG C reaction 3h of temperature control, sulfurous is added dropwise to -10 DEG C~0 DEG C in temperature
Sour hydrogen sodium water solution destroys hydrolysis, carries out conventional post-processing, is recrystallized to give light yellow solid (compound BYLC-15-2)
32.1g, LC:98.8%, yield 81.4%；
Other steps are the same as embodiment 1
Gained white solid BYLC-15 is analyzed using GC-MS, the m/z of product are as follows: 520.1 (M+).
1H-NMR(300MHz,CDCl3):1.15-2.25(m,10H),2.65-4.25(m,9H),4.35-5.65(m,5H),
5.65-6.65(m,3H),6.75-7.75(m,4H)。
Embodiment 16
The structural formula of liquid-crystal compounds are as follows:
By raw materialIt is changed toOther
Part is same
Embodiment 9.
Gained white solid BYLC-16 is analyzed using GC-MS, the m/z of product are as follows: 520.1 (M+).
1H-NMR(300MHz,CDCl3):1.15-2.25(m,10H),2.65-4.25(m,9H),4.35-5.65(m,4H),
5.65-6.65(m,3H),6.75-7.75(m,4H)。
Embodiment 17
Technical solution according to above embodiments, it is only necessary to which the corresponding raw material of simple replacement does not change any substantive behaviour
Make, following liquid-crystal compounds can be synthesized.
Test example 1
The property of mixed crystal BHR87800 is listed in Table 1 below:
1 mixed crystal BHR87800 property summary sheet of table
Wherein, mixture BHR87800 is purchased from Bayi Space liquid crystal Science and Technology Co., Ltd..The embodiment of addition 0.3%
In the liquid-crystal composition BHR87800 of polymerizable compound BYLC-01 to 99.7% provided by 1, uniform dissolution is mixed
Close object PM-1.The liquid crystal compound of polymerizable compound BYLC-03 to 99.7% provided by the embodiment 3 of addition 0.3%
In BHR87800, uniform dissolution obtains mixture PM-2.Polymerizable compound provided by the embodiment 7 of addition 0.3%
In the liquid-crystal composition BHR87800 of BYLC-07 to 99.7%, uniform dissolution obtains mixture PM-3.The implementation of addition 0.3%
In the liquid-crystal composition BHR87800 of polymerizable compound BYLC-08 to 99.7% provided by example 8, uniform dissolution is mixed
Close object PM-4.The physical property of PM-1, PM-2, PM-3, PM-4 and the physical property of said mixture BHR87800 are almost without difference.
PM-1, PM-2, PM-3, PM-4 injection gap are 4.0 μm and have vertical orientation using priming by vacuum method
In testing cassete.Applying frequency on one side is 60HZ, and driving voltage is the square wave of 16V, on one side with high-pressure mercury ultraviolet lamp to testing cassete
Ultraviolet light is irradiated, the exposure intensity adjusted to box surface is 30mW/cm2, irradiate 600s, the liquid of the vertical orientation after being polymerize
Crystal display element measures pre-tilt angle using LCT-5016E liquid crystal electro-optic parameter tester, testing cassete is then decomposed, using efficient
Liquid chromatogram HPLC measures remaining polymerizable compound in liquid-crystal composition, is as a result summarized in table 2 and table 3.
Comparative example
In the mixture BHR87800 of the polymerizable compound to 99.7% of the CP of addition 0.3%, uniform dissolution is mixed
Close object PM-2.The physical property of PM-2 and the physical property of said mixture BHR87800 are almost without difference.Using priming by vacuum method by PM-
2 injection gaps are 4.0 μm and have in the testing cassete of vertical orientation.Applying frequency on one side is 60HZ, and driving voltage is 16V's
Square wave irradiates ultraviolet light to testing cassete with high-pressure mercury ultraviolet lamp on one side, and the exposure intensity adjusted to box surface is 30mW/cm2,
600s is irradiated, the liquid crystal display element of the vertical orientation after being polymerize is surveyed using LCT-5016E liquid crystal electro-optic parameter tester
Determine pre-tilt angle, then decompose testing cassete, uses remaining polymerism chemical combination in high-efficient liquid phase chromatogram HPLC measurement liquid-crystal composition
As a result object is summarized in table 2 and table 3.
Pre-tilt angle summary sheet before and after table 2UV
3 polymer residue data summary table of table
From the correlation data of table 2 and table 3 it is found that polymerizable compound relative polymerization liquid-crystal compounds CP of the invention,
The orientation effect being formed by is more preferable, and faster, polymerization is more complete for rate of polymerization, and residual is lower, so that biggish improve display
Bad problem.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of dibenzofurans class can poly- property compound, which is characterized in that have the following structure:
Wherein, the ring A and ring B indicates Isosorbide-5-Nitrae-phenylene independently of one another, 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, or
The 1,4- phenylene that 1-4 hydrogen atom is replaced by F or Cl independently of one another；
The P1、P2、P3Acrylate-based, methacrylate, fluoropropenes acid ester group, chloro third are indicated independently of one another
Olefin(e) acid ester group, ethyleneoxy, oxetanyl or epoxy group；
The Z1、Z4Singly-bound ,-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-O- ,-CH=N- ,-N are indicated independently of one another
=CH- ,-N=N- ,-C ≡ C-, C1-C12Alkylidene or alkenyl, wherein the C1-C12Alkylidene or alkenyl in one or
Multiple hydrogen atoms can be replaced by F, Cl or CN independently of one another, and one or more non-conterminous-CH2Group can be each other
Independently by-O- ,-S- ,-NH- ,-CO-, COO- ,-OCO- ,-OCOO- ,-SCO- ,-COS- or ethylene linkage not to be connected directly mutually
Mode replace；
The Z2、Z3Singly-bound ,-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-O- ,-CH=N- ,-N are indicated independently of one another
=CH- ,-N=N- ,-C ≡ C-, C1-C12Alkylidene or alkenyl, the C1-C12Alkylidene or one or more of alkenyl
Hydrogen atom can be replaced by F, Cl or CN independently of one another, and one or more non-conterminous-CH2Group can be independent of one another
Ground is by-O- ,-S- ,-NH- ,-CO-, COO- ,-OCO- ,-OCOO- ,-SCO- or-the COS- generation in a manner of not being connected directly mutually
It replaces；
L1, L2Expression-F ,-Cl ,-CN ,-NO independently of one another2、-CH3、-C2H5、-C(CH3)3、-CH(CH3)2、-CH2CH(CH3)
C2H5、-OCH3、-OC2H5、-COCH3、-COC2H5、-COOCH3、-COOC2H5、-CF3、-OCF3、-OCHF2Or-OC2F5；
R, s indicates 0,1,2 or 3 independently of one another；
M, n indicates 0 or 1 independently of one another.
2. compound according to claim 1, which is characterized in that the ring A and ring B indicates Isosorbide-5-Nitrae-Asia benzene independently of one another
Isosorbide-5-Nitrae-phenylene that base, 1 or 4 cyclohexylidene or 1-4 hydrogen atom are replaced by F or Cl atom；
Preferably, the ring A and ring B indicates Isosorbide-5-Nitrae-phenylene independently of one another, 1 or 4 cyclohexylidene, the fluoro- Isosorbide-5-Nitrae-phenylene of 2-,
The fluoro- 1,4- phenylene of 2-.
3. compound according to claim 1 or 2, which is characterized in that the P1、P2、P3Methyl-prop is indicated independently of one another
Olefin(e) acid ester group is acrylate-based；
And/or described r, s indicate 0 or 1 independently of one another
And/or described m, n indicate 0 or 1, and m+n≤1 independently of one another.
4. compound according to claim 1-3, which is characterized in that the Z1、Z4It indicates independently of one another single
Key ,-O- or C1-C5Alkylidene and alkoxy.
5. compound according to claim 1-4, which is characterized in that the Z2、Z3Singly-bound is indicated independently of one another
Or-(CH2)k, k expression 1-8；
Preferably, k indicates 1,2,3,4 or 5；
It is further preferred that k indicates 1,2 or 3.
6. compound according to claim 1-5, which is characterized in that the L1, L2Independently of one another expression-F ,-
Cl ,-CN or C1-C3Alkyl or alkoxy；
Preferably, L1、L2It is identical or different, expression-F ,-Cl ,-CN ,-CH independently of one another3、-OCH3、-CF3、-OCF3Or-
OCHF2；
Further, the L1、L2It is identical or different, expression-F ,-Cl independently of one another.
7. compound according to claim 1-6, which is characterized in that the P1、P2、P3Indicate methacrylic acid
Ester group is acrylate-based；
The Z1、Z4Singly-bound ,-O- or C are indicated independently of one another1-C5Alkylidene and alkoxy；
The Z2、Z3Singly-bound or-(CH are indicated independently of one another2)k, k expression 1,2 or 3；
Wherein,
M=n=0, L1And L2Expression-F, r and s are independently from each other 0 or 1；
Or, m=1, n=0, L1And L2Expression-F, ring A are selected from Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene or 1-2 hydrogen atom by F
Or one or more Isosorbide-5-Nitrae-phenylenes replaced in Cl atom, r and s are independently from each other 0 or 1；
Or, m=0, n=1, L1And L2Expression-F, ring B are selected from Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene or 1-2 hydrogen atom by F
Or one or more Isosorbide-5-Nitrae-phenylenes replaced in Cl atom, r and s are independently from each other 0 or 1.
8. compound according to claim 1-7, which is characterized in that the compound is in following compound
One kind:
It is above it is various in, P1、P2、P3Methacrylate or acrylate-based is indicated independently of one another；
The Z1、Z4Singly-bound ,-O- or C are indicated independently of one another1-C5Alkylidene and alkoxy；
Z2、Z3Singly-bound or-(CH are indicated independently of one another2)k, k expression 1,2 or 3；
Preferably, the compound is selected from one of following compound:
9. a kind of liquid-crystal composition, which is characterized in that include the compound as described in claim any one of 1-8；
Preferably, the mass percent of the compound in the composition be 0.01~10%, more preferably 0.01~
5%, further preferably 0.1~3%.
10. the described in any item compounds of claim 1-8 and/or liquid-crystal composition as claimed in claim 9 are in liquid crystal display
The application in field；Application preferably in liquid crystal display device；It is highly preferred that the liquid crystal display device include TN,
ADS, VA, PSVA, FFS or IPS liquid crystal display.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2018102845212 | 2018-04-02 | ||
| CN201810284521 | 2018-04-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110343082A true CN110343082A (en) | 2019-10-18 |
Family
ID=68173321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810326676.8A Withdrawn CN110343082A (en) | 2018-04-02 | 2018-04-12 | A kind of dibenzofurans class can poly- property compound and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110343082A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922986A (en) * | 2018-09-20 | 2020-03-27 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition containing dibenzofuran polymerizable compound and application thereof |
| CN113149943A (en) * | 2021-05-10 | 2021-07-23 | 吉林奥来德光电材料股份有限公司 | Fluorescent compound, preparation method thereof and organic electroluminescent device comprising same |
| CN113913194A (en) * | 2021-10-22 | 2022-01-11 | 北京云基科技有限公司 | Fluorine-containing liquid crystal compound and application thereof |
| CN114149397A (en) * | 2021-12-06 | 2022-03-08 | 江苏创拓新材料有限公司 | Dibenzofurans-based polymerizable compound and preparation method and application thereof |
| CN114381279A (en) * | 2022-01-17 | 2022-04-22 | 烟台显华科技集团股份有限公司 | Polymerizable compound, composition, and liquid crystal display device |
| WO2023134598A1 (en) * | 2022-01-13 | 2023-07-20 | 烟台显华科技集团股份有限公司 | Polymerisable compound, composition, and liquid crystal display device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104797688A (en) * | 2012-11-21 | 2015-07-22 | 默克专利股份有限公司 | Polymerisable compounds and the use thereof in liquid-crystal displays |
| CN107814783A (en) * | 2016-09-14 | 2018-03-20 | 江苏和成显示科技股份有限公司 | Polymerizable compound and its preparation method and application |
-
2018
- 2018-04-12 CN CN201810326676.8A patent/CN110343082A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104797688A (en) * | 2012-11-21 | 2015-07-22 | 默克专利股份有限公司 | Polymerisable compounds and the use thereof in liquid-crystal displays |
| CN107814783A (en) * | 2016-09-14 | 2018-03-20 | 江苏和成显示科技股份有限公司 | Polymerizable compound and its preparation method and application |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922986A (en) * | 2018-09-20 | 2020-03-27 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition containing dibenzofuran polymerizable compound and application thereof |
| CN113149943A (en) * | 2021-05-10 | 2021-07-23 | 吉林奥来德光电材料股份有限公司 | Fluorescent compound, preparation method thereof and organic electroluminescent device comprising same |
| CN113149943B (en) * | 2021-05-10 | 2023-08-22 | 吉林奥来德光电材料股份有限公司 | Fluorescent compound, preparation method thereof and organic electroluminescent device comprising fluorescent compound |
| CN113913194A (en) * | 2021-10-22 | 2022-01-11 | 北京云基科技有限公司 | Fluorine-containing liquid crystal compound and application thereof |
| CN114149397A (en) * | 2021-12-06 | 2022-03-08 | 江苏创拓新材料有限公司 | Dibenzofurans-based polymerizable compound and preparation method and application thereof |
| CN114149397B (en) * | 2021-12-06 | 2023-11-07 | 江苏创拓新材料有限公司 | Dibenzofurane-based polymerizable compound, preparation method and application thereof |
| WO2023134598A1 (en) * | 2022-01-13 | 2023-07-20 | 烟台显华科技集团股份有限公司 | Polymerisable compound, composition, and liquid crystal display device |
| CN114381279A (en) * | 2022-01-17 | 2022-04-22 | 烟台显华科技集团股份有限公司 | Polymerizable compound, composition, and liquid crystal display device |
| TWI810035B (en) * | 2022-01-17 | 2023-07-21 | 大陸商煙台顯華科技集團股份有限公司 | Polymeric compound, composition and liquid crystal display device |
| CN114381279B (en) * | 2022-01-17 | 2024-01-30 | 烟台显华科技集团股份有限公司 | Polymerizable compound, composition, and liquid crystal display device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110343082A (en) | A kind of dibenzofurans class can poly- property compound and its application | |
| CN105143164B (en) | Liquid crystal compounds, liquid-crystal composition and liquid crystal display element | |
| KR102071090B1 (en) | Negative dielectric anisotropic liquid crystal mixture | |
| CN104245757B (en) | Polymerizable compound, polymer thereof, liquid crystal composition, and liquid crystal display element | |
| CN110407783A (en) | A kind of benzofurans can poly- property compound and its application | |
| KR20190074987A (en) | Liquid crystal composition and liquid crystal display element | |
| CN110343531A (en) | A kind of dibenzothiophenes class can poly- property compound and its application | |
| JP5333685B2 (en) | Compound, polymer, liquid crystal alignment layer, liquid crystal display element and optical anisotropic body | |
| CN110386917A (en) | A kind of novel dibenzothiophenes class can poly- property compound and its application | |
| WO2010134430A1 (en) | Chlorobenzene derivative, optically isotropic liquid crystal medium, and optical element | |
| CN110386912A (en) | A kind of novel dibenzofurans class can poly- property compound and its application | |
| TWI694068B (en) | Liquid crystal compound with benzothiophene, liquid crystal composition and liquid crystal display element | |
| TWI550074B (en) | Polymerizable compound, composition, polymer and usage thereof, and liquid crystal display element | |
| KR20130133214A (en) | Compound having dihydrophenanthrene, liquid crystal composition and liquid crystal display device | |
| CN109486499A (en) | Liquid crystal compounds, liquid-crystal composition and the liquid crystal display element that dielectric anisotropy with fluorine xenyl is negative | |
| CN106565652A (en) | Compound having tetrahydropyran ring, liquid crystal composition and liquid crystal display device | |
| CN107848955A (en) | Polymerism polar compound, liquid-crystal composition and liquid crystal display cells | |
| CN113214083B (en) | Self-alignment polymerizable compound and application thereof | |
| CN110358547A (en) | A kind of novel polymerizable compound and its application | |
| CN110407803A (en) | A kind of benzothiophene kind can poly- property compound and its application | |
| WO2014065293A1 (en) | Liquid-crystal compound, liquid-crystalline medium and optical element | |
| CN113149839B (en) | Self-aligned liquid crystal medium compound and application thereof | |
| CN110452202A (en) | A kind of novel benzofurans polymerizability compound and its application | |
| JP6115303B2 (en) | Phenol compound having carbonyl group as adjacent group and use thereof | |
| CN110484278A (en) | A kind of novel biphenyl class polymerizability compound and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20191018 |
|
| WW01 | Invention patent application withdrawn after publication |