CN110343531A - A kind of dibenzothiophenes class can poly- property compound and its application - Google Patents
A kind of dibenzothiophenes class can poly- property compound and its application Download PDFInfo
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- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
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Abstract
It can poly- property compound and its application the present invention relates to a kind of dibenzothiophenes class, the compound has the structure as shown in general formula I, polymerizable liquid crystal compound of the present invention is compared to the prior art, it is more preferable with good dissolubility, orientation effect, rate of polymerization is faster, polymerization is more complete, and residual is lower, shows bad problem to largely improve.Further, liquid-crystal composition containing the compound has lower viscosity, quick response may be implemented, there is moderate dielectric anisotropy △ ￡ simultaneously, liquid crystal display element or liquid crystal display comprising the liquid-crystal composition have the performances such as wider nematic temperature range, suitable or higher birefringence anisotropy △ n, higher resistivity, good anti-ultraviolet property, high charge retention rate and low-steam pressure.
Description
Technical field
The invention belongs to liquid-crystal compounds and its application field, be related to a kind of dibenzothiophenes class can poly- property compound and its
Using.
Background technique
In recent years liquid crystal display device development it is more and more rapider, liquid crystal material as environmentally conscious materials information display material,
Application in the fields such as organic optoelectronic material has great researching value and fine application prospect, also develops inhomogeneity
Type, such as vehicle-mounted small-sized liquid crystal display device, portable liquid crystal device, ultrathin liquid crystal display device etc., this field is opened
Hair making progress, by taking TV as an example, its main feature is that it is light-weight, take up space small, conveniently moving, there are also notebook type individual
Computer, palm PC, mobile phone etc., commercial TFT-LCD product use TN display pattern substantially, and greatest problem is visual angle
It is narrow.With the increase of product size, application especially in the field TV has the characteristics that the IPS display pattern of wide view angle, VA are aobvious
Show that mode is successively developed and is applied, be based especially on the improvement of VA display pattern, is taken up in order of priority in each major company
Breakthrough development is obtained, this depends primarily on wide angle of visibility, high contrast possessed by VA mode itself and without friction
The advantages such as orientation, then have and be exactly, the contrast that VA mode is shown is to the optical anisotropy (Dn) of liquid crystal, the thickness of liquid crystal cell
(d) smaller with the wavelength of incident light (λ) dependence, degree, this mode of VA will be made to become the display technology of great prospect.
But liquid crystal media used in the display element of the active array addressing mode of VA mode etc., itself is simultaneously imperfect,
Such as 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
The disadvantages of.At this point, a little novel VA display technologies are quietly given birth to: as PSVA technology realizes the similar wide visual field MVA/PVA
Angle display pattern also simplifies CF technique, to improve aperture opening ratio while reducing CF cost, can also obtain higher
Brightness, and then obtain higher contrast.Further, since entire liquid crystal has pre-tilt angle, there is no domino delay phenomenon,
The faster response time can also be obtained under the driving voltage maintained like, image retention level will not be affected, but due to
Fine Slit dense distribution electrode in pixel, therefore if electrode width cannot be uniformly distributed, it is easy to there is asking for display unevenness
Topic.As UVVA technology, due to not having Slit structure in TFT side, pixel electrode occurs on the basis of keeping PSVA technical advantage
Show that improvement is also obtained in uneven problem caused by width is uneven.Although display device is constantly developing, people are also wanted
Have been devoted to study new liquid-crystal compounds, obtain so that liquid crystal media and its performance applied to display device constantly forward
Development.
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 PSA
It in terms of VA, is very important using the high VHR after the irradiation of (UV) light, otherwise will lead to final display and image retention etc. occur and ask
Topic.Up to the present, the combination of not all LC mixture and polymerizable components composition is adapted to PSA display.This
Mainly due to there is no inclination angle to occur or occur insufficient to incline after polymerizable unit is too short for UV sensibility wavelength or illumination
The homogeneity of angle or polymerizable components after illumination is poor, or because VHR is lower for TFT display application after UV
Etc. influence.
Accordingly, there exist for can apply in optically anisotropic body and polymer stabilized liquid crystal display element can
The needs of poly- property compound.
Summary of the invention
The first object of the present invention be to provide a kind of dibenzothiophenes class can poly- property compound, polymerism liquid of the present invention
Brilliant compound is compared to the prior art, more preferable with good dissolubility, orientation effect, and rate of polymerization faster, polymerize completeer
Entirely, residual is lower, shows bad problem to largely improve.
Liquid-crystal composition containing the compound has lower viscosity, quick response may be implemented, while having moderate
Dielectric anisotropy A ￡, liquid crystal display element or liquid crystal display comprising the liquid-crystal composition have wider nematic phase
Temperature range, suitable or higher birefringence anisotropy A n, higher resistivity, good anti-ultraviolet property, height
The performances such as charge conservation rate and low-steam pressure.
Liquid-crystal compounds of the present invention, has the following structure:
Wherein, the P1、P2And P3It is identical or different, each independently represent ethyleneoxy, acrylate-based, methyl-prop
Olefin(e) acid ester group, fluoropropenes acid ester group, chloropropene perester radical or oxetanyl or epoxy group；
The L1、L2It is identical or different, each independently represent-F ,-Cl ,-CN ,-NO2、-CH3、-C2H5、-C(CH3)3、-
CH(CH3)2、-CH2CH(CH3)C2H5、-OCH3、-OC2H5、-COCH3、-COC2H5、-COOCH3、-COOC2H5、-CF3、-OCF3、-
OCHF2Or-OC2F5；
The Z1、Z4It is identical or different, each independently represent singly-bound ,-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-
CO-O- ,-CH=N- ,-N=CH- ,-N=N- ,-C ≡ C-, C1-C12One of alkylidene or alkenyl, the C1-C12Alkylene
Base or C2-C12Alkenyl in one or more hydrogen atoms can be replaced each independently by-F ,-Cl or-CN, and one
Or multiple non-conterminous-CH2Group can each independently by-O- ,-S- ,-NH- ,-CO ,-COO- ,-OCO- ,-OCOO- ,-
SCO- ,-COS- are replaced in a manner of not being connected directly mutually；
The Z2、Z3It is identical or different, each independently represent singly-bound ,-O-, C1-C12Alkylidene or C2-C12Alkenyl,
The C1-C12In one or more hydrogen atoms can be replaced each independently by-F ,-Cl or-CN, and it is one or more not
Adjacent-CH2Group can each independently by-O- ,-S- ,-NH- ,-CO- ,-COO- ,-OCO- ,-OCOO- ,-SCO- ,-
COS- is replaced in a manner of not being connected directly mutually；
The ring A, ring B are identical or different, each independently represent Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-Asia ring
The 1,4- phenylene that hexenyl or 1-4 hydrogen atom are replaced by F；M, n each independently represent 0 or 1；r1、r2Table each independently
Show 0,1,2 or 3.
As the preferred technical solution of the present invention:
In general formula I, about the P1、P2And P3:
Preferably, the P1、P2And P3It is identical or different, each independently represent ethyleneoxy, acrylate-based, methyl
Acrylate-based, fluoropropenes acid ester group or chloropropene perester radical；
It is highly preferred that the P1、P2And P3It is identical or different, it is described to each independently represent acrylate-based, metering system
Perester radical, fluoropropenes acid ester group or chloropropene perester radical.
In general formula I, about the L1、L2: preferably, the L1、L2It is identical or different, each independently represent-F ,-
Cl、-CN、-NO2、-CH3、-C2H5、-OCH3、-OC2H5、-CF3、-OCF3、-OCHF2Or-OC2F5；It is highly preferred that the L1、L2Phase
It is same or different, each independently represent-F ,-Cl ,-CN ,-CH3、-OCH3、-CF3、-OCF3Or-OCHF2；It is further preferred that institute
State L1、L2It is identical or different, each independently represent-F ,-Cl.
In general formula I, about Z1And Z4: preferably, the Z1、Z4It is identical or different, each independently represent singly-bound ,-
O-、-S-、-COO-、-C≡C-、C1-C12Alkylidene or alkenyl, the C1-C12Alkylidene or C2-C12Alkenyl in
One or more hydrogen atoms can be replaced by-F ,-Cl or-CN each independently, and one or more non-conterminous CH2Group
It can be each independently by-O- ,-S- ,-NH- ,-CO- ,-COO- ,-OCO- ,-OCOO- ,-SCO- ,-COS- with mutually not direct
Connected mode replaces；It is highly preferred that the Z1、Z4It is identical or different, each independently represent singly-bound ,-O- or C1-C8Asia
Alkyl or C2-C8Alkenyl, the C1-C8Alkylidene or C2-C8Alkenyl in one or more hydrogen atoms can be respective
Independently replaced by F, Cl or CN；It is further preferred that the Z1、Z4It is identical or different, each independently represent singly-bound ,-O-
Or C1-C5Alkylidene.
In general formula I, about Z2、Z3: preferably, the Z2、Z3It is identical or different, each independently represent singly-bound ,-O-,
C1-C6Alkylidene or C2-C6Alkenyl, the C1-C6Alkylidene or C2-C6Alkenyl in one or more hydrogen it is former
Son can be replaced by-F ,-Cl or-CN each independently, and one or more non-conterminous CH2Group can be each independently
It is replaced in a manner of not being connected directly mutually by-O- ,-S- ,-CO ,-COO；It is highly preferred that the Z2、Z3It is identical or different, respectively
Independently indicate singly-bound ,-O-, C1-C5Alkylidene or C2-C5Alkenyl, the C1-C5Alkylidene or C2-C5Alkenyl
In one or more hydrogen atoms can each independently by-F ,-Cl or-CN replace；It is further preferred that the Z2、Z3It is identical
Or it is different, each independently represent singly-bound, C1-C3Alkylidene.
In general formula I, about ring A, ring B: preferably, the ring A, ring B are identical or different, each independently represent Isosorbide-5-Nitrae-
The 1,4- phenylene that phenylene, 1,4- cyclohexylidene or 1-4 hydrogen atom are replaced by fluorine atoms.
In general formula I, about m, n: preferably, the m, n each independently represent 0 or 1, and m+n≤1.
In general formula I, about r1、r2: preferably, the r1、r2It is each independently selected from 0,1,2 or 3；It is more preferably selected from
0,1 or 2.
Or, it is preferable that in general formula I, the P1、P2And P3It is identical or different, each independently represent ethyleneoxy, third
Olefin(e) acid ester group, methacrylate, fluoropropenes acid ester group or chloropropene perester radical；The L1、L2It is identical or different, respectively
From independently expression-F ,-Cl ,-CN ,-NO2、-CH3、-C2H5、-OCH3、-OC2H5、-CF3、-OCF3、-OCHF2Or-OC2F5；Institute
State Z1、Z4It is identical or different, each independently represent singly-bound ,-O- ,-S- ,-COO- ,-C ≡ C-, C1-C12Alkylidene or C2-C12
Alkenyl, the C1-C12Alkylidene or C2-C12Alkenyl in one or more hydrogen atoms can each independently by-
F ,-Cl or-CN replaces, and one or more non-conterminous-CH2Group can each independently by-O- ,-S- ,-NH- ,-
CO- ,-COO- ,-OCO- ,-OCOO- ,-SCO- ,-COS- are replaced in a manner of not being connected directly mutually；The Z2、Z3It is identical or not
Together, singly-bound ,-O-, C are each independently represented1-C6Alkylidene or C2-C6Alkenyl, the C1-C6Alkylidene or C2-C6
Alkenyl in one or more hydrogen atoms can be replaced in-F ,-Cl or-CN each independently, and it is one or more not
Adjacent-CH2Group can be replaced in a manner of not being connected directly mutually by-O- ,-S- ,-CO- ,-COO- each independently；
The ring A, ring B are identical or different, each independently represent Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene or 1-4 hydrogen atom by fluorine
The 1,4- phenylene that atom replaces；M, n each independently represent 0 or 1, and m+n≤1；r1、r2Each independently represent 0,1,2 or
3。
It is further preferred that in general formula I, P1、P2And P3It is identical or different, each independently represent acrylate-based, first
Base is acrylate-based, fluoropropenes acid ester group or chloropropene perester radical；The L1、L2It is identical or different, table each independently
Show-F ,-Cl ,-CN ,-CH3、-OCH3、-CF3、-OCF3Or-OCHF2；The Z1、Z4It is identical or different, each independently represent list
Key ,-O- or C1-C8Alkylidene or C2-C8Alkenyl, the C1-C8Alkylidene or C2-C8Alkenyl in one or
Multiple hydrogen atoms can be replaced by F, Cl or CN each independently, and one or more non-conterminous-CH2Group can be respective
Independently replaced in a manner of not being connected directly mutually by-O- ,-S- ,-COO-；The Z2、Z3It is identical or different, each independently
Indicate singly-bound ,-O-, C1-C5Alkylidene or C2-C5Alkenyl, the C1-C5Alkylidene or C2-C5Alkenyl in one
A or multiple hydrogen atoms can be replaced by-F ,-Cl or-CN each independently；Ring A, ring B are identical or different, each independently represent
One of the 1,4- phenylene that 1,4- phenylene, 1,4- cyclohexylidene or 1-4 hydrogen atom are replaced by fluorine atoms；M, n are respectively
Independently indicate 0 or 1, and m+n≤1；r1、r2Each independently represent 0,1 or 2.
It is further preferable that in general formula I, P1、P2And P3It is identical or different, each independently represent acrylate-based, methyl
Acrylate-based, fluoropropenes acid ester group or chloropropene perester radical；L1、L2It is identical or different, each independently represent-F ,-
Cl；The Z1、Z4It is identical or different, each independently represent singly-bound ,-O- or C1-C5Alkylidene；The Z2、Z3It is identical or not
Together, singly-bound, C are each independently represented1-C3Alkylidene；The ring A, ring B are identical or different, each independently represent Isosorbide-5-Nitrae-Asia
The 1,4- phenylene that phenyl, 1,4- cyclohexylidene or 1-2 hydrogen atom are replaced by fluorine atoms；The m, n are each independently represented
0 or 1, and m+n≤1；The r1、r2Each independently represent 0,1 or 2.
As still more preferably technical solution of the invention:
In general formula I, wherein the P1、P2And P3It is identical or different, each independently represent acrylate-based, methyl-prop
Olefin(e) acid ester group or fluoropropenes acid ester group；The Z1、Z4It is identical or different, each independently represent singly-bound ,-O-, C1-C5Asia
Alkyl；The Z2、Z3It is identical or different, each independently represent singly-bound or C1-C3Alkylidene,
Wherein, in general formula I, m+n=1, ring A and ring B are Isosorbide-5-Nitrae-phenylene, L1、L2Indicate F, r1And r2Each independently
Selected from 0 or 1；Or, in general formula I, m+n=1, ring A and ring B are that Isosorbide-5-Nitrae-phenylene or 1-2 hydrogen atom are replaced by fluorine atoms
One of Isosorbide-5-Nitrae-phenylene, L1、L2Indicate F, r1+r2=1；Or, in general formula I, m+n=1, ring A and ring B are Isosorbide-5-Nitrae-Asia benzene
One of Isosorbide-5-Nitrae-phenylene that base or 1-2 hydrogen atom are replaced by fluorine atoms, r1And r2It is 0；Or, in general formula I, m+n=
1, ring A and ring B are one of Isosorbide-5-Nitrae-phenylene that Isosorbide-5-Nitrae-phenylene or 1-2 hydrogen atom are replaced by fluorine atoms, r1And r2It is
1；Or, in general formula I, m=1, n=0, ring A are 1 or 4 cyclohexylidene, L1、L2Indicate F, r1And r2Be each independently selected from 0 or
1；Or, in general formula I, m=0, n=1, ring B are 1 or 4 cyclohexylidene, L1、L2Indicate F, r1And r2Be each independently selected from 0 or
1；Or, in general formula I, m=n=0, L1、L2Indicate F, r1And r2It is each independently selected from 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 most preferred technique scheme of the invention, the liquid-crystal compounds is selected from one kind of following compound:
Wherein P1、P2And P3It is identical or different, each independently represent acrylate-based, methacrylate, fluoro third
Olefin(e) acid ester group；Z1、Z4It is identical or different, each independently represent singly-bound ,-O-, C1-C5Alkylidene；Z2、Z3It is identical or different,
Each independently represent singly-bound, C1-C3Alkylidene；
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.Preferably, the compound is in group
Closing the mass percent in object is 0.01~10%, more 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.It has used the liquid-crystal compounds or has contained the LCD compound
The composition of object has wider nematic temperature range, suitable or higher birefringence anisotropy △ n, higher electricity
The performances such as resistance rate, good anti-ultraviolet property, high charge retention rate and low-steam pressure.
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:
Addition bromo- 4, the 6- difluorodiphenyl bithiophene of 40.5g 3- benzyloxy -7- in reaction flask, 20g malonic acid diethyl vinegar,
14g potassium tert-butoxide, 300ml tetrahydrofuran, 50 DEG C~60 DEG C reaction 6h of temperature control are down to room temperature, adjust pH value into dilute hydrochloric acid
Property, conventional post-processing is carried out, light yellow solid (compound BYLC-01-1) 43.5g is recrystallized to give, HPLC:99.4%, yield
85.0%；
(2) synthesis of compound BYLC-01-2:
10.0g aluminum hydride reason and 500mL tetrahydrofuran are added in reaction flask, is cooled to 0 DEG C, 0 DEG C~10 DEG C of temperature control dropwise additions
The solution of 43.5g compound BYLC-01-1 and 100ml tetrahydrofuran composition, rise to room after then keeping 0 DEG C~10 DEG C reaction lh
Temperature reaction 8h, is quenched with acetic acid ethyl ester and is reacted, and adjusts pH value to faintly acid with dilute hydrochloric acid, is carried out conventional post-processing, is obtained class
White solid (compound BYLC-01-2): 30.0g, LC:99.2%, yield: 88.2%；
(2) synthesis of compound BYLC-01-3:
30.0g compound BYLC-01-2,90ml toluene, 60ml ethyl alcohol, 1.5g palladium carbon, hydrogen displacement are added in reaction flask
Three times, 30 DEG C~35 DEG C of temperature control plus the de- benzyl 6h of hydrogen, conventional post-processing is carried out, white solid (compound BYLC-01-3) is obtained:
21.5g, LC:99.6%, yield: 92.7%；
(3) synthesis of compound BYLC-01:
Under nitrogen protection, 21.5g compound BYLC-01-3,25.5g triethylamine and 200mL dichloro are added into reaction flask
Methane is cooled to -10 DEG C, and 25.2g methacrylic chloride is added dropwise in -10 DEG C of temperature control~0 DEG C, is warmed to room temperature reaction 6h and falls reaction solution
Enter in water, neutralized with bicarbonate uranium aqueous solution, carry out conventional post-processing, through chromatogram purification, n-hexane elution, ethyl alcohol recrystallization is obtained
To white solid (compound BYLC-01) 27.3g, LC:99.5%, yield: 76.8%.
Gained white solid BYLC-01 is analyzed using GC-MS, the m/z of product is 514.1 (M+).
1H-NMR(300MHz,CDCl3): 1.35-2.20 (m, 9H), 3.63-4.45 (m, 5H), 5.35-6.45 (m, 6H),
6.65-7.65(m,4H)。
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, 31.0g compound BYLC-01-3,38.4g 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) 38.9g, LC:99.6%, yield: 82.5%.
Gained white solid BYLC-02 is analyzed using GC-MS, the m/z of product is 472.1 (M+).
1H-NMR(300MHz,CDCl3): 2.75-4.45 (m, 5H), 5.63-6.45 (m, 9H), 7.05-7.55 (m, 4H).
Embodiment 3
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 bithiophene of 40.5g 3- benzyloxy -7-, 300ml tetra- are added in reaction flask
Hydrogen furans is cooled to -70 DEG C~-80 DEG C, and 0.13mol n-BuLi is added dropwise, and -70 DEG C~-80 DEG C reaction 1h of temperature control are added dropwise
18.0g 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, recrystallization
Obtain light yellow solid (compound BYLC-03-1) 32.3g, LC:98.5%, yield 87.3%；
(2) synthesis of compound BYLC-03-2:
32.3g compound BYLC-03-1,18.5g are added in reaction flask to bromo-iodobenzene, 18.0g Anhydrous potassium carbonate, 200ml
Toluene, 150ml ethyl alcohol, 150ml water, tetra- triphenylphosphine of 0.3g close palladium, and heating reflux reaction 8h carries out conventional post-processing, obtains
Off-white powder (compound BYLC-03-2): 34.5g, LC:99.3%, yield: 82.6%；
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:
592.1(M+)。
1H-NMR(300MHz,CDCl3): 1.35-2.20 (m, 9H), 3.63-4.45 (m, 5H), 5.65-6.45 (m, 4H),
7.05-8.10(m,8H))。
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 548.1 (M+).
1H-NMR(300MHz,CDCl3): 3.35-4.45 (m, 5H), 5.63-6.45 (m, 9H), 7.05-7.65 (m, 8H).
Embodiment 5
The bromo- 4,6- difluorodiphenyl of 3- benzyloxy -7- is replaced with 3- benzyloxy -7- bromomethyl -4,6- difluorodiphenyl bithiophene
Bithiophene, other conditions analyze gained white solid BYLC-05 using GC-MS with embodiment 1, and the m/z of product is
528.1(M+)。
1H-NMR(300MHz,CDCl3): 1.35-2.55 (m, 8H), 3.03-4.25 (m, 5H), 5.35-6.45 (m, 6H),
7.05-7.50(m,4H)。
Embodiment 6
The synthetic line of prepare compound BYLC-06 is as follows:
Specific step is as follows:
(1) synthesis of compound BYLC-06-1:
Addition 34.2g 3- benzyloxy -7- hydroxyl -4,6- difluorodiphenyl bithiophene in reaction flask, 20.7g Anhydrous potassium carbonate,
Reaction mixture is heated to 60 DEG C by 300mlN, dinethylformamide, and the bromo- 1- propyl alcohol of 20.7g 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) 31.4g, LC:99.2%, yield 78.5%；
(2) synthesis of compound BYLC-06-2:
Under nitrogen protection, 31.4g compound BYLC-06-1,30.8g 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) 30.0g, LC:97.6%, yield 82.5%；
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:
572.1(M+)。
1H-NMR(300MHz,CDCl3): 1.15-2.70 (m, 11H), 3.63-4.25 (m, 6H), 4.95-5.65 (m, 3H),
5.75-6.85(m,4H),7.05-7.75(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:
Specific step is as follows:
(1) synthesis of compound BYLC-07-1:
The bromo- dibenzothiophenes of 36.7g 3- benzyloxy -7-, 19.8g malonic acid diethyl vinegar, uncle 13.9g are added in reaction flask
Butanol potassium, 300ml tetrahydrofuran, 50 DEG C~60 DEG C reaction 6h of temperature control are down to room temperature, adjust pH value to neutrality with dilute hydrochloric acid, into
The conventional post-processing of row, is recrystallized to give light yellow solid (compound BYLC-07-1-1) 36.8g, HPLC:99.5%, yield
86.2%；
(2) synthesis of compound BYLC-07-2-2:
11.2g aluminum hydride reason and 500mL tetrahydrofuran are added in reaction flask, is cooled to 0 DEG C, 0 DEG C~10 DEG C of temperature control dropwise additions
The solution of 36.8g compound BYLC-07-1 and 100ml tetrahydrofuran composition, rise to room after then keeping 0 DEG C~10 DEG C reaction lh
Temperature reaction 8h, is quenched with acetic acid ethyl ester and is reacted, and adjusts pH value to faintly acid with dilute hydrochloric acid, is carried out conventional post-processing, is obtained class
White solid (compound BYLC-07-2): 25.8g, LC:99.4%, yield: 86.4%；
(2) synthesis of compound BYLC-07-3:
25.8g compound BYLC-07-2,90ml toluene, 60ml ethyl alcohol, 1.2g palladium carbon, hydrogen displacement are added in reaction flask
Three times, 30 DEG C~35 DEG C of temperature control plus the de- benzyl 6h of hydrogen, conventional post-processing is carried out, white solid (compound BYLC-01-3) is obtained:
18.2g, LC:99.5%, yield: 93.5%；
(3) synthesis of compound BYLC-07:
Under nitrogen protection, 18.2g compound BYLC-07-3,23.4g triethylamine and 200mL dichloro are added into reaction flask
Methane is cooled to -10 DEG C, and 24.2g methacrylic chloride is added dropwise in -10 DEG C of temperature control~0 DEG C, is warmed to room temperature reaction 6h and falls reaction solution
Enter in water, neutralized with bicarbonate uranium aqueous solution, carry out conventional post-processing, through chromatogram purification, n-hexane elution, ethyl alcohol recrystallization is obtained
To white solid (compound BYLC-07) 23.5g, LC:99.6%, yield: 75.2%.
Gained white solid BYLC-07 is analyzed using GC-MS, the m/z of product is 478.1 (M+).
1H-NMR(300MHz,CDCl3):1.35-2.20(m,9H),3.63-4.45(m,5H),5.35-6.45(m,6H),
6.65-7.65(m,6H)。
Embodiment 8
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-08 is as follows:
Specific step is as follows:
The synthesis of compound BYLC-08:
Under nitrogen protection, 35.0g compound BYLC-07-3,42.0g triethylamine and 250mL dichloro are added into reaction flask
Methane is cooled to -10 DEG C, and 35.2g 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-08) 47.6g, LC:99.7%, yield: 85.5%.
Gained white solid BYLC-08 is analyzed using GC-MS, the m/z of product is 436.1 (M+).
1H-NMR(300MHz,CDCl3):2.75-4.45(m,5H),5.63-6.45(m,9H),7.05-7.55(m,6H)。
Embodiment 9
The synthetic line of prepare compound BYLC-09 is as follows:
Specific step is as follows:
(1) synthesis of compound BYLC-09-1:
Under nitrogen protection, the addition bromo- dibenzothiophenes of 37.0g 3- benzyloxy -7- in reaction flask, 300ml tetrahydrofuran,
- 70 DEG C~-80 DEG C are cooled to, 0.13mol n-BuLi is added dropwise, 18.5g boric acid three is added dropwise in -70 DEG C~-80 DEG C reaction 1h of temperature control
Methyl esters 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-09-1) 28.9g, LC:97.3%, yield 86.5%；
(2) synthesis of compound BYLC-09-2:
28.9g compound BYLC-09-1,16.4g are added in reaction flask to bromo-iodobenzene, 17.8g Anhydrous potassium carbonate, 200ml
Toluene, 150ml ethyl alcohol, 150ml water, tetra- triphenylphosphine of 0.25g close palladium, and heating reflux reaction 8h carries out conventional post-processing, obtains
Off-white powder (compound BYLC-09-2): 32.0g, LC:99.5%, yield: 83.5%；
Other steps are the same as embodiment 1.
Compound BYLC-09: gained white solid BYLC-09 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,9H),3.63-4.45(m,5H),5.65-6.45(m,4H),
7.05-8.10(m,10H))。
Embodiment 10
The structural formula of liquid-crystal compounds are as follows:
Reaction condition is the same as embodiment 1,2.
Gained white solid BYLC-10 is analyzed using GC-MS, the m/z of product is 512.1 (M+).
1H-NMR(300MHz,CDCl3):3.35-4.45(m,5H),5.63-6.45(m,9H),7.05-7.65(m,10H)。
Embodiment 11
The bromo- dibenzothiophenes of 3- benzyloxy -7- is replaced with 3- benzyloxy -7- bromomethyl-dibenzothiophenes, other conditions are same
Embodiment 1 analyzes gained white solid BYLC-11 using GC-MS, and the m/z of product is 492.1 (M+).
1H-NMR(300MHz,CDCl3):1.35-2.55(m,8H),3.03-4.25(m,5H),5.35-6.45(m,6H),
7.05-7.50(m,6H)。
Embodiment 12
The synthetic line of prepare compound BYLC-12 is as follows:
Specific step is as follows:
(1) synthesis of compound BYLC-12-1:
Addition 36.5g 3- benzyloxy -7- hydroxyl-dibenzothiophenes in reaction flask, 21.2g Anhydrous potassium carbonate, 300mlN,
Reaction mixture is heated to 60 DEG C by dinethylformamide, to its be added dropwise the bromo- 1- propyl alcohol of 22.3g 3-, 100 DEG C of temperature control~
110 DEG C of reaction 6h are down to room temperature, carry out conventional post-processing, are recrystallized to give off-white color color solid (compound BYLC-12-1)
31.8g, LC:99.3%, yield 79.6%；
(2) synthesis of compound BYLC-12-2:
Under nitrogen protection, 31.8g compound BYLC-12-1,29.4g triphenylphosphine, 200ml tetrahydro furan are added in reaction flask
It mutters, is cooled to -10 DEG C~0 DEG C, the solution of 17.5g 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-
12-2) 31.0g, LC:98.2%, yield 83.6%；
Other steps are the same as embodiment 1.
Compound BYLC-12: gained white solid BYLC-12 is analyzed using GC-MS, the m/z of product are as follows:
536.1(M+)。
1H-NMR(300MHz,CDCl3):1.15-2.70(m,11H),3.63-4.25(m,6H),4.95-5.65(m,3H),
5.75-6.85(m,6H),7.05-7.75(m,3H)。
Embodiment 13
Reaction condition is the same as embodiment 1,2.
Compound BYLC-13: gained white solid BYLC-13 is analyzed using GC-MS, the m/z of product are as follows:
496.1(M+)。
1H-NMR(300MHz,CDCl3):1.35-2.20(m,9H),3.63-4.45(m,5H),5.35-6.45(m,6H),
6.65-7.65(m,5H)。
Embodiment 14
Reaction condition is the same as embodiment 1,2.
Compound BYLC-14: gained white solid BYLC-08 is analyzed using GC-MS, the m/z of product are as follows:
454.1(M+)。
1H-NMR(300MHz,CDCl3):2.75-4.45(m,5H),5.63-6.45(m,9H),7.05-7.55(m,5H)。
Embodiment 15
Reaction condition is the same as embodiment 1,2.
Compound BYLC-15: gained white solid BYLC-15 is analyzed using GC-MS, the m/z of product are as follows:
574.1(M+)。
1H-NMR(300MHz,CDCl3):1.35-2.20(m,9H),3.63-4.45(m,5H),5.65-6.45(m,4H),
7.05-8.10(m,9H))。
Embodiment 16
Reaction condition is the same as embodiment 1,2.
Compound BYLC-16: gained white solid BYLC-16 is analyzed using GC-MS, the m/z of product are as follows:
532.1(M+)。
1H-NMR(300MHz,CDCl3):3.35-4.45(m,5H),5.63-6.45(m,9H),7.05-7.65(m,9H)。
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.
Embodiment 18
The property of mixture 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
Object PM-1.
The liquid-crystal composition of polymerizable compound BYLC-02 to 99.7% provided by the embodiment 2 of addition 0.3%
In BHR87800, uniform dissolution obtains mixture PM-2.
The liquid-crystal composition of polymerizable compound BYLC-07 to 99.7% provided by the embodiment 7 of addition 0.3%
In BHR87800, uniform dissolution obtains mixture PM-3.
The liquid-crystal composition of polymerizable compound BYLC-08 to 99.7% provided by the embodiment 8 of addition 0.3%
In BHR87800, uniform dissolution obtains mixture 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.It uses
PM-1, PM-2, PM-3, PM-4 injection gap are 4.0 μm and had in the testing cassete of vertical orientation by priming by vacuum method.On one side
Application frequency is 60HZ, and driving voltage is the square wave of 16V, irradiates ultraviolet light to testing cassete with high-pressure mercury ultraviolet lamp on one side, adjusts
The exposure intensity for saving box surface is 30mW/cm2, 600s is irradiated, the liquid crystal display element of the vertical orientation after being polymerize makes
Pre-tilt angle is measured with LCT-5016E liquid crystal electro-optic parameter tester, testing cassete is then decomposed, is surveyed using high-efficient liquid phase chromatogram HPLC
Determine remaining polymerizable compound in liquid-crystal composition, is as a result summarized in table 2 and table 3.
Comparative example 1
In the liquid-crystal composition BHR87800 of the polymerizable compound to 99.7% of the CP of addition 0.3%, uniform dissolution is obtained
To mixture PM-5.The physical property of PM-5 and the physical property of said mixture BHR87800 are almost without difference.Use priming by vacuum method
PM-5 injection gap is 4.0 μm and had in the testing cassete of vertical orientation.Applying frequency on one side is 60HZ, and driving voltage is
The square wave of 16V, 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 joined using LCT-5016E liquid crystal electro-optic
Number tester measures pre-tilt angle, then decomposes testing cassete, using remaining in high-efficient liquid phase chromatogram HPLC measurement liquid-crystal composition
As a result polymerizable compound is summarized in table 2 and table 3.
Pre-tilt angle summary sheet before and after 2 UV of table
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 dibenzothiophenes class can poly- property compound, which is characterized in that have the following structure:
Wherein, the P1、P2And P3It is identical or different, each independently represent ethyleneoxy, acrylate-based, methacrylic acid
Ester group, fluoropropenes acid ester group, chloropropene perester radical or oxetanyl or epoxy group；
The L1、L2It is identical or different, each independently represent-F ,-Cl ,-CN ,-NO2、-CH3、-C2H5、-C(CH3)3、-CH
(CH3)2、-CH2CH(CH3)C2H5、-OCH3、-OC2H5、-COCH3、-COC2H5、-COOCH3、-COOC2H5、-CF3、-OCF3、-
OCHF2Or-OC2F5；
The Z1、Z4It is identical or different, each independently represent singly-bound ,-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-
O- ,-CH=N- ,-N=CH- ,-N=N- ,-C ≡ C-, C1-C12One of alkylidene or alkenyl, the C1-C12Alkylidene
Or C2-C12Alkenyl in one or more hydrogen atoms can each independently by-F ,-Cl or-CN replace, and one or
Multiple non-conterminous-CH2Group can each independently by-O- ,-S- ,-NH- ,-CO ,-COO- ,-OCO- ,-OCOO- ,-
SCO- ,-COS- are replaced in a manner of not being connected directly mutually；
The Z2、Z3It is identical or different, each independently represent singly-bound ,-O-, C1-C12Alkylidene or C2-C12Alkenyl, it is described
C1-C12In one or more hydrogen atoms can be replaced each independently by-F ,-Cl or-CN, and it is one or more non-conterminous
- CH2Group can each independently by-O- ,-S- ,-NH- ,-CO- ,-COO- ,-OCO- ,-OCOO--SCO- ,-COS- with
The mode not being connected directly mutually replaces；
The ring A, ring B are identical or different, each independently represent Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-Asia cyclohexene
The 1,4- phenylene that base or 1-4 hydrogen atom are replaced by F；
M, n each independently represent 0 or 1；
r1、r2Each independently represent 0,1,2 or 3.
2. compound according to claim 1, which is characterized in that the P1、P2And P3It is identical or different, each independently
Indicate ethyleneoxy, acrylate-based, methacrylate, fluoropropenes acid ester group or chloropropene perester radical；
Preferably, the P1、P2And P3It is identical or different, it is described to each independently represent acrylate-based, methacrylate
Base, fluoropropenes acid ester group or chloropropene perester radical.
3. compound according to claim 1 or 2, which is characterized in that the L1、L2It is identical or different, table each independently
Show-F ,-Cl ,-CN ,-NO2、-CH3、-C2H5、-OCH3、-OC2H5、-CF3、-OCF3、-OCHF2Or-OC2F5；
Preferably, the L1、L2It is identical or different, each independently represent-F ,-Cl ,-CN ,-CH3、-OCH3、-CF3、-OCF3
Or-OCHF2；
It is further preferred that the L1、L2It is identical or different, each independently represent-F ,-Cl.
4. compound according to claim 1-3, which is characterized in that
The Z1、Z4It is identical or different, each independently represent singly-bound ,-O- or C1-C8Alkylidene or C2-C8Alkenyl, institute
State C1-C8Alkylidene or C2-C8Alkenyl in one or more hydrogen atoms can be replaced each independently by F, Cl or CN；
Preferably, the Z1、Z4It is identical or different, each independently represent singly-bound ,-O- or C1-C5Alkylidene.
5. compound according to claim 1-4, which is characterized in that the Z2、Z3It is identical or different, respectively solely
On the spot indicate singly-bound ,-O-, C1-C6Alkylidene or C2-C6Alkenyl, the C1-C6Alkylidene or C2-C6Alkenyl in
One or more hydrogen atoms can be replaced each independently by-F ,-Cl or-CN, and one or more non-conterminous-CH2-
Group can be replaced in a manner of not being connected directly mutually by-O- ,-S- ,-CO ,-COO each independently；
Preferably, the Z2、Z3It is identical or different, each independently represent singly-bound ,-O-, C1-C5Alkylidene or alkenyl, it is described
C1-C5Alkylidene or C2-C5Alkenyl in one or more hydrogen atoms can be taken each independently by-F ,-Cl or-CN
Generation；
It is further preferred that the Z2、Z3It is identical or different, each independently represent singly-bound, C1-C3Alkylidene.
6. compound according to claim 1-5, which is characterized in that the ring A, ring B are identical or different, respectively
Independently indicate the 1,4- phenylene that 1,4- phenylene, 1,4- cyclohexylidene or 1-4 hydrogen atom are replaced by fluorine atoms；
And/or the m, n each independently represent 0 or 1, and m+n≤1；
And/or the r1、r2It is each independently selected from 0,1 or 2.
7. compound according to claim 1-6, which is characterized in that in general formula I, the P1、P2And P3It is identical
Or it is different, each independently represent acrylate-based, methacrylate or fluoropropenes acid ester group；
The Z1、Z4It is identical or different, each independently represent singly-bound ,-O-, C1-C5Alkylidene；
The Z2、Z3It is identical or different, each independently represent singly-bound or C1-C3Alkylidene；
Wherein, m+n=1, ring A and ring B are Isosorbide-5-Nitrae-phenylene, L1、L2Indicate F, r1And r2It is each independently selected from 0 or 1；
Or, one in Isosorbide-5-Nitrae-phenylene that m+n=1, ring A and ring B are replaced by fluorine atoms for Isosorbide-5-Nitrae-phenylene or 1-2 hydrogen atom
Kind, L1、L2Indicate F, r1+r2=1；
Or, one in Isosorbide-5-Nitrae-phenylene that m+n=1, ring A and ring B are replaced by fluorine atoms for Isosorbide-5-Nitrae-phenylene or 1-2 hydrogen atom
Kind, r1And r2It is 0；
Or, one in Isosorbide-5-Nitrae-phenylene that m+n=1, ring A and ring B are replaced by fluorine atoms for Isosorbide-5-Nitrae-phenylene or 1-2 hydrogen atom
Kind, r1And r2It is 1；
Or, m=1, n=0, ring A is 1 or 4 cyclohexylidene, L1、L2Indicate F, r1And r2It is each independently selected from 0 or 1；
Or, m=0, n=1, ring B is 1 or 4 cyclohexylidene, L1、L2Indicate F, r1And r2It is each independently selected from 0 or 1；
Or, m=n=0, L1、L2Indicate F, r1And r2It is each independently selected from 0 or 1.
8. compound according to claim 1, which is characterized in that one kind selected from following compound:
Wherein P1、P2And P3It is identical or different, each independently represent acrylate-based, methacrylate or fluoropropenes
Perester radical；
Z1、Z4It is identical or different, each independently represent singly-bound ,-O-, C1-C5Alkylidene；
Z2、Z3It is identical or different, each independently represent singly-bound, C1-C3Alkylidene；
Preferably, the compound is selected from one of following compound:
9. a kind of liquid-crystal composition, which is characterized in that contain the described in any item compounds of claim 1-8；
It is preferred that the mass percent of the compound in the composition is 0.01~10%, more preferably 0.01~5%, into
One step is 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 further preferred that the liquid crystal display device include TN, ADS,
VA, PSVA, FFS or IPS liquid crystal display.
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| CN110922983A (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 dibenzothiophene polymerizable monomer and application thereof |
| CN114394953A (en) * | 2022-01-13 | 2022-04-26 | 烟台显华科技集团股份有限公司 | Polymerizable compound, composition, and liquid crystal display device |
| TWI764733B (en) * | 2020-06-16 | 2022-05-11 | 大陸商石家莊誠志永華顯示材料有限公司 | Liquid crystal composition, liquid crystal display element, liquid crystal display |
| TWI769856B (en) * | 2020-06-28 | 2022-07-01 | 大陸商江蘇和成顯示科技有限公司 | A liquid crystal composition comprising dibenzo derivatives and liquid crystal display device |
| TWI769857B (en) * | 2020-06-28 | 2022-07-01 | 大陸商江蘇和成顯示科技有限公司 | A liquid crystal composition comprising dibenzo derivatives and liquid crystal display device |
| CN115247067A (en) * | 2021-04-27 | 2022-10-28 | 江苏和成显示科技有限公司 | Liquid crystal compound, liquid crystal composition and liquid crystal display device |
| WO2023134596A1 (en) * | 2022-01-13 | 2023-07-20 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropic liquid crystal composition, optical anisotropier, and liquid crystal display component |
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| CN110922983A (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 dibenzothiophene polymerizable monomer and application thereof |
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| TWI769856B (en) * | 2020-06-28 | 2022-07-01 | 大陸商江蘇和成顯示科技有限公司 | A liquid crystal composition comprising dibenzo derivatives and liquid crystal display device |
| TWI769857B (en) * | 2020-06-28 | 2022-07-01 | 大陸商江蘇和成顯示科技有限公司 | A liquid crystal composition comprising dibenzo derivatives and liquid crystal display device |
| CN115247067A (en) * | 2021-04-27 | 2022-10-28 | 江苏和成显示科技有限公司 | Liquid crystal compound, liquid crystal composition and liquid crystal display device |
| CN115247067B (en) * | 2021-04-27 | 2024-04-23 | 江苏和成显示科技有限公司 | Liquid crystal compound, liquid crystal composition thereof and liquid crystal display device |
| CN114394953A (en) * | 2022-01-13 | 2022-04-26 | 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 |
| WO2023134596A1 (en) * | 2022-01-13 | 2023-07-20 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropic liquid crystal composition, optical anisotropier, and liquid crystal display component |
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