CN110386917A - A kind of novel dibenzothiophenes class can poly- property compound and its application - Google Patents
A kind of novel dibenzothiophenes class can poly- property compound and its application Download PDFInfo
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- CN110386917A CN110386917A CN201810338167.7A CN201810338167A CN110386917A CN 110386917 A CN110386917 A CN 110386917A CN 201810338167 A CN201810338167 A CN 201810338167A CN 110386917 A CN110386917 A CN 110386917A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/76—Dibenzothiophenes
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- 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
- C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
Abstract
The invention belongs to liquid-crystal compounds and its application field, being related to a kind of novel dibenzothiophenes class can poly- property compound and its application.It is described can poly- property compound have general formula I shown in structure.The polymerizable liquid crystal compound is compared to the prior art, more preferable with good dissolubility, orientation effect, and faster, polymerization is more complete for rate of polymerization, and residual is lower, shows bad problem to largely improve.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, being related to a kind of novel dibenzothiophenes class can poly- property compound
And its application.
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, In
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 novel dibenzothiophenes class can poly- property compound, polymerization of the present invention
Property liquid-crystal compounds compared to the prior art, it is more preferable with good dissolubility, orientation effect, rate of polymerization faster, polymerization
More completely, 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,
The performances such as high charge retention rate and low-steam pressure.
Liquid-crystal compounds of the present invention, has the following structure:
Wherein, P1、P2And P3It is identical or different, each independently represent ethyleneoxy, acrylate-based, methacrylic acid
Ester group, fluoropropenes acid ester group, chloropropene perester radical, oxetanyl or epoxy group；
L1、L2、L3、L4It 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；
Z1、Z2、Z3It 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-C12Alkylidene or C2-C12One of alkenyl, it is described
C1-C12Alkylidene or C2-C12Alkenyl in one or more hydrogen atoms can be taken each independently by-F ,-Cl or-CN
Generation, 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；
r1、r2、r3、r4Each independently represent 0,1,2 or 3；
M, n each independently represent 0 or 1, and m, n are not 0 simultaneously.
As the preferred technical solution of the present invention, in general formula I, about P1、P2And P3: preferably, P1、P2And P3It is identical or
Difference each independently represents ethyleneoxy, acrylate-based, methacrylate, fluoropropenes acid ester group or chloro third
Olefin(e) acid ester group；It is highly preferred that P1、P2And P3It is identical or different, each independently represent acrylate-based, methacrylate,
Fluoropropenes acid ester group or chloropropene perester radical；Further, P1、P2And P3It is identical or different, each independently represent third
Olefin(e) acid ester group, methacrylate or fluoropropenes acid ester group；
About L1、L2、L3、L4: preferably, L1、L2、L3、L4It is identical or different, each independently represent-F ,-Cl ,-CN ,-
NO2、-CH3、-C2H5、-OCH3、-OC2H5、-CF3、-OCF3、-OCHF2Or-OC2F5；It is highly preferred that L1、L2、L3、L4It is identical or not
Together ,-F ,-Cl ,-CN ,-CH are each independently represented3、-C2H5、-OCH3、-OC2H5Or-CF3；Further, L1、L2It is identical or
Difference each independently represents-F ,-Cl；And/or L3、L4It is identical or different, each independently represent-F ,-Cl-, CH3、-
C2H5、-OCH3Or-OC2H5；
About Z1、Z2、Z3: preferably, Z1、Z2、Z3It is identical or different, each independently represent singly-bound ,-O-, C1-C8Asia
Alkyl or C2-C8Alkenyl, and one or more non-conterminous CH2Group can each independently by-O- ,-S- or-
COO- is replaced in a manner of not being connected directly mutually；It is highly preferred that Z1、Z2、Z3It is identical or different, each independently represent list
Key ,-O-, C1-C8Alkylidene, alkoxy or C2-C8Alkenyl；Further, Z1、Z2、Z3It is identical or different, respectively solely
On the spot indicate singly-bound ,-O-, C1-C6Alkylidene or alkoxy；
About r1、r2、r3、r4: preferably, r1、r2、r3、r4Each independently represent 0,1 or 2；It is highly preferred that r1、r2Respectively
From independently expression 0 or 1.
Compound of the present invention, in general formula I, it is preferable that P1、P2And P3It is identical or different, each independently represent second
Alkenyloxy group, acrylate-based, methacrylate, fluoropropenes acid ester group or chloropropene perester radical；
L1、L2、L3、L4It is identical or different, each independently represent-F ,-Cl ,-CN ,-NO2、-CH3、-C2H5、-OCH3、-
OC2H5、-CF3、-OCF3、-OCHF2Or-OC2F5；
Z1、Z2、Z3It is identical or different, each independently represent singly-bound ,-O-, C1-C8Alkylidene or alkenyl, and one
A or multiple non-conterminous CH2Group can each independently by-O- ,-S- or-COO- in a manner of not being connected directly mutually generation
It replaces；
r1、r2、r3、r4Each independently represent 0,1 or 2；
M, n each independently represent 0 or 1, and m, n are not 0, m+n=1 simultaneously.
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；
L1、L2、L3、L4It is identical or different, each independently represent-F ,-Cl ,-CN ,-CH3、-C2H5、-OCH3、-OC2H5
Or-CF3；
Z1、Z2、Z3It is identical or different, each independently represent singly-bound ,-O-, C1-C8Alkylidene, alkoxy or C2-C8's
Alkenyl；
r1、r2、r3、r4Each independently represent 0,1 or 2；
M, n each independently represent 0 or 1, and m, n are not 0 simultaneously.
It is highly preferred that P1、P2And P3It is identical or different, each independently represent acrylate-based, methacrylate or
Fluoropropenes acid ester group；
L1、L2It is identical or different, each independently represent-F ,-Cl；
L3、L4It is identical or different, each independently represent-F ,-Cl-, CH3、-C2H5、-OCH3Or-OC2H5；
Z1、Z2、Z3It is identical or different, each independently represent singly-bound ,-O-, C1-C6Alkylidene or alkoxy；
r1、r2Each independently represent 0 or 1；
r3、r4Each independently represent 0,1 or 2；
M, n each independently represent 0 or 1, and m, n are not 0, m+n=1 simultaneously.
As technical solution still more preferably of the invention, in general formula I, wherein m=0, L1、L2、L4For F or
Cl, r1、r2Each independently represent 0 or 1, r4Indicate 0,1 or 2；
Or, m=0, L1、L2For F or Cl, L4Expression-CH3、-OCH3、-C2H5Or-OC2H5One of, r1、r2It is respectively independent
Ground indicates 0 or 1, r4Indicate 1；
Or, n=0, L1、L2、L3For F or Cl, r1、r2Each independently represent 0 or 1, r3Indicate 0,1 or 2；
Or, n=0, L1、L2For F or Cl, L3Expression-CH3、-OCH3、-C2H5Or-OC2H5One of, r1、r2It is respectively independent
Ground indicates 0 or 1, r3Indicate 1；
More preferable P1、P2、P3Indicate methacrylate or acrylate-based；Z1、Z2、Z3It indicates independently of one another single
Key ,-O-, C1-C6Alkylidene or alkoxy.
As most preferred technique scheme of the invention, the compound is selected from one kind of following compound:
Preferably, in above-mentioned general formula I-1~general formula I-30, P1、P2And P3It is identical or different, each independently represent third
Olefin(e) acid ester group, methacrylate, fluoropropenes acid ester group；Z1、Z2、Z3It is identical or different, each independently represent singly-bound ,-
O-、C1-C6Alkylidene or alkoxy.
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 A 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:
Bromo- 4, the 6- difluorodiphenyl bithiophene of 40.5g 3- benzyloxy -7-, 15.5g3,4- dihydroxy benzenes are added in reaction flask
Boric acid, 14.0g Anhydrous potassium carbonate, 200ml toluene, 150ml ethyl alcohol, 150ml water, tetra- triphenylphosphine of 0.3g close palladium, are heated to reflux
8h is reacted, conventional post-processing is carried out, obtains off-white powder (compound BYLC-01-1) 37.3g, HPLC:99.5%, yield
86.0%；
(2) synthesis of compound BYLC-01-2:
37.3g compound BYLC-01-1,90ml 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-01-2) is obtained:
27.7g, LC:99.5%, yield: 93.8%；
(3) synthesis of compound BYLC-01:
Under nitrogen protection, 27.7g compound BYLC-01-2,28.5g triethylamine and 200mL dichloro are added into reaction flask
Methane is cooled to -10 DEG C, and 29.5g 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) 33.3g, LC:99.6%, yield: 75.5%.
Gained white solid BYLC-01 is analyzed using GC-MS, the m/z of product is 548.1 (M+).
1H-NMR(300MHz,CDCl3):1.55-2.15(m,9H),5.35-6.65(m,6H),7.25-7.95(m,7H)。
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, 35.0g compound BYLC-01-2,32.5g triethylamine and 250mL dichloro are added into reaction flask
Methane is cooled to -10 DEG C, and 28.0g 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) 43.0g, LC:99.7%, yield: 83.6%.
Gained white solid BYLC-02 is analyzed using GC-MS, the m/z of product is 506.1 (M+).
1H-NMR(300MHz,CDCl3):5.15-5.75(m,3H),5.85-6.45(m,6H),7.15-7.95(m,7H)。
Embodiment 3
Bromo- 4, the 6- difluorodiphenyl bithiophene of 3- benzyloxy -7- is replaced with 3- benzyloxy -7- bromodiphenylthiophene, reacts item
Part is the same as embodiment 1,2.
Gained white solid BYLC-03 is analyzed using GC-MS, the m/z of product is 470.1 (M+).
1H-NMR(300MHz,CDCl3):5.15-5.75(m,3H),5.85-6.45(m,6H),7.15-7.95(m,9H)。
Embodiment 4
Bromo- 4, the 6- difluorodiphenyl bithiophene of 3- benzyloxy -7- is replaced with 3- benzyloxy -7- bromodiphenylthiophene, reacts item
Part is the same as embodiment 1,2.
Gained white solid BYLC-04 is analyzed using GC-MS, the m/z of product is 512.1 (M+).
1H-NMR(300MHz,CDCl3):1.55-2.15(m,9H),5.35-6.65(m,6H),7.25-7.95(m,9H)。
Embodiment 5
3,4- dihydroxy benzenes boric acid is replaced with 3,5- dihydroxy benzenes boric acid, reaction condition is the same as embodiment 1,2.
Gained white solid BYLC-05 is analyzed using GC-MS, the m/z of product is 548.1 (M+).
1H-NMR(300MHz,CDCl3):1.45-2.25(m,9H),5.25-6.55(m,6H),7.15-8.15(m,7H)。
Embodiment 6
3,4- dihydroxy benzenes boric acid is replaced with 3,5- dihydroxy benzenes boric acid, reaction condition is the same as embodiment 1,2.
Gained white solid BYLC-06 is analyzed using GC-MS, the m/z of product is 506.1 (M+).
1H-NMR(300MHz,CDCl3):5.05-5.65(m,3H),5.75-6.55(m,6H),7.20-8.15(m,7H)。
Embodiment 7
3,4- dihydroxy benzenes boric acid is replaced with 3,5- dihydroxy benzenes boric acid, 3- benzyloxy -7- bromodiphenylthiophene replaces 3-
Bromo- 4, the 6- difluorodiphenyl bithiophene of benzyloxy -7-, reaction condition is the same as embodiment 1,2.
Gained white solid BYLC-07 is analyzed using GC-MS, the m/z of product is 470.1 (M+).
1H-NMR(300MHz,CDCl3):5.05-5.65(m,3H),5.75-6.55(m,6H),7.20-8.15(m,9H)。
Embodiment 8
3,4- dihydroxy benzenes boric acid is replaced with 3,5- dihydroxy benzenes boric acid, 3- benzyloxy -7- bromodiphenylthiophene replaces 3-
Bromo- 4, the 6- difluorodiphenyl bithiophene of benzyloxy -7-, reaction condition is the same as embodiment 1,2.
Gained white solid BYLC-08 is analyzed using GC-MS, the m/z of product is 512.1 (M+).
1H-NMR(300MHz,CDCl3):1.45-2.25(m,9H),5.25-6.55(m,6H),7.15-8.15(m,9H)。
Embodiment 9
Gained white solid BYLC-09 is analyzed using GC-MS, the m/z of product is 530.1 (M+).
1H-NMR(300MHz,CDCl3):1.45-2.25(m,9H),5.25-6.55(m,6H),7.15-8.15(m,8H)。
Embodiment 10
Gained white solid BYLC-10 is analyzed using GC-MS, the m/z of product is 526.1 (M+).
1H-NMR(300MHz,CDCl3):1.55-2.15(m,12H),5.35-6.65(m,6H),7.25-8.25(m,8H)。
Embodiment 11
Gained white solid BYLC-11 is analyzed using GC-MS, the m/z of product is 562.1 (M+).
1H-NMR(300MHz,CDCl3):1.55-2.15(m,12H),5.35-6.65(m,6H),7.25-8.25(m,6H)。
Embodiment 12
Gained white solid BYLC-12 is analyzed using GC-MS, the m/z of product is 562.1 (M+).
1H-NMR(300MHz,CDCl3):1.55-2.15(m,6H),4.55-5.25(m,2H),5.55-6.65(m,6H),
7.25-8.25(m,7H)。
Embodiment 13
Gained white solid BYLC-13 is analyzed using GC-MS, the m/z of product is 512.1 (M+).
1H-NMR(300MHz,CDCl3):1.55-2.15(m,6H),5.55-6.65(m,6H),7.25-8.25(m,9H)。
Embodiment 14
Gained white solid BYLC-14 is analyzed using GC-MS, the m/z of product is 530.1 (M+).
1H-NMR(300MHz,CDCl3):1.55-2.15(m,6H),5.55-6.65(m,6H),7.25-8.25(m,8H)。
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 15
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-03 to 99.7% provided by the embodiment 3 of addition 0.3%
In BHR87800, uniform dissolution obtains mixture PM-3.
The liquid-crystal composition of polymerizable compound BYLC-05 to 99.7% provided by the embodiment 5 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 novel dibenzothiophenes class can poly- property compound, which is characterized in that have structure shown in general formula I:
Wherein, P1、P2And P3It is identical or different, each independently represent ethyleneoxy, acrylate-based, methacrylate,
Fluoropropenes acid ester group, chloropropene perester radical, oxetanyl or epoxy group；
L1、L2、L3、L4It 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；
Z1、Z2、Z3It 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-C12Alkylidene or C2-C12One of alkenyl, the C1-C12
Alkylidene or C2-C12Alkenyl in one or more hydrogen atoms can each independently by-F ,-Cl or-CN replace, and
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；
r1、r2、r3、r4Each independently represent 0,1,2 or 3；
M, n each independently represent 0 or 1, and m, n are not 0 simultaneously.
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, P1、P2And P3It is identical or different, each independently represent acrylate-based, methacrylate, fluoro third
Olefin(e) acid ester group or chloropropene perester radical；
Further, P1、P2And P3It is identical or different, each independently represent acrylate-based, methacrylate or fluoro
It is acrylate-based.
3. compound according to claim 1 or 2, which is characterized in that the L1、L2、L3、L4It is identical or different, respectively solely
On the spot expression-F ,-Cl ,-CN ,-NO2、-CH3、-C2H5、-OCH3、-OC2H5、-CF3、-OCF3、-OCHF2Or-OC2F5；
Preferably, L1、L2、L3、L4It is identical or different, each independently represent-F ,-Cl ,-CN ,-CH3、-C2H5、-OCH3、-OC2H5
Or-CF3；
Further, L1、L2It is identical or different, each independently represent-F ,-Cl；And/or L3、L4It is identical or different, respectively solely
On the spot expression-F ,-Cl-, CH3、-C2H5、-OCH3Or-OC2H5。
4. compound according to claim 1-3, which is characterized in that the Z1、Z2、Z3It is identical or different, respectively
Independently indicate singly-bound ,-O-, C1-C8Alkylidene or C2-C8Alkenyl, and one or more non-conterminous CH2Group can
It is replaced in a manner of not being connected directly mutually by each independently by-O- ,-S- or-COO-；
Preferably, Z1、Z2、Z3It is identical or different, each independently represent singly-bound ,-O-, C1-C8Alkylidene, alkoxy or C2-C8
Alkenyl；
Further, Z1、Z2、Z3It is identical or different, each independently represent singly-bound ,-O-, C1-C6Alkylidene or alkoxy.
5. compound according to claim 1-4, which is characterized in that the r1、r2、r3、r4Table each independently
Show 0,1 or 2；
Preferably, r1、r2Each independently represent 0 or 1.
6. compound according to claim 1-5, which is characterized in that in general formula I, wherein m=0, L1、L2、
L4For F or Cl, r1、r2Each independently represent 0 or 1, r4Indicate 0,1 or 2；
Or, m=0, L1、L2For F or Cl, L4Expression-CH3、-OCH3、-C2H5Or-OC2H5One of, r1、r2Table each independently
Show 0 or 1, r4Indicate 1；
Or, n=0, L1、L2、L3For F or Cl, r1、r2Each independently represent 0 or 1, r3Indicate 0,1 or 2；
Or, n=0, L1、L2For F or Cl, L3Expression-CH3、-OCH3、-C2H5Or-OC2H5One of, r1、r2Table each independently
Show 0 or 1, r3Indicate 1.
7. compound according to claim 1-6, which is characterized in that one kind selected from following compound:
8. compound according to claim 1, which is characterized in that 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；
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 composition as claimed in claim 9 are in field of liquid crystal display
Application；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.
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| CN110922982A (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 novel dibenzothiophene polymerizable compound and application thereof |
| CN113461658A (en) * | 2021-06-15 | 2021-10-01 | 深圳市勇泰运科技有限公司 | High-refraction high-temperature-resistant optical monomer, optical resin and preparation method thereof |
| CN114133938A (en) * | 2020-09-04 | 2022-03-04 | 江苏和成显示科技有限公司 | Liquid crystal composition containing polymerizable compound and liquid crystal display device |
| CN114133937A (en) * | 2020-09-04 | 2022-03-04 | 江苏和成显示科技有限公司 | Liquid crystal composition containing polymerizable compound 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 |
| 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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| CN113461658A (en) * | 2021-06-15 | 2021-10-01 | 深圳市勇泰运科技有限公司 | High-refraction high-temperature-resistant optical monomer, optical resin and preparation method thereof |
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| 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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