CN110527521A - A kind of polymerizability compound and the preparation method and application thereof containing indane structural - Google Patents
A kind of polymerizability compound and the preparation method and application thereof containing indane structural Download PDFInfo
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Abstract
The present invention relates to a kind of polymerizability compound containing indane structural, the compound have the structure as shown in general formula I.Liquid-crystal composition orientation effect containing the compound is more preferable, it polymerize more complete, it remains lower, and the compound is cheap, performance is stablized, with performances such as wider nematic temperature range, suitable or higher birefringence anisotropy A n, higher resistivity, good anti-ultraviolet property, high charge retention rate and low-steam pressures, it can be widely used for field of liquid crystal display, there is important application value.
Description
Technical field
The invention belongs to liquid crystal material technical fields, are related to a kind of polymerizability compound and its system containing indane structural
Preparation Method and 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, and residual is 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.
Specifically, the present invention provides a kind of polymerizability compound containing indane structural, which has such as
Structure shown in general formula I:
The P1、P2、P3Acrylate-based, methacrylate, haloacrylic acid ester group, second are indicated independently of one another
Alkenyloxy group, 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 C2-C12Alkenyl, wherein the C1-C12Alkylidene or
C2-C12Alkenyl in one or more hydrogen atoms can be replaced independently of one another by F, Cl or CN, and one or more not phase
Adjacent-CH2Group can be independently of one another by-O- ,-S- ,-NH- ,-CO-, COO- ,-OCO- ,-OCOO- ,-SCO- ,-COS-
Or ethylene linkage is replaced in a manner of not being connected directly mutually；
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 C2-C12Alkenyl, the C1-C12Alkylidene or C2-C12
Alkenyl in one or more hydrogen atoms can be replaced independently of one another by F, Cl or CN, and it is one or more it is non-conterminous-
CH2Group can be independently of one another by-O- ,-S- ,-NH- ,-CO-, COO- ,-OCO- ,-OCOO- ,-SCO- or-COS- or alkene
Key is replaced in a manner of not being connected directly mutually；
The ring A and ring B expression 1,4- cyclohexylidene independent of each other or 1,4- phenylene；
The L1, L2, L3Expression-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；
The r1、r2Each independently represent 0,1,2,3 or 4；r3Indicate 0,1,2 or 3；
Described m, n indicate 0 or 1, and m and n are not 0 simultaneously.
The present invention carries out preferably, to obtain comprehensive performance superior compound group each in the general formula I.Specifically
For:
For the P in general formula I1、P2、P3: the structure of methacrylate of the present invention isIt is described halogenated
Acrylate-based structure isWherein, X represents halogen, preferably fluorine or chlorine.The P1、P2、P3Three bases represented
Group can be all identical, can also be with P2、P3The group of representative is identical and and P1The group of representative is different, can also be with three groups each other
It is different.The preferably described P of the present invention1、P2、P3Methacrylate or acrylate-based is indicated independently of one another.As one kind
Concrete scheme, the P1、P2、P3Represent methacrylate.As a kind of concrete scheme, the P1、P2、P3Represent third
Olefin(e) acid ester group.
For the Z in general formula I1、Z4: Z of the present invention1、Z4The group represented each other may be the same or different.This
Invent the preferably Z1、Z4Singly-bound ,-O-, alkyl or alkoxy are indicated independently of one another；Wherein, the alkyl or alkoxy are preferred
For C1-C8Alkyl or alkoxy, more preferably C1-C5Alkyl or alkoxy, further preferably C1~C3Alkyl or alkane
Oxygroup.As a kind of concrete scheme, the Z1、Z4In any one group indicate singly-bound, another group indicate singly-bound, C1、C2
Or C3Alkyl or C1、C2Or C3Alkoxy.As the Z1When representing alkoxy, carbon atom in the preferably described alkoxy with
The P1Group is connected directly.As the Z4When representing alkoxy, the oxygen atom and the ring A in the preferably described alkoxy are direct
It is connected.
For the Z in general formula I2、Z3: Z of the present invention2、Z3The group represented each other may be the same or different.This
Invent the preferably Z2、Z3Singly-bound or-(CH are indicated independently of one another2)k-；Wherein, k expression 1~8, preferably 1~5, more preferably
It is 1,2 or 3.As a kind of concrete scheme, the Z2、Z3Represent singly-bound.
For the preferably described ring A and ring B Asia the expression 1,4- hexamethylene independent of each other of ring A and ring B: the present invention in general formula I
Base or 1,4- phenylene.
For m, n in general formula I: m represents the number of ring A in the present invention, and n represents the number of ring B.The present invention is preferably described
M, n each independently represents 0 or 1, and m and n are not 0 simultaneously.It is 1 and n is 0 that concrete scheme, which includes: m, and ring A can be 1 at this time,
4- cyclohexylidene or 1,4- phenylene；M is 0 and n is 1, and ring B can be 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene at this time；M is 1
And n be 1, can be at this time 1 or 4 cyclohexylidene with ring A, ring B, can be Isosorbide-5-Nitrae-phenylene with ring A, ring B, can with ring A be 1,
4- cyclohexylidene and ring B are Isosorbide-5-Nitrae-phenylene, can also be using ring A as Isosorbide-5-Nitrae-phenylene and ring B is 1 or 4 cyclohexylidene.
For the L in general formula I1, L2, L3And r1、r2、r3: (L of the present invention1)r1It is the r of any position on finger ring A1
A hydrogen atom is respectively by L1Group replaces, in the absence of m takes 0 i.e. ring A, the L1It is not present and r1It is 0；(the L2)r2Refer to
The r of any position on ring B2A hydrogen atom is respectively by L2Group replaces, in the absence of n takes 0 i.e. ring B, the L2It is not present and r2
It is 0；(the L3)r3Refer to the r of any position on phenyl ring3A hydrogen atom is respectively by L3Group replaces.
L of the present invention1, L2, L3Can be all the same with three groups, can it is identical with any two of them but with remaining one
Difference, can also be all different each other with three groups.The preferably described L of the present invention1, L2, L3Independently of one another expression-F ,-Cl ,-
CH3、-C2H5、-C(CH3)3、-CH(CH3)2、-CH2CH(CH3)C2H5、-OCH3、-OC2H5、-CF3、-OCF3、-OCHF2Or-
OC2F5, expression-F ,-Cl ,-CH preferably independently of one another3、-C2H5、-OCH3Or-OC2H5.The further preferably described L of the present invention1、
L2Expression-F independent of each other ,-Cl ,-CH3、-OCH3、-C2H5Or-OC2H5, L3Indicate F or Cl.
R of the present invention1、r2、r3The number of representative can be all the same, and the number that can be represented with any two of them is identical
But with remaining difference, the number that can also be represented is all different each other.The preferably described r of the present invention1、r2、r3Table each independently
Show 0,1,2 or 3, the more preferable r1、r2、r3Each independently represent 0,1 or 2.R of the present invention1、r2、r3In, it can be any
One is 0, can also be 0 with three with any two for 0.Further preferred 0≤the r of the present invention1+r2+r3≤3；When m, n it
One be 0 when, preferably 0≤r1+r2+r3≤2.Specifically, when the ring A is Isosorbide-5-Nitrae-phenylene, the preferably described r1For 0,1 or
2；When the ring A is 1 or 4 cyclohexylidene, the preferably described r1It is 0.When the ring B is Isosorbide-5-Nitrae-phenylene, the preferably described r2For
0,1 or 2；When the ring B is 1 or 4 cyclohexylidene, the preferably described r2It is 0.The preferably described r of the present invention3It is 0 or 1.
As a preferred solution of the present invention, in the general formula I, P1、P2、P3Methacrylic acid is indicated independently of one another
Ester group is acrylate-based；
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 C2-C12Alkenyl, wherein the C1-C12Alkylidene or
C2-C12Alkenyl in one or more hydrogen atoms can be replaced independently of one another by F, Cl or CN, and one or more not phase
Adjacent-CH2Group can be independently of one another by-O- ,-S- ,-NH- ,-CO-, COO- ,-OCO- ,-OCOO- ,-SCO- ,-COS-
Or ethylene linkage 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 expression 1~8；
The ring A and ring B expression 1,4- cyclohexylidene independent of each other or 1,4- phenylene；
The L1, L2, L3Independently of one another expression-F ,-Cl ,-CH3、-C2H5、-C(CH3)3、-CH(CH3)2、-CH2CH
(CH3)C2H5、-OCH3、-OC2H5、-CF3、-OCF3、-OCHF2Or-OC2F5；
r1、r2、r3Each independently represent 0,1,2 or 3；
M, n indicates 0 or 1, and m and n are not 0 simultaneously.
As a preferred solution of the present invention, in the general formula I, P1、P2、P3Methacrylic acid is indicated independently of one another
It is ester group, acrylate-based；
The Z1、Z4Singly-bound ,-O-, C are indicated independently of one another1-C8Alkyl or alkoxy；
The Z2、Z3Singly-bound or-(CH are indicated independently of one another2)k, k expression 1~5；
The ring A and ring B expression 1,4- cyclohexylidene independent of each other or 1,4- phenylene；
L1、L2, L3Independently of one another expression-F ,-Cl ,-CH3、-OCH3、-C2H5、-OC2H5；
r1、r2、r3Each independently represent 0,1 or 2；
M, n indicates 0 or 1, and m and n are not 0 simultaneously.
As a preferred solution of the present invention, in the general formula I, P1、P2、P3Methacrylic acid is indicated independently of one another
It is ester group, acrylate-based；
The Z1、Z4Singly-bound ,-O-, C are indicated independently of one another1-C5Alkyl or alkoxy；
The Z2、Z3Singly-bound or-(CH are indicated independently of one another2)k, k expression 1~3；
The ring A and ring B expression 1,4- cyclohexylidene independent of each other or 1,4- phenylene；
L1、L2Expression-F independent of each other ,-Cl ,-CH3、-OCH3、-C2H5、-OC2H5；
L3Indicate F or Cl；
r1、r2、r3Each independently represent 0,1 or 2；
M, n indicates 0 or 1, and m and n are not 0 simultaneously.
As the preferred technical solution of the present invention, the liquid-crystal compounds is selected from the one or more of following compound:
In the I-1~I-75, P1、P2、P3And Z1、Z2、Z3、Z4Representative group is as described above.
As preferred forms of the invention, the compound is selected from one of following compound or a variety of:
The second object of the present invention is to protect the preparation method of the compound.
The synthetic route of the compound is as follows:
Specifically includes the following steps:
(1) withFor raw material, after carrying out metallization reaction with organolithium reagent, then with borate
Reaction obtains
It (2) will be obtained by step (1)WithPass through suzuki
Reaction, obtains
It (3) will be obtained by step (2)It is obtained by substitution reaction
It (4) will be obtained by step (3)It is obtained by hydrolysis
It (5) will be obtained by step (4)It is obtained by reduction reaction
It (6) will be obtained by step (5)It is obtained by esterification
L in above each step reaction in involved compound1、L2、L3、r1、r2、r3, m, n and gained LCD compound produce
L in object1、L2、L3、r1、r2、r3, m, n corresponding (ibid), X indicate H or CH3。
In step described in the above method (1),Molar ratio with organolithium reagent is 1:
1.0~2.0；Molar ratio with borate is 1:1.0~3.0；Reaction temperature can be at -50~-100 DEG C.
Wherein, raw materialIt can be obtained by public commercial source；The organolithium reagent choosing
From one or more of s-butyl lithium, tert-butyl lithium or n-BuLi；It is different that the borate is selected from trimethylborate, boric acid three
One or more of three isobutyl ester of propyl ester, butyl borate or boric acid.
In step described in the above method (2),WithThrowing
Material molar ratio is 1.0:1.0~1.5；Reaction temperature can be at 50~150 DEG C.
Wherein, raw materialIt can be obtained by public commercial source.
In step described in the above method (3),With diethyl malonate
Molar ratio be 1.0:1.0~1.4；Reaction temperature can be at 10~40 DEG C.
In step described in the above method (4),With aluminum hydride
The molar ratio of lithium is 1.0:1.0~1.8；Reaction temperature can be at -30~0 DEG C.
In step described in the above method (5), reaction temperature can be at 20~50 DEG C.
In step described in the above method (6),With methacrylic chloride or third
The molar ratio of alkene acyl chlorides is 1.0:3.0~4.0；Reaction temperature can be at -20~0 DEG C.
The third object of the present invention is the composition that protection contains the liquid-crystal compounds.Preferably, the compound exists
Mass percent in composition is 0.01~10%, more preferably 0.01~5%, further preferably 0.1~3%.
The fourth 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 An, 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:
Under nitrogen protection, 30g 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-01-1,0.116mol) 31.1g, LC:99.5%, yield 87.7%；
(2) synthesis of compound BYLC-01-2:
Under nitrogen protection, 31.1g compound BYLC-01-1 (0.116mol) is added into reaction flask, 46.2g compound200ml n,N-Dimethylformamide, 100ml deionized water, 72.8g Anhydrous potassium carbonate
(0.53mol), 0.5g tetra-triphenylphosphine palladium are heated to 70 DEG C and react 3 hours.Carry out conventional post-processing, through chromatogram purification, just oneself
Alkane elution, ethyl alcohol recrystallization obtain white solid (compound BYLC-01-2,0.098mol): 44.5g, LC:99.6%, yield:
84.6%；
(3) synthesis of compound BYLC-01-3:
Under nitrogen protection, 44.5g (0.098mol) compound BYLC-01-2,13.4g are added into 1000ml reaction flask
Diethyl malonate (0.102mol), 74.1g cesium carbonate, 1g cuprous iodide, 500ml tetrahydrofuran react at room temperature 48h.It will be anti-
It answers liquid to be poured into water, adjusts pH to neutrality with dilute hydrochloric acid.Carry out conventional post-processing, extracted through ethyl acetate, chromatogram purification, just oneself
Alkane elution, ethyl alcohol recrystallization obtain white solid (compound BYLC-01-3,0.090mol) 48.2g, GC:99.7%, yield:
92.1%.
(4) synthesis of compound BYLC-01-4:
Under nitrogen protection, addition 5g 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 48.2g compound BYLC-01-3 (0.090mol) 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-01-4,0.082mol) 37.1g, GC:99.8%, yield: 91.6%.
(5) synthesis of compound BYLC-01-5:
37.1g compound BYLC-01-4,90ml 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 hydrogen take off benzyl 6h, carry out conventional post-processing, obtain white solid (compound BYLC-01-5,
0.076mol): 27.4g, LC:99.6%, yield: 92.8%；
(6) synthesis of compound BYLC-01:
Under nitrogen protection, 27.4g compound BYLC-01-3,25.5g triethylamine and 200mL dichloro are added into reaction flask
Methane is cooled to -10 DEG C, and 28.5g methacrylic chloride (0.274mol) is added dropwise in -10 DEG C of temperature control~0 DEG C, is warmed to room temperature reaction 6h
Reaction solution is poured into water, is neutralized with bicarbonate uranium aqueous solution, conventional post-processing is carried out, through chromatogram purification, n-hexane elution, second
Alcohol is recrystallized to give white solid (compound BYLC-01,0.061mol) 34.6g, LC:99.5%, yield: 80.8%.
Gained white solid BYLC-01 is analyzed using GC-MS, the m/z of product is 564.1 (M+).
1H-NMR(300MHz,CDCl3): 1.35-2.20 (m, 9H), 2.95-4.45 (m, 9H), 5.35-6.45 (m, 4H),
6.65-7.65(m,11H)。
Embodiment 2
The structural formula of liquid-crystal compounds are as follows:
WithInstead ofOther conditions are the same as embodiment 1.
Gained white solid BYLC-02 is analyzed using GC-MS, the m/z of product is 582.1 (M+).
1H-NMR(300MHz,CDCl3): 1.35-2.20 (m, 9H), 2.95-4.45 (m, 8H), 5.35-6.45 (m, 4H),
6.65-7.65(m,11H)。
Embodiment 3
The structural formula of liquid-crystal compounds are as follows:
WithInstead ofOther reaction conditions are the same as embodiment 1.
Gained white solid BYLC-03 is analyzed using GC-MS, the m/z of product is 574.1 (M+).
1H-NMR(300MHz,CDCl3): 1.35-2.20 (m, 9H), 2.95-4.45 (m, 11H), 5.35-6.45 (m, 4H),
6.65-7.65(m,11H)。
Embodiment 4
The structural formula of liquid-crystal compounds are as follows:
WithInstead ofOther reaction conditions are the same as embodiment 1
Gained white solid BYLC-04 is analyzed using GC-MS, the m/z of product is 582.1 (M+).
1H-NMR(300MHz,CDCl3): 1.35-2.20 (m, 9H), 2.95-4.45 (m, 9H), 5.35-6.45 (m, 4H),
6.65-7.65(m,10H)。
Embodiment 5
The structural formula of liquid-crystal compounds are as follows:
WithInstead ofOther conditions are the same as embodiment 1.
Gained white solid BYLC-05 is analyzed using GC-MS, the m/z of product is 578.1 (M+).
1H-NMR(300MHz,CDCl3): 1.35-2.20 (m, 9H), 2.95-4.45 (m, 9H), 5.35-6.45 (m, 4H),
6.65-7.65(m,12H)。
Embodiment 6
The structural formula of liquid-crystal compounds are as follows:
WithInstead ofOther reaction conditions are the same as embodiment 1.
Gained white solid BYLC-06 is analyzed using GC-MS, the m/z of product is 570.1 (M+).
1H-NMR(300MHz,CDCl3): 1.35-2.20 (m, 18H), 2.35-4.55 (m, 11H), 5.35-6.45 (m,
6H),6.65-7.65(m,7H)。
Embodiment 7
The structural formula of liquid-crystal compounds are as follows:
WithInstead ofOther conditions are the same as embodiment 1.
Gained white solid BYLC-07 is analyzed using GC-MS, the m/z of product is 488.1 (M+).
1H-NMR(300MHz,CDCl3): 1.35-2.20 (m, 9H), 2.35-4.55 (m, 10H), 5.35-6.45 (m, 6H),
6.65-7.65(m,7H)。
Embodiment 8
The structural formula of liquid-crystal compounds are as follows:
WithInstead ofOther conditions are the same as embodiment 7.
Gained white solid BYLC-08 is analyzed using GC-MS, the m/z of product is 506.1 (M+).
1H-NMR(300MHz,CDCl3): 1.35-2.20 (m, 9H), 2.35-4.55 (m, 9H), 5.35-6.45 (m, 6H),
6.65-7.65(m,7H)。
Embodiment 9
The structural formula of liquid-crystal compounds are as follows:
Specific step is as follows:
WithInstead ofOther conditions are obtained with embodiment 1
The synthesis of compound BYLC-09:
Under nitrogen protection, 30.0g compound is added into reaction flask
37.6g triethylamine and 250mL methylene chloride are cooled to -10 DEG C, and 32.0g acryloyl chloride is added dropwise in -10 DEG C of temperature control~0 DEG C, rises to room
Reaction solution is poured into water by temperature reaction 6h, is neutralized with bicarbonate uranium aqueous solution, is carried out conventional post-processing, through chromatogram purification, just oneself
Alkane elution, ethyl alcohol recrystallization obtain white solid (compound BYLC-09,0.091mol) 40.7g, LC:99.7%, yield:
86.4%.
Gained white solid BYLC-09 is analyzed using GC-MS, the m/z of product is 446.1 (M+).
1H-NMR(300MHz,CDCl3):3.05-4.05(m,5H),4.23-5.85(m,7H),5.95-6.65(m,6H),
7.05-7.95(m,7H)。
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 10
The property of liquid crystal compound BHR87800 is listed in Table 1 below:
1 mixed crystal BHR87800 property summary sheet of table
| Property | Cp | Δn | Δε | ε‖ | K3/K1 |
| Numerical value | +70℃ | 0.095 | -3.5 | 3.3 | 0.97 |
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 6 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 7 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, irradiates 600s, 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
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, irradiates 600s, and 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,
It is more preferable to be formed by orientation effect, faster, polymerization is more complete for rate of polymerization, and residual is lower, so that biggish improve display not
Good 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 polymerizability compound containing indane structural, which is characterized in that have the structure as shown in general formula I:
The P1、P2、P3Acrylate-based, methacrylate, haloacrylic acid ester group, ethylene oxy are indicated independently of one another
Base, 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 C2-C12Alkenyl, wherein the C1-C12Alkylidene or C2-C12's
One or more hydrogen atoms in alkenyl can be replaced by F, Cl or CN independently of one another, and it is one or more it is non-conterminous-
CH2Group can be independently of one another by-O- ,-S- ,-NH- ,-CO-, COO- ,-OCO- ,-OCOO- ,-SCO- ,-COS- or ethylene linkage
It is replaced in a manner of not being connected directly mutually；
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 C2-C12Alkenyl, the C1-C12Alkylidene or C2-C12Alkenyl
In one or more hydrogen atoms can be replaced independently of one another by F, Cl or CN, and one or more non-conterminous-CH2Base
Group can be independently of one another by-O- ,-S- ,-NH- ,-CO-, COO- ,-OCO- ,-OCOO- ,-SCO- ,-COS- or ethylene linkage with not phase
The mode being mutually connected directly replaces；
The ring A and ring B expression 1,4- cyclohexylidene independent of each other or 1,4- phenylene；
The L1, L2, L3Expression-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；
The r1、r2Each independently represent 0,1,2,3 or 4；r3Indicate 0,1,2 or 3；
Described m, n indicate 0 or 1, and m, n are not 0 simultaneously.
2. compound according to claim 1, which is characterized in that in the general formula I, P1、P2、P3It indicates independently of one another
Methacrylate is acrylate-based；
And/or the Z1、Z4Singly-bound ,-O-, C are indicated independently of one another1-C8Alkyl or alkoxy；Wherein, the alkyl or alcoxyl
Base is preferably C1-C5Alkyl or alkoxy, more preferably C1~C3Alkyl or alkoxy；
And/or the Z2、Z3Singly-bound or-(CH are indicated independently of one another2)k-；Wherein, k expression 1~8, preferably 1~5, it is more excellent
It is selected as 1,2 or 3；
And/or the L1, L2, L3Expression-F ,-Cl ,-CH independently of one another3、-C2H5、-C(CH3)3、-CH(CH3)2、-CH2CH
(CH3)C2H5、-OCH3、-OC2H5、-CF3、-OCF3、-OCHF2Or-OC2F5, expression-F ,-Cl ,-CH preferably independently of one another3、-
C2H5、-OCH3Or-OC2H5；
And/or the r1、r2、r30,1,2 or 3 are indicated independently of one another, preferably each independently represent 0,1 or 2.
3. compound according to claim 1, which is characterized in that in the general formula I, P1、P2、P3It indicates independently of one another
Methacrylate is acrylate-based；
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 C2-C12Alkenyl, wherein the C1-C12Alkylidene or C2-C12's
One or more hydrogen atoms in alkenyl can be replaced by F, Cl or CN independently of one another, and it is one or more it is non-conterminous-
CH2Group can be independently of one another by-O- ,-S- ,-NH- ,-CO-, COO- ,-OCO- ,-OCOO- ,-SCO- ,-COS- or ethylene linkage
It 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 expression 1~8；
The ring A and ring B expression 1,4- cyclohexylidene independent of each other or 1,4- phenylene；
The L1, L2, L3Independently of one another expression-F ,-Cl ,-CH3、-C2H5、-C(CH3)3、-CH(CH3)2、-CH2CH(CH3)
C2H5、-OCH3、-OC2H5、-CF3、-OCF3、-OCHF2Or-OC2F5；
The r1、r2、r3Each independently represent 0,1,2 or 3；
Described m, n indicate 0 or 1, and m and n are not 0 simultaneously.
4. compound according to claim 1, which is characterized in that in the general formula I, P1、P2、P3It indicates independently of one another
It is methacrylate, acrylate-based；
The Z1、Z4Singly-bound ,-O-, C are indicated independently of one another1-C8Alkyl or alkoxy；
The Z2、Z3Singly-bound or-(CH are indicated independently of one another2)k, k expression 1~5；
The ring A and ring B expression 1,4- cyclohexylidene independent of each other or 1,4- phenylene；
The L1、L2, L3Independently of one another expression-F ,-Cl ,-CH3、-OCH3、-C2H5Or-OC2H5；
The r1、r2、r3Each independently represent 0,1 or 2；
Described m, n indicate 0 or 1, and m and n are not 0 simultaneously.
5. compound according to claim 1, which is characterized in that P1、P2、P3Methacrylate is indicated independently of one another
It is base, acrylate-based；
The Z1、Z4Singly-bound ,-O-, C are indicated independently of one another1-C5Alkyl or alkoxy；
The Z2、Z3Singly-bound or-(CH are indicated independently of one another2)k, k expression 1~3；
The ring A and ring B expression 1,4- cyclohexylidene independent of each other or 1,4- phenylene；
The L1、L2Expression-F independent of each other ,-Cl ,-CH3、-OCH3、-C2H5Or-OC2H5；L3Indicate F or Cl；
The r1、r2、r3Each independently represent 0,1 or 2；
Described m, n indicate 0 or 1, and m and n are not 0 simultaneously.
6. compound described in any one according to claim 1~5, which is characterized in that one kind selected from following compound or
It is a variety of:
In the I-1~I-75, P1、P2、P3And Z1、Z2、Z3、Z4Representative group such as Claims 1 to 5 any one institute
It states.
7. compound according to claim 1, which is characterized in that be selected from one of following compound or a variety of:
8. the preparation method of compound described in claim 1~7 any one, which is characterized in that synthetic route is as follows:
Specifically includes the following steps:
(1) withFor raw material, after carrying out metallization reaction with organolithium reagent, then react with borate
It obtains
It (2) will be obtained by step (1)It is reacted by suzuki,
It obtains
It (3) will be obtained by step (2)It is obtained by substitution reaction
It (4) will be obtained by step (3)It is obtained by hydrolysis
It (5) will be obtained by step (4)It is obtained by reduction reaction
It (6) will be obtained by step (5)It is obtained by esterification
Each substituent group in compound involved by above each step reaction is as described in claim 1~7 any one.
9. the composition containing compound described in claim 1~7 any one；The quality hundred of the compound in the composition
Divide than preferably 0.01~10%, more preferably 0.01~5%, further preferably 0.1~3%.
10. liquid-crystal composition described in compound described in claim 1~7 any one or claim 9 is in field of liquid crystal display
Application, the application preferably in liquid crystal display device, more preferably in TN, ADS, VA, PSVA, FFS or IPS liquid crystal display
In application.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003286319A (en) * | 2002-03-28 | 2003-10-10 | Chisso Corp | Optically active fumaric acid diester derivative and liquid crystal polymer made of the same |
| WO2009030322A1 (en) * | 2007-08-30 | 2009-03-12 | Merck Patent Gmbh | Liquid crystal display |
| WO2012055473A1 (en) * | 2010-10-26 | 2012-05-03 | Merck Patent Gmbh | Liquid-crystal medium and process for preparing a liquid-crystal device |
| CN102575167A (en) * | 2009-11-18 | 2012-07-11 | 株式会社艾迪科 | Liquid crystal composition comprising polymerizable compound, and liquid crystal display element using said liquid crystal composition |
| WO2013178333A1 (en) * | 2012-06-02 | 2013-12-05 | Merck Patent Gmbh | Liquid crystal medium |
| CN104557545A (en) * | 2013-10-10 | 2015-04-29 | 江苏和成显示科技股份有限公司 | Polymerizable compound and its application in optical anisotropic body and liquid crystal display element |
| 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 |
| CN104927876A (en) * | 2014-03-21 | 2015-09-23 | 默克专利股份有限公司 | Polymerisable Compounds And The Use Thereof In Liquid-Crystal Displays |
-
2018
- 2018-05-23 CN CN201810501173.XA patent/CN110527521A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003286319A (en) * | 2002-03-28 | 2003-10-10 | Chisso Corp | Optically active fumaric acid diester derivative and liquid crystal polymer made of the same |
| WO2009030322A1 (en) * | 2007-08-30 | 2009-03-12 | Merck Patent Gmbh | Liquid crystal display |
| CN102575167A (en) * | 2009-11-18 | 2012-07-11 | 株式会社艾迪科 | Liquid crystal composition comprising polymerizable compound, and liquid crystal display element using said liquid crystal composition |
| WO2012055473A1 (en) * | 2010-10-26 | 2012-05-03 | Merck Patent Gmbh | Liquid-crystal medium and process for preparing a liquid-crystal device |
| WO2013178333A1 (en) * | 2012-06-02 | 2013-12-05 | Merck Patent Gmbh | Liquid crystal medium |
| 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 |
| CN104557545A (en) * | 2013-10-10 | 2015-04-29 | 江苏和成显示科技股份有限公司 | Polymerizable compound and its application in optical anisotropic body and liquid crystal display element |
| CN104927876A (en) * | 2014-03-21 | 2015-09-23 | 默克专利股份有限公司 | Polymerisable Compounds And The Use Thereof In Liquid-Crystal Displays |
Non-Patent Citations (1)
| Title |
|---|
| 崔青 等: "聚合物稳定液晶垂直取向技术的研究现状概述", 《现代显示》 * |
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