CN113528152B - Liquid crystal compound, liquid crystal composition thereof and liquid crystal display device - Google Patents

Liquid crystal compound, liquid crystal composition thereof and liquid crystal display device Download PDF

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CN113528152B
CN113528152B CN202010316356.1A CN202010316356A CN113528152B CN 113528152 B CN113528152 B CN 113528152B CN 202010316356 A CN202010316356 A CN 202010316356A CN 113528152 B CN113528152 B CN 113528152B
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liquid crystal
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carbon atoms
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CN113528152A (en
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姜志炜
宋晓龙
徐爽
陈法兵
陈俊利
胡步洋
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Jiangsu Hecheng Advanced Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
    • C09K2019/3408—Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems

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  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

The invention provides a liquid crystal compound with a general formula I, a liquid crystal composition containing the liquid crystal compound and a liquid crystal display device containing the liquid crystal composition. Compared with the prior art, the liquid crystal compound with the general formula I provided by the invention also has a larger clearing point, larger optical anisotropy and larger absolute value of dielectric anisotropy under the condition of maintaining proper rotational viscosity, so that the liquid crystal composition containing the liquid crystal compound also has a larger clearing point, larger optical anisotropy, larger absolute value of dielectric anisotropy, larger elastic constant and smaller ratio of rotational viscosity to splay elastic constant under the condition of maintaining proper low-temperature storage stability and proper rotational viscosity, and further the liquid crystal display device containing the liquid crystal composition has a wider nematic phase temperature range, better contrast ratio, lower threshold voltage and shorter response time.

Description

Liquid crystal compound, liquid crystal composition thereof and liquid crystal display device
Technical Field
The invention relates to the field of liquid crystals, in particular to a liquid crystal compound, a liquid crystal composition containing the liquid crystal compound and a liquid crystal display device containing the liquid crystal composition.
Background
The liquid crystal display device can be used in various household electrical appliances such as a timepiece and an electronic calculator, a measuring device, an automobile panel, a word processor, a computer, a printer, a television, and the like. The liquid crystal display element may be classified into a type of PC (phase change), TN (twisted nematic), STN (super twisted nematic ), ECB (electrically controlled birefringence, electrically controlled birefringence), OCB (optically compensated bend ), IPS (in-plane switching), VA (vertical alignment), and the like according to the type of display mode. Liquid crystal display elements can be classified into a PM (passive matrix) type and an AM (active matrix) type according to the driving method of the elements. PM is classified into static (static) and multiplex (multiplex) types. AM is classified into TFT (thin film transistor ), MIM (metal insulator metal, metal-insulator-metal) and the like. The types of TFTs include amorphous silicon (amorphous silicon) and polysilicon (polycrystal silicon). The latter is classified into a high temperature type and a low temperature type according to the manufacturing process. The liquid crystal display element can be classified into a reflective type using natural light, a transmissive type using backlight, and a semi-transmissive type using both natural light and backlight, depending on the types of light sources.
In the case of low information content, passive driving is generally employed. However, as the amount of information increases and the display size and the number of display paths increases, crosstalk and contrast decrease become serious, and thus Active Matrix (AM) driving is generally used, and Thin Film Transistors (TFTs) are currently used for driving. In an AM-TFT element, TFT switching devices are addressed in a two-dimensional grid, charging the pixel electrode for a limited time in on-state, and then turning off again until addressed again in the next cycle. Thus, between two addressing periods, a change in voltage across the pixel is undesirable, as the transmittance of the pixel may change, resulting in display instability. The discharge rate of a pixel depends on the electrode capacity and the resistivity of the inter-electrode dielectric material. Therefore, the liquid crystal material is required to have higher resistivity, good chemical stability and thermal stability and stability to electric field and electromagnetic radiation, and simultaneously has proper optical anisotropy delta n and lower threshold voltage so as to achieve the purposes of reducing driving voltage and reducing power consumption; it is also desirable that the liquid crystal material have a low viscosity to meet the need for a fast response. There have been many reports on such liquid crystal compositions, for example, WO9202597, WO9116398, WO9302153, WO9116399, CN1157005A and the like.
The liquid crystal display element contains a liquid crystal composition having a nematic phase, and the liquid crystal composition has appropriate characteristics. By improving the characteristics of the liquid crystal composition, an AM element having good characteristics can be obtained. The correlation between the characteristics of the liquid crystal composition and the AM element is summarized in table 1 below. The characteristics of the liquid crystal composition are further described based on a commercially available AM element. The temperature range of the nematic phase is associated with the temperature range in which the element can be used. The preferred upper temperature limit of the nematic phase is above about 70℃and the preferred lower temperature limit of the nematic phase is below about-10 ℃. The viscosity of the liquid crystal composition is related to the response time of the element. In order to display a dynamic image on the device, the response time of the device is preferably short.
TABLE 1 Properties of liquid Crystal composition and AM element
The optical anisotropy of the liquid crystal composition is related to the contrast of the element. Depending on the element display mode, a large optical anisotropy or a small optical anisotropy (i.e., appropriate optical anisotropy) is required. The product (Δn×d) of the optical anisotropy (Δn) of the liquid crystal composition and the cell thickness (d) of the element is designed to maximize the contrast ratio. The value of the product is dependent on the type of operation mode, and a liquid crystal composition having a large optical anisotropy is preferable for an element having a small cell thickness.
The liquid crystal display element containing the liquid crystal composition having a large absolute value of dielectric anisotropy can lower the base voltage value, lower the driving voltage, and further lower the power consumption.
A liquid crystal display element containing a liquid crystal composition with a lower threshold voltage can effectively reduce display power consumption,particularly in consumables (such as mobile phones, tablet computers, and other portable electronic products), the battery pack has longer endurance. However, for liquid crystal compositions with lower threshold voltages (generally containing large dielectric polar groups), the order of the liquid crystal molecules is low, K reflecting the order of the liquid crystal molecules ave The value is also reduced, thereby affecting both the light leakage and contrast of the liquid crystal material, which are often difficult to combine.
The liquid crystal composition having a small viscosity can improve the response speed of the liquid crystal display element. When the response speed of the liquid crystal display element is high, it can be applied to animation display. In addition, when the liquid crystal composition is injected into the liquid crystal cell of the liquid crystal display element, the injection time can be shortened, and the workability can be improved. Rotational viscosity gamma 1 Directly influencing the response time of the liquid crystal composition after being powered up, wherein the rise time (τ on ) And fall time (τ) off ) Are all in contact with the rotational viscosity gamma of the liquid crystal composition 1 And in direct proportion. Due to the rise time (τ on ) Is dependent on the cell and the driving voltage, so that the rise time (τ) can be adjusted by increasing the driving voltage and decreasing the cell thickness of the cell on ). Fall time (τ) off ) Independent of the driving voltage, which is mainly related to the elastic constant of the liquid crystal composition and the cell thickness of the liquid crystal cell, the thinning of the cell thickness reduces the fall time (τ off ) The liquid crystal molecules in different display modes have different movement modes, and the fall time (τ) in the three modes TN, IPS, VA off ) Respectively, inversely proportional to the average elastic constant, the torsional elastic constant, and the flexural elastic constant.
The response time is simultaneously limited by the rotational viscosity (gamma) 1 ) Ratio to the elastic constant (K). In view of the aspect of liquid crystal materials, the rotational viscosity of the liquid crystal medium needs to be reduced as much as possible while the elastic constant is increased to achieve the purpose of accelerating the response time. However, the rotational viscosity and the elastic constant are a pair of contradictory parameters, and a decrease in rotational viscosity causes a decrease in the elastic constant. Therefore, it is necessary to study γ for different display modes 1 /K 11 The most preferred use of values is a range value.
U.S. patent application publication No. US20180030020A1 discloses the following compounds of general formula S having a difluorodibenzo ring structure:
Further disclosed are specific compounds of the following formulas S-1, S-2 and S-3:
wherein,,
alkyl represents an alkyl group having 1 to 15 carbon atoms;
R 2 represents an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or an alkynyl group.
Although these fluorodibenzo compounds have a large absolute value of dielectric anisotropy, they have problems of large viscosity and small use temperature range, and are disadvantageous in constructing a liquid crystal display device having a high reaction rate and a wide use temperature range.
Therefore, further improvement of the structure of these difluorodibenzo compounds in order to obtain liquid crystal compounds satisfying simultaneously the large absolute value of dielectric anisotropy, short response time, and wide nematic phase temperature range is a new development direction in the liquid crystal field.
Disclosure of Invention
The invention aims to: in view of the drawbacks of the prior art, an object of the present invention is to provide a liquid crystal compound having a larger clearing point, a larger optical anisotropy and a larger absolute value of dielectric anisotropy while maintaining a suitable rotational viscosity.
The invention also aims at providing a liquid crystal composition containing the liquid crystal compound.
It is a further object of the present invention to provide a liquid crystal display device comprising the above liquid crystal composition.
The technical scheme is as follows: in order to achieve the above object, the present invention provides a liquid crystal compound of the general formula I:
wherein,,
R 1 represents a linear or branched alkyl group having 1 to 12 carbon atoms,One or not adjacent two or more-CH in the straight-chain or branched alkyl group containing 1 to 12 carbon atoms 2 -can be replaced independently of one another by-c=c-, -c≡c-, -O-, -CO-O-or-O-CO-, and the straight-chain or branched alkyl radical having 1 to 12 carbon atoms, -or>Or->Wherein one or more of-H's may each be independently substituted with-F or-Cl;
ring(s)And (C) a ring->Each independently representsOr->Wherein->Andone or more of-CH 2 Can be replaced by-O-and one or more single bonds in the ringCan be replaced by double bond, wherein->And->In (C) may be-H, one or more of-CN, -F, -Cl, -CH 3 or-OCH 3 Substituted, and-ch=in one or more rings may be replaced by-n=;
x represents-O-, -S-, -CO-, -CF 2 -, -NH-or-NF-;
y represents halogen, halogenoalkyl or halogenoalkoxy having 1 to 5 carbon atoms, or halogenoalkenyl or halogenoalkenyloxy having 2 to 5 carbon atoms;
Z 1 、Z 2 and Z 3 Each independently represents a single bond, -CO-O-, -O-CO-, -CH 2 O-、-OCH 2 -、-CH＝CH-、-C≡C-、-CH 2 CH 2 -、-CF 2 CF 2 -、-(CH 2 ) 4 -、-CF 2 O-or-OCF 2 -；
n 1 And n 2 Each independently represents 0, 1, 2 or 3, wherein when n 1 When=2 or 3, the ringZ, which may be the same or different 1 May be the same or different; wherein when n is 2 When=2 or 3, the ring->Z, which may be the same or different 2 May be the same or different; and is also provided with
L 1 、L 2 、L 3 And L 4 Each independently represents-H, halogen, -OCH 3 or-CH 3 。
In some embodiments of the invention, preferably, R 1 Represents a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 9 carbon atoms, or a linear group having 2 to 10 carbon atomsOr branched alkenyl; further preferably, R 1 Represents a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 7 carbon atoms, or a linear or branched alkenyl group having 2 to 8 carbon atoms; still further preferably, R 1 Represents a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or a linear or branched alkenyl group having 2 to 5 carbon atoms.
In some embodiments of the invention, the ringAnd (C) a ring->Each independently represents
Preferably, the ringAnd (C) a ring->Each independently represents-> It is further preferred that the composition comprises,and (C) a ring->Each of which is a single pieceIndependently represent- >
In some embodiments of the invention, the liquid crystal compound of formula I is selected from the group consisting of:
and
In some embodiments of the present invention, preferably, the method comprises the steps of, X represents-O- -S-or-CO-.
In some embodiments of the invention, preferably Y represents-F, -CF 3 、-OCF 3 or-CH 2 CH 2 CH＝CF 2 。
In some embodiments of the invention, preferably, Z 1 And Z 2 Each independently represents a single bond, -CH 2 O-、-OCH 2 -、-CH＝CH-、-C≡C-、-CH 2 CH 2 -、-CF 2 CF 2 -、-(CH 2 ) 4 -、-CF 2 O-or-OCF 2 -; further preferably, Z 1 And Z 2 Each independently represents a single bond, -CH 2 O-、-OCH 2 -、-CH 2 CH 2 -、-CF 2 O-or-OCF 2 -。
In some embodiments of the invention, preferably, Z 3 Represents a single bond, -CH 2 O-、-OCH 2 -、-CH＝CH-、-C≡C-、-CH 2 CH 2 -、-CF 2 CF 2 -or- (CH) 2 ) 4 -; further preferably, Z 3 Represents a single bond, -CH 2 O-、-OCH 2 -、-CH 2 CH 2 -、-CF 2 CF 2 -or- (CH) 2 ) 4 -。
In some embodiments of the invention, the compound of formula I-2 is selected from the group consisting of:
wherein,,
L 1 、L 2 、L 5 、L 6 and L 7 Each independently represents-F or-Cl.
In some embodiments of the invention, the compound of formula I-3 is selected from the group consisting of:
wherein,,
H 1 and H 2 Each independently represents-CH 2 -or-O-; and is also provided with
L 1 、L 2 、L 8 、L 9 And L 10 Each independently represents-F or-Cl.
In some embodiments of the invention, the compound of formula I is selected from the group consisting of:
in another aspect, the present invention also provides a liquid crystal composition comprising at least one liquid crystal compound of formula I.
The liquid crystal compound of the general formula I comprises the following components in percentage by weight: the preferred lower limit value of the weight percent of the liquid crystal compound of the general formula I is 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 10%, 12%, 14%, 15% or 20% relative to the total weight of the liquid crystal composition of the present invention; the preferred upper limit of the weight percent of the liquid crystal compounds of the general formula I is 40%, 38%, 36%, 30%, 25%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 12%, 10%, 8%, 6%, 5%, 4% or 3% relative to the total weight of the liquid crystal composition of the invention.
In some embodiments of the invention, the liquid crystal compound of formula I comprises 0.1% to 40% by weight of the liquid crystal composition; preferably, the liquid crystal compound of the general formula I accounts for 1-40% of the weight of the liquid crystal composition; further preferably, the liquid crystal compound of formula I comprises 1% to 30% by weight of the liquid crystal composition.
In some embodiments of the invention, the liquid crystal composition further comprises at least one compound of formula M:
wherein,,
R M1 and R is M2 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, One or not adjacent two or more of the straight-chain or branched alkyl groups having 1 to 12 carbon atomsOf (C) CH 2 -may each be independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-;
ring(s)Ring->And (C) a ring->Each independently represents->Or (b)Wherein->One or more of-CH 2 Can be replaced by-O-and +.>At most one-H of (c) may be substituted by halogen;
Z M1 and Z M2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH 2 O-、-OCH 2 -、-C≡C-、-CH＝CH-、-CH 2 CH 2 -or- (CH) 2 ) 4 -; and is also provided with
n M Represents 0, 1 or 2, wherein when n M When=2, the ringZ, which may be the same or different M2 May be the same or different.
In some embodiments of the invention, preferably, R M1 And R is M2 Each independently represents a straight chain alkyl group having 1 to 10 carbon atoms, a straight chain alkoxy group having 1 to 9 carbon atoms, or a straight chain alkyl group having 2 to 10 carbon atomsAlkenyl groups of the chain; further preferably, R M1 And R is M2 Each independently represents a linear alkyl group having 1 to 8 carbon atoms, a linear alkoxy group having 1 to 7 carbon atoms, or a linear alkenyl group having 2 to 8 carbon atoms; still further preferably, R M1 And R is M2 Each independently represents a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or a linear alkenyl group having 2 to 5 carbon atoms.
In some embodiments of the invention, preferably, R M1 And R is M2 Each independently represents a straight chain alkenyl group having 2 to 8 carbon atoms; further preferably, R M1 And R is M2 Each independently represents a straight chain alkenyl group having 2 to 5 carbon atoms.
In some embodiments of the invention, preferably, R M1 And R is M2 Either one of them is a linear alkenyl group having 2 to 5 carbon atoms, and the other is a linear alkyl group having 1 to 5 carbon atoms.
In some embodiments of the invention, preferably, R M1 And R is M2 Each independently represents a linear alkyl group having 1 to 8 carbon atoms or a linear alkoxy group having 1 to 7 carbon atoms; further preferably, R M1 And R is M2 Each independently represents a linear alkyl group having 1 to 5 carbon atoms or a linear alkoxy group having 1 to 4 carbon atoms.
In some embodiments of the invention, preferably, R M1 And R is M2 Either one of them is a linear alkyl group having 1 to 5 carbon atoms, and the other is a linear alkyl group having 1 to 5 carbon atoms, or a linear alkoxy group having 1 to 4 carbon atoms; further preferably, R M1 And R is M2 Each of which is independently a straight-chain alkyl group having 1 to 5 carbon atoms.
The alkenyl group in the present invention is preferably selected from the group represented by any one of the formulas (V1) to (V9), and particularly preferably is formula (V1), formula (V2), formula (V8) or (V9). The groups represented by the formulas (V1) to (V9) are as follows:
wherein represents a carbon atom in the bonded ring structure.
The alkenyloxy group in the present invention is preferably selected from the group represented by any one of the formulas (OV 1) to (OV 9), and particularly preferably is formula (OV 1), formula (OV 2), formula (OV 8) or (OV 9). The groups represented by the formulas (OV 1) to (OV 9) are as follows:
wherein represents a carbon atom in the bonded ring structure.
In some embodiments of the invention, the compound of formula M is selected from the group consisting of:
/>
in some embodiments of the present invention, the content of the compound of formula M must be appropriately adjusted according to the desired properties of solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, drop marks, burn-in, dielectric anisotropy, etc.
The compounds of formula M comprise the weight percentage of the liquid crystal composition of the invention: preferred lower limits for the weight percentages of the compounds of the general formula M are 0.1%, 1%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 25%, 30%, 35%, 40%, 45% or 50% relative to the total weight of the liquid crystal composition of the invention; the preferred upper limit of the weight percent of the compound of the general formula M is 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45.5%, 45%, 40%, 35%, 30%, 28%, 27%, 26%, 25.5%, 25%, 24%, 23%, 22%, 21% or 20% relative to the total weight of the liquid crystal composition of the present invention.
In some embodiments of the invention, the compound of formula M comprises 0.1% to 90% by weight of the liquid crystal composition; preferably, the compound of the general formula M accounts for 1-80% of the weight of the liquid crystal composition; further preferably, the compound of formula M is 5% to 60% by weight of the liquid crystal composition.
Regarding the content of the compound of the general formula M, when it is necessary to keep the viscosity of the liquid crystal composition of the present invention low and the response time short, it is preferable that the lower limit value is high and the upper limit value is high; further, when it is necessary to keep the clear point of the liquid crystal composition of the present invention high and the temperature stability is good, it is preferable that the lower limit value is high and the upper limit value is high; in order to keep the drive voltage low and to increase the absolute value of the dielectric anisotropy, it is preferable to make the lower limit value and the upper limit value low.
In some embodiments of the invention, R is preferred when reliability is important M1 And R is M2 Are all alkyl groups; in the case where importance is attached to reducing the volatility of the compound, R is preferably M1 And R is M2 Are all alkoxy groups; when importance is attached to the reduction of viscosity, R is preferable M1 And R is M2 At least one of which is alkenyl.
In some embodiments of the invention, the liquid crystal composition further comprises at least one compound of formula N:
Wherein,,
R N1 and R is N2 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, One or not adjacent two or more-CH in the straight-chain or branched alkyl group containing 1 to 12 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-;
ring(s)And (C) a ring->Each independently represents->Or->Wherein the method comprises the steps ofOne or more of-CH 2 Can be replaced by-O-and one or more single bonds in the ring can be replaced by double bonds, wherein +.>In which one or more of-H may be substituted by-F, -Cl or-CN and one or more of-ch=may be substituted by-n=in the ring;
Z N1 and Z N2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH 2 O-、-OCH 2 -、-CH＝CH-、-C≡C-、-CH 2 CH 2 -、-CF 2 CF 2 -、-(CH 2 ) 4 -、-CF 2 O-or-OCF 2 -；
L N1 And L N2 Each independently represents-H, an alkyl group having 1 to 3 carbon atoms, or halogen; and is also provided with
n N1 Represents 0, 1, 2 or 3, n N2 Represents 0 or 1, and 0.ltoreq.n N1 +n N2 Not more than 3, wherein when n N1 When=2 or 3, the ringZ, which may be the same or different N1 May be the same or different.
The compounds of formula N are present in the liquid crystal composition according to the invention in weight percent: the lower limit of the weight percent of the compound of formula N is 0%, 0.1%, 1%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 26%, 28%, 30% or 35% relative to the total weight of the liquid crystal composition of the present invention; the upper limit of the weight percent of the compound of the general formula N is 60%, 58%, 56%, 54%, 52%, 50%, 45%, 40%, 35%, 30%, 28%, 25.5%, 25%, 24%, 22%, 20%, 18%, 15% or 10% relative to the total weight of the liquid crystal composition of the present invention.
In some embodiments of the invention, the compound of formula N comprises 0% to 60% by weight of the liquid crystal composition; preferably, the compound of formula N comprises 0.1 to 55 weight percent of the liquid crystal composition.
In some embodiments of the present invention, when it is desired to keep the viscosity of the liquid crystal composition of the present invention low and the response time short, it is preferable that the lower limit value and the upper limit value of the content of the compound of the general formula N be low; further, when it is desired to keep the clearing point of the liquid crystal composition of the present invention high and the temperature stability is good, it is preferable that the lower limit value and the upper limit value of the content of the compound of the formula N be low; in order to keep the drive voltage low and to increase the absolute value of the dielectric anisotropy, it is preferable that the lower limit value and the upper limit value of the content of the compound of the formula N be high.
In some embodiments of the invention, preferably, R N1 And R is N2 Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 9 carbon atoms, or a linear or branched alkenyl group having 2 to 10 carbon atoms; further preferably, R N1 And R is N2 Each independently represents 1 to 8A linear or branched alkyl group of carbon atoms, a linear or branched alkoxy group of 1 to 7 carbon atoms, or a linear or branched alkenyl group of 2 to 8 carbon atoms; still further preferably, R N1 And R is N2 Each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or a linear or branched alkenyl group having 2 to 5 carbon atoms.
In some embodiments of the invention, R N1 Still more preferably a linear or branched alkyl group having 1 to 5 carbon atoms, or a linear or branched alkenyl group having 2 to 5 carbon atoms; r is R N1 Even more preferred are straight or branched alkyl groups containing 2 to 5 carbon atoms, or straight or branched alkenyl groups containing 2 to 3 carbon atoms; r is R N2 Still more preferred are straight or branched chain alkoxy groups containing 1 to 5 carbon atoms.
In some embodiments of the invention, the ringAnd (C) a ring->Each independently represents
In some embodiments of the invention, the compound of formula N is selected from the group consisting of:
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in some embodiments of the present invention, the liquid crystal composition further comprises at least one compound selected from the group consisting of compounds of formula A-1 and formula A-2:
Wherein,,
R A1 and R is A2 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms,Or->One or not adjacent two or more-CH in the straight-chain or branched alkyl group containing 1 to 12 carbon atoms 2 -can be replaced independently of one another by-ch=ch-, -c≡c-, -O-, -CO-O-or-O-CO-, and the straight-chain or branched alkyl radical having 1 to 12 carbon atoms, -or>Wherein one or more of-H's may each be independently substituted with-F or-Cl;
ring(s)Ring->Ring->And (C) a ring->Each independently representsWherein->Andone or more of-CH 2 Can be replaced by-O-and one or more single bonds in the ring can be replaced by double bonds, wherein +.>And->In which-H may be substituted by-F, -Cl or-CN, and-ch=may be substituted by-n=in one or more rings;
Z A11 、Z A21 and Z A22 Each independently represents a single bond, -CH 2 CH 2 -、-CF 2 CF 2 -、-CO-O-、-O-CO-、-O-CO-O-、-CH＝CH-、-CF＝CF-、-CH 2 O-or-OCH 2 -；
L A11 、L A12 、L A13 、L A21 And L A22 Each independently represents-H, an alkyl group having 1 to 3 carbon atoms, or halogen;
X A1 and X A2 Each independently represents halogen, haloalkyl or haloalkoxy having 1 to 5 carbon atoms, or haloalkenyl or haloalkenoxy having 2 to 5 carbon atoms;
n A11 represents 0, 1, 2 or 3, wherein when n A11 When=2 or 3, the ringZ, which may be the same or different A11 May be the same or different;
n A12 represents 1 or 2, wherein when n A12 When=2, the ringMay be the same or different; and is also provided with
n A2 Represents 0, 1, 2 or 3, wherein when n A2 When=2 or 3, the ringZ, which may be the same or different A21 May be the same or different.
The compounds related to the group consisting of the compounds of the general formula A-1 and the general formula A-2 account for the weight percentage of the liquid crystal composition of the invention: the lower limit value of the weight percentage of the compounds of the group consisting of the compounds of the general formula a-1 and the general formula a-2 is 0%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% or 20% with respect to the total weight of the liquid crystal composition of the present invention; the upper limit of the weight percentage of the compounds of the group consisting of the compounds of the general formula a-1 and the general formula a-2 is 60%, 55%, 50%, 45%, 40%, 38%, 35%, 30%, 28%, 27%, 26%, 25.5% or 25% with respect to the total weight of the liquid crystal composition of the present invention.
In some embodiments of the present invention, the compounds of the group consisting of compounds of formula A-1 and formula A-2 comprise 0% to 60% by weight of the liquid crystal composition.
In some embodiments of the invention, the compound of formula a-1 is selected from the group consisting of:
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wherein,,
R A1 represents a linear or branched alkyl group having 1 to 8 carbon atoms,Said straight or branched chain having 1 to 8 carbon atomsOf one or more than two non-adjacent-CH groups in the chain alkyl groups 2 -may each independently be replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-, and one or more-H of said straight or branched alkyl groups containing 1-8 carbon atoms may each independently be replaced by-F or-Cl;
R v and R is w Each independently represents-CH 2 -or-O-;
L A11 、L A12 、L A11 ’、L A12 ’、L A14 、L A15 and L A16 Each independently represents-H or-F;
L A13 and L A13 ' each independently represents-H or-CH 3 ；
X A1 representing-F, -CF 3 or-OCF 3 The method comprises the steps of carrying out a first treatment on the surface of the And is also provided with
v and w each independently represent 0 or 1.
The weight percentage of the compound of the general formula A-1 in the liquid crystal composition is as follows: the lower limit of the weight percent of the compound of the general formula a-1 is 0%, 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% or 20% relative to the total weight of the liquid crystal composition of the present invention; the upper limit of the weight percentage of the compound of the general formula a-1 is 50%, 45%, 40%, 38%, 35%, 30%, 28%, 27%, 26%, 25.5% or 25% with respect to the total weight of the liquid crystal composition of the present invention.
In some embodiments of the invention, the compound of formula A-1 comprises 0% to 50% by weight of the liquid crystal composition.
In the case where the viscosity of the liquid crystal composition of the present invention is kept low and the response speed is high, the preferable content of the compound of the general formula a-1 is preferably set to a low lower limit and the upper limit; further, when the clearing point of the liquid crystal composition of the present invention is kept high and the temperature stability is good, it is preferable to keep the lower limit value slightly low and the upper limit value slightly low; in order to keep the drive voltage low and to increase the absolute value of the dielectric anisotropy, it is preferable to have a slightly higher lower limit value and a slightly higher upper limit value.
In some embodiments of the invention, the compound of formula a-2 is selected from the group consisting of:
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wherein,,
R A2 represents a linear or branched alkyl group having 1 to 8 carbon atoms, one or not adjacent two or more-CH groups in the linear or branched alkyl group having 1 to 8 carbon atoms 2 -may each independently be replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-, and one or more-H present in these groups may each independently be substituted by-F or-Cl;
L A21 、L A22 、L A23 、L A24 And L A25 Each independently represents-H or F; and is also provided with
X A2 representing-F, -CF 3 、-OCF 3 or-CH 2 CH 2 CH＝CF 2 。
The weight percentage of the compound of the general formula A-2 in the liquid crystal composition is as follows: the lower limit of the weight percent of the compound of the general formula a-2 is 0%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% or 20% relative to the total weight of the liquid crystal composition of the present invention; the upper limit of the weight percentage of the compound of the general formula a-2 is 60%, 55%, 50%, 45.5%, 45%, 42.5%, 40%, 35%, 30%, 28%, 27%, 26% or 25% with respect to the total weight of the liquid crystal composition of the present invention.
In some embodiments of the invention, the compound of formula A-2 comprises 0% to 60% by weight of the liquid crystal composition.
In the case where the viscosity of the liquid crystal composition of the present invention is kept low and the response speed is high, the preferable content of the compound of the general formula a-2 is preferably set to a low lower limit and the upper limit; further, when the clearing point of the liquid crystal composition of the present invention is kept high and the temperature stability is good, it is preferable to keep the lower limit value slightly low and the upper limit value slightly low; in order to keep the drive voltage low and to increase the absolute value of the dielectric anisotropy, it is preferable to have a slightly higher lower limit value and a slightly higher upper limit value.
In addition to the above-mentioned compounds, the liquid crystal composition of the present invention may contain a usual nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, antioxidant, ultraviolet absorber, infrared absorber, polymerizable monomer, light stabilizer, or the like.
Possible dopants which are preferably added to the liquid crystal composition according to the invention are shown below.
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In some embodiments of the invention, the dopant comprises 0% to 5% by weight of the liquid crystal composition; preferably, the dopant comprises 0.01% to 1% by weight of the liquid crystal composition.
The additives such as antioxidants and light stabilizers used in the liquid crystal composition of the present invention are preferably the following:
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wherein n represents a positive integer of 1 to 12.
Preferably, the light stabilizer is selected from the group consisting of the light stabilizers shown below:
in some embodiments of the invention, the light stabilizer comprises 0% to 5% by weight of the total weight of the liquid crystal composition; preferably, the light stabilizer comprises 0.01% -1% of the total weight of the liquid crystal composition; more preferably, the light stabilizer comprises 0.01% to 0.1% by weight of the total weight of the liquid crystal composition.
In yet another aspect, the present invention provides a liquid crystal display device comprising the liquid crystal composition of the present invention.
The beneficial effects are that:
compared with the prior art, the liquid crystal compound with the general formula I provided by the invention also has a larger clearing point, larger optical anisotropy and larger absolute value of dielectric anisotropy under the condition of maintaining proper rotational viscosity, so that the liquid crystal composition containing the liquid crystal compound also has a larger clearing point, larger optical anisotropy, larger absolute value of dielectric anisotropy, larger elastic constant and smaller ratio of rotational viscosity to splay elastic constant under the condition of maintaining proper low-temperature storage stability and proper rotational viscosity, and further the liquid crystal display device containing the liquid crystal composition has a wider nematic phase temperature range, better contrast ratio, lower threshold voltage and shorter response time.
Detailed Description
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
For ease of expression, in the following examples, the group structures of the liquid crystal compounds are represented by the codes listed in Table 2:
TABLE 2 group Structure codes for liquid Crystal Compounds
Take as an example a compound of the formula:
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the structural formula is expressed by codes listed in table 1, and can be expressed as follows: nCCGF, where n in the code represents the number of C atoms in the left-hand alkyl group, e.g., n is "3", i.e., the alkyl group is-C 3 H 7 The method comprises the steps of carrying out a first treatment on the surface of the C in the code represents 1, 4-cyclohexylene, G represents 2-fluoro-1, 4-phenylene and F represents fluorine.
The shorthand designations for the test items in the following examples are as follows:
cp clearing point (nematic phase-isotropic phase transition temperature, DEG C)
Delta n optical anisotropy (589 nm,25 ℃ C.)
Delta epsilon dielectric anisotropy (1 KHz,25 ℃ C.)
t -30℃ Low temperature storage time (h, -30 ℃ C.)
γ 1 Rotational viscosity (mPa.s, 25 ℃ C.)
K 11 Elastic constant of splay
K 33 Flexural spring constant
γ 1 /K 11 Ratio of rotational viscosity to splay elastic constant
Wherein,,
cp: obtained by a melting point tester test.
An: the product was obtained by testing at 25℃under a sodium light (589 nm) source using an Abbe refractometer.
Δε：Δε＝ε ∥ -ε ⊥ Wherein ε is ∥ For dielectric constant parallel to the molecular axis ε ⊥ For dielectric constants perpendicular to the molecular axis, test conditions: VA type test box with 25 deg.C, 1KHz and box thickness of 6 μm.
t -30℃ : the nematic liquid crystal medium was placed in a glass bottle, stored at-30℃and the time recorded when crystal precipitation was observed.
γ 1 : the liquid crystal display is obtained by testing by using an LCM-2 liquid crystal physical property evaluation system; test conditions: 25 ℃, 240V, 20 μm thick test box.
K 11 And K 33 : testing the C-V curve of the liquid crystal by using an LCR instrument and a VA test box and calculating; test conditions: the thickness of the cell is 6 μm and v=0.1 to 20V.
The liquid-crystalline compounds of the general formula I according to the invention can be prepared by conventional organic synthesis methods, in which the introduction of the target end groups, ring structures and linking groups into the starting materials is described in the following documents: organic synthesis (Organic Synthesis, john wili parent-child publishing company (John Wiley & Sons inc.), organic reaction (Organic Reactions, john wili parent-child publishing company (John Wiley & Sons inc.), and comprehensive organic synthesis (Comprehensive Organic Synthesis, pegman publishing company (Pergamon Press)), and the like.
Generating the linking group Z in the liquid-crystalline compounds of the formula I 1 、Z 2 And Z 3 The method of (1) can be referred to the following scheme, wherein MSG 1 Or MSG 2 Is a 1-valent organic group having at least one ring, a plurality of MSGs used in the following schemes 1 (or MSG) 2 ) May be the same or different.
(1) Synthesis of Single bond
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Arylboronic acid 1 is combined with compound 2 synthesized by known methods in aqueous sodium carbonate in the presence of a catalyst (e.g., tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) In the presence of a single bond to give the single bond compound IA. It is also possible to synthesize the compound 3 by known methods by reacting it with n-butyllithium (n-BuLi) and then with zinc chloride, and then reacting it with a catalyst such as bis (triphenylphosphine) palladium dichloride (PdCl 2 (PPh 3 ) 2 ) With compound 2) in the presence of a catalyst to produce compound IA.
(2) -CO-O-and-O Synthesis of-CO-
Compound 3 was reacted with n-butyllithium and then reacted with carbon dioxide to obtain carboxylic acid 4. Compound 4 was dehydrated with phenol 5 synthesized by a known method in the presence of 1, 3-Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) to synthesize compound IB having-CO-O-. Compounds having-O-CO-can also be synthesized by this method.
(3)-CF 2 O-and-OCF 2 -synthesis of
Reference m. kuroboshi et al, chem. Rapid et al (chem. Lett.), 1992,827, compound 6 was obtained by treatment of compound IB with a sulfiding agent, such as lawsen's reagent, followed by fluorination of compound 6 with hydrogen fluoride-pyridine (HF-Py) and N-bromosuccinimide (NBS) to synthesize a compound having-CF 2 Compound IC of O-. Reference may also be made to W.H. Bunnelle et al, journal of organic chemistry (J. Org. Chem), 1990, 55, 768, by fluorinating compound 6 with (diethylamino) sulfur trifluoride (DAST) Preparation of the compositions having-CF 2 Compound IC of O-. Synthesis of the polypeptide having-OCF by these methods is also possible 2 -a compound.
(4) -ch=ch-synthesis
Compound 3 is reacted with N-butyllithium and then with a formamide, such as N, N-Dimethylformamide (DMF), to obtain aldehyde 7. Potassium tert-butoxide (t-BuOK) was reacted with phosphonium and aldehyde 7 produced by reacting phosphonium salt 8 synthesized by a known method to give compound ID. The above process yields the cis-isomer due to the reaction conditions. It will be appreciated that the cis-isomer may be converted to the trans-isomer by known methods, as desired.
(5)-CH 2 CH 2 -synthesis of
Compound IE can be prepared by subjecting compound ID to hydrogenation reaction with a catalyst such as palladium on carbon (Pd/C).
(6)-CH 2 O-or-OCH 2 -synthesis of
Sodium borohydride (NaBH) 4 ) The compound 7 was reduced to obtain a compound 9. Then, compound 9 is halogenated with hydrobromic acid to obtain compound 10, or the hydroxyl group of compound 9 is protected with p-toluenesulfonic acid (TsOH) to obtain compound 11. Then, compound 10 or compound 11 is reacted with compound 5 in the presence of potassium carbonate to obtain compound IF. Synthesis of the compounds having-OCH by these methods is also possible 2 -a compound.
Regarding the rings such as 1, 4-cyclohexylene, 1, 3-dioxane-2, 5-diyl, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, 2,3,5, 6-tetrafluoro-1, 4-phenylene, starting materials or synthetic methods thereof have been commercially available and are well known in the art.
Preferred synthetic methods for representative compounds are set forth below.
Example 1
The synthetic route for compound I-1-1 is shown below:
step 1 preparation of the Compound of formula B-3
160g of the compound of formula B-1 ((4-ethoxy-2, 3-difluorophenyl) boric acid), 160.5g of the compound of formula B-2 (2-bromo-6-fluorophenol) and 72g of sodium carbonate were charged into a 3L reaction flask, and sufficiently dissolved with 1.2L of a mixed solvent consisting of toluene, ethanol and water (toluene, ethanol and water in a volume ratio of 2:1:1). Under the protection of nitrogen, 0.5g of dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium (II) is added and the mixture is refluxed for 6 hours. After the completion of the reaction, the reaction solution was cooled, 500mL of water was added to separate the solution, the aqueous phase was extracted with toluene, the organic phases were combined, the organic phase was washed with saturated brine to neutrality, dried, concentrated, and recrystallized from isopropyl alcohol to obtain 182.8g of a compound of formula B-3 (4 '-ethoxy-2', 3 '-trifluoro- [1,1' -biphenyl ] -2-ol) as a white solid (purity: 99.35%, yield: 86%).
MS：164(20％)、191(13％)、240(100％)、268(70％)。
Step 2 preparation of the Compound of formula B-4
180g of the compound of formula B-3 and 180g of potassium carbonate are placed in a 3L reaction flask and are fully dissolved with 800mL of N, N-dimethylformamide. The reaction was carried out at 130℃for 12h. After the reaction was completed, the reaction solution was cooled, 3L of water was added, stirred, suction-filtered to obtain a crude product, which was slurried with ethanol, suction-filtered, and dried to obtain 142g of a compound of formula B-4 (3-ethoxy-4, 6-difluorodibenzo [ B, d ] furan) as a white solid (purity: 99.25%, yield: 85.4%).
MS：144(20％)、191(15％)、220(100％)、248(70％)。
Step 3 preparation of the Compound of formula B-5
120g of the compound of formula B-4 was placed in a 2L reaction flask and dissolved well with 700mL of tetrahydrofuran under nitrogen. 168mL of n-butyllithium was added at-80℃and the reaction was carried out at-80℃for 3 hours. 79.18g of triisopropyl borate is added and the temperature is controlled at-80 ℃ to react for 3 hours. Dilute hydrochloric acid was added to adjust ph=2-3, slurried once with 200mL of water and once with 300mL of petroleum ether, suction filtration, and filter cake drying gave 118.6g of a white solid of the compound of formula B-5 ((7-ethoxy-4, 6-difluorodibenzo [ B, d ] furan-3-yl) boronic acid) as a white solid (purity: 99.04%, yield: 84%).
MS：43.9(100％)、206(33％)、236(100％)、263(25％)、292(35％)。
Step 4 preparation of the Compound of formula I-1-1
Into a 1L reaction flask were charged 60g of the compound of formula B-5, 45.5g of the compound of formula B-6 (3, 4, 5-trifluorobromobenzene) and 15.5g of sodium carbonate, and sufficiently dissolved with 0.6L of a mixed solvent consisting of toluene, ethanol and water (the volume ratio of toluene, ethanol and water is 2:1:1). Under the protection of nitrogen, 0.2g of dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium (II) is added and the mixture is refluxed for 4 hours. After the completion of the reaction, the reaction solution was cooled, 300mL of water was added, the aqueous phase was separated, toluene was extracted, the organic phases were combined, the organic phase was washed with saturated brine until ph=7, dried, concentrated, and recrystallized from petroleum ether to obtain 65g of a compound of formula I-1-1 (3-ethoxy-4, 6-difluoro-7- (3, 4, 5-trifluorophenyl) dibenzo [ b, d ] furan) (purity: 99.57%, yield: 84%) as a white solid.
MS：274(18％)、292(15％)、350(100％)、378(35％)。
According to the above synthesis method, the compound of formula B-6 can be replaced with the compound of formula B-12 shown in Table 3 below to give the objective compound I-1-2:
TABLE 3 Table 3
Example 2
The synthetic route for compound I-3-5-1 is shown below:
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step 1 preparation of the Compound of formula B-8
120g of the compound of formula B-7 ((2, 3-difluoro-4 '-propyl- [1,1' -biphenyl ] -4-yl) boric acid), 160.5g of the compound of formula B-2 (2-bromo-6-fluorophenol) and 83g of sodium carbonate were charged into a 3L reaction flask, and sufficiently dissolved with 1.2L of a mixed solvent composed of toluene, ethanol and water (toluene, ethanol and water in a volume ratio of 2:1:1). Under the protection of nitrogen, 0.5g of dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium (II) is added and the mixture is refluxed for 6 hours. After the reaction was completed, the reaction solution was cooled, 500mL of water was added to separate the aqueous phase, toluene was used to extract the aqueous phase 2 times, the organic phase was combined, the organic phase was washed with saturated brine to neutrality, dried, concentrated, and recrystallized with a mixed solvent of toluene and ethanol (volume ratio of toluene and ethanol: 1:1) to obtain 130g of a compound of the formula B-8 (2 ', 3' -trifluoro-4 "-propyl- [1,1':4',1" -terphenyl ] -2-ol) as a white solid (purity: 99.44%, yield: 87.3%).
MS：111(15％)、231(46％)、299(100％)、342(30％)。
Step 2 preparation of the Compound of formula B-9
120g of the compound of formula B-8 and 120g of sodium carbonate are placed in a 2L reaction flask and are fully dissolved with 800mL of N, N-dimethylformamide. The reaction was carried out at 130℃for 12h. After the reaction was completed, the reaction solution was cooled, 3L of water was added, stirred, suction-filtered to obtain a crude product, which was slurried with ethanol, suction-filtered, and dried to obtain 101g of a compound of formula B-9 (4, 6-difluoro-3- (4-propylphenyl) dibenzo [ B, d ] furan) as a white solid (purity: 99.15%, yield: 89.3%).
MS：119(26％)、203(36％)、279(100％)、322(33％)。
Step 3 preparation of the Compound of formula B-10
Into a 2L reaction flask was charged 95g of the compound of formula B-9 and dissolved well with 600mL of tetrahydrofuran. 141mL of n-butyllithium was added at-80℃under nitrogen protection, and the temperature was controlled at-80℃for 3 hours. 49.5g of triisopropyl borate was added thereto, and the reaction was carried out at-80℃for 3 hours. Dilute hydrochloric acid was added to adjust ph=2-3, and the mixture was sequentially slurried with water and petroleum ether, suction-filtered, and the cake was dried to obtain 90g of a compound of formula B-10 ((4, 6-difluoro-7- (4-propylphenyl) dibenzo [ B, d ] furan-3-yl) boronic acid) as a white solid (purity: 99.26%, yield: 83.4%).
MS：247(85％)、321(100％)、323(60％)、366(30％)。
Step 4 preparation of the Compounds of formula I-3-5-1
Into a 2L reaction flask were charged 80g of the compound of formula B-10, 46.3g of the compound of formula B-11 (3, 4-difluorobromobenzene) and 18g of sodium carbonate, and sufficiently dissolved with 0.8L of a mixed solvent consisting of toluene, ethanol and water (the volume ratio of toluene, ethanol and water is 2:1:1). Under the protection of nitrogen, 0.1g of dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium (II) is added and the mixture is refluxed for 4 hours. After the completion of the reaction, the reaction solution was cooled, 300mL of water was added, the aqueous phase was separated, the organic phases were extracted with toluene, and the organic phases were washed with saturated brine to ph=7, dried, concentrated, and recrystallized from petroleum ether to give 70g of a compound of formula I-3-5-1 (3- (3, 4-difluorophenyl) -4, 6-difluoro-7- (4-propylphenyl) dibenzo [ b, d ] furan) (purity: 99.69%, yield: 73.7%) as a white solid.
MS：119(24％)、315(39％)、321(75％)、391(100％)、434(37％)。
The liquid crystal compound of the general formula I prepared in the above example and the compound DB-1 known in the art (structural formula:respectively with mother liquid crystal according toThe mixture is formed by mixing 10 percent by weight and 90 percent by weight of the mixture. Values of various performance parameters of the test compounds were calculated by extrapolation (extrapolation method), wherein extrapolated values of Cp, Δn and Δε = ((measured value of mixture) -0.9× (measured value of parent liquid crystal))/0.1, γ 1 Extrapolated value = 10 10(lgA-0.9lgB) Wherein A is gamma of the mixture 1 B is gamma of mother liquid crystal 1 . The clearing point Cp, the optical anisotropy Deltan, the dielectric anisotropy Deltaepsilon and the rotational viscosity gamma are carried out according to the method 1 Derivation of the values of the equal performance parameters.
The mother liquid crystals were liquid crystal compositions shown in the following table 4:
TABLE 4 Table 4
The extrapolated results of the liquid crystal performance parameters for the above compounds are shown in Table 5 below:
TABLE 5
Codes of the general formula Component code Cp Δn γ 1 Δε
DB-1 2OB(O)O2 55 0.189 126 -13.5
I-1-1 2OB(O)UF 80 0.210 130 -16
I-1-2 2OB(O)POCF3 75.3 0.213 133 -17.5
I-3-5-1 3PB(O)GF 120.6 0.215 150 -17
As is clear from table 5 above, the liquid crystal compound of the general formula I of the present invention also has a larger clearing point, a larger optical anisotropy and a larger absolute value of dielectric anisotropy while maintaining a proper rotational viscosity, as compared with the liquid crystal compound of the prior art.
Comparative example 1 was used
The liquid crystal composition of comparative example 1 was prepared by the respective compounds listed in table 6 and their weight percentages, and was filled between two substrates of a liquid crystal display for performance test.
TABLE 6 formulation of liquid Crystal composition and results of Performance parameter test
Application example 1
The liquid crystal composition of application example 1 was prepared according to each of the compounds listed in table 7 and weight percentages thereof, and was filled between two substrates of a liquid crystal display for performance test.
TABLE 7 formulation of liquid Crystal composition and results of Performance parameter test
Comparative example 2 was used
The liquid crystal composition of comparative example 2 was prepared by the respective compounds listed in table 8 and their weight percentages, and was filled between two substrates of a liquid crystal display for performance test.
TABLE 8 formulation of liquid Crystal composition and results of Performance parameter test
Application example 2
The liquid crystal composition of application example 2 was prepared according to each of the compounds listed in table 9 and weight percentages thereof, and was filled between two substrates of a liquid crystal display for performance test.
TABLE 9 formulation of liquid Crystal composition and results of Performance parameter test
Application example 3
The liquid crystal composition of application example 3 was prepared according to each of the compounds listed in table 10 and weight percentages thereof, and was filled between two substrates of a liquid crystal display for performance test.
TABLE 10 formulation of liquid Crystal composition and results of Performance parameter test
Application example 4
The liquid crystal composition of application example 4 was prepared according to each of the compounds listed in table 11 and its weight percentage, and was filled between two substrates of a liquid crystal display for performance test.
TABLE 11 formulation of liquid Crystal composition and results of Performance parameter test
Application example 5
The liquid crystal composition of application example 5 was prepared according to each of the compounds listed in table 12 and weight percentages thereof, and was filled between two substrates of a liquid crystal display for performance test.
TABLE 12 formulation of liquid Crystal composition and results of Performance parameter tests
As can be seen from the comparison of application comparative example 1 and application example 1 and the comparison of application comparative example 2 and application example 2, the liquid crystal composition provided by the present invention also has a larger clearing point, a larger optical anisotropy, a larger absolute value of dielectric anisotropy, a larger elastic constant and a smaller ratio of rotational viscosity to splay elastic constant while maintaining suitable low-temperature storage stability and suitable rotational viscosity, thereby enabling a liquid crystal display device comprising the liquid crystal composition to have a wider nematic phase temperature range, a better contrast ratio, a lower threshold voltage and a shorter response time.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement it, but not limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.

Claims (7)

1. A liquid crystal compound of formula I selected from the group consisting of:
and
Wherein,,
R 1 represents a linear or branched alkyl group having 1 to 12 carbon atoms,One or not adjacent two or more-CH in the straight-chain or branched alkyl group containing 1 to 12 carbon atoms 2 -can be replaced independently of one another by-c=c-, -c≡c-, -O-, -CO-O-or-O-CO-, and the straight-chain or branched alkyl radical having 1 to 12 carbon atoms, -or>Wherein one or more of-H's may each be independently substituted with-F or-Cl;
ring(s)And (C) a ring->Each independently represents->
X represents-O-or-S-;
y represents-F, -CF 3 、-OCF 3 or-CH 2 CH 2 CH＝CF 2 ；
Z 1 、Z 2 And Z 3 Each independently represents a single bond; and is also provided with
L 1 、L 2 And L 3 Each independently represents-H, halogen, -OCH 3 or-CH 3 。
2. A liquid crystal composition comprising at least one liquid crystal compound of the general formula I according to claim 1.
3. The liquid crystal composition according to claim 2, wherein the liquid crystal compound of formula I is 0.1 to 40% by weight of the liquid crystal composition.
4. The liquid crystal composition according to claim 2, characterized in that it further comprises at least one compound of formula M:
wherein,,
R M1 and R is M2 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, One or not adjacent two or more-CH in the straight-chain or branched alkyl group containing 1 to 12 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-;
ring(s)Ring->And (C) a ring->Each independently represents-> Wherein->One or more of-CH 2 Can be replaced by-O-and +.>At most one-H of (c) may be substituted by halogen;
Z M1 and Z M2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH 2 O-、-OCH 2 -、-C≡C-、-CH＝CH-、-CH 2 CH 2 -or- (CH) 2 ) 4 -; and is also provided with
n M Represents 0, 1 or 2, wherein when n M When=2, the ringZ, which may be the same or different M2 May be the same or different.
5. The liquid crystal composition according to claim 4, wherein the compound of formula M is selected from the group consisting of:
and
6. The liquid crystal composition according to claim 2, characterized in that it further comprises at least one compound of formula N:
Wherein,,
R N1 and R is N2 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, One or not adjacent two or more-CH in the straight-chain or branched alkyl group containing 1 to 12 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-;
ring(s)And (C) a ring->Each independently represents->Wherein the method comprises the steps ofOne or more of-CH 2 Can be replaced by-O-and one or more single bonds in the ring can be replaced by double bonds, wherein +.>In which-H may be substituted by-F, -Cl or-CN, and-ch=may be substituted by-n=in one or more rings;
Z N1 and Z N2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH 2 O-、-OCH 2 -、-CH＝CH-、-C≡C-、-CH 2 CH 2 -、-CF 2 CF 2 -、-(CH 2 ) 4 -、-CF 2 O-or-OCF 2 -；
L N1 And L N2 Each independently represents-H, alkyl having 1 to 3 carbon atoms or halogen; and is also provided with
n N1 Represents 0, 1, 2 or 3, n N2 Represents 0 or 1, and 0.ltoreq.n N1 +n N2 Not more than 3, wherein when n N1 When=2 or 3, the ringZ, which may be the same or different N1 May be the same or different.
7. A liquid crystal display device comprising the liquid crystal composition of any one of claims 2 to 6.
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