CN110804005A - Compound, liquid crystal composition, liquid crystal display element and liquid crystal display - Google Patents
Compound, liquid crystal composition, liquid crystal display element and liquid crystal display Download PDFInfo
- Publication number
- CN110804005A CN110804005A CN201810880672.4A CN201810880672A CN110804005A CN 110804005 A CN110804005 A CN 110804005A CN 201810880672 A CN201810880672 A CN 201810880672A CN 110804005 A CN110804005 A CN 110804005A
- Authority
- CN
- China
- Prior art keywords
- carbon atoms
- group
- substituted
- liquid crystal
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C317/18—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D331/00—Heterocyclic compounds containing rings of less than five members, having one sulfur atom as the only ring hetero atom
- C07D331/04—Four-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
-
- 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
- C09K19/42—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
-
- 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
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention relates to a compound, a liquid crystal composition, a liquid crystal display element and a liquid crystal display. The compound is shown in the formula I. The liquid crystal composition contains a compound shown in a formula I. The compound shown in the formula I has the advantages of good intersolubility with other compounds, good ultraviolet ray tolerance and the like. The Reactive Mesogen (RM) has the advantages of good intersolubility, high charge retention rate (VHR), high polymerization activity (less monomer residue) and the like, and not onlyThe self-aligning agent can be used as the self-aligning agent of the liquid crystal composition alone or used as a vertical alignment material and other RM copolymerized for the liquid crystal composition of PSA (polymer supported alignment) and PS (polymer stabilized) modes, can avoid PI (polyimide) process, simplifies the process of a liquid crystal display element or a liquid crystal display and improves the production efficiency.
Description
Technical Field
The invention belongs to the technical field of liquid crystal display, and particularly relates to a compound, a liquid crystal composition containing the compound, and a liquid crystal display element or a liquid crystal display containing the compound or the liquid crystal composition.
Background
The liquid crystal medium used for display elements of active matrix addressing type such as VA mode is not perfect, and for example, the image sticking level is significantly inferior to that of display elements of positive dielectric anisotropy, and the liquid crystal medium has disadvantages of relatively slow response time, relatively high driving voltage, and the like. At this time, some of the novel VA display technologies are silent but are still living: the PSVA technology realizes a wide-field-angle display mode similar to MVA/PVA, and simplifies the CF process, thereby reducing the CF cost, improving the aperture opening ratio, obtaining higher brightness and further obtaining higher contrast. In addition, because the liquid crystal of the whole surface has the pretilt angle and does not have domino delay phenomenon, the liquid crystal can obtain faster response time under the condition of keeping the same driving voltage, and the afterimage level can not be influenced. Like UVVA technique, on the basis of keeping PSVA technical advantage, because do not have Slit structure on TFT side, the uneven problem of display that the uneven pixel electrode width arouses has still been improved. Despite the continuous development of display devices, there is a continuing effort to develop new liquid-crystalline compounds which lead to a continuous development of liquid-crystalline media and their properties for use in display devices.
The polymerizable mesogenic unit (RMs) is currently a very popular and important topic in the display industry, and the possible applications include Polymer Sustained Alignment (PSA) liquid crystal display, polymer sustained blue phase (PS-BP) liquid crystal display, and patterned Retarder Film (Pattern recorder Film).
The PSA principle is being applied in different typical LC displays, such as PSA-VA, PSA-OCB, PS-IPS/FFS and PS-TN liquid crystal displays. Taking the PSA-VA display, which is currently most widely used, as an example, the pretilt angle of the liquid crystal cell can be obtained by the PSA method, which has a positive effect on the response time. For PSA-VA displays, standard MVA or PVA pixel and electrode designs can be used, but if the electrode design on one side is specially patterned and the other side is not raised, the production can be significantly simplified, while achieving very good contrast and very high light transmission of the display.
The prior art has found that the application of LC mixtures and RMs in PSA displays still has some disadvantages. For example, the panel process requires PI coating, which not only complicates the process and affects the production line capacity, but also causes the emission of organic pollutants.
Disclosure of Invention
The invention provides a compound capable of realizing a self-alignment function, a liquid crystal composition containing the compound, a liquid crystal display element or a liquid crystal display comprising the compound or the liquid crystal composition, and a PSVA liquid crystal composition especially suitable for display or TV application.
The compound has the advantages of good intersolubility with other compounds and good ultraviolet ray tolerance. The Reactive Mesogen (RM) has the advantages of high charge retention rate (VHR) and high polymerization activity (less monomer residue), can be used as a self-alignment agent of the liquid crystal composition alone, can also be used as a self-alignment agent of a vertical alignment material copolymerized with other RMs and used for liquid crystal compositions in PSA and PS modes, can avoid a PI process and improve the production efficiency.
The liquid crystal composition contains one or more compounds shown in the formula I, a layer of polymer with rough surface is spontaneously formed through polymerization of the compounds shown in the formula I, the effects of PI insulation and vertical alignment of liquid crystal molecules can be achieved, the PI manufacturing process can be avoided, the manufacturing process of a liquid crystal display element or a liquid crystal display is simplified, and the production efficiency is improved. In addition, the liquid crystal composition has lower viscosity, can realize quick response, and simultaneously has moderate dielectric anisotropy delta epsilon, moderate optical anisotropy delta n and high stability to heat and light. The liquid crystal display element or the liquid crystal display comprising the liquid crystal composition has the properties of wide nematic phase temperature range, proper or higher birefringence anisotropy delta n, very high resistivity, good ultraviolet resistance, high charge retention rate, low vapor pressure and the like.
In order to achieve the above object, the present invention provides a compound represented by the following formula I:
wherein R is0Represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R is0Any one or more of the radicals indicated being unconnected-CH2-may each independently be replaced by-O-or cycloalkylene;
examples of the cycloalkylene group include a cyclopentylene group, a cyclobutyl group and a cyclopropylene group, that is, a cycloalkylene group having 3 to 5 carbon atoms;
q represents 1, 2 or 3;
K1、K2each independently represents an aromatic ring, a heteroaromatic ring, an aliphatic ring, a condensed ring, a spiro ring or a bridged ring, any of which is-CH2-optionally substituted by-O-, -S-, one or more H on the ring optionally being replaced by L or-Sp1-P5Substitution;
l represents F, -Sp2-X1Alkyl group having 1 to 10 carbon atoms, fluorine-substituted alkyl group having 1 to 10 carbon atomsA group which is a group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and any of-CH2-may be replaced by cyclopentylene, cyclobutyl, cyclopropylene;
P5represents H or a polymerizable group;
Sp1、Sp2each independently represents a single bond or a spacer;
X1each independently represents an alkyl-substituted sulfone having 1 to 10 carbon atoms, a cyclic sulfone, an alkyl-substituted sulfoxide having 1 to 10 carbon atoms, a cyclic sulfoxide, a hydroxyl group, an ester group, a carbonyl group or a mercapto group, wherein at least one X1Represents an alkyl-substituted sulfone having 1 to 10 carbon atoms, a cyclic sulfone, an alkyl-substituted sulfoxide having 1 to 10 carbon atoms or a cyclic sulfoxide; wherein any H in said alkyl as a substituent is optionally substituted by F, any one or more unconnected-CH2-optionally substituted by-O-, -S-;
Z0represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, -OCH2-、-CH2O-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-(CH2)n1-、-CF2CH2-、-CH2CF2-、-(CF2)n2-、-CH＝CH-、-C≡C-、-CF＝CF-、-CH＝CH-COO-、-OCO-CH＝CH-、-(CRYRZ)n3-、-CH(-Sp-P6)-、-CH2CH(-Sp-P6)-、-CH(-Sp-P6)CH(-Sp-P6)-，
n1、n2、n3Each independently represents 1, 2, 3 or 4;
RY、RZeach independently represents H or an alkyl group having 1 to 5 carbon atoms, and at least one is an alkyl group having 1 to 5 carbon atoms;
sp represents a single bond or a spacer;
P6represents H or a polymerizable group;
Rxrepresents (a), (b) or (c):
m1represents 1, 2, 3 or 4;
represents an aromatic, aliphatic or fused ring, any of which is-CH2-optionally substituted by-O-, -S-, one or more H on the ring optionally being replaced by L1or-Sp5-P4Substitution;
Sp3、Sp4、Sp5each independently represents a single bond or a spacer;
P4represents H or a polymerizable group;
L1represents F, -Sp3-X2An alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and any of-CH2-optionally substituted by cyclopentyl, cyclobutyl, cyclopropyl;
X2each independently represents an alkyl-substituted sulfone having 1 to 10 carbon atoms, a cyclic sulfone, an alkyl-substituted sulfoxide having 1 to 10 carbon atoms, or a cyclic sulfoxide; hydroxy, ester, carbonyl or mercapto, at least one of which is X1Represents an alkyl-substituted sulfone or cyclic sulfone having 1 to 10 carbon atoms; C1-C10 alkyl substituted sulfoxide or cyclic sulfoxide; any one H in said alkyl group being optionally substituted by F, any one or more unconnected-CH2-optionally substituted by-O-, -S-;
S1represents a trivalent radical, S2Represents a tetravalent group;
as the trivalent group, S may be mentioned1Represents the case of a trivalent group of carbon or silicon; as the tetravalent group, S may be mentioned2Represents the case of a tetravalent group of phosphorus.
The compound shown in the formula I has better solubility in the liquid crystal composition, the adding amount of the compound in the liquid crystal composition is generally between 0.5 and 5 percent, preferably between 1 and 2 percent, and the compound shown in the formula I is easy to absorb UV and is polymerized rapidly to form a polymer with an alignment function.
X1、X2Denotes an anchor group, X1、X2Each independently represents an alkyl-substituted sulfone having 1 to 10 carbon atoms, a cyclic sulfone, an alkyl-substituted sulfoxide having 1 to 10 carbon atoms, or a cyclic sulfoxide; hydroxyl, ester, carbonyl; wherein at least one X1、X2Represents an alkyl-substituted sulfone having 1 to 10 carbon atoms, a cyclic sulfone, an alkyl-substituted sulfoxide having 1 to 10 carbon atoms or a cyclic sulfoxide. After the liquid crystal composition is subjected to an ODF process, the compound shown in the formula I is spontaneously and vertically arranged on the surface of a panel (glass surface, ITO or polyimide), and a stable pretilt angle is formed after UV illumination polymerization under the condition of voltage application.
Anchoring group X1、X2Each independently is preferably selected from the group consisting of:
P4、P5、P6when representing a polymerizable group, a methacrylate group, an acrylate group, a vinyl group or an ethylene oxide group is preferable.
The "spacer" in the present invention means a chain-like group, preferably a branched or straight-chain alkyl group having 1 to 10 carbon atoms, wherein-CH is optionally disconnected in the alkyl group2-optionally substituted by-O-, optionally-CH2-optionally substituted by cyclopropylene, cyclobutylene or cyclopentylene.
K1、K2Each independently represents an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a fused ringA ring, spiro or bridged ring, any of which is-CH2-optionally substituted by-O-, -S-, one or more H on the ring optionally being replaced by L or-Sp1-a P substitution. The aromatic ring is preferably a benzene ring or a naphthalene ring; the heteroaromatic ring is preferably a benzene or naphthalene ring in which at least one-CH-is substituted by-N-; the aliphatic ring is preferably cyclohexane, cyclohexene, at least one-CH2Cyclohexane substituted by-O-or-S-, and at least one-CH2-cyclohexene substituted by-O-or-S-; fused rings are preferably indane, indene, indane substituted by-O-or-S-, and indene substituted by-O-or-S-; the spiro ring or bridged ring is preferably bicyclo (1,1,1) pentane, bicyclo (2,2,2) octane, bicyclo (3,3,0) octane, spiro (3,3) heptane, decahydronaphthalene or tetrahydronaphthalene, etc.
Optionally, the compound of formula I is selected from the group consisting of compounds of formula I1 through formula I37, described below.
The invention also provides a liquid crystal composition which comprises one or more compounds shown in the formula I.
Optionally, the liquid crystal composition of the present invention may further comprise one or more compounds of formula II, and one or more compounds of formula III,
in the formula II, R1、R2Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms,
In the formula III, R3、R4Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R3、R4Any one or more of unconnected-CH2Optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene,
Z1、Z2each independently represents a single bond, -CH2CH2-or-CH2O-，
m represents 1 or 2; n represents 0, 1 or 2.
Optionally, the one or more compounds represented by formula II are selected from compounds represented by formulas II 1-II 14; the one or more compounds shown in the formula III are selected from compounds shown in formulas III 1-III 11;
in the formulae III1 to III11, R3、R4Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R3、R4Any one or more of unconnected-CH2-may be replaced by cyclopentylene, cyclobutyl or cyclopropylene.
In the liquid crystal composition, in the compound shown in the formula I, X1、X2The anchor functional group, X1、X2Each independently an anchoring functional group having a sulfone or sulfoxide structure, or an anchoring functional group which may be a hydroxyl, carbonyl or ester structure. After the panel is processed by the ODF process, due to the acting force between the anchoring functional group and the molecules on the surface of the panel (glass surface, ITO electrode surface), the liquid crystal molecules close to the compound shown in the formula I are spontaneously vertically arranged on the upper surface of the panel glass or the ITO transparent electrode substrate, so that the liquid crystal molecules are vertically arranged. Under the irradiation of UV light, the compound shown in the formula I can be polymerized on a substrate to form a layer of polymer with rough surface, and the effect of insulating PI and vertically aligning liquid crystal molecules is achieved. The thickness of PI is usually 50nm to 120nm, and the amount of the compound represented by formula I added is preferably 1% or more in order to form a thin film having a thickness equivalent to that of PI after polymerization of the compound represented by formula I. In this case, the compound of the formula I is added in a relatively large amount, and therefore, a high demand is placed on its storage stability at low temperatures.
Since hydroxyl groups are likely to form hydrogen bonds and have a strong anchoring ability, however, since hydrogen atoms of hydroxyl groups are almost exposed protons, excessive use of the liquid crystal composition tends to cause a drop in VHR of the liquid crystal composition after heat and UV irradiation, which adversely affects the display effect of a liquid crystal display element or a liquid crystal display, for example, a problem of display afterimage of the liquid crystal display. The compound shown in the formula I provided by the invention uses less or no hydroxyl functional group as an anchoring functional group, but uses a functional group with a more stable sulfone or sulfoxide structure and a hydroxyl group or other functional groups (ester group and carbonyl group) with anchoring effect to be combined as the anchoring functional group of the compound shown in the formula I, so that the liquid crystal composition can show better stability to heat and UV, and VHR is kept from being reduced.
The compound shown in the formula I has the advantages of good intersolubility with other compounds, good ultraviolet ray tolerance and the like. The Reactive Mesogen (RM) has the advantages of good intersolubility, high charge retention rate (VHR), high polymerization activity (little monomer residue) and the like, can be used as a self-alignment agent of a liquid crystal composition independently, and can also be used as a self-alignment agent of a liquid crystal composition for copolymerization of a vertical alignment material and other RMs and used for PSA (polymer-supported alignment) and PS (polymer-stabilized) mode liquid crystal compositions, so that a PI (polyimide) process can be avoided, the process of a liquid crystal display element or a liquid crystal display is simplified, and the production efficiency is improved.
In addition, a liquid crystal composition or an optically anisotropic body of a liquid crystal composition comprising a compound represented by formula I also belongs to the protection scope of the present invention:
the compounds shown in the formula I have slightly different solubility in the liquid crystal composition due to different substituents, but can be added into the liquid crystal composition in an amount of 0.5-5% by mass. Since a certain thickness of the polymer formed by the compound of formula I is necessary to function as an insulator for PI, the compound of formula I should have sufficient solubility.
The compound shown in the formula I can be added into the liquid crystal composition in an amount of 0.5-5 wt%, preferably 1-3 wt%.
The amount (mass percentage) of the compound represented by the formula II added to the liquid crystal composition may be 15 to 60%, preferably 20 to 40%.
The amount (mass percentage) of the compound represented by the formula III added to the liquid crystal composition may be 20 to 60%, preferably 30 to 50%.
Optionally, the liquid crystal composition of the invention can also comprise one or more compounds shown as a formula IV
Wherein R is5、R6Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R5、R6Any one of-CH2-may be replaced by cyclopentylene, cyclobutyl or cyclopropylene; w represents-O-, -S-or-CH2O-。
Optionally, the one or more compounds of formula iv are selected from the group consisting of compounds of formulae iv 1-iv 6:
wherein R is61Represents an alkyl group having 2 to 6 carbon atoms.
The amount (mass percentage) of the compound represented by the formula IV added to the liquid crystal composition may be 1 to 15%, preferably 2 to 10%.
Optionally, the liquid crystal composition of the invention may further comprise one or more compounds represented by formula V
Wherein R is7、R8Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;
Optionally, the one or more compounds of formula v are selected from the group consisting of compounds of formulae v 1-v 4:
wherein R is71、R81Each independently represents an alkyl group having 2 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms; r82Represents an alkoxy group having 1 to 5 carbon atoms; among them, examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, a 2-propenyl group, or a 3-pentenyl group.
The amount (mass%) of the compound represented by the formula V added to the liquid crystal composition may be 1 to 40%, preferably 5 to 30%.
Optionally, the liquid crystal composition of the invention may further comprise one or more polymerizable compounds of formula VI,
P1、P2、P3Each independently represents a methacrylate group or an acrylate group.
Optionally, the one or more compounds of formula VI are selected from the group consisting of compounds of formulae VI 1-VI 3:
the compounds of formula VI are slightly less sensitive to UV and polymerize at a slower rate than the compounds of formula I, and are relatively superficial when the polymer is actually formed. When the compound shown in the formula VI and the compound shown in the formula I are added for copolymerization, the display effect can be improved, the polymer layer provides continuous and stable pretilt, and the pretilt of liquid crystal molecules is very favorable for improving the response speed of liquid crystals under an electric field. In the case of copolymerization of the compound of the formula VI with the compound of the formula I, the compound of the formula VI may be added in an amount of 0.1 to 1% by mass, preferably 0.2 to 0.5% by mass.
The liquid crystal composition of the present invention does not contain a particular amount of the componentsMeanwhile, the liquid crystal composition shows slightly different properties such as dielectric anisotropy Delta epsilon, optical anisotropy Delta n, transition temperature point Cp of a nematic phase of liquid crystal converted into liquid and stability at low temperature, but has the same characteristic that the rotational viscosity gamma1Lower. The liquid crystal display device can realize quick response. The liquid crystal composition has high stability to heat and light. The liquid crystal display element or the liquid crystal display comprising the liquid crystal composition has the properties of wide nematic phase temperature range, proper or higher birefringence anisotropy delta n, very high resistivity, good ultraviolet resistance, high charge retention rate, low vapor pressure and the like. PSVA liquid crystal compositions suitable for display or TV applications, in particular after long run, have no or significantly reduced image sticking.
The liquid crystal composition of the present invention may further comprise various functional dopants, preferably in an amount of 0.01 to 1% by mass, and the dopants are mainly antioxidants, ultraviolet absorbers, and chiral agents.
Examples of the antioxidant and ultraviolet absorber include:
s represents an integer of 1 to 10.
The invention also provides a liquid crystal display element or a liquid crystal display comprising any one of the liquid crystal compounds or the liquid crystal composition; the display element or display is an active matrix display element or display or a passive matrix display element or display.
Optionally, the liquid crystal display element or liquid crystal display is preferably an active matrix addressed liquid crystal display element or liquid crystal display.
Optionally, the active matrix display element or display is a PSVA-TFT liquid crystal display element or display without a PI alignment layer.
Drawings
FIG. 1 is a mass spectrum of compound I37.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The progress of the reaction is generally monitored by TLC, and the post-treatment after the completion of the reaction is generally water washing, extraction, combination of organic phases, drying, evaporation of the solvent under reduced pressure, recrystallization, and column chromatography, and those skilled in the art can implement the present invention as described below.
The percentages in the specification are mass percentages, the temperature is centigrade (DEG C), and the specific meanings and test conditions of other symbols are as follows:
cp represents a liquid crystal clearing point (DEG C), and is measured by a DSC quantitative method;
Δ n represents optical anisotropy, and Δ n ═ ne-no，noRefractive index of ordinary light, neThe refractive index of the extraordinary ray is measured under the conditions of 25 +/-2 ℃ and 589nm, and the Abbe refractometer is used for testing;
Δ ε represents dielectric anisotropy, and Δ ε∥-ε⊥Wherein, epsilon∥Is a dielectric constant parallel to the molecular axis,. epsilon⊥Dielectric constant perpendicular to the molecular axis, at 25 + -0.5 deg.C, 20 μm parallel box, INSTEC: ALCT-IR1 test;
VHR represents the voltage holding ratio (%), and the test conditions are 20 +/-2 ℃, voltage +/-5V, pulse width 10ms and voltage holding time 16.7 ms. The testing equipment is a TOYO Model6254 liquid crystal performance comprehensive tester.
The preparation method of the liquid crystal composition comprises the following steps: weighing each liquid crystal monomer according to a certain proportion, putting the liquid crystal monomers into a stainless steel beaker, putting the stainless steel beaker filled with each liquid crystal monomer on a magnetic stirring instrument for heating and melting, adding a magnetic rotor into the stainless steel beaker after most of the liquid crystal monomers in the stainless steel beaker are melted, uniformly stirring the mixture, and cooling to room temperature to obtain the liquid crystal composition.
The liquid crystal monomer structure of the embodiment of the invention is represented by codes, and the code representation methods of the liquid crystal ring structure, the end group and the connecting group are shown in the following table (I) and table (II).
Table (one): corresponding code of ring structure
Table (ii): corresponding codes for end groups and linking groups
Examples are:
the compounds of formula I can be prepared by the following schematic synthetic route:
the first scheme is as follows: chain (sulfoxide) sulfone structure without polymerizable functional group
Scheme II: chain (sulfoxide) sulfone structure containing one polymerizable functional group
The third scheme is as follows: cyclic sulfone structure containing two polymerizable functional groups
And the scheme is as follows: bis (sulfoxide) sulfone structure containing two polymerizable functional groups
And a fifth scheme: alcohol + (sulfoxide) structure containing two polymerizable functional groups
Scheme six: bis-alcohol + (ene) sulfone structure containing two polymerizable functional groups
Wherein k represents 0 to 20; j represents 1 or 2; riRepresents an alkyl or alkenyl group of 1 to 10 carbon atoms, wherein any hydrogen may be substituted by fluorine, and any one methylene group or a plurality of methylene groups not directly connected may be substituted by oxygen;
represents 1, 4-cyclohexylene or 1, 4-cyclohexylene in which any methylene group or methylene groups not directly connected are replaced by oxygen, 1, 4-phenylene, and H in the 1, 4-phenylene may be replaced by LiSubstitution; l isiRepresents H, or an alkyl, branched alkyl, cycloalkyl, alkenyl group having 1 to 20 carbon atoms, wherein any one methylene group or a plurality of methylene groups not directly connected are optionally replaced by oxygen, and any hydrogen atom is optionally substituted by fluorine.
Example 1:
According to the method described in patent CN105001879A, 4-bromo-2-ethyliodobenzene and 4-hydroxyphenylboronic acid are used as raw materials, and Pd (dppf)2Cl2Catalyzing, carrying out coupling reaction and then processing to obtain a brown oily substance 1; catalyzing the oily matter 1 and the 4-pentylphenylboronic acid by using tetrakis (triphenylphosphine) palladium, performing coupling reaction, and then processing to obtain a light yellow solid compound 2, wherein the total amount of the compound is 50g, and the purity of the compound is determined by HPLC: 98.5 percent.
Step 2
Adding 15.5g (0.10mol) of 2-bromoethyl methyl sulfide, 0.62g (0.01mol) of boric acid and 150ml of tetrahydrofuran into a reaction bottle, slowly adding 13.6g (0.12mol) of 30% hydrogen peroxide, stirring at room temperature, stopping the reaction when the raw materials disappear, adding water and petroleum ether, stirring, extracting, separating, extracting the water layer twice by using the petroleum ether, combining the petroleum ether layers, washing with water, spin-drying the solvent to obtain 13.5g of a compound 3 which is light yellow liquid,
GC:95.2％。
step 3
A reaction flask was charged with 17.2g (0.05mol) of Compound 2, 10.3g (0.06mol) of Compound 3, 11.0g (0.08mol) of potassium carbonate and 200ml of DMF, and heated and stirred, followed by reaction at 70 ℃ until disappearance of Compound 2 was detected on a plaque. Adding water and toluene, stirring, extracting, separating, extracting water layer with toluene twice, mixing toluene layers, washing with water, subjecting to silica gel column chromatography, spin-drying solvent, and recrystallizing with toluene and ethanol for 3 times to obtain white solid 10.5g, GC: 99.8%.
Example 2:
According to the method disclosed in patent CN105001879A, dissolving the compound 2 in dichloromethane, slowly adding a dichloromethane solution of bromine dropwise at low temperature, washing and separating the solution by using a saturated sodium bisulfite aqueous solution after the reaction is finished, combining organic layers after dichloromethane extraction, drying the organic layers by using anhydrous sodium sulfate after washing, spin-drying the solvent, performing silica gel column chromatography, and recrystallizing toluene and petroleum ether to obtain 53g of a compound 4 white solid, wherein GC is 95.6%.
Step 2
42.3g (0.10mol) of Compound 4, 8.4g (0.15mol) of propiolic alcohol, 1.9g (0.01mol) of cuprous iodide, 50ml of triethylamine and 500ml of toluene were charged into a reaction flask, heated to reflux under nitrogen protection, 0.5g of tetrakis (triphenylphosphine) palladium was added, and the reaction was refluxed until disappearance of Compound 4 was detected on a spot plate. Adding water and toluene, stirring, extracting, separating, extracting the water layer twice with toluene, mixing the toluene layers, washing with water, drying with anhydrous sodium sulfate, spin-drying the solvent, and recrystallizing with toluene and ethanol to obtain yellow solid 35g of compound 5, with GC content of 96.7%.
Step 3
Adding 35g of compound 5 and 400ml of tetrahydrofuran into a reaction bottle, stirring until the mixture is completely dissolved, adding 2g of 5% Pd/C, hydrogenating at room temperature for 6 hours, filtering to remove palladium carbon after the reaction is finished, and spin-drying the solvent to obtain 35g of compound 6 yellow solid, wherein GC is 96.0%.
Step 4
15.5g (0.10mol) of 2-bromoethyl methyl sulfide, 1.86g (0.03mol) of boric acid and 300ml of tetrahydrofuran are added into a reaction bottle, 40.8g (0.36mol) of 30% hydrogen peroxide are slowly added, stirring is carried out at room temperature, the reaction is stopped when the raw materials disappear by point plate detection, water and petroleum ether are added for stirring, extraction and liquid separation are carried out, a water layer is extracted twice by the petroleum ether, then the petroleum ether layer is combined, the solvent is dried after washing by water, 14.6g of light yellow liquid is obtained, and GC is 96.8%.
Step 5
Referring to step 3 in example 1, compound 8 was obtained as a pale yellow solid 16g, GC: 98.2 percent
Adding 16g (0.031mol) of compound 8, 6.1g (0.06mol) of triethylamine and 300ml of dichloromethane into a reaction bottle, stirring to dissolve completely, adding 6.2g (0.06mol) of methacryloyl chloride at room temperature, heating and refluxing to react until the compound 8 disappears; adding water, stirring, separating, extracting water layer with dichloromethane twice, mixing dichloromethane layers, washing with water, drying with anhydrous sodium sulfate, spin-drying solvent, dissolving with toluene, performing silica gel column chromatography, recrystallizing with toluene and ethanol for 3 times to obtain white solid 8.6g, HPLC 99.7%.
Example 3:
The starting material, 4-bromo-2, 5-dimethoxyphenethyl alcohol, was prepared according to the method described in patent CN 105001879A. Adding 210ml of DMF into a reaction bottle, adding 86.4g (0.33mol) of triphenylphosphine under the protection of nitrogen, stirring for dissolving, cooling to below 10 ℃, dropwise adding 52.8g (0.33mol) of bromine, stirring for 30min at room temperature after dropwise adding, dropwise adding a mixed solution of 78.3g (0.30mol) of 4-bromo-2, 5-dimethoxyphenethyl alcohol and 200ml of DMF, heating to about 55 ℃ for reaction until the raw materials disappear, cooling to room temperature, pouring into ice water, extracting with toluene, then spin-drying the solvent, dissolving the product with petroleum ether, performing silica gel column chromatography, spin-drying the solvent, and pumping the solvent at low temperature by an oil pump to obtain 75.0g of a yellow viscous liquid of a compound 9, wherein GC is 94.6%.
Step 2
Adding 75.0g (0.23mol) of the compound 9 into a reaction bottle, adding 400ml of ethyl acetate, stirring to dissolve completely, adding 65.5g (0.25mol) of triphenylphosphine, refluxing to react until the raw material 9 disappears, cooling to 0-10 ℃, separating out a solid, performing suction filtration to obtain a white solid, washing with ethyl acetate, and drying the solvent to obtain 120g of a compound 10 white solid, wherein HPLC (high performance liquid chromatography) is 96.9%.
Step 3
Adding 120g (0.20mol) of compound 10 into a reaction bottle, adding 600ml of tetrahydrofuran, stirring for complete dissolution, cooling to 0-10 ℃ under the protection of nitrogen, slowly adding 22.4g (0.20mol) of potassium tert-butoxide, controlling the temperature to be 0-10 ℃, reacting for 1h, dropwise adding a mixed solution of 21.0g (0.18mol) of tetrahydrothiopyran-4-one and 100ml of tetrahydrofuran, reacting for 3h at room temperature, pouring into ice water, extracting with toluene, then spin-drying the solvent, dissolving the product with petroleum ether, performing silica gel column chromatography, spin-drying the solvent, and recrystallizing toluene and ethanol to obtain 51.0g of compound 11 yellow solid, wherein GC is 96.9%.
Step 4
51g (0.15mol) of compound 11, 55.2g (0.15mol) of pentylcyclohexylidenebiphenylboronic acid, 500ml of toluene, 250ml of ethanol and 120ml of potassium carbonate (0.18mol) are added into a reaction flask, stirred under nitrogen protection until complete dissolution, 1.5g of tetrakis (triphenylphosphine) palladium is added, heating and refluxing are carried out for 4h, the mixture is poured into water, extracted by toluene, and subjected to silica gel column chromatography, partial solvent is removed, and toluene is recrystallized to obtain 69g of compound 12 yellow solid, wherein GC is 97.8%.
Step 5
Referring to step 3 of example 2, the compound 12 was hydrogenated to palladium on carbon to obtain the product compound 13, 68g of a yellow solid,
GC:97.2％。
Referring to step 4 of the reference example 2, the compound 13 was oxidized with hydrogen peroxide to obtain the product compound 14, which was recrystallized to obtain 58g of yellow solid, 96.7% GC.
Step 7
Adding 31g (0.05mol) of compound 14 into a reaction bottle, stirring and dissolving in 300ml of dichloromethane, cooling to-40 ℃ under the protection of nitrogen, slowly adding 27.8g (0.11mol) of boron tribromide, preserving heat and reacting for 3h, pouring the reaction liquid into ice water under stirring, separating out a solid, performing suction filtration, stirring and pulping a filter cake by using a mixed solution of petroleum ether and toluene, performing suction filtration, and drying in the air to obtain 18g of a white solid, and performing HPLC: 98.5 percent.
Step 8
Referring to example 2, step 6, compound 15 was esterified with methacryloyl chloride to give the product, which was recrystallized to give 10g of white solid, HPLC: 99.5 percent.
Example 4:
Dibromo compound 16 was prepared from compound 2 according to the procedure described in patent CN105001879A, giving 56g of a yellow viscous oil, GC: 97.8%.
Step 2
Referring to step 2 of reference example 2, a dibromo compound and an excess amount of propargyl alcohol were coupled to prepare a disubstituted compound 17, and further referring to step 3 of reference example 2, hydrogenation was carried out to obtain a reduced product compound 18, and after-treatment was carried out to obtain 42g of a viscous liquid, HPLC: 97.2%.
Step 3
According to the method described in patent CN105001879A, compound 19 was obtained from 2-bromoethoxymethylbenzene and diethyl malonate in the presence of sodium methoxide, and reduced with lithium aluminum hydride to obtain compound 20 as pale yellow oil, 67g in total, 94.2% by HPLC.
Step 4
Referring to step 1 in example 3, dibromo compound 21 was obtained as a yellow oil (66 g), 96.5% by GC.
Step 5
Adding 66g (0.20mol) of compound 21 into a reaction flask, dissolving in 300ml of DMF under stirring, cooling to 0 ℃ under the protection of nitrogen, slowly adding 39.2g (0.56mol) of a 300ml DMF mixed solution of sodium methyl mercaptide, reacting at room temperature overnight under the protection of nitrogen, pouring the reaction solution into ice water under stirring, extracting with toluene, performing silica gel column chromatography, removing the solvent by rotation to obtain 39g of light yellow liquid, and performing GC: 96.4 percent.
Referring to step 4 of the example 2, the compound 22 was oxidized with hydrogen peroxide to obtain the product compound 23, which was purified to obtain 38g of yellow liquid, 96.9% GC.
Step 7
Reference example 2, step 3, the compound 23 palladium on carbon was hydrodebenzylated to give the product compound 24 as a yellow liquid, 20g, GC: 96.2%.
Step 8
Referring to step 1 in reference example 3, bromo-product compound 25 was obtained from compound 24, which was reacted with compound 18, step 3 in reference example 1, to give etherified product compound 26, referring to step 6 in reference example 2, and column recrystallization was carried out to obtain the objective product, 11.2g white solid, 99.3% by HPLC.
Example 5:
Reference example 4 step 3, Compound 9 and Ethylacetoacetate under the action of sodium methoxide to give Compound 27
Step 2
With reference to Tetrahedron Letters 45(2004), 1873-1876, α -bromo product compound 28 was prepared from compound 27 according to literature procedures.
Step 3
Referring to step 5 of example 4, methylthio compound 29 was synthesized from compound 28; referring to step 4 of example 3, compound 29 and pentylcyclohexylidenebiphenylboronic acid were coupled under tetrakis (triphenylphosphine) palladium catalysis to give compound 30.
Step 4
Referring to step 3 of example 4, compound 31 was obtained by reducing compound 30 with lithium aluminum hydride; referring to step 4 of example 2, the compound 31 was oxidized with hydrogen peroxide to obtain a compound 32.
Step 5
Referring to step 7 of example 3, compound 33 was demethylated from compound 32 with boron tribromide.
Referring to step 6 of reference example 2, 2-bromoethanol reacts with methacryloyl chloride to produce compound 34, which reacts with compound 33 in step 3 of reference example 1 to obtain an etherification target product, which is purified and recrystallized to obtain 11g of white solid, HPLC:99.3 percent.
Example 6:
66g (0.20mol) of compound 19 was charged into a reaction flask, and the mixture was dissolved in 300ml of dry DMSO with stirring under nitrogen, 9.6g (0.24mol, content 60%) of sodium hydride was slowly added at room temperature, 30.2g (0.24mol) of methyl methylthiosulfonate was slowly added after 1 hour of reaction, the mixture was allowed to stand overnight at room temperature, the reaction mixture was slowly poured into ice water with stirring, extracted with toluene, subjected to silica gel column chromatography, and the solvent was removed by spinning to obtain compound 34, a pale yellow liquid 42g, GC: 94.3 percent.
Step 2
Referring to step 3 of reference example 4, compound 34 was reduced with lithium aluminum hydride to give diol product compound 35; referring to step 4 of example 2, compound 35 was oxidized with hydrogen peroxide to give compound 36.
Step 3
According to the method described in patent CN105001879A, bis-alcohol compound 36 is di-protected with tert-butyldimethylsilyl chloride to give compound 37; referring to step 3 of reference example 2, compound 37 was subjected to palladium on carbon to obtain product compound 38.
Step 4
Referring to step 1 of reference example 3, bromo product compound 39 is obtained from compound 38 and reacted with compound 18, step 3 of reference example 1, to give etherification product compound 40, which is further reacted with methacryloyl chloride to give compound 41, referring to step 6 of reference example 2.
Step 5
19.7g (0.02mol) of Compound 41 was dissolved in 250ml of tetrahydrofuran, cooled to 0 ℃, slowly added dropwise with 23.5ml (0.047mol) of 2N hydrochloric acid, the reaction solution was stirred at room temperature for 3 hours, carefully neutralized with saturated sodium bicarbonate ice water, the reaction solution was extracted with toluene, subjected to silica gel column chromatography, the solvent was removed by spinning, and recrystallized from petroleum ether and toluene to give the objective compound as a white solid (8.5 g, GC: 99.2 percent.
Example 7
Reference example 1, step 1, starting from pentylidenebiphenylboronic acid and 4-bromophenol via Pd (dppf)2Cl2Catalytic coupling to obtain a product 42; reference example 2, step 5, after etherification of compound 42 and compound 7, work-up afforded compound I37 as a white solid, totaling 10g, HPLC: 99.6 percent. The mass spectrum of compound I37 is shown in fig. 1.
Example 8: the components and their mass percentages in the liquid crystal composition are shown in the following table.
Example 9: the components and their mass percentages in the liquid crystal composition are shown in the following table.
Example 10: the components and their mass percentages in the liquid crystal composition are shown in the following table.
Example 11: the components and their mass percentages in the liquid crystal composition are shown in the following table.
Comparative example 1
I37 in example 11 was replaced by the existing reactive mesogen (A) having a dihydroxy structure
Comparing example 11 with comparative example 1, the liquid crystal composition provided in example 11 of the present invention has a higher VHR, and is more advantageous for improving the problem of image sticking of a liquid crystal display element or a liquid crystal display.
In summary, the compound of formula I can have an insulating effect of PI after polymerization, and can achieve vertical alignment. The polymer layer can provide continuous and stable pretilt after the voltage is removed, so that the liquid crystal molecules have stable pretilt, and the pretilt of the liquid crystal molecules is very favorable for improving the response speed of the liquid crystal molecules under an electric field.
Claims (10)
1. A compound of formula I:
wherein R is0Represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R is0Any one or more of the radicals indicated being unconnected-CH2-may each independently be replaced by-O-or cycloalkylene;
q represents 1, 2 or 3;
K1、K2each independently represents an aromatic ring, a heteroaromatic ring, an aliphatic ring, a fused ring, a spiro ring or a bridged ring, any of which-CH2Optionally substituted by-O-, -S-, K1、K2Optionally one or more H on the ring of (a) is substituted by L or-Sp1-P5Substitution;
l represents F, -Sp2-X1An alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and any of-CH2-optionally substituted by cyclopentylene, cyclobutyl, cyclopropylene;
P5represents H or a polymerizable group;
Sp1、Sp2each independently representA single bond or a spacer;
X1each independently represents an alkyl-substituted sulfone having 1 to 10 carbon atoms, a cyclic sulfone, an alkyl-substituted sulfoxide having 1 to 10 carbon atoms, or a cyclic sulfoxide; hydroxy, ester, carbonyl or mercapto, at least one of which is X1Represents an alkyl-substituted sulfone or cyclic sulfone having 1 to 10 carbon atoms; C1-C10 alkyl substituted sulfoxide or cyclic sulfoxide; any one H in said alkyl group being optionally substituted by F, any one or more unconnected-CH2-optionally substituted by-O-, -S-;
Z0represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, -OCH2-、-CH2O-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-(CH2)n1-、-CF2CH2-、-CH2CF2-、-(CF2)n2-、-CH＝CH-、-C≡C-、-CF＝CF-、-CH＝CH-COO-、-OCO-CH＝CH-、-(CRYRZ)n3-、-CH(-Sp-P6)-、-CH2CH(-Sp-P6) -, or, -CH (-Sp-P)6)CH(-Sp-P6)-；
n1、n2、n3Each independently represents 1, 2, 3 or 4;
RY、RZeach independently represents H or an alkyl group having 1 to 5 carbon atoms, and RY、RZAt least one of which is an alkyl group having 1 to 5 carbon atoms;
sp represents a single bond or a spacer;
P6represents H or a polymerizable group;
Rxrepresents (a), (b) or (c):
m1represents 1, 2, 3 or 4;
Sp3、Sp4、Sp5each independently represents a single bond or a spacer;
P4represents H or a polymerizable group;
L1represents F, -Sp3-X2An alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and any of-CH2-optionally substituted by cyclopentylene, cyclobutyl, cyclopropylene;
X2each independently represents an alkyl-substituted sulfone having 1 to 10 carbon atoms, a cyclic sulfone, an alkyl-substituted sulfoxide having 1 to 10 carbon atoms, or a cyclic sulfoxide; hydroxy, ester, carbonyl or mercapto, at least one of which is X1Represents an alkyl-substituted sulfone or cyclic sulfone having 1 to 10 carbon atoms; C1-C10 alkyl substituted sulfoxide or cyclic sulfoxide; any one H in said alkyl group being optionally substituted by F, any one or more unconnected-CH2-optionally substituted by-O-, -S-;
S1represents a trivalent radical, S2Represents a tetravalent group.
2. The compound of claim 1, selected from the group consisting of compounds represented by formula I1 to formula I37,
3. a liquid crystal composition comprising one or more compounds of claim 1 or claim 2.
4. The liquid crystal composition according to claim 3, further comprising one or more compounds represented by the following formula II and one or more compounds represented by the following formula III,
in the formula II, R1、R2Each independently represents a carbon atomA sub-number of 1 to 10 of an alkyl group, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, a carbon-1 to 10 alkoxy group, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, a carbon-2 to 10 alkenyl group, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, a carbon-3 to 8 alkenyloxy group or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms,
In the formula III, R3、R4Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R3、R4Any one or more of unconnected-CH2Optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene,
Z1、Z2each independently represents a single bond, -CH2CH2-or-CH2O-，
m represents 1 or 2; n represents 0, 1 or 2.
5. The liquid crystal composition of claim 4, wherein the one or more compounds of formula II are selected from the group consisting of compounds of formulae II 1-II 14; the one or more compounds shown in the formula III are selected from compounds shown in formulas III 1-III 11;
in the formulae III1 to III11, R3、R4Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R3、R4Any one or more of unconnected-CH2-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene.
6. The liquid crystal composition according to any one of claims 3 to 5, wherein the liquid crystal composition is a negative dielectric anisotropy liquid crystal composition further comprising one or more compounds represented by formula IV,
wherein R is5、R6Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms, a substituted alkoxy group having a fluorine-substituted alkyl group having a fluorine-,A fluorine-substituted alkenyl group having 2 to 10 carbon atoms, a carbon-3-8 alkenyloxy group or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R5、R6Any one of-CH2-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene; w represents-O-, -S-or-CH2O-。
7. The liquid crystal composition of any one of claims 3 to 6, wherein the liquid crystal composition is a negative dielectric anisotropy liquid crystal composition, and further comprises one or more compounds represented by formula V,
wherein R is7、R8Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;
8. The liquid crystal composition of any one of claims 3 to 7, further comprising one or more compounds of formula VI,
9. A liquid crystal display element or a liquid crystal display comprising the compound of claim 1 or 2, or the liquid crystal composition of any one of claims 3 to 8, which is an active matrix display element or a display or a passive matrix display element or a display.
10. The liquid crystal display element or the liquid crystal display according to claim 9, characterized in that: the active matrix display element or the active matrix display is a PSVA-TFT liquid crystal display element or a PSVA-TFT liquid crystal display without a PI alignment layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810880672.4A CN110804005A (en) | 2018-08-04 | 2018-08-04 | Compound, liquid crystal composition, liquid crystal display element and liquid crystal display |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810880672.4A CN110804005A (en) | 2018-08-04 | 2018-08-04 | Compound, liquid crystal composition, liquid crystal display element and liquid crystal display |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110804005A true CN110804005A (en) | 2020-02-18 |
Family
ID=69487039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810880672.4A Pending CN110804005A (en) | 2018-08-04 | 2018-08-04 | Compound, liquid crystal composition, liquid crystal display element and liquid crystal display |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110804005A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113493691A (en) * | 2020-04-01 | 2021-10-12 | Dic株式会社 | Polymerizable compound, liquid crystal composition containing polymerizable compound, and liquid crystal display element using same |
| CN113493690A (en) * | 2020-04-01 | 2021-10-12 | Dic株式会社 | Compound, liquid crystal composition and liquid crystal display element |
| CN113493694A (en) * | 2020-04-01 | 2021-10-12 | Dic株式会社 | Compound, liquid crystal composition and liquid crystal display element |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0670322A1 (en) * | 1994-03-01 | 1995-09-06 | Shin-Etsu Chemical Co., Ltd. | A silacyclohexane compound, a method of preparing it and a liquid crystal composition containing it |
| DE10335606A1 (en) * | 2002-08-29 | 2004-03-11 | Merck Patent Gmbh | Liquid crystalline compounds with tetrafluoro-oxyethylene and-or tetrafluoro-methyleneoxymethylene bridging groups, for use e.g. in media for electro-optical liquid crystal displays |
| CN101407482A (en) * | 2008-03-27 | 2009-04-15 | 河北迈尔斯通电子材料有限公司 | intermediate for synthesizing butene liquid crystal and synthetic method thereof |
| CN102888225A (en) * | 2012-10-13 | 2013-01-23 | 江苏和成显示科技股份有限公司 | Conjugated separate liquid crystal compound, and preparation method and application thereof |
| CN104478768A (en) * | 2014-12-26 | 2015-04-01 | 浙江永太科技股份有限公司 | Trifluoromethylsulfo fluorobenzene compound |
| CN105001879A (en) * | 2014-03-10 | 2015-10-28 | 默克专利股份有限公司 | Liquid crystalline media with homeotropic alignment |
| CN107955630A (en) * | 2016-10-18 | 2018-04-24 | 默克专利股份有限公司 | Liquid crystal media and the high frequency assembly for including it |
| CN108084029A (en) * | 2017-12-20 | 2018-05-29 | 石家庄诚志永华显示材料有限公司 | Liquid-crystal composition and liquid crystal display element |
-
2018
- 2018-08-04 CN CN201810880672.4A patent/CN110804005A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0670322A1 (en) * | 1994-03-01 | 1995-09-06 | Shin-Etsu Chemical Co., Ltd. | A silacyclohexane compound, a method of preparing it and a liquid crystal composition containing it |
| US5582764A (en) * | 1994-03-01 | 1996-12-10 | Shin-Etsu Chemical Co., Ltd. | Silacyclohexane compound, a method of preparing it and a liquid crystal composition containing it |
| DE10335606A1 (en) * | 2002-08-29 | 2004-03-11 | Merck Patent Gmbh | Liquid crystalline compounds with tetrafluoro-oxyethylene and-or tetrafluoro-methyleneoxymethylene bridging groups, for use e.g. in media for electro-optical liquid crystal displays |
| CN101407482A (en) * | 2008-03-27 | 2009-04-15 | 河北迈尔斯通电子材料有限公司 | intermediate for synthesizing butene liquid crystal and synthetic method thereof |
| CN102888225A (en) * | 2012-10-13 | 2013-01-23 | 江苏和成显示科技股份有限公司 | Conjugated separate liquid crystal compound, and preparation method and application thereof |
| CN105001879A (en) * | 2014-03-10 | 2015-10-28 | 默克专利股份有限公司 | Liquid crystalline media with homeotropic alignment |
| CN104478768A (en) * | 2014-12-26 | 2015-04-01 | 浙江永太科技股份有限公司 | Trifluoromethylsulfo fluorobenzene compound |
| CN107955630A (en) * | 2016-10-18 | 2018-04-24 | 默克专利股份有限公司 | Liquid crystal media and the high frequency assembly for including it |
| CN108084029A (en) * | 2017-12-20 | 2018-05-29 | 石家庄诚志永华显示材料有限公司 | Liquid-crystal composition and liquid crystal display element |
Non-Patent Citations (1)
| Title |
|---|
| PEER KIRSCH: ""Liquid crystals with polar substituents containing fluorine: synthesis and physical properties"", 《EUROPEAN JOURNAL OF ORGANIC CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113493691A (en) * | 2020-04-01 | 2021-10-12 | Dic株式会社 | Polymerizable compound, liquid crystal composition containing polymerizable compound, and liquid crystal display element using same |
| CN113493690A (en) * | 2020-04-01 | 2021-10-12 | Dic株式会社 | Compound, liquid crystal composition and liquid crystal display element |
| CN113493694A (en) * | 2020-04-01 | 2021-10-12 | Dic株式会社 | Compound, liquid crystal composition and liquid crystal display element |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI619801B (en) | Compound having four polymerizable groups, liquid crystal composition and liquid crystal display device | |
| KR102071090B1 (en) | Negative dielectric anisotropic liquid crystal mixture | |
| KR20190074987A (en) | Liquid crystal composition and liquid crystal display element | |
| JP5880992B2 (en) | Polymerizable compound and liquid crystal composition using the same | |
| JP2019112607A (en) | Polymerizable compound and liquid crystal composition containing the same | |
| CN110028976B (en) | Compound, liquid crystal composition, liquid crystal display element and liquid crystal display | |
| CN110803983A (en) | Compound, liquid crystal composition, liquid crystal display element and liquid crystal display | |
| KR20100126681A (en) | Liquid crystal composition containing polymerizable compound, and liquid crystal display element comprising the liquid crystal composition | |
| CN108794330B (en) | Polymerizable compound, liquid crystal medium containing polymerizable compound and liquid crystal display device | |
| JP4296821B2 (en) | Maleimide derivatives and polymers thereof | |
| CN110804005A (en) | Compound, liquid crystal composition, liquid crystal display element and liquid crystal display | |
| WO2023134598A1 (en) | Polymerisable compound, composition, and liquid crystal display device | |
| WO2017188001A1 (en) | Polymerizable compound and liquid crystal composition using same | |
| CN114381280A (en) | Negative dielectric anisotropy liquid crystal composition, optical anisotropic medium and liquid crystal display device | |
| TW201321483A (en) | Polymerizable compound, composition, polymer and usage thereof, and liquid crystal display element | |
| JP2008110948A (en) | Polymerizable liquid crystal compound | |
| CN110803990B (en) | Compound, liquid crystal composition, liquid crystal display element and liquid crystal display | |
| JP6270016B2 (en) | Polymerizable compound | |
| CN109384796B (en) | Polymerizable compound and liquid crystal composition | |
| JP6115303B2 (en) | Phenol compound having carbonyl group as adjacent group and use thereof | |
| CN110527520B (en) | Liquid crystal compound and liquid crystal composition | |
| JP4016670B2 (en) | Liquid crystalline sorbic acid ester and polymer thereof | |
| TW202130789A (en) | Polymerizable compound and application thereof | |
| CN113677657A (en) | Polymerizable liquid crystal composition, liquid crystal display element, and compound | |
| JP4088863B2 (en) | Fumaric acid diester and its liquid crystalline polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |