CN114806596A - Silicon-containing liquid crystal compound and preparation method and application thereof - Google Patents
Silicon-containing liquid crystal compound and preparation method and application thereof Download PDFInfo
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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
- C09K19/40—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals
- C09K19/406—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals containing silicon
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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
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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
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
Abstract
The invention relates to the technical field of liquid crystal materials, in particular to a silicon-containing liquid crystal compound and a preparation method and application thereof. The silicon-containing liquid crystal compound has a structure shown as a general formula I; the silicon-containing liquid crystal compound has the characteristics of larger vertical dielectric anisotropy, lower optical anisotropy, lower rotational viscosity, good liquid crystal intersolubility and the like, can be widely applied to the field of liquid crystal display, can achieve the application purposes of low power consumption, wide viewing angle and high contrast, effectively improves the display quality, and has important application value.
Description
Technical Field
The invention relates to the technical field of liquid crystal materials, in particular to a silicon-containing liquid crystal compound and a preparation method and application thereof.
Background
In recent years, liquid crystal display devices have been developed more and more rapidly, and various types such as a vehicle-mounted small-sized liquid crystal display device, a portable liquid crystal display device, an ultra-thin liquid crystal display device, and the like have been developed. Taking a television as an example, the television has the characteristics of light weight, small occupied space, convenience in movement and the like, and is also provided with a notebook type personal computer, a mobile phone and the like.
The liquid crystal material has great research value and good application prospect in the fields of information display materials, organic optoelectronic materials and the like as an environmental material. At present, the TFT-LCD product technology has matured, and successfully solves the technical problems of viewing angle, resolution, color saturation, brightness, etc., and large-size and medium-and small-size TFT-LCD displays have gradually occupied the mainstream status of flat panel displays in respective fields. However, the requirements for display technology are continuously increasing, and liquid crystal displays are required to achieve faster response, reduce driving voltage to reduce power consumption, and the like, and thus liquid crystal materials are required to have low-voltage driving, fast response, wide temperature range, and good low-temperature stability.
The liquid crystal material plays an important role in improving the performance of the liquid crystal display, and in order to improve the performance of the material and enable the material to adapt to new requirements, the synthesis of a novel structure liquid crystal compound and the research of the structure-performance relationship become important work in the field of liquid crystal.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a liquid crystal compound with a silicon-containing structure, which has the characteristics of larger vertical dielectric anisotropy, lower optical anisotropy, lower rotational viscosity, good liquid crystal intersolubility and the like, can be widely applied to the field of liquid crystal display, can achieve the application purposes of low power consumption, wide visual angle and high contrast, effectively improves the display quality, and has important application value; the invention also aims to provide a preparation method and application of the liquid crystal compound.
Specifically, the invention provides the following technical scheme:
the invention provides a silicon-containing liquid crystal compound, which has a structure shown as a general formula I:
in the formula I, the compound is shown in the specification,
V 1 、V 2 each independently selected from a single bond, -CH 2 -、-CH 2 CH 2 -、-CH＝CH-、-COO-、-OOC、-CF 2 O-、-OCH 2 -、-CH 2 O-、-OCF 2 -、-CF 2 CH 2 -、-CH 2 CF 2 -、-C 2 F 4 -or-CF ═ CF —;
R 1 、R 2 、R 3 、R 4 identical or different, each independently selected from hydrogen, deuterium, fluorine, nitrile group, having C 1 -C 40 Straight chain alkyl of (2) having C 1 -C 40 Linear alkoxy of (2) having C 1 -C 40 Linear heteroalkyl group of (A) having C 1 -C 40 Linear heteroalkoxy having C 3 -C 40 A branched or cyclic alkyl group having C 3 -C 40 Branched or cyclic alkoxy of (2), having C 3 -C 40 A branched or cyclic heteroalkyl group of (A) having C 3 -C 40 Has C as a branched or cyclic heteroalkoxy group 2 -C 40 Alkenyl or alkynyl, aryl having 6 to 80 carbon atoms or heteroaryl having 2 to 60 carbon atoms, R 2 And R 3 May be optionally joined or fused and together with the Si to which it is attached form a substituted or unsubstituted ring, with or without one or more additional N, O, S or Si heteroatoms in the ring so formed; at R 1 、R 4 One or more hydrogen atoms in (a) may be optionally substituted with fluorine atoms;
X 1 represents O or S;
R 0 is hydrogen or fluorine;
T 1 、T 2 is selected from the group consisting ofA single bond or a group consisting of:
and represents a bond.
Aryl in the sense of the present invention preferably contains from 6 to 60 carbon atoms and heteroaryl in the sense of the present invention contains from 2 to 60 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5; the heteroatom is preferably selected from N, O or S. Aryl or heteroaryl herein is considered to mean a simple aromatic ring, i.e. benzene, biphenyl, etc., or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, such as anthracene, phenanthrene, quinoline, isoquinoline, etc. The hydrogen on the aryl or heteroaryl group is simply substituted or substituted to form a substituted aryl or substituted heteroaryl group, such as fluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, cyclohexylbenzene, cyclohexylfluorobenzene, and the like, referred to as aryl or heteroaryl.
Alkyl, alkenyl or alkynyl groups having 1 to 40 carbon atoms in the sense of the present invention are preferably to be understood as meaning the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. The alkoxy group, preferably an alkoxy group having 1 to 40 carbon atoms, is considered to mean a methoxy group, a trifluoromethoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentyloxy group, a sec-pentyloxy group, a 2-methylbutyloxy group, a n-hexyloxy group, a cyclohexyloxy group, a n-heptyloxy group, a cycloheptyloxy group, a n-octyloxy group, a cyclooctyloxy group, a 2-ethylhexyloxy group, a pentafluoroethoxy group and a 2,2, 2-trifluoroethoxy group. The heteroalkyl group is preferably an alkyl group having 1 to 40 carbon atoms, meaning a hydrogen atom or-CH alone 2 The radicals-which may be substituted by oxygen, sulfur or halogen atoms-are understood to mean alkoxy, alkylthio, fluorinated alkoxy, fluorinated alkylthio, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, trifluoromethylthio, trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2,2, 2-trifluoroethoxy, 2,2, 2-trifluoroethylthio, vinyloxy, propenyloxy, propenylthio, butenylthio, butenyloxy, pentenylthio, cyclopentenyloxy, cyclopentenylthio, hexenyloxy, hexenylthio, cyclohexenyloxy, cyclohexenylthio, ethynyloxy, propenylthio, butenyloxy, cyclohexenylthio, ethynyloxy, Ethynylthio, propynyloxy, propynylthio, butynyloxy, butynylthio, pentynyloxy, pentynylthio, hexynyloxy, hexynylthio.
In general, cycloalkyl, cycloalkenyl groups according to the invention may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, wherein one or more-CH may be present 2 The radicals may be replaced by the radicals mentioned above; furthermore, one or more hydrogen atoms may also be replaced by deuterium atoms, halogen atoms, or nitrile groups.
Preferably, the silicon-containing liquid crystal compound comprises one or more of the following structures:
further, the V 1 、V 2 Each independently selected from a single bond, -CH 2 O-、-OCH 2 -、-CH 2 -、-CH 2 CH 2 -、-CF 2 O-、-OCF 2 -or-COO-.
Go to oneStep (a), the R 2 、R 3 Identical or different, each independently selected from the group consisting of methyl, ethyl, nitrile, R 2 And R 3 May optionally be joined and together with the Si to which they are attached form a substituted or unsubstituted ring, with or without one or more additional N, O, S or Si heteroatoms in the formed ring.
Further, said R 1 、R 4 Are the same or different and are each independently selected from the group consisting of 1 -C 40 Straight chain alkyl of (2) having C 1 -C 40 Linear alkoxy of (2) having C 1 -C 40 Linear heteroalkyl group of (A) having C 1 -C 40 Linear heteroalkoxy having C 3 -C 40 A branched or cyclic alkyl group having C 3 -C 40 Branched or cyclic alkoxy of (2), having C 3 -C 40 A branched or cyclic heteroalkyl group of (A) having C 3 -C 40 Has C as a branched or cyclic heteroalkoxy group 2 -C 40 Alkenyl or alkynyl groups of (a); at R 1 、R 4 One or more of the hydrogen atoms in (a) may be optionally substituted with fluorine atoms.
Further, said T 1 、T 2 Each independently selected from the group consisting of a single bond or the following groups:
and represents a bond.
According to an embodiment of the invention, said R 0 Is fluorine; x 1 Is S or O.
According to an embodiment of the invention, said R 2 、R 3 The same or different, each is independently selected from the group consisting of methyl and ethyl.
According to an embodiment of the invention, said R 1 、R 4 The same or different, each is independently selected from hydrogen, methyl, ethyl, propyl, butyl, propenyl, butenyl, pentyl, pentenyl, and the like,Methoxy, ethoxy, propoxy, butoxy, propenyloxy, butenyloxy, pentoxy, pentenyloxy, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, pentafluoroethyl, cyclopropoxy, cyclobutoxy, cyclopentyloxy or pentafluoroethoxy.
Preferably, X is 1 Is sulfur; r 1 、R 4 The same or different, each independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, propenyl, butenyl, pentyl, pentenyl.
Preferably, the silicon-containing liquid crystal compound comprises one or more of structures LS01-LS286 shown below:
the invention also provides a preparation method of the silicon-containing liquid crystal compound, which comprises the following steps:
wherein R is 0 -R 4 、X 1 、V 1 、V 2 、T 1 、T 2 Have the same meanings as defined above.
The raw materials for synthesizing the compound shown in the formula I can be purchased from commercial sources, the method principle, the operation process, the conventional post treatment, the column purification, the recrystallization purification and other means are well known by the synthesis personnel in the field, and the synthesis process can be completely realized to obtain the target product.
The reactions of all the steps of all the above processes are carried out in a solvent; the solvent is at least one selected from tetrahydrofuran, 2-methyltetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidin-2-one, ethanol, methanol, dichloromethane, acetone, toluene and deionized water.
The invention also provides a liquid crystal medium which comprises one or more silicon-containing liquid crystal compounds.
Preferably, the liquid-crystalline medium further comprises, as a second component:
wherein the content of the first and second substances,
R 7 、R 8 each independently selected from the group consisting of the groups defined by A, B, C:
a: having a structure of C 1 -C 7 Has a straight-chain alkyl group or has C 1 -C 7 Straight chain alkoxy of (a);
b: one or more-CH in any group in A 2 A group formed after being substituted by-O-, -COO-, -OOC-, or-CH ═ CH-;
c: one or more hydrogen atoms in any group in A are F, Cl, - (CH-CH ═ CH) 2 or-CH ═ CH-CH 3 Replacing the latter formed group;
ring B, ring C, ring D, ring E are each independently selected from the group consisting of:
m, n, o are each independently 0 or 1;
Z 1 、Z 2 、Z 3 each independently selected from the group consisting of a single bond, — C 2 H 4 -*、*-CH＝CH-*、
*-COO-*、*-OOC-*、*-CH 2 O-*、*-OCH 2 -*、*-CF 2 O-and-OCF 2 Any H may be replaced by F;
-and-indicate the position to which the substituent is bonded;
preferably, the liquid-crystalline medium further comprises one or more compounds of the formula III:
wherein the content of the first and second substances,
R 9 、R 10 each independently selected from the group consisting of 1 -C 10 Or with C 2 -C 10 Wherein any of-CH 2 Can be-CH 2 O-、-OCH 2 -、
Instead, any H atom may be replaced by F;
ring F, ring G, ring I, ring J are each independently selected from the group consisting of:
p, q, r are each independently 0 or 1;
Z 4 、Z 5 、Z 6 each independently selected from the group consisting of a single bond, — C 2 H 4 -*、*-CH＝CH-*、
*-COO-*、*-OOC-*、*-CH 2 O-*、*-OCH 2 -*、*-CF 2 O-and-OCF 2 Any H may be replaced by F;
and indicates the position to which the substituent is bonded.
Preferably, in the liquid crystal medium, the mass percentage of the liquid crystal compound is 1-24%, the mass percentage of the compound with the structural formula II is 35-58%, and the mass percentage of the compound with the structural formula III is 30-46%.
Further, the compounds of formula II include compounds represented by the following formulas II-1 to II-15:
wherein the content of the first and second substances,
R 7 、R 8 each independently selected from the group consisting of the groups defined by A, B, C:
a: having a structure of C 1 -C 7 Has a straight-chain alkyl group or has C 1 -C 7 Straight chain alkoxy of (a);
b: one or more-CH in any group in A 2 A group formed after being substituted by-O-, -COO-, -OOC-, or-CH ═ CH-;
c: one or more hydrogen atoms in any group in A are F, Cl, - (CH-CH ═ CH) 2 or-CH ═ CH-CH 3 Replacing the latter formed group;
the above ring H 1 Ring H 2 Each independently selected from the group consisting of:
further, the compounds of formula III include compounds of formulae III-1 to III-16 below:
wherein R is 9 、R 10 Each independently selected from the group consisting of 1 -C 10 Or with C 2 -C 10 Wherein any of-CH 2 Can be-CH 2 O-、-OCH 2 -、
Instead, any H atom may be replaced by F; (F) each independently represents F or H.
Preferably, the liquid-crystalline medium further comprises one or more functional additives; the functional additive comprises an antioxidant, a chiral agent, a light stabilizer or an ultraviolet absorber.
The invention also provides a consumer product comprising a liquid crystalline medium as described above.
The consumer products include, but are not limited to, flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior lighting and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cellular telephones, tablets, phablets, Personal Digital Assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays less than 2 inches diagonal, 3-D displays, virtual reality or augmented reality displays, vehicles, video walls containing multiple displays tiled together, theater or sports screens, phototherapy devices, and signs.
Unless otherwise specified, all starting materials for use in the present invention are commercially available and any range recited herein includes any endpoints and any numerical values therebetween and any subranges therebetween.
The invention has the following beneficial effects:
the silicon-containing liquid crystal compound provided by the invention has the chemical main structure of dibenzothiophene or dibenzofuran, the dielectric anisotropy of the structure is larger, and meanwhile, a silane-based structure is introduced into one side of the dibenzothiophene or dibenzofuran to form a strong synergistic effect, so that the negative dielectric anisotropy of the liquid crystal compound is extremely high, the clearing point is obviously improved, the optical anisotropy is higher, the moderate rotational viscosity and the liquid crystal intersolubility are realized, the low-temperature working effect is excellent, and the performances in the aspects of thermal stability, chemical stability, optical stability, mechanics and the like are good; therefore, the driving voltage is effectively reduced, the response speed of the liquid crystal display device is improved, and the liquid crystal display device has the characteristics of good charge retention rate and the like. Therefore, the compound shown in the formula I provided by the invention can improve the intersolubility and response speed of the liquid crystal compound, improve the low-temperature stability of mixed crystals, expand the application range of liquid crystal mixtures and have important application value.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
In the present invention, the preparation methods are all conventional methods unless otherwise specified. The starting materials used are available from published commercial sources unless otherwise specified, and the percentages are by mass unless otherwise specified. The novel liquid crystal compounds provided by the present invention all reactions are carried out under well-known suitable conditions, and some involve simple organic preparations, for example, the preparation of phenylboronic acid can be synthesized by skilled operating skills, and are not described in detail in the present invention.
Example 1
Preparation of compound LS 65:
under the protection of nitrogen, 20.0mmol of 4, 6-difluoro-3-propoxybenzodibenzo [ b, d ] thiophene (reactant 1) is dissolved in 60mL of dry THF, the temperature is reduced to-100 ℃, 20.0mmol of potassium tert-butoxide is added, 24.0mmol of n-butyllithium n-hexane solution is slowly added dropwise, the mixture is stirred and reacted for 30 minutes, 24.0mmol of n-pentyldimethylchlorosilane (reactant 2) is added dropwise, the mixture is heated to room temperature and stirred and reacted for 2 hours, 20mL of saturated aqueous ammonium chloride solution is added, ethyl acetate is used for extraction, an organic phase is collected, dried and filtered, filtrate is concentrated under reduced pressure and dried, silica gel column separation and purification are carried out, ethanol is recrystallized, and white solid is obtained, and the yield: 92%, HRMS, m/z: 407.1612[ M + H ].
Example 2
Preparation of compound LS 126:
under the protection of nitrogen, 20.0mmol of 4, 6-difluoro-3- ((4-propylcyclohexyl) methoxy) dibenzo [ b, d ] thiophene is dissolved in 80mL of dry THF, the temperature is reduced to-78 ℃, 24.0mmol of n-butyllithium n-hexane solution is added dropwise, stirring is carried out for 1 time, 24.0mmol of cyclopentyl dimethylchlorosilane is added dropwise again, the temperature is increased to room temperature, stirring is carried out for 1 hour, 20mL of saturated ammonium chloride aqueous solution is added, extraction is carried out by ethyl acetate, an organic phase is collected, drying and filtration are carried out, filtrate is concentrated under reduced pressure to be dried, separation and purification are carried out by a silica gel column, and ethanol recrystallization is carried out to obtain a white solid, and the yield: 87%, HRMS, m/z: 501.2393[ M + H ].
Referring to the similar synthetic methods of the above examples 1 and 2, liquid crystal compounds shown in the following table 1 were prepared:
TABLE 1
Examples of mixtures
Examples 3 to 15:
examples 3-15 show the preparation of different liquid crystal media, wherein the monomer structure, the amount (weight percentage) of the specific compounds in each example, and the results of the performance parameter tests of the obtained liquid crystal media are shown in the following tables 3-15, respectively.
The temperature units involved in the examples are, and the specific meanings of the other symbols and the test conditions are as follows:
p. shows the clearing point (. degree. C.) of the liquid crystal, the test apparatus: a Mettler-Toledo-FP System micro thermal analyzer;
γ 1 is rotational viscosity (mPa · s) and the test conditions are: at 25 ℃, INSTEC, ALCT-IR1 and 18 micron vertical box;
K 11 is a torsional elastic constant, K 33 For the splay elastic constant, the test conditions were: at 25 ℃, INSTEC, ALCT-IR1 and 18 micron vertical box;
Δ ∈ denotes dielectric anisotropy, Δ ∈/∈ where ∈/is the dielectric constant parallel to the molecular axis, ∈ ×) is the dielectric constant perpendicular to the molecular axis, test conditions: at 25 ℃, INSTEC, ALCT-IR1 and 18 micron vertical box;
Δ n represents optical anisotropy, and Δ n ═ n o -n e Wherein n is o Refractive index of ordinary light, n e For the refractive index of extraordinary rays, test conditions: 589nm, 25 + -0.2 ℃.
In the invention, compounds of general formulas I, II and III are weighed according to the proportion respectively to prepare the liquid crystal medium, wherein the equipment and the instrument for preparing the liquid crystal medium are as follows:
(1) electronic precision balance (precision 0.1 mg);
(2) stainless steel beaker: for weighing the compound raw materials;
(3) spoon: for adding raw materials;
(4) a magnetic rotor: is used for stirring;
(5) and (5) controlling the temperature of the electromagnetic stirrer.
The preparation method of the liquid crystal medium comprises the following steps:
(1) the raw materials are orderly placed;
(2) placing the stainless steel beaker on a balance, and placing the compound of formula I into the stainless steel beaker with a small spoon;
(3) sequentially adding other compound raw materials according to the required weight;
(4) placing the stainless steel beaker added with the materials on a magnetic stirring instrument for heating and melting;
(5) and after most of the mixture in the stainless steel beaker is melted, adding a magnetic rotor into the stainless steel beaker, uniformly stirring the liquid crystal mixture, and cooling to room temperature to obtain the liquid crystal medium.
And filling the obtained liquid crystal medium between two substrates of the liquid crystal display for performance test.
The component ratios and their performance parameters of the liquid-crystalline medium of example 3 are given in Table 2;
TABLE 2
The component ratios and their performance parameters of the liquid-crystalline medium of example 4 are given in Table 3;
TABLE 3
Table 4 sets of composition ratios and performance parameters for the liquid-crystalline media of example 5;
TABLE 4
Table 5 sets of composition ratios and performance parameters for the liquid-crystalline media of example 6;
TABLE 5
Table 6 for the component ratios and their performance parameters of the liquid-crystalline medium of example 7;
TABLE 7
Table 7 for the component ratios and their performance parameters of the liquid-crystalline medium of example 8;
TABLE 7
Table 8 for the component ratios and their performance parameters of the liquid-crystalline medium of example 9;
TABLE 8
Table 9 sets forth the component ratios and performance parameters for the liquid-crystalline media of example 10;
TABLE 9
Comparative example 1
The formulation is shown in the following table 10, and the components thereof do not contain the compound of the structural formula I, but contain the compound of the formula V.
Watch 10
And (4) conclusion: from the performance parameters of the liquid crystal compositions of examples 3 to 10, it can be seen that the liquid crystal composition provided by the invention has good intersolubility and a large negative dielectric constant, and from comparison between example 10 and comparative example 1, the liquid crystal of alkoxy group is replaced by the silane-based liquid crystal of the invention, so that the liquid crystal composition has good intersolubility and low-temperature stability, and has a large negative dielectric constant, and therefore, the compound shown by the formula I provided by the invention can improve the intersolubility of the liquid crystal compound, expand the application range of the liquid crystal mixture, and has important application value.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A silicon-containing liquid crystal compound having a structure represented by formula I:
in the formula I, the compound is shown in the specification,
V 1 、V 2 each independently selected from a single bond, -CH 2 -、-CH 2 CH 2 -、-CH＝CH-、-COO-、-OOC、-CF 2 O-、-OCH 2 -、-CH 2 O-、-OCF 2 -、-CF 2 CH 2 -、-CH 2 CF 2 -、-C 2 F 4 -or-CF ═ CF —;
R 1 、R 2 、R 3 、R 4 identical or different, each independently selected from hydrogen, deuterium, fluorine, nitrile group, having C 1 -C 40 Straight chain alkyl of (2) having C 1 -C 40 Linear alkoxy of (2) having C 1 -C 40 Linear heteroalkyl group of (A) having C 1 -C 40 Linear heteroalkoxy having C 3 -C 40 A branched or cyclic alkyl group having C 3 -C 40 Branched or cyclic alkoxy of (2), having C 3 -C 40 A branched or cyclic heteroalkyl group of (A) having C 3 -C 40 Has C as a branched or cyclic heteroalkoxy group 2 -C 40 Alkenyl or alkynyl of (A), having C 6 -C 80 Or have C 2 -C 60 Of (a) heteroaryl, R 2 And R 3 May be optionally joined or fused and together with the Si to which they are attached form a substituted or unsubstituted ring, in which caseWith or without one or more additional N, O, S or Si heteroatoms in the ring; at R 1 、R 4 One or more hydrogen atoms in (a) may be optionally substituted with fluorine atoms;
X 1 represents O or S;
R 0 is hydrogen or fluorine;
T 1 、T 2 selected from the group consisting of a single bond or the following groups:
and represents a bond.
2. The silicon-containing liquid crystal compound of claim 1, wherein the liquid crystal compound comprises one or more of the following structures:
wherein, V 1 、V 2 Each independently selected from a single bond, -CH 2 O-、-OCH 2 -、-CH 2 -、-CH 2 CH 2 -、-CF 2 O-、-OCF 2 -or-COO-;
R 2 、R 3 identical or different, each independently selected from the group consisting of methyl, ethyl, nitrile, R 2 And R 3 May optionally be joined and form, together with the Si to which they are attached, a substituted or unsubstituted ring, with or without one or more additional N, O, S or Si heteroatoms in the formed ring;
R 1 、R 4 are the same or different and are each independently selected from the group consisting of 1 -C 40 Straight chain alkyl of (2) having C 1 -C 40 Linear alkoxy of (2) having C 1 -C 40 Linear heteroalkyl group of (A) having C 1 -C 40 Linear heteroalkoxy having C 3 -C 40 A branched or cyclic alkyl group having C 3 -C 40 Branched or cyclic alkoxy of (2), having C 3 -C 40 A branched or cyclic heteroalkyl group of (A) having C 3 -C 40 Has C as a branched or cyclic heteroalkoxy group 2 -C 40 Alkenyl or alkynyl groups of (a); at R 1 、R 4 One or more hydrogen atoms in (a) may be optionally substituted with fluorine atoms;
T 1 、T 2 each independently selected from the group consisting of a single bond or the following groups:
and represents a bond.
3. The silicon-containing liquid crystal compound according to claim 1 or 2, wherein R is 0 Is fluorine;
R 2 、R 3 the same or different, each is independently selected from the group consisting of methyl and ethyl.
4. The silicon-containing liquid crystal compound according to any one of claims 1 to 3, wherein R is 1 、R 4 The same or different, each is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, propenyl, butenyl, pentyl, pentenyl, methoxy, ethoxy, propoxy, butoxy, propenyloxy, butenyloxy, pentoxy, pentenyloxy, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, pentafluoroethyl, cyclopropoxy, cyclobutoxy, cyclopentyloxy or pentafluoroethoxy.
5. The silicon-containing liquid crystal compound according to claim 4, wherein X is 1 Is sulfur; r 1 、R 4 The same or different, each is independently selected from hydrogen, methyl, ethyl, propyl, butyl, propenyl, buteneA pentyl group, a pentenyl group.
6. The silicon-containing liquid crystal compound of any one of claims 1 to 5, wherein the liquid crystal compound comprises one or more of structures LS01-LS286 as shown below:
7. a liquid crystal medium comprising one or more silicon-containing liquid crystal compounds according to any one of claims 1 to 6;
preferably, the liquid-crystalline medium further comprises one or more compounds of the formula II:
wherein the content of the first and second substances,
R 7 、R 8 each independently selected from the group consisting of the groups defined by A, B, C:
a: having a structure of C 1 -C 7 Has a straight-chain alkyl group or has C 1 -C 7 Straight chain alkoxy of (a);
b: one or more-CH in any group in A 2 A group formed after being substituted by-O-, -COO-, -OOC-, or-CH ═ CH-;
c: one of any one group in AOne or more hydrogen atoms are replaced by F, Cl, — CH ═ CH 2 or-CH ═ CH-CH 3 Replacing the latter formed group;
ring B, ring C, ring D, ring E are each independently selected from the group consisting of:
m, n, o are each independently 0 or 1;
Z 1 、Z 2 、Z 3 each independently selected from the group consisting of a single bond, — C 2 H 4 -*、*-CH＝CH-*、
*-COO-*、*-OOC-*、*-CH 2 O-*、*-OCH 2 -*、*-CF 2 O-and-OCF 2 Any H may be replaced by F;
-and-indicate the position to which the substituent is bonded;
more preferably, the liquid-crystalline medium further comprises one or more compounds of formula III:
wherein the content of the first and second substances,
R 9 、R 10 each independently selected from the group consisting of 1 -C 10 Or with C 2 -C 10 Wherein any of-CH 2 Can be-CH 2 O-、-OCH 2 -、
Instead, any H atom may be replaced by F;
ring F, ring G, ring I, ring J are each independently selected from the group consisting of:
p, q, r are each independently 0 or 1;
Z 4 、Z 5 、Z 6 each independently selected from the group consisting of a single bond, — C 2 H 4 -*、*-CH＝CH-*、
*-COO-*、*-OOC-*、*-CH 2 O-*、*-OCH 2 -*、*-CF 2 O-and-OCF 2 Any H may be replaced by F;
and indicates the position to which the substituent is bonded.
8. The liquid crystal medium of claim 7, wherein the liquid crystal medium comprises 1-24% by weight of the silicon-containing liquid crystal compound, 35-58% by weight of the compound of formula II, and 30-46% by weight of the compound of formula III.
9. Liquid-crystalline medium according to claim 7 or 8, characterized in that it further comprises one or more functional additives; the functional additive comprises an antioxidant, a chiral agent, a light stabilizer, or an ultraviolet absorber.
10. A consumer product, characterized in that it comprises a liquid-crystalline medium according to any one of claims 7 to 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1129581A (en) * | 1997-07-11 | 1999-02-02 | Chisso Corp | Liquid crystal compound with negative permitivity anisotropy value, liquid crystal composition containing the liquid crystal compound, and liquid crystal display element using the liquid crystal compound |
| US20050258396A1 (en) * | 2002-06-28 | 2005-11-24 | Qinetiq Limited | Potochromic liquid crystals |
| US20080230745A1 (en) * | 2007-03-23 | 2008-09-25 | Michael Wand | Liquid crystal compound, ferroelectric liquid crystal composition, and ferroelectric liquid crystal display |
| US20140160384A1 (en) * | 2012-09-10 | 2014-06-12 | Wenlei Li | Smectic a-phase liquid crystal material |
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- 2022-04-29 CN CN202210473425.9A patent/CN114806596A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1129581A (en) * | 1997-07-11 | 1999-02-02 | Chisso Corp | Liquid crystal compound with negative permitivity anisotropy value, liquid crystal composition containing the liquid crystal compound, and liquid crystal display element using the liquid crystal compound |
| US20050258396A1 (en) * | 2002-06-28 | 2005-11-24 | Qinetiq Limited | Potochromic liquid crystals |
| US20080230745A1 (en) * | 2007-03-23 | 2008-09-25 | Michael Wand | Liquid crystal compound, ferroelectric liquid crystal composition, and ferroelectric liquid crystal display |
| US20140160384A1 (en) * | 2012-09-10 | 2014-06-12 | Wenlei Li | Smectic a-phase liquid crystal material |
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