CN107722996B - Polymerizable liquid crystal compound and preparation method and application thereof - Google Patents

Polymerizable liquid crystal compound and preparation method and application thereof Download PDF

Info

Publication number
CN107722996B
CN107722996B CN201610659841.2A CN201610659841A CN107722996B CN 107722996 B CN107722996 B CN 107722996B CN 201610659841 A CN201610659841 A CN 201610659841A CN 107722996 B CN107722996 B CN 107722996B
Authority
CN
China
Prior art keywords
liquid crystal
compound
bylc
proper
added
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.)
Active
Application number
CN201610659841.2A
Other languages
Chinese (zh)
Other versions
CN107722996A (en
Inventor
高立龙
田会强
谭小玉
储士红
王杰
陈海光
姜天孟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Bayi Space LCD Technology Co Ltd
Original Assignee
Beijing Bayi Space LCD Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing Bayi Space LCD Technology Co Ltd filed Critical Beijing Bayi Space LCD Technology Co Ltd
Priority to CN201610659841.2A priority Critical patent/CN107722996B/en
Publication of CN107722996A publication Critical patent/CN107722996A/en
Application granted granted Critical
Publication of CN107722996B publication Critical patent/CN107722996B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • 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
    • C09K19/38—Polymers
    • C09K19/3833—Polymers with mesogenic groups in the side chain
    • C09K19/3842—Polyvinyl derivatives
    • C09K19/3852—Poly(meth)acrylate derivatives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/122—Ph-Ph

Abstract

The invention relates to the field of liquid crystal materials, in particular to a polymerizable liquid crystal compound which has a structure shown in a general formula I, wherein R represents alkyl or alkoxy with 1-10 carbon atoms; ring A represents a 1, 4-phenylene group or a 1, 4-phenylene group in which 1 to 4 hydrogen atoms are substituted with fluorine atoms; m is 1 or 2. The compound provided by the invention has the advantages of proper polymerization reactivity, high conversion rate, high heat resistance, higher solubility to liquid crystal compositions, better stability and weather resistance of the prepared optical anisotropic body, and the like. The liquid crystal composition containing the polymerizable compound of the present invention has physical properties such as a high upper limit temperature of a nematic phase, a low lower limit temperature of a nematic phase, a small viscosity, a proper optical anisotropy, a large dielectric anisotropy, a proper elastic constant, and a proper pretilt angle.

Description

Polymerizable liquid crystal compound and preparation method and application thereof
Technical Field
The invention relates to the field of liquid crystal display materials, in particular to a polymerizable liquid crystal compound, a preparation method and application thereof.
Background
The polymer-stabilized liquid crystal display technology is a technology for stabilizing an alignment state or a phase state of liquid crystal molecules by using additional energy supplied from a polymer, and has been disclosed, for example, a polymer-stabilized alignment mode (PSA) or a polymer-stabilized mode (PS) in which a liquid crystal composition to which a polymerizable compound is added is injected into a display element, ultraviolet light is irradiated in a state where a voltage is applied between electrodes to polymerize the polymerizable compound, and a polymer is generated in the liquid crystal composition, and a liquid crystal display element having a short response time and improved in an effect of afterimage is obtained by using the method.
In such a mode of element, although the ability of alignment of liquid crystal molecules is improved by using a polymer, the solubility of a liquid crystal composition is not greatly improved, and in the prior art, an optically anisotropic body is produced by using a polymerizable liquid crystal material, but the problem of poor long-term stability, poor weather resistance and the like is faced, and therefore, development of a novel polymerizable compound having a proper balance between solubility and polymerization reactivity and having excellent long-term stability and weather resistance for producing an optically anisotropic body has been desired.
Disclosure of Invention
The first object of the present invention is to provide a polymerizable liquid crystal compound which has the advantages of proper polymerization reactivity, high conversion rate, high heat resistance, high solubility to liquid crystal composition, good stability and weather resistance of the prepared optically anisotropic body, and the like, and has important application value.
The polymerizable liquid crystal compound has a structure shown in a general formula I:
Figure BDA0001076261680000021
in formula I, R represents an alkyl or alkoxy group having 1 to 10 carbon atoms; ring A represents a 1, 4-phenylene group or a 1, 4-phenylene group in which 1 to 4 hydrogen atoms are substituted with fluorine atoms;
m is 1 or 2.
Preferably, in formula I, R represents an alkyl or alkoxy group having 1 to 6 carbon atoms; ring A represents a 1, 4-phenylene group or a 1, 4-phenylene group in which 1 to 4 hydrogen atoms are substituted with fluorine atoms;
m is 1 or 2.
As a more preferred embodiment, in the general formula I, R represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms; ring A represents a 1, 4-phenylene group or a 1, 4-phenylene group in which 1 to 2 hydrogen atoms are substituted with fluorine atoms;
m is 1.
As a further preferable embodiment, the liquid crystal compound is selected from one of the following compounds:
Figure BDA0001076261680000022
Figure BDA0001076261680000031
in I-1 to I-4, R represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms;
as a preferred embodiment of the present invention, the liquid crystal compound is selected from one of the following compounds:
Figure BDA0001076261680000032
Figure BDA0001076261680000041
/>
the second object of the present invention is to provide a method for preparing the liquid crystal compound, and to achieve the object, the present invention adopts the following technical scheme:
the synthetic route of the compound with the structural general formula (I) is shown as follows:
Figure BDA0001076261680000042
the method specifically comprises the following steps:
(1)
Figure BDA0001076261680000051
reacting with an organolithium reagent and then with a borate to give +.>
Figure BDA0001076261680000052
(2)
Figure BDA0001076261680000053
And->
Figure BDA0001076261680000054
Through Suzuki reaction, obtain
Figure BDA0001076261680000055
(3)
Figure BDA0001076261680000056
And->
Figure BDA0001076261680000057
The preparation method comprises the steps of carrying out substitution reaction to obtain the product;
Figure BDA0001076261680000058
(4)
Figure BDA0001076261680000059
by hydrodebenzyl to give +.>
Figure BDA00010762616800000510
/>
(5)
Figure BDA00010762616800000511
Obtaining ∈10 by reduction reaction>
Figure BDA00010762616800000512
(6)
Figure BDA0001076261680000061
And->
Figure BDA0001076261680000062
Through esterification reaction, obtain
Figure BDA0001076261680000063
Wherein L is 1 Represent H, br; r, m, ring A in the compounds involved in each step correspond to R, m, ring A in the resulting liquid crystal compound product (see definition of each substituent in formula I).
In the step (1) of the above-mentioned process,
Figure BDA0001076261680000064
the molar ratio of the organic lithium reagent to the boric acid ester is 1:1.0-1.8:1.0-2.0;
preferably, the reaction temperature can be between-50 ℃ and-100 ℃;
wherein the organic lithium reagent is selected from one or more of n-butyllithium, sec-butyllithium, tert-butyllithium or n-butyllithium and tert-butylpotassium, and the borate is selected from one or more of trimethyl borate, triisopropyl borate, tributyl borate or triisobutyl borate.
In the step 2) of the above-mentioned process,
Figure BDA0001076261680000065
and->
Figure BDA0001076261680000066
The feeding mole ratio of (2) is 1:0.9-1.2;
preferably, the reaction temperature can be 60-120 ℃;
in the step 3) of the above-mentioned process,
Figure BDA0001076261680000067
and->
Figure BDA0001076261680000068
The feeding mole ratio of (2) is 1:1.0-3.0;
preferably, the reaction temperature can be 20-120 ℃;
in the step 4) of the above-mentioned process,
Figure BDA0001076261680000071
the mass ratio of the catalyst to the catalyst is 1:0.05-0.15;
preferably, the reaction temperature may be 10 to 70 ℃;
wherein the catalyst is selected from one or more of Pd/C, raney nickel and Pt/C, and Pd/C is preferable.
In the step 5) of the above-mentioned method,
Figure BDA0001076261680000072
the molar ratio of the catalyst to the reducing agent is 1:1.0-3.0;
preferably, the reaction temperature can be between-10 and 100 ℃;
wherein the reducing agent is selected from one or more of lithium aluminum hydride, red aluminum and potassium borohydride, and is preferably lithium aluminum hydride.
In the step 6) of the above-mentioned process,
Figure BDA0001076261680000073
and->
Figure BDA0001076261680000074
The feeding mole ratio of (2) is 1:3.0-6.0;
preferably, the reaction temperature can be between-10 and 30 ℃;
above-mentioned
Figure BDA0001076261680000075
Is->
Figure BDA0001076261680000076
Are synthesized by methods known per se in the art or in the literature.
The method according to the invention may, if necessary, involve conventional post-treatments, such as in particular: extracting with dichloromethane, ethyl acetate or toluene, separating, washing with water, drying, evaporating with vacuum rotary evaporator, and purifying the obtained product by vacuum distillation or recrystallization and/or chromatographic separation.
The liquid crystal compound can be stably and efficiently obtained by adopting the preparation method.
The invention also provides a liquid crystal composition containing the liquid crystal compound.
The liquid crystal compound has the advantages of proper polymerization reactivity, high conversion rate, high heat resistance, higher solubility to liquid crystal compositions, better stability and weather resistance of the prepared optical anisotropic body, and the like. The liquid crystal composition containing the polymerizable compound of the present invention has physical properties such as a high upper limit temperature of a nematic phase, a low lower limit temperature of a nematic phase, a small viscosity, a proper optical anisotropy, a large dielectric anisotropy, a proper elastic constant, and a proper pretilt angle.
Preferably, the liquid crystal compound is added in an amount of 0.05-20% by weight to the liquid crystal composition, and a good display effect can be obtained by selecting a proper addition ratio according to different polymer-stabilized liquid crystal display modes, for example, in the polymer-stabilized vertical alignment technology, the ideal addition ratio is selected to be 0.05-5%, preferably 0.1-2%; in the polymer stabilized blue phase technique, the ideal addition ratio is selected to be 1% to 20%, preferably 2% to 15%.
The invention also provides application of the liquid crystal compound or the liquid crystal composition in a liquid crystal display device, and the liquid crystal compound or the liquid crystal composition is particularly suitable for and not limited to PS-TN, PS-IPS, PS-FFS, PSA-VA or PSA-OCB liquid crystal displays. After the liquid crystal composition is applied to a liquid crystal display device, the liquid crystal display device has a wide temperature range, short response time, high voltage retention rate, large contrast ratio and long service life, and has wide application prospect.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The raw materials are available from public commercial sources such as Beijing eight hundred million space time liquid crystal technologies Inc. or other manufacturers, unless otherwise specified.
According to the conventional detection method in the field, various performance parameters of the liquid crystal compound are obtained through linear fitting.
Unless otherwise indicated, percentages in the present invention are weight percentages; the temperature unit is in degrees celsius; Δn represents optical anisotropy (25 ℃); delta epsilon represents dielectric anisotropy (25 ℃,1000 Hz); v10 represents a threshold voltage, which is a characteristic voltage (V, 25 ℃) at which the relative transmittance changes by 10%; γ1 represents the rotational viscosity (mPas, 25 ℃); cp represents the clearing point (. Degree. C.) of the liquid crystal composition; k11, K22, K33 represent the splay, twist and bend elastic constants (pN, 25 ℃ C.).
Example 1
The structural formula of the liquid crystal compound is as follows:
Figure BDA0001076261680000091
the synthetic route for preparing compound BYLC-01 is shown below:
Figure BDA0001076261680000092
the method comprises the following specific steps:
(1) Synthesis of Compound BYLC-01-1:
under the protection of nitrogen, 60.0g of 3-fluoro-4-benzyloxy bromobenzene and 450ml of tetrahydrofuran are added into a reaction bottle, 0.25mol of n-hexane solution of n-butyllithium is dripped at the temperature of-70 ℃ to-80 ℃, the dripping is carried out for 1 hour after the dripping, 33.3g of trimethyl borate is dripped at the temperature of-70 ℃ to-80 ℃, and then the temperature is naturally returned to-30 ℃. 300ml of 2M aqueous hydrochloric acid was added for acidification, conventional work-up and recrystallization from petroleum ether gave 43.4g of a pale yellow solid (compound BYLC-01-1), HPLC:95.6% and 82.7% yield;
(2) Synthesis of Compound BYLC-01-2:
40.0g of BYLC-01-1, 48.2g of 2-methyl-4-bromoiodobenzene, 300ml of N, N-dimethylformamide, 90ml of deionized water, 29.2g of anhydrous potassium carbonate and 0.6g of tetraphenylphosphine palladium are added into a reaction flask under the protection of nitrogen, and the mixture is heated and refluxed for 3 hours. Conventional work-up and purification by chromatography gave 48.5g of a pale yellow solid (compound BYLC-01-2), GC:99.2%, yield: 80.5%.
(3) Synthesis of Compound BYLC-01-3:
under the protection of nitrogen, 20.0g of compound potassium tert-butoxide, 200ml of N, N-dimethylformamide are added into a reaction bottle, 38.8g of diethyl malonate is dripped at room temperature for reaction for 1 hour, 45.0g of solution consisting of BYLC-01-2 and 50ml of N, N-dimethylformamide is dripped at the temperature of 75-85 ℃ for reaction for 6 hours. Conventional work-up, purification by evaporation reduced, gives 39.5g of a pale yellow liquid (compound BYLC-01-3), GC:98.2%, yield: 72.4%.
(4) Synthesis of Compound BYLC-01-4:
35.0g of compound BYLC-01-3,1.8g of palladium carbon, 100ml of toluene, 50ml of ethanol and hydrogen are added into a reaction bottle for replacement twice, hydrogenation reaction is carried out for 6 hours at the temperature of 10-30 ℃, conventional post-treatment is carried out, petroleum ether recrystallization is carried out to obtain white solid (compound BYLC-01-4): 26.4g, GC:99.3%, yield: 94.6%.
(5) Synthesis of Compound BYLC-01-5:
5.2g of lithium aluminum hydride, 100ml of tetrahydrofuran, and a solution of 25.0g of the compound BYLC-01-4 and 50ml of tetrahydrofuran were added dropwise at room temperature, and the mixture was heated and refluxed for 3 hours. Conventional work-up and recrystallization from petroleum ether gave a white solid (compound BYLC-01-5): 17.2g, GC:99.5%, yield: 89.5%.
(6) Synthesis of Compound BYLC-01:
under the protection of nitrogen, 17.0g of compound BYLC-01-5, 26.1g of anhydrous sodium carbonate, 100ml of acetone, 25.6g of methacryloyl chloride dropwise added at the temperature of minus 10 ℃ to 0 ℃ are reacted for 3 hours at room temperature after the dropwise addition, TLC tracking reaction is complete, conventional post-treatment is carried out, and 22.4g of white solid (compound BYLC-01) is obtained through chromatographic purification, normal hexane elution and ethanol recrystallization, wherein the LC is as follows: 99.7% and a yield of 76.8%;
the resulting white solid BYLC-01 was analyzed by GC-MS and the product had an M/z of 480.1 (M+).
1 H-NMR(300MHz,CDCl 3 ):1.15-2.10(m,9H),2.15-2.95(m,3H),
3.85-4.80(m,5H),5.35-6.30(m,6H),6.75-7.60(m,6H)。
Example 2
The structural formula of the liquid crystal compound is as follows:
Figure BDA0001076261680000111
the synthetic route for the preparation of compound BYLC-02 is shown below:
Figure BDA0001076261680000112
the method comprises the following specific steps:
(1) Synthesis of Compound BYLC-02-1:
50.0g of BYLC-01-1, 63.6g of 2-methoxy-4-bromoiodobenzene, 300ml of N, N-dimethylformamide, 90ml of deionized water, 29.2g of anhydrous potassium carbonate and 0.6g of tetraphenylphosphine palladium are added into a reaction flask under the protection of nitrogen, and the mixture is heated and refluxed for 3 hours. Conventional work-up and purification by chromatography gave 63.7g of a pale yellow solid (compound BYLC-02-1), GC:98.5%, yield: 82.3%.
(2) Synthesis of Compound BYLC-02-2:
under the protection of nitrogen, 31.2g of compound potassium tert-butoxide, 200ml of N, N-dimethylformamide are added into a reaction bottle, 44.6g of diethyl malonate is dripped at room temperature for reaction for 1 hour, a solution composed of 60.0g of BYLC-02-1 and 80ml of N, N-dimethylformamide is dripped at the temperature of 75-85 ℃ for reaction for 6 hours. Conventional work-up, purification by evaporation reduced, gave 54.3g of a pale yellow liquid (compound BYLC-02-2), GC:96.8%, yield: 75.2%.
(4) Synthesis of Compound BYLC-02-3:
50.0g of compound BYLC-02-2,3.0g of palladium carbon, 150ml of toluene, 80ml of ethanol and hydrogen are added into a reaction bottle for replacement twice, hydrogenation reaction is carried out for 6 hours at the temperature of 10-30 ℃, conventional post-treatment is carried out, petroleum ether recrystallization is carried out to obtain white solid (compound BYLC-02-3): 36.5g, GC:99.5%, yield: 90.5%.
(5) Synthesis of Compound BYLC-02-4:
7.0g of lithium aluminum hydride, 100ml of tetrahydrofuran, and a solution of 35.0g of the compound BYLC-02-3 and 50ml of tetrahydrofuran were added dropwise at room temperature, and the mixture was heated and refluxed for 3 hours. Conventional work-up and recrystallization from petroleum ether gave a white solid (compound BYLC-02-4): 23.2g, GC:99.2%, yield: 85.6%.
(6) Synthesis of Compound BYLC-02:
under the protection of nitrogen, 20.0g of compound BYLC-02-4, 36.3g of anhydrous sodium carbonate, 100ml of acetone, 32.3g of methacryloyl chloride dropwise added at the temperature of minus 10 ℃ to 0 ℃ are reacted for 3 hours at room temperature after the dropwise addition, TLC tracking reaction is complete, conventional post-treatment is carried out, and 25.5g of white solid (compound BYLC-02) is obtained through chromatographic purification, normal hexane elution and ethanol recrystallization, wherein the following steps are that: 99.5% and yield 75.3%;
the resulting white solid BYLC-02 was analyzed by GC-MS and the product had an M/z of 496.1 (M+).
1 H-NMR(300MHz,CDCl 3 ):1.15-2.10(m,9H),3.65-4.70(m,8H),5.35-6.30(m,6H),6.60-7.65(m,6H)。
Example 3
The structural formula of the liquid crystal compound is as follows:
Figure BDA0001076261680000131
the synthetic route for the preparation of the compound BYLC-03 is shown below:
Figure BDA0001076261680000132
the method comprises the following specific steps:
(1) Synthesis of Compound BYLC-03-1:
under the protection of nitrogen, 42.0g of 2-fluoro-4-benzyloxy bromobenzene and 300ml of tetrahydrofuran are added into a reaction bottle, 0.18mol of n-hexane solution of n-butyllithium is dripped at the temperature of-70 ℃ to-80 ℃, the dripping is carried out for 1 hour after the dripping, 22.0g of trimethyl borate is dripped at the temperature of-70 ℃ to-80 ℃, and then the temperature is naturally returned to-30 ℃. 300ml of 2M aqueous hydrochloric acid was added for acidification, conventional work-up and recrystallization from petroleum ether gave 30.1g of a pale yellow solid (compound BYLC-03-1), HPLC:95.5% and 82.5% yield;
(2) Synthesis of Compound BYLC-03-2:
under the protection of nitrogen, 30.0g of a compound BYLC-03-1, 38.1g of 2-methoxy-4-bromoiodobenzene, 210ml of N, N-dimethylformamide, 70ml of deionized water, 19.3g of anhydrous potassium carbonate and 0.6g of tetraphenylphosphine palladium are added into a reaction bottle, and the mixture is heated and refluxed for reaction for 3 hours. Conventional work-up and purification by chromatography gave 40.2g of a pale yellow solid (compound BYLC-03-2), GC:99.3%, yield: 85.2%.
(3) Synthesis of Compound BYLC-03-3:
under the protection of nitrogen, 23.1g of compound potassium tert-butoxide, 200ml of N, N-dimethylformamide are added into a reaction bottle, 33.0g of diethyl malonate is dripped into the reaction bottle at room temperature for 1 hour, a solution composed of 40.0g of BYLC-03-2 and 50ml of N, N-dimethylformamide is dripped into the reaction bottle at the temperature of 75-85 ℃ for 6 hours, and the reaction is carried out at the temperature of 75-85 ℃. Conventional work-up, purification by evaporation reduced, gave 36.2g of a pale yellow liquid (compound BYLC-03-3), GC:98.8%, yield: 75.3%.
(4) Synthesis of Compound BYLC-03-4:
35.0g of compound BYLC-03-3,1.0g of palladium carbon, 100ml of toluene, 50ml of ethanol and hydrogen are added into a reaction bottle for replacement twice, hydrogenation reaction is carried out for 6 hours at the temperature of 10-30 ℃, conventional post-treatment is carried out, petroleum ether recrystallization is carried out to obtain white solid (compound BYLC-03-4): 26.1g, GC:99.5%, yield: 92.7%.
(5) Synthesis of Compound BYLC-03-5:
a solution of 4.0g of lithium aluminum hydride, 100ml of tetrahydrofuran, 26.0g of BYLC-03-4 and 50ml of tetrahydrofuran was added dropwise at room temperature, and the mixture was heated and refluxed for 3 hours. Conventional work-up and recrystallization from petroleum ether gave a white solid (compound BYLC-03-5): 17.8g, GC:99.2%, yield: 88.6%.
(6) Synthesis of Compound BYLC-03:
under the protection of nitrogen, 15.0g of compound BYLC-03-5, 24.5g of anhydrous sodium carbonate, 100ml of acetone, 25.8g of methacryloyl chloride dropwise added at the temperature of minus 10 ℃ to 0 ℃ are reacted for 3 hours at room temperature after the dropwise addition, TLC tracking reaction is complete, conventional post-treatment is carried out, and the white solid (compound BYLC-03) 19.3g, LC is obtained through chromatographic purification, normal hexane elution and ethanol recrystallization: 99.6% and 75.8% yield;
the resulting white solid BYLC-03 was analyzed by GC-MS and the product had an M/z of 496.1 (M+).
1 H-NMR(300MHz,CDCl 3 ):1.15-2.10(m,9H),3.65-4.70(m,8H),
5.35-6.30(m,6H),6.60-7.65(m,6H)。
Example 4
The structural formula of the liquid crystal compound is as follows:
Figure BDA0001076261680000151
the synthetic route for the preparation of compound BYLC-04 is shown below:
Figure BDA0001076261680000152
the method comprises the following specific steps:
(1) Synthesis of Compound BYLC-04-1:
under the protection of nitrogen, 40.0g of 4-benzyloxy bromobenzene and 300ml of tetrahydrofuran are added into a reaction bottle, a normal hexane solution of 0.19mol of n-butyllithium is dripped at the temperature of-70 to-80 ℃, the dripping is carried out for 1 hour after the dripping, 25.2.0g of trimethyl borate is dripped at the temperature of-70 to-80 ℃, and then the temperature is naturally returned to-30 ℃. 300ml of 2M aqueous hydrochloric acid was added for acidification, conventional work-up and recrystallization from petroleum ether gave 30.7g of a pale yellow solid (compound BYLC-04-1), HPLC:96.3% and 88.7% yield;
(2) Synthesis of Compound BYLC-04-2:
under the protection of nitrogen, 30.0g of compound BYLC-04-1, 41.1g of 2-methoxy-4-bromoiodobenzene, 210ml of N, N-dimethylformamide, 70ml of deionized water, 27.8g of anhydrous potassium carbonate and 0.5g of tetraphenylphosphine palladium are added into a reaction bottle, and the mixture is heated and refluxed for 3 hours. Conventional work-up and purification by chromatography gave 40.5g of a pale yellow solid (compound BYLC-04-2), GC:99.5%, yield: 83.5%.
(3) Synthesis of Compound BYLC-04-3:
under the protection of nitrogen, 18.2g of compound potassium tert-butoxide, 200ml of N, N-dimethylformamide are added into a reaction bottle, 34.5g of diethyl malonate is dripped at room temperature for reaction for 1 hour, a solution composed of 40.0g of BYLC-04-2 and 50ml of N, N-dimethylformamide is dripped at the temperature of 75-85 ℃ for reaction for 6 hours. Conventional work-up, purification by evaporation reduced, gives 38.0g of a pale yellow liquid (compound BYLC-04-3), GC:97.6%, yield: 78.6%.
(4) Synthesis of Compound BYLC-04-4:
35.0g of compound BYLC-04-3,1.75g of palladium carbon, 100ml of toluene, 50ml of ethanol and hydrogen are added into a reaction bottle for replacement twice, hydrogenation reaction is carried out for 6 hours at the temperature of 10-30 ℃, conventional post-treatment is carried out, petroleum ether recrystallization is carried out to obtain white solid (compound BYLC-04-4): 26.4g, GC:99.2%, yield: 94.5%.
(5) Synthesis of Compound BYLC-04-5:
a solution of the compound BYLC-04-4 (4.5 g) and 50ml of tetrahydrofuran (100 ml) was added dropwise to the flask at room temperature, and the mixture was heated to reflux for 3 hours. Conventional work-up and recrystallization from petroleum ether gave a white solid (compound BYLC-04-5): 17.0g, GC:99.3%, yield: 85.5%.
(6) Synthesis of Compound BYLC-04:
under the protection of nitrogen, 15.0g of compound BYLC-04-5, 24.0g of anhydrous sodium carbonate, 100ml of acetone, 25.5g of methacryloyl chloride dropwise added at the temperature of-10 ℃ to 0 ℃ are reacted for 3 hours at room temperature after the dropwise addition, TLC tracking reaction is complete, conventional post-treatment is carried out, and 20.0g of white solid (compound BYLC-04) is obtained through chromatographic purification, normal hexane elution and ethanol recrystallization, wherein the LC is as follows: 99.7% and a yield of 76.4%;
the resulting white solid BYLC-04 was analyzed by GC-MS and the M/z of the product was 478.1 (M+).
1 H-NMR(300MHz,CDCl 3 ):1.15-2.10(m,9H),3.65-4.70(m,8H),5.35-6.30(m,6H),6.60-7.65(m,7H)。
According to the technical scheme of the embodiment, the following liquid crystal compounds can be synthesized by a person skilled in the art without changing any substantial operation by simply replacing corresponding raw materials.
Figure BDA0001076261680000171
Figure BDA0001076261680000181
Experimental example
The liquid crystal compounds used in the following compositions are all prepared by Beijing eight hundred million space time liquid crystal technology
Supplied by stock limited. The contents of the components in the examples are, unless otherwise specified, all indicated
Mass percent.
Figure BDA0001076261680000182
Example 2 (BYLC-02)
Figure BDA0001076261680000183
Comparative example 1 (DJ-1, known Compound)
Experimental example 1
The liquid crystal composition BYHJ-1 is selected, and the specific formula is as follows:
Figure BDA0001076261680000184
Cp：91.0℃，Δn：0.100，Δε：-2.2，γ1：79。
the following compounds were added in a proportion of 0.3% by weight, based on the abovementioned composition BYHJ-1:
Figure BDA0001076261680000191
obtaining a liquid crystal composition BYHJ-11;
Figure BDA0001076261680000192
liquid crystal composition BYHJ-22 was obtained.
The solubility of the liquid crystal compositions BYHJ-11 and BYHJ-22 was measured, and the measurement results are shown in Table 1-1:
table 1-1: solubility test results of liquid Crystal composition
Figure BDA0001076261680000193
As is apparent from the test results of Table 1-1, the liquid crystal compound provided by the invention has better solubility to the liquid crystal composition than the conventional compound with similar chemical structure.
Experimental example 2
Will be the same as in Experimental example 1
Figure BDA0001076261680000201
BYHJ-11 and contain +.>
Figure BDA0001076261680000202
The composition BYHJ-22, the ratio of the pretilt angles before and after UV (ultraviolet) was varied and the residue content was varied with the lapse of the polymerization time, resulting inAs shown in tables 2-1 and 2-2:
table 2-1: pretilt angle detection result
Figure BDA0001076261680000203
Table 2-2: polymer residue detection results
Figure BDA0001076261680000204
As can be seen from the comparative data of tables 2-1 and 2-2, the polymerizable liquid crystal compound BYLC-02 of the present invention has a better alignment effect, a faster and more complete polymerization rate and lower residue than the polymerizable liquid crystal compound DJ-1, thereby improving the display effect.
Experimental example 3
The liquid crystal composition BYHJ-11 (same as in Experimental example 1) to which the polymerizable liquid crystal compound of the present invention was added and the liquid crystal composition BYHJ-1 (same as in Experimental example 1) to which the polymer of the present invention was not added were each prepared. Polymerizing for 3min under UV light, and respectively testing threshold voltage and response time; the results of the test are shown in Table 3-1 below:
table 3-1:
Figure BDA0001076261680000211
as is clear from Table 3-1, the threshold voltage is reduced, the response time is reduced, the energy consumption problem is well improved, and the response speed and the display effect are improved by the alignment of the polymerizable liquid crystal compound of the present invention.
Other liquid crystal compositions to which other liquid crystal compounds provided by the present invention are added can obtain the same excellent optical and electrical properties in addition to the compositions exemplified in the experimental examples.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (7)

1. A polymerizable liquid crystal compound characterized by: the structure of the polymerizable liquid crystal compound is as follows:
Figure FDA0002745001650000011
2. a liquid crystal composition comprising the liquid crystal compound according to claim 1.
3. The liquid crystal composition according to claim 2, wherein the liquid crystal compound is added in an amount of 0.05 to 20% by weight to the composition.
4. A liquid crystal composition according to claim 3, wherein the liquid crystal compound is added in an amount of 0.05% to 5% or 1% to 20% by weight to the composition.
5. The liquid crystal composition according to claim 4, wherein the liquid crystal compound is added in an amount of 0.1 to 2% or 2 to 15% by weight to the composition.
6. Use of the liquid crystal compound according to claim 1 in a liquid crystal display device.
7. The method according to claim 6, wherein the liquid crystal display device is a PS-TN, PS-IPS, PS-FFS, PSA-VA or PSA-OCB liquid crystal display.
CN201610659841.2A 2016-08-11 2016-08-11 Polymerizable liquid crystal compound and preparation method and application thereof Active CN107722996B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610659841.2A CN107722996B (en) 2016-08-11 2016-08-11 Polymerizable liquid crystal compound and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610659841.2A CN107722996B (en) 2016-08-11 2016-08-11 Polymerizable liquid crystal compound and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN107722996A CN107722996A (en) 2018-02-23
CN107722996B true CN107722996B (en) 2023-06-09

Family

ID=61200627

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610659841.2A Active CN107722996B (en) 2016-08-11 2016-08-11 Polymerizable liquid crystal compound and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN107722996B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110627750A (en) * 2018-06-25 2019-12-31 北京八亿时空液晶科技股份有限公司 Tetrahydrofuran polymerizable compound and preparation and application thereof
CN111961477A (en) * 2019-05-20 2020-11-20 北京八亿时空液晶科技股份有限公司 Polymerizable compound and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102786936A (en) * 2012-05-09 2012-11-21 深圳市华星光电技术有限公司 Liquid crystal medium composition
CN102911052A (en) * 2012-10-13 2013-02-06 江苏和成显示科技股份有限公司 Polymerized star compound and polymerized product and application thereof in liquid crystal device
CN104364348A (en) * 2012-06-02 2015-02-18 默克专利股份有限公司 Liquid crystal medium
CN104797688A (en) * 2012-11-21 2015-07-22 默克专利股份有限公司 Polymerisable compounds and the use thereof in liquid-crystal displays
CN104927876A (en) * 2014-03-21 2015-09-23 默克专利股份有限公司 Polymerisable Compounds And The Use Thereof In Liquid-Crystal Displays

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102786936A (en) * 2012-05-09 2012-11-21 深圳市华星光电技术有限公司 Liquid crystal medium composition
CN104364348A (en) * 2012-06-02 2015-02-18 默克专利股份有限公司 Liquid crystal medium
CN102911052A (en) * 2012-10-13 2013-02-06 江苏和成显示科技股份有限公司 Polymerized star compound and polymerized product and application thereof in liquid crystal device
CN104797688A (en) * 2012-11-21 2015-07-22 默克专利股份有限公司 Polymerisable compounds and the use thereof in liquid-crystal displays
CN104927876A (en) * 2014-03-21 2015-09-23 默克专利股份有限公司 Polymerisable Compounds And The Use Thereof In Liquid-Crystal Displays

Also Published As

Publication number Publication date
CN107722996A (en) 2018-02-23

Similar Documents

Publication Publication Date Title
CN102964226B (en) Liquid crystal compound containing cyclobutyl and difluoromethylenedioxy connecting radical as well as preparation method and application thereof
CN103030534B (en) Negative liquid crystal compound containing 2,3-difluorophenyl group, and preparation method and application thereof
KR102080953B1 (en) Liquid Crystal Compound And Liquid Crystal Mixture Containing Cyclopropyl
CN109206400B (en) Liquid crystal compound containing dibenzothiophene structure and application thereof
CN109207160B (en) Liquid crystal compound with negative dielectric anisotropy as well as preparation method and application thereof
TW201139354A (en) Liquid-crystalline compounds and liquid-crystalline media
CN109423296B (en) Dibenzothiophene negative dielectric anisotropy compound and preparation method and application thereof
TWI507386B (en) Cycloheptane derivative and preparation method and application thereof
CN105176542A (en) Liquid crystal compound, and preparation method and application thereof
CN111748355B (en) Liquid crystal compound, liquid crystal composition containing liquid crystal compound and liquid crystal display element
CN107835802B (en) Stabilizer compound, liquid crystal composition and display element
CN113698942A (en) Liquid crystal compound with negative dielectric anisotropy, liquid crystal composition and display device thereof
CN107722996B (en) Polymerizable liquid crystal compound and preparation method and application thereof
CN105131971A (en) Liquid crystal compound with 2-fluorophenyl group and difluoro methyleneoxy group and preparing method and application thereof
CN107699252B (en) Polymeric liquid crystal compound and preparation method and application thereof
CN109082281B (en) Liquid crystal compound with negative dielectric anisotropy as well as preparation method and application thereof
CN107722995B (en) Polymerizable liquid crystal compound and preparation method and application thereof
CN108690636B (en) Liquid crystal compound with negative dielectric anisotropy as well as preparation method and application thereof
CN107345140B (en) Liquid crystal compound with isobutyl negative dielectric anisotropy and application thereof
CN107400517B (en) Cyclopentyl negative dielectric anisotropy liquid crystal compound, composition and application
CN107345138B (en) Isobutyl liquid crystal compound, preparation method and application
TW201722924A (en) A compound containing a 2,5-benzofuran group, a liquid crystal composition containing same, and a display unit having specific characteristics like light and heat stability and UV stability after curing by a light
CN103788039A (en) Liquid crystal compound containing tetrahydropyrane difluoro methoxy-linking group and preparation method and application thereof
CN110616074A (en) Novel liquid crystal compound and preparation and application thereof
CN113528151B (en) Liquid crystal compound, liquid crystal composition thereof and liquid crystal display device

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
GR01 Patent grant
GR01 Patent grant