CN110229679B - Self-alignment additive for liquid crystal medium and preparation method and application thereof - Google Patents
Self-alignment additive for liquid crystal medium and preparation method and application thereof Download PDFInfo
- Publication number
- CN110229679B CN110229679B CN201810184733.3A CN201810184733A CN110229679B CN 110229679 B CN110229679 B CN 110229679B CN 201810184733 A CN201810184733 A CN 201810184733A CN 110229679 B CN110229679 B CN 110229679B
- Authority
- CN
- China
- Prior art keywords
- self
- phenylene
- molar ratio
- liquid crystal
- preparation
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/32—Oxygen atoms
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Mathematical Physics (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Liquid Crystal Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a self-alignment additive for liquid crystal medium and a preparation method and application thereof; the self-alignment additive is a compound with a structure shown in a general formula I; wherein R represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group or an alkenyloxy group; ring A represents 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene, or 1, 4-phenylene in which 1 to 4 hydrogen atoms are substituted by fluorine; ring B represents 1, 4-phenylene, 1, 4-cyclohexylene or 1, 4-phenylene in which 1 to 4 hydrogen atoms are substituted by fluorine; l and m independently represent 0, 1 or 2, and l + m is more than 0 and less than or equal to 3; n represents 0, 1, 2,3, 4, 5, 6, 7, 8, 9 or 10. The self-alignment additive realizes the vertical alignment of liquid crystal molecules under the condition of not containing a PI alignment film; and the liquid crystal display panel has low price and stable performance, can be widely applied to the field of liquid crystal display and has important application value.
Description
Technical Field
The invention belongs to the technical field of liquid crystal materials, and relates to a self-alignment additive, and a preparation method and application thereof.
Background
In recent years, liquid crystal display devices have been widely used in various electronic devices, such as smart phones, tablet computers, car navigators, televisions, and the like. Representative liquid crystal display modes include a Twisted Nematic (TN) mode, a Super Twisted Nematic (STN) mode, an in-plane switching (IPS) mode, a Fringe Field Switching (FFS) mode, and a Vertical Alignment (VA) mode. Among them, the VA mode receives increasing attention because of having a fast fall time, a high contrast ratio, a wide viewing angle, and a high quality image.
In a conventional VA display, after a glass substrate is formed into an electrode, a Polyimide (PI) alignment film is coated on the surface of the glass substrate to achieve vertical alignment of liquid crystal molecules. However, this method has significant disadvantages: the coating process of the PI oriented film is complicated, the consumed time is long, and the production cost is greatly increased. The friction alignment type PI oriented film can generate dust and static electricity in the friction preparation process, influence the performance of a liquid crystal medium and even damage a liquid crystal display element in the friction process; although the photoalignment type PI alignment material avoids the defects, the photoalignment type PI alignment material has weak anchoring capability on liquid crystal molecules, is limited by the performance of the material, and has limited application. Therefore, a self-alignment (SAVA) technique capable of vertically aligning liquid crystal molecules without a PI alignment film has been developed.
In order to realize vertical self-alignment of the liquid crystal medium, a certain amount of self-alignment additive is required to be added into the mixed crystal medium. Therefore, for the improvement and improvement of SAVA technology, the synthesis of self-alignment additives with novel structure and the structure-performance relationship research become an important work in the liquid crystal field.
Disclosure of Invention
A first object of the present invention is to provide a compound of a self-aligning additive for liquid crystal media, which can be used in SAVA technology. The compound realizes vertical alignment of liquid crystal molecules under the condition of not containing a PI alignment film through the interaction of-OH and the surface of a substrate. And the compound has low price and stable performance, can be widely applied to the field of liquid crystal display and has important application value.
The self-alignment additive is a compound with a structure shown in a general formula I;
in the general formula I, R represents alkyl, alkoxy, alkenyl or alkenyloxy with 1-10 carbon atoms; ring A represents 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene, or 1, 4-phenylene in which 1 to 4 hydrogen atoms are substituted by fluorine; ring B represents 1, 4-phenylene, 1, 4-cyclohexylene or 1, 4-phenylene in which 1 to 4 hydrogen atoms are substituted by fluorine; l and m independently represent 0, 1 or 2, and l + m is more than 0 and less than or equal to 3; n represents 0, 1, 2,3, 4, 5, 6, 7, 8, 9 or 10.
Preferably, in the general formula I, R represents an alkyl group, an alkoxy group, an alkenyl group or an alkenyloxy group having 1 to 10 carbon atoms; more preferably, R represents an alkyl or alkoxy group having 1 to 10 carbon atoms; further preferably, R represents an alkyl or alkoxy group having 1 to 5 carbon atoms.
Preferably, in the formula I, ring A represents 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene, or 1, 4-phenylene in which 1 to 4 hydrogen atoms are substituted by fluorine; more preferably, ring A represents 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene
Preferably, in said formula I, ring B represents 1, 4-phenylene, 1, 4-cyclohexylene or 1, 4-phenylene in which 1 to 4 hydrogen atoms are substituted by fluorine; more preferably, ring B represents 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene
Preferably, in the general formula I, l and m independently represent 0, 1 or 2, and 0 < l + m is less than or equal to 3; more preferably, l and m are respectively 0, 1 or 2, and 0 < l + m < 2; further preferably l and m are both 1
Preferably, in the general formula I, n represents 0, 1, 2,3, 4, 5, 6, 7, 8, 9 or 10; more preferably, n represents 0, 1, 2,3, 4 or 5.
Preferably, in the general formula I, R represents alkyl and alkoxy with 1-10 carbon atoms; ring A represents 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene, or 1, 4-phenylene in which 1 to 4 hydrogen atoms are substituted by fluorine; ring B represents a 1, 4-phenylene group, or a 1, 4-phenylene group in which 1 to 4 hydrogen atoms are substituted with fluorine; l and m are respectively 0, 1 or 2, and l + m is more than 0 and less than or equal to 2; n represents 0, 1, 2,3, 4 or 5;
more preferably, in the general formula I, R represents an alkyl group or an alkoxy group having 1 to 5 carbon atoms; ring A represents 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene; ring B represents 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene; l and m are both 1; n represents 0, 1, 2,3, 4 or 5;
as the best embodiment of the invention, the compound represented by the general formula I is selected from one of the following structures:
in the structure, R represents an alkyl or alkoxy group having 1 to 5 carbon atoms; n represents 0, 1, 2,3, 4 or 5.
The second purpose of the invention is to provide a preparation method of the compound of the self-alignment additive
(1) When ring A represents 1, 4-phenylene or 1, 4-phenylene in which 1 to 4 hydrogen atoms are substituted by fluorine, the synthetic route is specifically as follows:
wherein R, l, m, n and products in each compound in the synthetic route
Wherein R, l, m and n are consistent; x1Represents Br, Cl or I;
preferably, the preparation method specifically comprises the following steps:
1) will be provided with
Carrying out metallization reaction with an organic lithium reagent, and then reacting with boric acid ester to obtain
2) Will be provided with
And prepared by the step 1)
By suzuki reaction, obtaining
3) Prepared by the step 2)
Obtaining a product through hydrolysis reaction
More preferably, the hydrolysis reaction of step 3) is specifically carried out
Adding boron tribromide to react.
The invention further provides that, in the step 1), the
The feeding molar ratio of the organic lithium reagent to the organic lithium reagent is 1: 1.0-2.0; the above-mentioned
The feeding molar ratio of the boric acid ester to the boric acid ester is 1: 1.0-3.0;
preferably, the organic lithium reagent is selected from one or more of sec-butyl lithium, tert-butyl lithium or n-butyl lithium;
the boric acid ester is selected from one or more of trimethyl borate, triisopropyl borate, tributyl borate or triisobutyl borate.
Preferably, the reaction temperature of the step 1) is-50 to-100 ℃;
the invention further provides that, in the step 2), the
And the above-mentioned
The feeding molar ratio of (A) to (B) is 1.0: 1.0 to 1.5;
preferably, the reaction temperature of the step 2) can be 50-150 ℃;
wherein, the
Are commercially available through the open.
The invention further provides that, in the step 3), the
The feeding molar ratio of the boron tribromide to the boron tribromide is 1:1.0 to 1.3;
preferably, the reaction temperature of the step 3) may be-30 to-5 ℃.
(2) When the ring A represents 1, 4-cyclohexenylene, the synthetic route is specifically as follows:
wherein R, l, m, n and products in each compound in the synthetic route
Wherein R, l, m and n are consistent; x1Represents Br, Cl or I;
preferably, the preparation method specifically comprises the following steps:
1) will be provided with
After the metalation reaction with organic lithium, the organic lithium is reacted with
Reacting to obtain
2) Subjecting the product obtained in step 1)
Acid-catalyzed dehydration treatment is carried out to obtain
3) Prepared by the step 2)
Obtaining a product through hydrolysis reaction
The invention further provides that, in the step 1), the
The molar ratio of the organic lithium reagent to the organic lithium reagent is 1: 1.0-2.0, and the organic lithium reagent is
And the above-mentioned
The feeding molar ratio of (A) to (B) is 1: 0.8-1.5;
preferably, the organic lithium reagent is selected from one or more of sec-butyl lithium, tert-butyl lithium or n-butyl lithium; preferably n-butyllithium;
the above-mentioned
And the above-mentioned
Are all available from public commercial sources;
preferably, the reaction temperature of the step 1) is-50 to-100 ℃;
the invention further provides that, in the step 2), the
The feeding molar ratio of the acid to the acid is 1: 0.02-0.2;
preferably, the acid is selected from one or more of hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid and potassium hydrogen sulfate; preferably p-toluenesulfonic acid;
preferably, the reaction temperature of the step 2) can be 50-120 ℃;
the invention further provides that, in the step 3), the
The feeding molar ratio of the boron tribromide to the boron tribromide is 1:1.0 to 1.3;
preferably, the reaction temperature of the step 3) may be-30 to-5 ℃.
(3) When the ring A represents 1, 4-cyclohexylene, the synthetic route is specifically as follows:
wherein R, l, m, n and products in each compound in the synthetic route
Wherein R, l, m and n are consistent; x1Represents Br, Cl or I;
preferably, the preparation method specifically comprises the following steps:
1) will be provided with
After the metalation reaction with organic lithium, the organic lithium is reacted with
Reacting to obtain
2) Subjecting the product obtained in step 1)
Reacting with boron trifluoride diethyl etherate and triethylsilane to obtain
3) Prepared by the step 2)
Obtaining a product through hydrolysis reaction
More preferably, the hydrolysis reaction of step 3) is specifically carried out
Adding boron tribromide to react.
The invention further provides that, in the step 1), the
The feeding molar ratio of the organic lithium reagent to the organic lithium reagent is 1: 1.0-2.0, and the organic lithium reagent is prepared by
And the above-mentioned
The feeding molar ratio of (A) to (B) is 1: 0.8-1.5;
preferably, the organic lithium reagent is selected from one or more of sec-butyl lithium, tert-butyl lithium or n-butyl lithium, and more preferably n-butyl lithium;
the above-mentioned
And the above-mentioned
Are all available from public commercial sources;
preferably, the reaction temperature of the step 1) is-50 to-100 ℃;
the invention further provides that, in the step 2), the
The feeding molar ratio of the boron trifluoride diethyl etherate to the boron trifluoride diethyl etherate is 1: 1.0-3.0; the above-mentioned
The feeding molar ratio of the triethyl silane to the triethyl silane is 1: 1.0-3.0;
preferably, the reaction temperature of the step 2) may be 30 to-90 ℃;
the invention further provides that, in the step 3), the
The feeding molar ratio of the boron tribromide to the boron tribromide is 1:1.0 to 1.3;
preferably, the reaction temperature of the step 3) may be-30 to-5 ℃.
The preparation method of the invention, including the three methods, can involve conventional post-treatment if necessary, and the conventional post-treatment specifically comprises the following steps: extracting with dichloromethane, ethyl acetate or toluene, separating liquid, washing with water, drying, evaporating with vacuum rotary evaporator, and purifying the obtained product by vacuum distillation or recrystallization and/or chromatographic separation.
The preparation method can stably and efficiently obtain the compound.
The third object of the present invention is to provide a composition containing the self-alignment additive, based on the self-alignment additive of the present invention, the composition provided by the present invention has an effect of protecting the self-alignment additive.
Preferably, in the composition, the mass percentage of the self-alignment additive in the composition is 0.01-15%, preferably 0.1-10%, and more preferably 0.1-5%.
In addition to the self-alignment additives of the present invention, the composition may further comprise conventional protective agents in the art, and the specific selection/combination manner is known to those skilled in the art, and the present invention is not particularly limited thereto.
By way of preference only, the composition consists, in addition to the self-aligning additive, at 100%, of the components of the following table.
The fourth object of the present invention is to provide the use of the self-alignment additive or the composition containing the self-alignment additive in the field of liquid crystal display; preferably in liquid crystal display devices;
the liquid crystal display device includes, but is not limited to, a VA, TN, STN, FFS or IPS liquid crystal display.
The self-alignment additive can realize the vertical self-alignment of liquid crystal molecules under the condition of not containing a polyimide alignment layer; the negative dielectric anisotropy is extremely high, and simultaneously has high definition bright point, higher optical anisotropy, moderate rotary viscosity and liquid crystal intersolubility, excellent low-temperature working effect, good thermal stability, chemical stability, optical stability, mechanical property and other properties; 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 moderate optical anisotropy value, high charge retention rate and the like.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The starting materials are commercially available from the open literature 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, wherein the specific meanings of the performance parameters are as follows:
Δ n represents optical anisotropy (25 ℃); Δ represents the dielectric anisotropy (25 ℃, 1000 Hz); i represents the dielectric constant (25 ℃, 1000Hz) in the direction parallel to the molecular axis; cp represents a clearing point; k represents the elastic constant (25 ℃).
Example 1
The structural formula of the liquid crystal compound is as follows:
the synthetic route for the preparation of compound BYLC-01 is shown below:
the method comprises the following specific steps:
(1) synthesis of Compound BYLC-01-1:
under the protection of nitrogen, 35g of the mixture is added into a reaction bottle
(0.287mol) and 150ml of tetrahydrofuran, controlling the temperature to be-70 to-80 ℃, dropwise adding 0.37mol of n-butyllithium n-hexane solution, controlling the temperature to react for 1 hour after dropwise adding, controlling the temperature to be-60 to-70 ℃, dropwise adding 46.6g of trimethyl borate (0.44mol), and naturally returning the temperature to be-30 ℃. Adding 2M hydrochloric acid aqueous solution 400ml for acidification, performing conventional post-treatment, and recrystallizing with petroleum ether to obtain light yellow43.0g of a colored solid (Compound BYLC-01-1, 0.259mol), HPLC: 99.7%, yield: 90.2 percent.
(2) Synthesis of Compound BYLC-01-2:
43.0g of compound BYLC-01-1(0.259mol), 78.5g of compound were added to a reaction flask under nitrogen atmosphere
(0.259mol), 200ml of N, N-dimethylformamide, 100ml of deionized water, 72.8g of anhydrous potassium carbonate (0.53mol), 0.5g of tetratriphenylphosphine palladium, and heating to 70 ℃ for reaction for 3 hours. Conventional work-up was carried out, and purification by chromatography, elution with n-hexane, and recrystallization from ethanol gave 66.1g of a white solid (compound BYLC-01-2, 0.192mol), 99.7% GC, yield: 74.1 percent.
(3) Synthesis of Compound BYLC-01:
66.1g of the compound BYLC-01-2(0.192mol) are introduced at-10 ℃ into 1000ml of dichloromethane and 250ml (0.25mol) of a 1M solution of boron tribromide in hexane are added dropwise. The cooling was stopped and the mixture was stirred at room temperature for 3 hours. Then cooled to-10 deg.C, 500ml deionized water was added and stirred for 3 hours. Then, the mixture was subjected to a conventional post-treatment operation, dissolved and separated with dichloromethane, purified by chromatography, and recrystallized from a mixed solution of n-heptane and toluene at a volume ratio of 3:1 to obtain 51.5g (0.156mol) of a white solid (BYLC-01). 99.8% of GC and 81.3% of yield.
The resulting white solid BYLC-01 was analyzed by GC-MS and the M/z of the product was 330.1(M +).
1H-NMR(300MHz,CDCl3):0.75-1.25(m,3H),1.95-2.65(m,3H),4.75-5.05(m,2H),6.55-7.45(m,8H)。
Example 1
According to the technical scheme of example 1, the following compounds can be synthesized by simply replacing the corresponding raw materials without changing any substantial operation:
r represents an alkyl or alkoxy group having 1 to 5 carbon atoms; n represents 0, 1, 2,3, 4 or 5.
Example 3
The structural formula of the liquid crystal compound is as follows:
the synthetic route for the preparation of compound BYLC-02 is shown below:
the method comprises the following specific steps:
(1) synthesis of Compound BYLC-02-1:
35g of the reaction flask was charged
(0.287mol) and 450ml of tetrahydrofuran, dropwise adding 0.315mol of n-butyl lithium n-hexane solution at the temperature of-70 to-80 ℃, after the temperature control reaction is finished for 1 hour, dropwise adding 59.7g at the temperature of-70 to-80 DEG
And 100ml of tetrahydrofuran, then naturally returning the temperature to-30 ℃, adding 500ml of 2M hydrochloric acid aqueous solution for acidification, carrying out conventional post-treatment, and spin-drying the solvent to obtain 88.8g (0.269mol) of light yellow liquid (compound BYLC-02-1). GC: 91.3% (cis + trans) and yield 93.7%.
(2) Synthesis of Compound BYLC-02-2:
88.8g of compound BYLC-02-1(0.269mol), 0.84g of p-toluenesulfonic acid and 500ml of toluene were charged into a reaction flask, and subjected to reflux dehydration for 4 hours, conventional post-treatment, purification by chromatography, elution with n-hexane, and recrystallization with ethanol to obtain 72.4g (0.232mol) of a white solid (compound BYLC-02-2), GC: 99.7%, and yield: 86.2%.
(3) Synthesis of Compound BYLC-02:
72.4g of the compound BYLC-02-2(0.232mol) are introduced into 1200ml of dichloromethane at-10 ℃ and 300ml (0.3mol) of a 1M solution of boron tribromide in hexane are added dropwise. The cooling was stopped and the mixture was stirred at room temperature for 3 hours. Then cooled to-10 deg.C, 600ml deionized water was added and stirred for 3 hours. Then, the mixture was subjected to a conventional post-treatment operation, dissolved and separated with dichloromethane, purified by chromatography, and recrystallized from a mixed solution of n-heptane and toluene at a volume ratio of 3:1 to obtain 62.0g (0.208mol) of a white solid (BYLC-02). 99.8 percent of GC and 89.7 percent of yield.
The obtained white solid BYLC-02 was analyzed by GC-MS and the M/z of the product was 298.1(M +).
1H-NMR(300MHz,CDCl3):0.95-1.97(m,7H),1.98-2.95(m,6H),4.55-5.96(m,3H),6.25-7.35(m,6H)。
Example 4
According to the technical scheme of example 3, the following compounds can be synthesized by simply replacing the corresponding raw materials without changing any substantial operation:
r represents an alkyl or alkoxy group having 1 to 5 carbon atoms; n represents 0, 1, 2,3, 4 or 5.
Example 5
The structural formula of the liquid crystal compound is as follows:
the synthetic route for the preparation of compound BYLC-03 is shown below:
(1) synthesis of Compound BYLC-03-1:
35g of the reaction flask was charged
450ml of tetrahydrofuran, temperature control0.315mol of n-butyl lithium n-hexane solution is dripped at the temperature of between 70 and 80 ℃ below zero, the temperature is controlled after dripping for reaction for 1 hour, and 59.7g of the n-hexane solution is dripped at the temperature of between 70 ℃ below zero and 80 ℃ below zero
And 100ml of tetrahydrofuran, then naturally returning the temperature to-30 ℃, adding 500ml of 2M hydrochloric acid aqueous solution for acidification, carrying out conventional post-treatment, and spin-drying the solvent to obtain 87.5g (0.265mol) of light yellow liquid (compound BYLC-02-1). GC: 90.7% (cis + trans) and yield: 92.3%.
(2) Synthesis of Compound BYLC-03-2:
under the protection of nitrogen, 87.5g of compound BYLC-03-1(0.265mol) and 250ml of dichloromethane are added into a reaction bottle, 62.7g of triethylsilane (0.54mol) is added dropwise at the temperature of-70 to-80 ℃, the temperature is controlled to react for 0.5 hour after the dropwise addition is finished, 84.3g of boron trifluoride ethyl ether (0.585mol) is added dropwise at the temperature of-70 to-80 ℃, and then the temperature is naturally returned to-10 ℃. The reaction mixture was quenched with 500ml of water and worked up conventionally to give 64.9g (Compound BYLC-03-2) (0.207mol) of a white solid, 99.7% by GC and 78.1% by yield.
(2) Synthesis of Compound BYLC-03:
64.9g of the compound BYLC-03-2(0.207mol) are introduced into 1000ml of dichloromethane at-10 ℃ and 270ml (0.27mol) of a 1M solution of boron tribromide in hexane are added dropwise. The cooling was stopped and the mixture was stirred at room temperature for 3 hours. Then cooled to-10 deg.C, 550ml deionized water was added and stirred for 3 hours. Then, the mixture was subjected to a conventional post-treatment operation, dissolved and separated with dichloromethane, purified by chromatography, and recrystallized from a mixed solution of n-heptane and toluene at a volume ratio of 3:1 to obtain 55.2g (0.184mol) of a white solid (BYLC-03). 99.6 percent of GC and 88.9 percent of yield.
The resulting white solid BYLC-03 was analyzed by GC-MS and the M/z of the product was 300.1(M +).
1H-NMR(300MHz,CDCl3):0.95-1.75(m,11H),1.85-2.75(m,5H),4.75-5.05(m,2H),6.35-7.15(m,6H)。
Example 5
According to the technical scheme of example 5, the following compounds can be synthesized by simply replacing the corresponding raw materials without changing any substantial operation:
r represents an alkyl or alkoxy group having 1 to 5 carbon atoms; n represents 0, 1, 2,3, 4 or 5.
Examples of the experiments
The composition of the liquid-crystal mixture M is given in Table 1
TABLE 1 liquid-crystal mixture M composition Table
The properties of mixture M are given in Table 2
TABLE 2 summary of mixed crystal M Properties
| Properties of | Cp | Δn | Δε | ε|| | K3/K1 |
| Numerical value | +70℃ | 0.095 | -3.5 | 3.3 | 0.97 |
Mixture Experimental example 1
Compound BYLC-01 and comparative CM were each added to composition M at a rate of 3 wt% and mixed homogeneously. The mixture was poured on a 100 ℃ heat-carrying table into an element having no alignment film with a spacing of 4 μm of two glass substrates. The element was placed in a polarizing microscope, and light was irradiated from below to observe the presence or absence of light leakage. When the liquid crystal molecules were sufficiently aligned and light did not pass through the element, the vertical alignment property was judged to be "good". When light passing through the element was observed, the vertical alignment was judged to be "poor".
The two elements were charged by applying a pulse voltage (1V and 60 μ sec) at 60 ℃. The decayed voltage was measured by a high-speed voltmeter over a period of 2 seconds (0.5HZ), and the area a between the voltage curve per unit period and the horizontal axis was determined. The area B is an area at the time of attenuation. The voltage holding ratio is expressed as a ratio of the area a to the area B.
Specific results are shown in Table 3
Table 3 summary of properties of the mixture of experimental example 1
Mixture Experimental example 2
Compound BYLC-02 and comparative CM were each added to composition M at a rate of 3 wt% and mixed homogeneously. The mixture was poured on a 100 ℃ heat-carrying table into an element having no alignment film with a spacing of 4 μm of two glass substrates. The element was placed in a polarizing microscope, and light was irradiated from below to observe the presence or absence of light leakage. When the liquid crystal molecules were sufficiently aligned and light did not pass through the element, the vertical alignment property was judged to be "good". When light passing through the element was observed, the vertical alignment was judged to be "poor".
The two elements were charged by applying a pulse voltage (1V and 60 μ sec) at 60 ℃. The decayed voltage was measured by a high-speed voltmeter over a period of 2 seconds (0.5HZ), and the area a between the voltage curve per unit period and the horizontal axis was determined. The area B is an area at the time of attenuation. The voltage holding ratio is expressed as a ratio of the area a to the area B.
Specific results are shown in Table 4
Table 4 summary of properties of the mixture of experimental example 2
Mixture Experimental example 3
Compound BYLC-03 and comparative CM were each added to composition M at a rate of 3 wt% and mixed homogeneously. The mixture was poured on a 100 ℃ heat-carrying table into an element having no alignment film with a spacing of 4 μm of two glass substrates. The element was placed in a polarizing microscope, and light was irradiated from below to observe the presence or absence of light leakage. When the liquid crystal molecules were sufficiently aligned and light did not pass through the element, the vertical alignment property was judged to be "good". When light passing through the element was observed, the vertical alignment was judged to be "poor".
The two elements were charged by applying a pulse voltage (1V and 60 μ sec) at 60 ℃. The decayed voltage was measured by a high-speed voltmeter over a period of 2 seconds (0.5HZ), and the area a between the voltage curve per unit period and the horizontal axis was determined. The area B is an area at the time of attenuation. The voltage holding ratio is expressed as a ratio of the area a to the area B.
Specific results are shown in Table 5
Table 5 summary of properties of the mixture, experimental example 3
As can be seen from the above experimental examples of mixtures, the self-alignment additive provided by the invention can realize vertical self-alignment of liquid crystal molecules under the conditions of small addition and no polyimide alignment layer. As compared with the comparative material CM, the voltage holding ratio was not lowered while the good vertical alignment property of the liquid crystal molecules was ensured.
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 (25)
1. The self-alignment additive for the liquid crystal medium is characterized by being a compound with a structure shown in a general formula I;
in the general formula I, R represents an alkyl or alkoxy group having 1 to 5 carbon atoms; ring A represents 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene; ring B represents 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene; l and m are both 1; n represents 0, 1, 2,3, 4 or 5.
2. The self-aligning additive of claim 1 wherein the compound represented by formula I is selected from one of the following structures:
in the structure, R represents an alkyl or alkoxy group having 1 to 5 carbon atoms; n represents 0, 1, 2,3, 4 or 5.
3. A process for the preparation of a self-aligning additive according to claim 1 or 2 wherein ring a represents a 1, 4-phenylene group or a 1, 4-phenylene group in which 1 to 4 hydrogen atoms are replaced by fluorine, as specified in the scheme:
wherein R, l, m and n in each compound in the synthetic route are consistent with R, l, m and n in the product; x1Represents Br, Cl or I.
4. The preparation method according to claim 3, characterized in that the preparation method comprises the following steps:
1) will be provided with
Carrying out metallization reaction with an organic lithium reagent, and then reacting with boric acid ester to obtain
2) Will be provided with
And prepared by the step 1)
By suzuki reaction, obtaining
3)Prepared by the step 2)
Obtaining a product through hydrolysis reaction
5. The method according to claim 4, wherein the hydrolysis reaction of step 3) is carried out by
Adding boron tribromide to react.
6. The method according to claim 5, wherein in the step 1), the step
The feeding molar ratio of the organic lithium reagent to the organic lithium reagent is 1: 1.0-2.0; the above-mentioned
The feeding molar ratio of the boric acid ester to the boric acid ester is 1: 1.0-3.0;
and/or, in the step 2), the
And the above-mentioned
The feeding molar ratio of (A) to (B) is 1.0: 1.0 to 1.5;
and/or, in the step 3), the
The feeding molar ratio of the boron tribromide to the boron tribromide is 1:1.0 to 1.3.
7. The preparation method according to claim 6, wherein the organolithium reagent is selected from one or more of sec-butyllithium, tert-butyllithium or n-butyllithium;
and/or the boric acid ester is selected from one or more of trimethyl borate, triisopropyl borate, tributyl borate and triisobutyl borate.
8. The method according to claim 7, wherein the reaction temperature of step 1) is-50 to-100 ℃;
and/or the reaction temperature of the step 2) is 50-150 ℃;
and/or the reaction temperature of the step 3) is-30 to-5 ℃.
9. The method for preparing the self-aligning additive of claim 1 or 2, wherein the ring A represents 1, 4-cyclohexenylene, and the synthetic route is as follows:
wherein R, m and n in each compound in the synthetic route are consistent with R, m and n in the product.
10. The preparation method according to claim 9, comprising the following steps:
1) will be provided with
After the metalation reaction with organic lithium, the organic lithium is reacted with
Reacting to obtain
2) Prepared by the step 1)Is/are as follows
Acid-catalyzed dehydration treatment is carried out to obtain
3) Prepared by the step 2)
Obtaining a product through hydrolysis reaction
11. The method according to claim 10, wherein in the step 1), the step
The molar ratio of the organic lithium reagent to the organic lithium reagent is 1: 1.0-2.0, and the organic lithium reagent is
And the above-mentioned
The feeding molar ratio of (A) to (B) is 1: 0.8-1.5;
and/or, in the step 2), the
The feeding molar ratio of the acid to the acid is 1: 0.02-0.2;
and/or, in the step 3), the
The feeding molar ratio of the boron tribromide to the boron tribromide is 1:1.0 to 1.3.
12. The preparation method according to claim 11, wherein the organolithium reagent is selected from one or more of sec-butyllithium, tert-butyllithium, and n-butyllithium;
and/or the acid is selected from one or more of hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid and potassium hydrogen sulfate.
13. The method according to claim 12, wherein the reaction temperature of step 1) is-50 to-100 ℃;
and/or the reaction temperature of the step 2) is 50-120 ℃;
and/or the reaction temperature of the step 3) is-30 to-5 ℃.
14. A process for the preparation of a self-aligning additive according to claim 1 or 2 wherein ring a represents a 1, 4-cyclohexylene group, the synthetic route being in particular:
wherein R, m and n in each compound in the synthetic route are consistent with R, m and n in the product.
15. The method according to claim 14, comprising in particular the steps of:
1) will be provided with
After the metalation reaction with organic lithium, the organic lithium is reacted with
Reacting to obtain
2) Subjecting the product obtained in step 1)
Reacting with boron trifluoride diethyl etherate and triethylsilane to obtain
3) Prepared by the step 2)
Obtaining a product through hydrolysis reaction
16. The method according to claim 15, wherein the hydrolysis reaction of step 3) is carried out by
Adding boron tribromide to react.
17. The method according to claim 16, wherein in the step 1), the step
The feeding molar ratio of the organic lithium reagent to the organic lithium reagent is 1: 1.0-2.0, and the organic lithium reagent is prepared by
And the above-mentioned
The feeding molar ratio of (A) to (B) is 1: 0.8-1.5;
and/or, in the step 2), the
The feeding molar ratio of the boron trifluoride diethyl etherate1: 1.0-3.0; the above-mentioned
The feeding molar ratio of the triethyl silane to the triethyl silane is 1: 1.0-3.0;
and/or, in the step 3), the
The feeding molar ratio of the boron tribromide to the boron tribromide is 1:1.0 to 1.3.
18. The method of claim 17, wherein the organolithium reagent is selected from the group consisting of sec-butyllithium, tert-butyllithium, and n-butyllithium.
19. The method for preparing the catalyst according to claim 18, wherein the reaction temperature of the step 1) is-50 to-100 ℃;
and/or the reaction temperature of the step 2) is 30 to-90 ℃;
and/or the reaction temperature of the step 3) is-30 to-5 ℃.
20. A composition containing a self-alignment additive, which comprises the self-alignment additive of claim 1 or 2 or the self-alignment additive prepared by the preparation method of any one of claims 3 to 19, wherein the mass percent of the self-alignment additive in the composition is 0.01 to 15%.
21. The composition according to claim 20, wherein the self-alignment additive is 0.1-10% by mass of the composition.
22. The composition according to claim 21, wherein the self-alignment additive is 0.1-5% by mass of the composition.
23. Use of the self-aligning additive of claim 1 or 2 or the self-aligning additive prepared by the preparation method of any one of claims 3 to 19, or the composition of any one of claims 20 to 22 in the field of liquid crystal display.
24. Use of the self-aligning additive of claim 1 or 2 or the self-aligning additive prepared by the preparation method of any one of claims 3 to 19, or the composition of any one of claims 20 to 22 in a liquid crystal display device.
25. The use according to claim 24, wherein the liquid crystal display device is selected from one of VA, TN, STN, FFS or IPS liquid crystal displays.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810184733.3A CN110229679B (en) | 2018-03-06 | 2018-03-06 | Self-alignment additive for liquid crystal medium and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810184733.3A CN110229679B (en) | 2018-03-06 | 2018-03-06 | Self-alignment additive for liquid crystal medium and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110229679A CN110229679A (en) | 2019-09-13 |
| CN110229679B true CN110229679B (en) | 2020-11-17 |
Family
ID=67862210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810184733.3A Active CN110229679B (en) | 2018-03-06 | 2018-03-06 | Self-alignment additive for liquid crystal medium and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110229679B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11359142B2 (en) * | 2019-12-20 | 2022-06-14 | Merck Patent Gmbh | Liquid-crystalline medium and liquid-crystal display comprising the same |
| WO2024133361A1 (en) * | 2022-12-23 | 2024-06-27 | Merck Patent Gmbh | Liquid-crystal medium |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04124190A (en) * | 1990-09-17 | 1992-04-24 | Canon Inc | Liquid crystalline compound, liquid crystal composition containing the same and liquid crystal element using the same |
| JP5623433B2 (en) * | 2009-02-19 | 2014-11-12 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Thiophene derivative and liquid crystal medium containing the same |
| EP2239310B1 (en) * | 2009-04-06 | 2012-06-27 | Merck Patent GmbH | Liquid crystal medium and liquid crystal display |
| CN107011920B (en) * | 2010-07-29 | 2021-06-22 | 默克专利股份有限公司 | Liquid-crystalline medium comprising thiophene derivatives |
| DE102011108708A1 (en) * | 2010-09-25 | 2012-03-29 | Merck Patent Gmbh | Liquid crystal displays and liquid crystal media with homeotropic alignment |
| CN103492531B (en) * | 2011-02-05 | 2016-06-22 | 默克专利股份有限公司 | There is the liquid crystal display of vertical plane orientation |
| WO2013004372A1 (en) * | 2011-07-07 | 2013-01-10 | Merck Patent Gmbh | Liquid-crystalline medium |
| WO2014090362A1 (en) * | 2012-12-12 | 2014-06-19 | Merck Patent Gmbh | Liquid-crystalline medium |
| EP2883934B1 (en) * | 2013-12-16 | 2019-11-13 | Merck Patent GmbH | Liquid-crystalline medium |
| CN106398717B (en) * | 2016-08-30 | 2018-05-22 | 北京燕化集联光电技术有限公司 | A kind of epoxypentyl class liquid-crystal compounds and preparation method and application |
| CN107418598B (en) * | 2017-05-26 | 2019-06-11 | 深圳市华星光电技术有限公司 | Liquid crystal material, liquid crystal display panel and its manufacturing method |
-
2018
- 2018-03-06 CN CN201810184733.3A patent/CN110229679B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110229679A (en) | 2019-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| 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 | |
| CN109423296B (en) | Dibenzothiophene negative dielectric anisotropy compound and preparation method and application thereof | |
| CN111592517A (en) | Liquid crystal compound containing dibenzofuran structure and preparation method and application thereof | |
| CN109423297B (en) | Dibenzothiophene liquid crystal compound and preparation method and application thereof | |
| CN112266794B (en) | Liquid crystal compound containing thiophene and preparation method and application thereof | |
| CN110229679B (en) | Self-alignment additive for liquid crystal medium and preparation method and application thereof | |
| CN114105921B (en) | Cyclopentyl benzofuran liquid crystal compound and application thereof | |
| CN108728112A (en) | A kind of liquid-crystal compounds of negative dielectric anisotropic and the preparation method and application thereof | |
| CN114105941B (en) | Novel 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 | |
| CN108690636B (en) | Liquid crystal compound with negative dielectric anisotropy as well as preparation method and application thereof | |
| CN113881443A (en) | Liquid crystal compound containing dibenzothiophene structure and application thereof | |
| CN107286953B (en) | Cyclopentyl negative dielectric anisotropy liquid crystal compound and composition and application thereof | |
| CN107400517B (en) | Cyclopentyl negative dielectric anisotropy liquid crystal compound, composition and application | |
| CN110229678B (en) | Self-alignment additive and preparation method and application thereof | |
| CN111040779B (en) | Liquid crystal vertical self-alignment additive and preparation method and application thereof | |
| CN114686242B (en) | Liquid crystal compound and preparation method and application thereof | |
| CN107345141B (en) | Liquid crystal compound with negative dielectric anisotropy of isoamyl and application thereof | |
| CN110358550B (en) | Novel liquid crystal vertical self-alignment additive and preparation method and application thereof | |
| CN110396414B (en) | Self-alignment additive and preparation method and application thereof | |
| CN111592889B (en) | Liquid crystal compound and preparation method and application thereof | |
| CN110396415B (en) | Novel liquid crystal vertical alignment agent and preparation method and application thereof | |
| CN114196417A (en) | Liquid crystal compound containing cyclopentyl and application | |
| CN111073663A (en) | Novel self-alignment additive and preparation method and application thereof |
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 |