CN102153441A - Fluorinated terphenyl liquid crystal compound containing two 3-butenyls and preparation method thereof - Google Patents
Fluorinated terphenyl liquid crystal compound containing two 3-butenyls and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a novel monomeric fluorinated terphenyl liquid crystal compound containing two 3-butenyls and a preparation method thereof. The monomeric fluorinated terphenyl liquid crystal compound containing two 3-butenyls and intermediates thereof are applicable to compound structural formulae (I) and (II). In the formulae (I) and (II), the number of fluorine atoms is two, and the two fluorine atoms can be in ortho-position, or meta-position or para-position; and X1 and X2 are iodine or bromine. The preparation method comprises the following steps: carrying out cross-coupling reaction on p-formylphenylboronic acid and the (II) under the catalytic action of a palladium catalyst in the alkaline environment to obtain a 4,4''-diformyl fluorinated terphenyl; and carrying out reduction, chlorination and coupling reaction to obtain the (I). The novel monomeric terphenyl liquid crystal compound provided by the invention has the advantages of moderate synthesis conditions, high conversion rate and low cost.
Description
Technical field
The invention belongs to liquid crystal material and technical field of chemistry, be specifically related to the structure and the preparation method of novel liquid crystal compound, especially a kind of novel can be widely used in STN-LCD and TFT-LCD contain two fluorine-containing terphenyl liquid crystalline cpds of 3-butenyl and preparation method thereof.
Background technology
Since Austrian scientist in 1888 finds liquid crystal material, liquid crystal material has had very large-scale development, not only being widely used in instrument shows, vehicle-mounted demonstration, and along with the Application and Development of TFT, it has been widely used in large-size screen monitors demonstrations such as TV, and is more and more closer, therefore more and more higher to the performance requriements of liquid crystal material with people's life relation.Common being seen TN pattern requires wide nematic phase range, low threshold voltage, high clearing point, big specific refractory power and premium properties such as can switch under utmost point low temperature.The STN pattern also requires more multichannel to drive lower threshold voltage etc. except that above-mentioned TN pattern requires.And require material to possess high resistivity based on the liquid crystal mode of TFT technology, excellent stability, and good response speed etc.The VA pattern then requires big negative permittivity, good low temperature mutual solubility etc.
Compare with CRT monitor, the response speed of liquid-crystal display is slow partially, though liquid-crystal display has become mass consumption, response is still one of important indicator of liquid-crystal display fast, the means that reach quick response are a lot, and the performance of improving liquid crystal material is one of important means.
The monomer liquid crystal that contains the 3-alkenylene chain on the phenyl ring generally has higher K33/K11 value, has and other liquid crystal mutual solubility preferably, mesomorphic phase broad.Introduce the viscosity that fluorine atom can reduce liquid crystal in the liquid crystal molecule.These performances all help improving response speed of liquid crystal.The liquid crystalline cpd viscosity of finding to have the butenyl structure in the former report is low, and the K33/K11 value is bigger, with other monocrystalline the good low-temperature mutual solubility is arranged, and high temperature resistant ultraviolet performance is good.Good response speed is arranged in the TN pattern, good steepness is arranged in the STN pattern.Disclosed structure has: (JP2001011456, JP10017500A, EP0825176A,, CN101351432)
1.
Bigger degree of birefringence is arranged, high clearing point, the K33/K11 value is bigger, but mutual solubility is relatively poor.
2.
Bigger degree of birefringence is arranged, good mutual solubility, the K33/K11 value is bigger, but clearing point is lower, stable bad to UV-light.
3.
Degree of birefringence is very big, and clearing point is also than higher, and the K33/K11 value is bigger, but mutual solubility is relatively poor relatively, hydrolabil.
4.
Have bigger degree of birefringence, clearing point is higher.
Summary of the invention
The object of the present invention is to provide a kind of novel texture, have high clearing point, low viscosity, big degree of birefringence, good good characteristics such as low temperature mutual solubility can be used for preparing the novel of various liquid-crystal compositions and contain the two fluorine-containing terphenyl monomer liquid crystal of 3-butenyl compounds, and a kind of reaction conditions gentleness, transformation efficiency is higher, step is few, be applicable to the preparation method who contains the two fluorine-containing terphenyl monomer liquid crystal of 3-butenyl compounds of suitability for industrialized production.
The present invention designs and has synthesized a kind of novel terphenyl monomer liquid crystal compound, and technical solution is as follows:
The novel pair fluorine-containing terphenyl monomer liquid crystal of the 3-butenyl compounds that contain of the present invention, it has following general structure:
The number of fluorine atoms that contains in the formula I is 2, and described two fluorine can be ortho position or a position or contraposition.
The preparation method that the present invention contains the two fluorine-containing terphenyl monomer liquid crystal of 3-butenyl compounds is:
The first step is with doubling dose two cross-coupling reactions to be taken place for formylphenylboronic acid or its acetal derivant and compound with following general structural formula (II), obtain 4,4 ' '-the fluorine-containing terphenyl of two formyl radicals, when using the acetal derivant of formylphenylboronic acid, need hydrolysis remove protection, the method for described deprotection be toluene be solvent, in the presence of 85% formic acid, reacted 20 hours in 35 degrees centigrade; The catalyzer that cross-coupling reaction uses is that four triphenylphosphines close wherein a kind of of palladium, two triphenylphosphine palladium chlorides, palladium carbon, palladium; The alkali that uses is wherein a kind of as potassiumphosphate, yellow soda ash, sodium bicarbonate, sodium hydroxide, potassium hydroxide, salt of wormwood; The solvent that uses is the mixture of dimethyl formamide, N,N-DIMETHYLACETAMIDE, toluene, ethanol, tetrahydrofuran (THF), Virahol, acetone, water one or both or three kinds wherein; Temperature of reaction is between 20-150 degree centigrade;
Second step be with 4,4 ' '-the fluorine-containing terphenyl of two formyl radicals is reduced to 4,4 ' '-the fluorine-containing terphenyl of two hydroxymethyls, the reductive agent that reduction reaction is used is wherein a kind of of lithium aluminum hydride, POTASSIUM BOROHYDRIDE, sodium borohydride; Solvent is tetrahydrofuran (THF), dioxane, methylene dichloride, dimethyl formamide, water one or both a mixture wherein; Temperature of reaction is between 0-100 degree centigrade;
The 3rd step was with 4,4 ' '-the fluorine-containing terphenyl halo of two hydroxymethyls, obtain 4,4 ' '-the fluorine-containing terphenyl of two chlorine (bromine) methyl, the halogenating agent that halogenating reaction uses is wherein a kind of of sulfur oxychloride, triphenylphosphine-tetracol phenixin, hydrogen bromide, dibrominated triphenylphosphine; Solvent is wherein a kind of of tetrahydrofuran (THF), tetracol phenixin, methylene dichloride, dimethyl formamide, and temperature of reaction is between 0-100 degree centigrade;
The 4th step was 4,4 ' '-the Grignard reagent generation linked reaction of the fluorine-containing terphenyl of dichloride methyl and allyl halide, and obtain (I), the Grignard reagent that linked reaction is used is the Grignard reagent of chlorallylene or allyl bromide 98; Solvent is wherein a kind of of ether, tetrahydrofuran (THF); Temperature of reaction is 0 degree centigrade of reflux temperature to solvent; In the 4th step linked reaction, can use catalyzer or not use catalyzer; If the use catalyzer, catalyzer can be cupric chloride lithium, cuprous bromide-lithiumbromide;
The number of fluorine atoms that contains in the described compound of described formula II is 2, and two fluorine can be ortho position or a position or contraposition, X
1, X
2Be bromine or iodine;
Its preparation route is as follows:
The number of fluorine atoms that is contained in above-mentioned each reaction equation is 2, and two fluorine can be ortho position or a position or contraposition; X is a chlorine or bromine, X
1, X
2Be bromine or iodine; Acetal derivant to formylphenylboronic acid is ethylene glycol or neopentyl glycol or 1, the 2-propylene glycol acetal.
Among the preparation method who contains the two fluorine-containing terphenyl monomer liquid crystal of 3-butenyl compounds of the present invention:
Preferred four triphenylphosphines of catalyzer that the first step cross-coupling reaction uses close palladium; The preferred yellow soda ash of alkali that uses; Three kinds of solvent systems of the preferred toluene-alcohol-water of solvent of using; The preferred 50-110 of temperature of reaction degree centigrade.
The preferred POTASSIUM BOROHYDRIDE of reductive agent that the second step reduction reaction is used; The preferred tetrahydrofuran (THF) of solvent; Preferred 65 degrees centigrade of temperature of reaction.
The preferred halogenating agent of the 3rd step halogenating reaction is triphenylphosphine-tetracol phenixin; The preferred tetracol phenixin of solvent.Preferred temperature is 50-70 degree centigrade.
The preferred chlorallylene Grignard reagent of Grignard reagent that the 4th step linked reaction is used; The preferred ether of solvent; Preferred 50 degrees centigrade of temperature of reaction; Preferably do not use catalyzer.
The intermediate of using in the synthetic route of the present invention is not new compound, wherein to formylphenylboronic acid, 1, and 4-two bromo-2,5-two fluorobenzene can be bought on market and obtain.Two intermediates 1 in addition, 4-two iodo-2,3-two fluorobenzene, 4-bromo-3,5 difluoro iodobenzenes can by following method synthetic to, the following synthetic method of using all is the organic chemistry filed method that arrives commonly used, can consult to obtain in general organic chemistry textbook commonly used.
(A) 1,2-Difluorobenzene is dissolved in tetrahydrofuran (THF), cools to-70 ℃, drip the butyllithium that doubles the 1,2-Difluorobenzene molar weight, keep in reaction solution, drip the iodine that doubles the 1,2-Difluorobenzene molar weight half an hour (B), be warmed up to-20 ℃, hydrolysis, separatory, recrystallization can obtain the purpose product
(A) with 3, the 5-difluoroaniline is dissolved in tetrahydrofuran (THF), drip 1.2 times to 3, the diacetyl oxide of 5-difluoroaniline reacted after dripping 2 hours again, and decompression is steamed down and desolventized and by-product acetic acid, can obtain 3 with the sherwood oil recrystallization, 5-two fluoroacetanilides (B) are with 3, and 5-two fluoroacetanilides are dissolved in methylene dichloride, drip the bromine of equimolar amount, reacted again after dripping 2 hours, steaming desolventizes the back and obtains 3 with the Virahol recrystallization, and 5-two fluoro-4-acetobromanilides (C) are 3, and 5-two fluoro-4-acetobromanilides join in 20% the dilute sulphuric acid heating hydrolysis to all dissolving, cool to-5 ℃, drip sodium nitrite solution, prepare 3,5-two fluoro-4-bromaniline diazonium salts.This diazonium salt is added drop-wise in 50 ℃ the potassium iodide aqueous solution, is cooled to 10 ℃ after adding, filter the crystal of separating out, obtain 4-bromo-3,5 difluoro iodobenzenes with ethyl alcohol recrystallization.
The invention has the beneficial effects as follows:
1 this monomer liquid crystal compound can be used for TN, liquid-crystal display patterns such as STN, and owing to possess good stability and heat-resisting and ultra-violet resistance, show applicable to TN-TFT.This monomer liquid crystal compound be used in can be very big in the mixed crystal the response speed of liquid crystal of improving, the steepness that improves liquid crystal is to adapt to higher driving way.And when fluorine atom was substituted in the same side of phenyl ring, it had good negative permittivity, can be used in the VA pattern.
2 the present invention contain the preparation method of the two fluorine terphenyl monomer liquid crystal compounds of two 3-alkenylene chains; cross-coupling reaction, takes place, obtains (I) through reduction, chloro, coupling again under palladium catalyst catalysis formylphenylboronic acid and acetal derivant thereof and (II) in utilization in alkaline environment.Have the reaction conditions gentleness, transformation efficiency is higher, step is few, be applicable to the effect of suitability for industrialized production.
3 the present invention design to contain the two fluorine terphenyl monomer liquid crystal compounds of two 3-alkenylene chains are a kind of novel liquid crystals, the liquid crystalline cpd with this class formation is not seen the domestic and foreign literature report.This type of liquid crystalline cpd has high clearing point, low viscosity, big degree of birefringence, good low temperature mutual solubility, bigger good characteristics such as K33/K11 value, can be used for preparing various liquid-crystal compositions.
Pair fluorine-containing terphenyl liquid crystalline cpds of 3-butenyl that contain of the present invention, this liquid crystal material compound is than formula 1
With formula 4
Has better consistency, bigger K33/K11 value; Than formula 2
Higher clearing point is arranged, than formula 3
Better low temperature mutual solubility is arranged, stable to light and water.
Embodiment
Embodiment 1:
4,4 ' '-two (3-butenyls)-3 ', 5 '-two fluoro-(1,1 ', 4 ', 1 ' ') preparation of terphenyl.
Step 14,4 ' '-two formyl radicals-3 ', 5 '-two fluoro-(1,1 ', 4 ', 1 ' ') preparation of terphenyl:
Add 36.6g2 in the 1000ml there-necked flask, 6-two fluoro-1,4-diiodo-benzene, 36g are to formylphenylboronic acid, 300ml toluene, and 200ml ethanol, 200ml water, the inflated with nitrogen displaced air adds tetra-triphenylphosphine palladium 1.6g, is heated to backflow under stirring, and keeps 6 hours.
Filtered while hot is removed the inorganic salt in the reaction solution, and with the toluene flush cake of heat, the filtrate branch vibration layer freezes into refrigerator behind the hot water wash organic layer.The crystallization that filtration is separated out obtains lurid crystal 2 4.6g.
Step 24,4 ' '-two hydroxymethyls-3 ', 5 '-two fluoro-(1,1 ', 4 ', 1 ' ') preparation of terphenyl
Add the 24.6g4 in the step 1 in the 1000ml there-necked flask; 4 ' '-two formyl radicals-3 '; 5 '-two fluoro-(1,1 ', 4 '; 1 ' ') terphenyl; the 400ml tetrahydrofuran (THF) is heated to 50 degrees centigrade together, drips the solution of the 40ml water of 8.1g POTASSIUM BOROHYDRIDE; added with 20 minutes approximately, add the back reheat and refluxed 4 hours.
Reaction solution is cooled to 20 degrees centigrade, adds entry 1000ml, separate out white solid, filter, washing, oven dry obtains white solid 21g.
Step 34,4 ' '-dichloride methyl-3 ', 5 '-two fluoro-(1,1 ', 4 ', 1 ' ') preparation of terphenyl:
21g 4,4 ' '-two hydroxymethyls-3 in the 500ml there-necked flask in the adding step 2 ', 5 '-two fluoro-(1,1 ', 4 ', 1 ' ') terphenyl, the 26.2g triphenylphosphine, the 200ml tetracol phenixin, reflux is 4 hours together.Reaction solution is concentrated into cumulative volume 150ml, is cooled to 60 degrees centigrade, add ethanol 150ml, freeze, filter the crystal of separating out, more once, obtain white crystal 15g. with ethyl alcohol recrystallization into refrigerator
Step 44,4 ' '-two (3-butenyls)-3 ', 5 '-two fluoro-(1,1 ', 4 ', 1 ' ') preparation of terphenyl:
1. the preparation of Grignard reagent
Add 9.2g metal magnesium chips in the 250ml there-necked flask, the 20ml anhydrous diethyl ether, the inflated with nitrogen displaced air, drip the solution that is made into by 26.3g chlorallylene and 20ml anhydrous diethyl ether on a small quantity under the magnetic agitation, continue to drip the diethyl ether solution of remaining chlorallylene after waiting to find obviously to heat up, keep reflux state, 30 minutes times spent added approximately, refluxed again after adding 20 minutes, stand-by.
2. linked reaction
Add the 15g4 in the step 3 in the 500ml there-necked flask, 4 ' '-dichloride methyl-3 ', 5 '-two fluoro-(1,1 ', 4 ', 1 ' ') terphenyl, 50ml anhydrous diethyl ether, inflated with nitrogen displaced air, stir and drip the above-mentioned Grignard reagent that has just prepared down, exothermic heat of reaction, approximately half hour, drip, and refluxed after adding 3 hours again.
Be cooled to 20 degrees centigrade, reaction solution poured in the 100ml frozen water of 10ml hydrochloric acid, stirring makes organic phase clear with inorganic layering mutually, tell organic layer, water layer with the 20ml ether extraction once merges organic layer, be washed to neutrality, anhydrous sodium sulfate drying, neat solvent is steamed in decompression down.
The solid that obtains 50ml petroleum ether dissolution is crossed silicagel column, dashes with the 100ml sherwood oil and drenches, and merges, and decompression is steamed neat solvent down, uses sherwood oil recrystallization 5-6 time again, obtains the 8.1g white crystal, and gas chromatographic purity is 99.9%.
Embodiment 2:
4,4 ' '-two (3-butenyls)-2 ', 3 '-two fluoro-(1,1 ', 4 ', 1 ' ') preparation of terphenyl
With reference to utilizing the similar preparation method of embodiment 1; initial feed adopts formylphenylboronic acid and 2; 3-two fluoro-1, the coupling of 4-diiodo-benzene, process is as the reaction of four steps of embodiment 1; can prepare 4; 4 ' '-two (3-butenyls)-2 ', 3 '-two fluoro-(1,1 '; 4 ', 1 ' ') terphenyl
Embodiment 3:
4,4 ' '-two (3-butenyls)-3 ', 6 '-two fluoro-(1,1 ', 4 ', 1 ' ') preparation of terphenyl
With reference to utilizing the similar preparation method of embodiment 1; initial feed adopts formylphenylboronic acid and 2; 5-two fluoro-1, the coupling of 4-diiodo-benzene, process is as the reaction of four steps of embodiment 1; can prepare 4; 4 ' '-two (3-butenyls)-3 ', 6 '-two fluoro-(1,1 '; 4 ', 1 ' ') terphenyl.
Claims (3)
1. one kind contains the two fluorine-containing terphenyl monomer liquid crystal of 3-butenyl compounds, and it is characterized in that: it is applicable to that following compound structure leads to formula I, and the number of fluorine atoms that contains in the logical formula I is 2, and described two fluorine can be ortho position or a position or contraposition,
?
2. the described preparation method who contains the two fluorine-containing terphenyl monomer liquid crystal of 3-butenyl compounds of claim 1 is characterized in that:
The first step be with doubling dose to formylphenylboronic acid or its acetal derivant and have the described compound of following general structural formula (II) two cross-coupling reactions take place, obtain 4,4 ' '-the fluorine-containing terphenyl of two formyl radicals, when using the acetal derivant of formylphenylboronic acid, need hydrolysis to remove protection; The catalyzer that cross-coupling reaction uses is that four triphenylphosphines close wherein a kind of of palladium, two triphenylphosphine palladium chlorides, palladium carbon, palladium; The alkali that uses is wherein a kind of as potassiumphosphate, yellow soda ash, sodium bicarbonate, sodium hydroxide, potassium hydroxide, salt of wormwood; The solvent that uses is the mixture of dimethyl formamide, N,N-DIMETHYLACETAMIDE, toluene, ethanol, tetrahydrofuran (THF), Virahol, acetone, water one or both or three kinds wherein; Temperature of reaction is between 20-150 degree centigrade;
Second step be with 4,4 ' '-the fluorine-containing terphenyl of two formyl radicals is reduced to 4,4 ' '-the fluorine-containing terphenyl of two hydroxymethyls, the reductive agent that reduction reaction is used is wherein a kind of of lithium aluminum hydride, POTASSIUM BOROHYDRIDE, sodium borohydride; Solvent is tetrahydrofuran (THF), dioxane, methylene dichloride, dimethyl formamide, water, ethanol one or both a mixture wherein; Temperature of reaction is between 0-100 degree centigrade;
The 3rd step was with 4,4 ' '-the fluorine-containing terphenyl halo of two hydroxymethyls, obtain 4,4 ' '-the fluorine-containing terphenyl of two chlorine (bromine) methyl, the halogenating agent that halogenating reaction uses is wherein a kind of of sulfur oxychloride, triphenylphosphine-tetracol phenixin, hydrogen bromide, dibrominated triphenylphosphine; Solvent is wherein a kind of of tetrahydrofuran (THF), tetracol phenixin, methylene dichloride, dimethyl formamide, and temperature of reaction is between 0-100 degree centigrade;
The 4th step was 4,4 ' '-the Grignard reagent generation linked reaction of the fluorine-containing terphenyl of two chlorine (bromine) methyl and allyl halide, and obtain (I), the Grignard reagent that linked reaction is used is the Grignard reagent of chlorallylene or allyl bromide 98; Solvent is wherein a kind of of ether, tetrahydrofuran (THF); Temperature of reaction is 0 degree centigrade of reflux temperature to solvent; In the 4th step linked reaction, can use catalyzer or not use catalyzer; If the use catalyzer, catalyzer can be cupric chloride lithium, cuprous bromide-lithiumbromide;
The number of fluorine atoms that contains in (II) described compound is 2, and two fluorine can be ortho position or a position or contraposition, X
1, X
2Be bromine or iodine;
Its preparation route is as follows:
2 of the number of fluorine atoms that is contained in above-mentioned each reaction equation, two fluorine can be ortho position or a position or contraposition; X is a chlorine or bromine, X
1, X
2Be bromine or iodine; Acetal derivant to formylphenylboronic acid is ethylene glycol or neopentyl glycol or 1, the 2-propylene glycol acetal.
3. the preparation method who contains the two fluorine-containing terphenyl monomer liquid crystal of 3-butenyl compounds according to claim 2 is characterized in that
(a) preferred four triphenylphosphines of catalyzer of the first step cross-coupling reaction use close palladium; The preferred yellow soda ash of alkali that uses; Three kinds of solvent systems of the preferred toluene-alcohol-water of solvent of using; The preferred 50-110 of temperature of reaction degree centigrade;
(b) the preferred POTASSIUM BOROHYDRIDE of reductive agent of second step reduction reaction use; The preferred tetrahydrofuran (THF) of solvent; Preferred 65 degrees centigrade of temperature of reaction;
(c) the preferred halogenating agent of the 3rd step halogenating reaction is triphenylphosphine-tetracol phenixin; The preferred tetracol phenixin of solvent; Preferred temperature is 50-70 degree centigrade;
(d) the preferred chlorallylene Grignard reagent of Grignard reagent of the 4th step linked reaction use; The preferred ether of solvent; Preferred 35 degrees centigrade of temperature of reaction; Preferably do not use catalyzer.
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Cited By (6)
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| CN102826953A (en) * | 2012-07-24 | 2012-12-19 | 烟台万润精细化工股份有限公司 | Preparation method of 4-(alkyl-3-ene)-( fluoro)benzene derivative |
| WO2016115719A1 (en) * | 2015-01-23 | 2016-07-28 | 北京欣奕华科技有限公司 | Liquid crystal compound and preparation method therefor, liquid crystal composition and liquid crystal display panel |
| CN108165278A (en) * | 2017-12-26 | 2018-06-15 | 陕西师范大学 | A kind of tolans butene-based liquid crystal compounds and its synthetic method |
| CN111378456A (en) * | 2018-12-29 | 2020-07-07 | 江苏和成新材料有限公司 | Negative liquid crystal compound containing terminal alkenyl and synthetic method thereof |
| CN111704912A (en) * | 2020-06-29 | 2020-09-25 | 烟台丰蓬液晶材料有限公司 | Novel preparation method of 3-alkenyl benzyne liquid crystal compound |
| CN116426295A (en) * | 2022-11-23 | 2023-07-14 | 河北凡克新材料有限公司 | Preparation method of side fluorine-containing terphenyl liquid crystal monomer |
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| CN101351432A (en) * | 2006-01-06 | 2009-01-21 | 智索株式会社 | Monofluorinated terphenyl compound having alkenyl, liquid crystal composition and liquid crystal display element |
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| JP2001011456A (en) * | 1999-06-29 | 2001-01-16 | Dainippon Ink & Chem Inc | Nematic liquid crystal composition and liquid crystal display device using the composition |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102826953A (en) * | 2012-07-24 | 2012-12-19 | 烟台万润精细化工股份有限公司 | Preparation method of 4-(alkyl-3-ene)-( fluoro)benzene derivative |
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| WO2016115719A1 (en) * | 2015-01-23 | 2016-07-28 | 北京欣奕华科技有限公司 | Liquid crystal compound and preparation method therefor, liquid crystal composition and liquid crystal display panel |
| CN108165278A (en) * | 2017-12-26 | 2018-06-15 | 陕西师范大学 | A kind of tolans butene-based liquid crystal compounds and its synthetic method |
| CN111378456A (en) * | 2018-12-29 | 2020-07-07 | 江苏和成新材料有限公司 | Negative liquid crystal compound containing terminal alkenyl and synthetic method thereof |
| CN111704912A (en) * | 2020-06-29 | 2020-09-25 | 烟台丰蓬液晶材料有限公司 | Novel preparation method of 3-alkenyl benzyne liquid crystal compound |
| CN116426295A (en) * | 2022-11-23 | 2023-07-14 | 河北凡克新材料有限公司 | Preparation method of side fluorine-containing terphenyl liquid crystal monomer |
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Application publication date: 20110817 |