CN104099105A - Liquid crystal chemical compound containing dioxane ring and application thereof - Google Patents

Liquid crystal chemical compound containing dioxane ring and application thereof Download PDF

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CN104099105A
CN104099105A CN201410306790.6A CN201410306790A CN104099105A CN 104099105 A CN104099105 A CN 104099105A CN 201410306790 A CN201410306790 A CN 201410306790A CN 104099105 A CN104099105 A CN 104099105A
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姜天孟
田会强
储士红
陈海光
高立龙
班全志
梁现丽
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Beijing Bayi Space LCD Technology Co Ltd
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Abstract

本发明提供一种含有二噁烷环和二氟甲氧基桥键的液晶化合物,所述液晶化合物具有如式I所示的结构:该化合物具有介电各向异性大、光学各向异性大和清亮点高的特点。该化合物应用至液晶组合物后,能够进一步改善已有惯用液晶组合物的介电各向异性、光学各向异性和清亮点,具有降低驱动电压和拓宽温度使用范围的技术效果。The invention provides a liquid crystal compound containing a dioxane ring and a difluoromethoxy bridge, the liquid crystal compound has a structure as shown in formula I: The compound has the characteristics of large dielectric anisotropy, large optical anisotropy and high clearing point. After the compound is applied to the liquid crystal composition, it can further improve the dielectric anisotropy, optical anisotropy and clearing point of the conventional liquid crystal composition, and has the technical effects of reducing the driving voltage and widening the temperature range.

Description

一种含有二噁烷环的液晶化合物及其应用A kind of liquid crystal compound containing dioxane ring and its application

技术领域technical field

本发明涉及液晶显示材料领域,具体涉及一种含有二噁烷环的液晶化合物及其应用。The invention relates to the field of liquid crystal display materials, in particular to a liquid crystal compound containing a dioxane ring and an application thereof.

背景技术Background technique

目前,液晶在信息显示领域得到广泛应用,同时在光通讯中的应用也取得了一定的进展(S.T.Wu,D.K.Yang.Reflective LiquidCrystal Displays.Wiley,2001)。近几年,液晶化合物的应用领域已经显著拓宽到各类显示器件、电光器件、电子元件、传感器等。为此,已经提出许多不同的结构,特别是在向列型液晶领域,向列型液晶化合物迄今已经在平板显示器中得到最为广泛的应用。特别是用于TFT有源矩阵的系统中。At present, liquid crystals are widely used in the field of information display, and at the same time, some progress has been made in the application of optical communication (S.T.Wu, D.K.Yang. Reflective Liquid Crystal Displays. Wiley, 2001). In recent years, the application fields of liquid crystal compounds have been significantly expanded to various display devices, electro-optic devices, electronic components, sensors, etc. For this reason, many different structures have been proposed, especially in the field of nematic liquid crystals, and nematic liquid crystal compounds have been most widely used in flat panel displays so far. Especially for TFT active matrix systems.

液晶显示伴随液晶的发现经历了漫长的发展道路。1888年奥地利植物学家Friedrich Reinitzer发现了第一种液晶材料安息香酸胆固醇(cholesteryl benzoate)。1917年Manguin发明了摩擦定向法,用以制作单畴液晶和研究光学各向异性。1909年E.Bose建立了攒动(Swarm)学说,并得到L.S.Ormstein及F.Zernike等人的实验支持(1918年),后经De Gennes论述为统计性起伏。G.W.Oseen和H.Zocher1933年创立连续体理论,并得到F.C.Frank完善(1958年)。M.Born(1916年)和K.Lichtennecker(1926年)发现并研究了液晶的介电各向异性。1932年,W.Kast据此将向列相分为正、负性两大类。1927年,V.Freedericksz和V.Zolinao发现向列相液晶在电场(或磁场)作用下,发生形变并存在电压阈值(Freederichsz转变)。这一发现为液晶显示器的制作提供了依据。Liquid crystal display has experienced a long development path with the discovery of liquid crystal. In 1888, Austrian botanist Friedrich Reinitzer discovered the first liquid crystal material, cholesterol benzoate. In 1917, Manguin invented the rubbing orientation method to make monodomain liquid crystals and study optical anisotropy. In 1909, E.Bose established the theory of Swarm, which was supported by the experiments of L.S.Ormstein and F.Zernike (1918), and was later discussed as statistical fluctuations by De Gennes. G.W.Oseen and H.Zocher founded the continuum theory in 1933, and it was perfected by F.C.Frank (1958). M.Born (1916) and K.Lichtennecker (1926) discovered and studied the dielectric anisotropy of liquid crystals. In 1932, W.Kast divided the nematic phase into two categories, positive and negative. In 1927, V.Freedericksz and V.Zolinao discovered that the nematic liquid crystal was deformed and had a voltage threshold (Freederichsz transition) under the action of an electric field (or magnetic field). This finding provides a basis for the production of liquid crystal displays.

1968年美国RCA公司R.Williams发现向列相液晶在电场作用下形成条纹畴,并有光散射现象。G.H.Heilmeir随即将其发展成动态散射显示模式,并制成世界上第一个液晶显示器(LCD)。七十年代初,Helfrich及Schadt发明了TN原理,人们利用TN光电效应和集成电路相结合,将其做成显示器件(TN-LCD),为液晶的应用开拓了广阔的前景。七十年代以来,由于大规模集成电路和液晶材料的发展,液晶在显示方面的应用取得了突破性的发展,1983~1985年T.Scheffer等人先后提出超扭曲向列相(Super Twisred Nematic:STN)模式以及P.Brody在1972年提出的有源矩阵(Active matrix:AM)方式被重新采用。传统的TN-LCD技术已发展为STN-LCD及TFT-LCD技术,尽管STN的扫描线数可达768行以上,但是当温度升高时仍然存在着响应速度、视角以及灰度等问题,因此大面积、高信息量、In 1968, R.Williams of RCA Company in the United States discovered that the nematic liquid crystal forms stripe domains under the action of an electric field, and has light scattering phenomenon. G.H.Heilmeir then developed it into a dynamic scattering display mode and made it the world's first liquid crystal display (LCD). In the early 1970s, Helfrich and Schadt invented the TN principle. People combined the TN photoelectric effect with integrated circuits to make it into a display device (TN-LCD), which opened up broad prospects for the application of liquid crystals. Since the 1970s, due to the development of large-scale integrated circuits and liquid crystal materials, the application of liquid crystals in display has achieved breakthrough development. From 1983 to 1985, T. Scheffer and others successively proposed super twisted nematic phase (Super Twisred Nematic: STN) mode and the active matrix (Active matrix: AM) method proposed by P.Brody in 1972 were re-adopted. The traditional TN-LCD technology has been developed into STN-LCD and TFT-LCD technology. Although the number of scanning lines of STN can reach more than 768 lines, there are still problems such as response speed, viewing angle and gray scale when the temperature rises. Therefore, Large area, high information content,

彩色显示大多采用有源矩阵显示方式。TFT-LCD已经广泛用于直视型电视、大屏幕投影电视、计算机终端显示和某些军用仪表显示,相信TFT-LCD技术具有更为广阔的应用前景。Most color displays use active matrix display. TFT-LCD has been widely used in direct-view TV, large-screen projection TV, computer terminal display and some military instrument display. It is believed that TFT-LCD technology has a broader application prospect.

其中“有源矩阵”包括两种类型:1、在作为基片的硅晶片上的OMS(金属氧化物半导体)或其它二极管。2、在作为基片的玻璃板上的薄膜晶体管(TFT)。The "active matrix" includes two types: 1. OMS (Metal Oxide Semiconductor) or other diodes on a silicon wafer as a substrate. 2. A thin film transistor (TFT) on a glass plate as a substrate.

单晶硅作为基片材料限制了显示尺寸,因为各部分显示器件甚至模块组装在其结合处出现许多问题。因而,第二种薄膜晶体管是具有前景的有源矩阵类型,所利用的光电效应通常是TN效应。TFT包括化合物半导体,如Cdse,或以多晶或无定形硅为基础的TFT。Monocrystalline silicon as a substrate material limits the size of the display, because there are many problems in the combination of various display devices and even module assembly. Thus, the second thin-film transistor is a promising active-matrix type, where the photoelectric effect used is usually the TN effect. TFTs include compound semiconductors, such as Cdse, or TFTs based on polycrystalline or amorphous silicon.

目前,TFT-LCD产品技术已经成熟,成功地解决了视角、分辨率、色饱和度和亮度等技术难题,其显示性能已经接近或超过CRT显示器。大尺寸和中小尺寸TFT-LCD显示器在各自的领域已逐渐占据平板显示器的主流地位。但是因受液晶材料本身的限制,TFT-LCD仍然存在着响应不够快,电压不够低,电荷保持率不够高等诸多缺陷。因此寻找低粘度、高介电各向异性的单晶化合物尤为重要。At present, the technology of TFT-LCD products has matured and successfully solved technical problems such as viewing angle, resolution, color saturation and brightness, and its display performance has approached or surpassed that of CRT displays. Large size and small and medium size TFT-LCD displays have gradually occupied the mainstream position of flat panel displays in their respective fields. However, due to the limitations of the liquid crystal material itself, TFT-LCD still has many defects such as insufficient fast response, insufficient voltage, and insufficient charge retention rate. Therefore, it is particularly important to find single crystal compounds with low viscosity and high dielectric anisotropy.

早在1990年德国默克公司在专利EP0482157中对同时含有F(CH2)n-和二噁烷的单体液晶的合成方法进行阐述,得到的相应化合物在液晶组合物中应用并不理想。As early as 1990, Merck of Germany described the synthesis method of monomeric liquid crystals containing both F(CH2) n- and dioxane in patent EP0482157, but the obtained corresponding compounds were not ideal for use in liquid crystal compositions.

1996年日本智索公司在专利WO9820006中也对该类单体液晶的合成方法进行阐述,得到的相应化合物综合性能也不够理想。In 1996, Chisso Corporation of Japan also described the synthesis method of this type of monomer liquid crystal in the patent WO9820006, and the comprehensive properties of the obtained corresponding compounds were not ideal.

发明内容Contents of the invention

针对上述背景,本发明的目的在于提供一种新型的液晶化合物,该化合物具有介电各向异性大、光学各向异性大和清亮点高的特点。In view of the above background, the object of the present invention is to provide a novel liquid crystal compound, which has the characteristics of large dielectric anisotropy, large optical anisotropy and high clearing point.

本发明提供了一种具有二噁烷环的液晶化合物,该化合物同时含有二噁烷环和二氟甲氧基桥键,具有如式I所示的结构:The present invention provides a liquid crystal compound with a dioxane ring, which contains both a dioxane ring and a difluoromethoxy bridge, and has a structure as shown in formula I:

其中,in,

A1和A2各自独立地代表1,4-苯基,其中一个或多个H原子可被F原子取代;A 1 and A 2 each independently represent 1,4-phenyl, wherein one or more H atoms may be replaced by F atoms;

X选自F、OCF3、OCHF2、CF3、CF2H、Cl、OCH=CF2或OCF2CF=CF2X is selected from F, OCF 3 , OCHF 2 , CF 3 , CF 2 H, Cl, OCH=CF 2 or OCF 2 CF=CF 2 ;

Y1和Y2各自独立地代表H或F;Y 1 and Y 2 each independently represent H or F;

n为2~10。n is 2-10.

优选地,所述液晶化合物中,Preferably, in the liquid crystal compound,

A1和A2各自独立地代表1,4-苯基,其中一个或多个H原子可被F原子取代;A 1 and A 2 each independently represent 1,4-phenyl, wherein one or more H atoms may be replaced by F atoms;

X选自F、OCF3、OCHF2或CF3X is selected from F, OCF 3 , OCHF 2 or CF 3 ;

Y1和Y2各自独立地代表H或F,并且不同时为H;Y 1 and Y 2 each independently represent H or F, and are not H at the same time;

n为2、3或4。n is 2, 3 or 4.

进一步优选地,所述液晶化合物中,Further preferably, in the liquid crystal compound,

A1和A2各自独立地代表1,4-苯基,其中一个或多个H原子可被F原子取代;A 1 and A 2 each independently represent 1,4-phenyl, wherein one or more H atoms may be replaced by F atoms;

X选自F或OCF3X is selected from F or OCF 3 ;

Y1和Y2各自独立地代表H或F,并且不同时为H;Y 1 and Y 2 each independently represent H or F, and are not H at the same time;

n为2、3或4。n is 2, 3 or 4.

更优选地,所述液晶化合物选自如下通式结构化合物:More preferably, the liquid crystal compound is selected from compounds of the following general formula:

其中,X选自F或OCF3;n为2,3或4。Wherein, X is selected from F or OCF 3 ; n is 2, 3 or 4.

作为本发明最佳实施方式,所述液晶化合物结构为:As the best implementation mode of the present invention, the structure of the liquid crystal compound is:

本发明所述液晶化合物具有介电各向异性大、光学各向异性大和清亮点高的显著特点。将所述化合物应用至组合物中后,组合物具有驱动电压低和温度使用范围广的特点。The liquid crystal compound of the invention has the remarkable characteristics of large dielectric anisotropy, large optical anisotropy and high clearing point. After the compound is applied to the composition, the composition has the characteristics of low driving voltage and wide temperature range.

本发明的第二目的在于提供一种含有二噁烷环的液晶化合物的制备方法,所述制备方法的合成路线如下:The second object of the present invention is to provide a preparation method of a liquid crystal compound containing a dioxane ring, the synthesis route of the preparation method is as follows:

包括如下步骤:Including the following steps:

1)起始原料化合物II和III,以甲苯为溶剂,以对甲苯磺酸为脱水催化剂,加热回流脱水3~9小时,得到化合物IV;1) The starting materials Compounds II and III, using toluene as a solvent and p-toluenesulfonic acid as a dehydration catalyst, heated and refluxed for 3 to 9 hours to obtain Compound IV;

2)化合物IV与化合物V,以四三苯基膦合钯为催化剂,回流反应4~12小时,得到目标化合物I。2) Compound IV and compound V were reacted under reflux for 4-12 hours using tetrakistriphenylphosphine palladium as a catalyst to obtain the target compound I.

其中,in,

A1、A2、X、Y1、Y2及n的指代同上;A 1 , A 2 , X, Y 1 , Y 2 and n refer to the same as above;

步骤2)所述回流时间优选为6小时。The reflux time of step 2) is preferably 6 hours.

采用上述制备方法能够批量化稳定得到含有二噁烷环的液晶化合物,所述化合物具有介电各向异性大、光学各向异性大和清亮点高的优势。By adopting the above preparation method, the liquid crystal compound containing dioxane ring can be stably obtained in batches, and the compound has the advantages of large dielectric anisotropy, large optical anisotropy and high clearing point.

本发明的第三目的在于保护上述含有二噁烷环的液晶化合物在液晶显示领域的应用。The third object of the present invention is to protect the application of the liquid crystal compound containing a dioxane ring in the field of liquid crystal display.

本发明要求保护含有二噁烷环的液晶化合物的液晶组合物。所述组合物中,含有二噁烷环的液晶化合物以合理的方式加入,液晶化合物占液晶组合物的质量百分比为1~80%,优选为3~50%。本领域技术人员可以预见,基于上述液晶化合物的加入,能够进一步改善已有惯用液晶组合物的介电各向异性、光学各向异性和清亮点,具有降低驱动电压和拓宽温度使用范围的技术效果。The present invention claims a liquid crystal composition containing a liquid crystal compound containing a dioxane ring. In the composition, the liquid crystal compound containing a dioxane ring is added in a reasonable manner, and the liquid crystal compound accounts for 1-80% by mass of the liquid crystal composition, preferably 3-50%. Those skilled in the art can predict that based on the addition of the above-mentioned liquid crystal compound, the dielectric anisotropy, optical anisotropy and clearing point of the existing conventional liquid crystal composition can be further improved, and it has the technical effect of reducing the driving voltage and widening the temperature range. .

本发明进一步请求保护上述液晶组合物在液晶显示装置中的应用,所述的液晶显示装置包括且不限于TN、ADS、FFS、IPS、VA或PSVA液晶显示器。将液晶组合物应用至液晶显示装置后,所述液晶显示装置具有驱动电压低和温度使用范围广的优点。The present invention further claims the application of the above-mentioned liquid crystal composition in liquid crystal display devices, and said liquid crystal display devices include but not limited to TN, ADS, FFS, IPS, VA or PSVA liquid crystal displays. After the liquid crystal composition is applied to a liquid crystal display device, the liquid crystal display device has the advantages of low driving voltage and wide temperature range.

本发明中各性能测试参数缩写如下所示:Each performance test parameter abbreviation is as follows among the present invention:

Δε代表在25℃和1kHz下的介电各向异性;Δε represents the dielectric anisotropy at 25°C and 1kHz;

△n代表光学各向异性;Δn represents optical anisotropy;

γ1代表在25℃下的旋转粘度(mPa·s);γ1 represents the rotational viscosity (mPa·s) at 25°C;

no代表折射率(589nm,25℃);no represents the refractive index (589nm, 25°C);

C.p代表液晶组合物的清亮点(℃);C.p represents the clearing point (°C) of the liquid crystal composition;

VHR代表电荷保持率(%);其测量方法为:将混合液晶注入液晶盒内,放入恒温箱中,待温度稳定后,进入测试程序,手动取点得到电荷保持率数值;测量电压为5V,加电时间为5ms,保持时间为500ms。VHR represents the charge retention rate (%); the measurement method is: inject the mixed liquid crystal into the liquid crystal box, put it in the incubator, and enter the test program after the temperature is stable, and manually take points to obtain the value of the charge retention rate; the measurement voltage is 5V , the power-on time is 5ms, and the hold time is 500ms.

具体实施方式Detailed ways

以下实施例用于说明本发明,但不用来限制本发明的范围。The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

实施例1Example 1

2-{4'-[1-(3,4,5-三氟苯氧基)二氟甲基]-3',5'-二氟联苯基}-5-(3-氟丙基)-[1,3]二噁烷(化合物5)的合成 2-{4'-[1-(3,4,5-trifluorophenoxy)difluoromethyl]-3',5'-difluorobiphenyl}-5-(3-fluoropropyl) Synthesis of -[1,3]dioxane (Compound 5)

1)2-(4-溴苯基)-5-(3-氟丙基)-[1,3]二噁烷(化合物3)的合成:1) Synthesis of 2-(4-bromophenyl)-5-(3-fluoropropyl)-[1,3]dioxane (compound 3):

向500mL三口瓶中加入0.3L甲苯,31.5g对溴苯甲醛(化合物2),23.1g2-(3-氟丙基)-1,3-丙二醇(化合物1),1.2g对甲苯磺酸。开搅拌加热,回流反应3小时。后处理,0.2L×2水洗,合并有机相加入20g无水硫酸钠干燥0.5h小时后,旋干溶剂,加入150mL甲苯与150mL石油醚,过30g硅胶柱,3倍柱高冲柱。旋干溶剂得67g,加入2倍乙醇与0.5倍甲苯,冰箱冷冻(-30℃)过夜抽滤。产品为白色固体,气相纯度(GC)99.0%,理论产量51.3g,实际产量27.1g,收率53%。Add 0.3 L of toluene, 31.5 g of p-bromobenzaldehyde (compound 2), 23.1 g of 2-(3-fluoropropyl)-1,3-propanediol (compound 1), and 1.2 g of p-toluenesulfonic acid into a 500 mL three-necked flask. Open stirring heating, reflux reaction 3 hours. After treatment, wash with 0.2L×2 water, combine the organic phases and add 20g of anhydrous sodium sulfate to dry for 0.5h, spin the solvent, add 150mL of toluene and 150mL of petroleum ether, pass through a 30g silica gel column, and flush the column 3 times higher. The solvent was spin-dried to obtain 67 g, which was added with 2 times of ethanol and 0.5 times of toluene, and then refrigerated (-30° C.) overnight for suction filtration. The product is a white solid, the gas phase purity (GC) is 99.0%, the theoretical yield is 51.3g, the actual yield is 27.1g, and the yield is 53%.

2)2-{4'-[1-(3,4,5-三氟苯氧基)二氟甲基]-3',5'-二氟联苯基}-5-(3-氟丙基)-[1,3]二噁烷(化合物5)的合成:2) 2-{4'-[1-(3,4,5-trifluorophenoxy)difluoromethyl]-3',5'-difluorobiphenyl}-5-(3-fluoropropane base)-[1,3]dioxane (compound 5):

200mL三口瓶中加入26mL无水乙醇,50mL甲苯和50mL水,开动搅拌,加入19.5g4-[1-(3,4,5-三氟苯氧基)二氟甲基]-3,5-二氟苯硼酸(化合物4),15.2g2-(4-溴苯基)-5-(3-氟丙基)-[1,3]二噁烷(化合物3)和11.7g无水碳酸钠。空置换氮气三次,加入0.25g四(三苯基膦)合钯。加热至液相60℃时,缓慢加热至回流,回流反应6小时。回流完毕,向反应釜中加入40mL水,搅拌10分钟,静置分液,有机相用40mL×2水洗两次。加入3倍石油醚加热溶解,柱层析。旋干溶剂用4倍乙醇冷冻重结晶三次,抽滤晾干得白色固体。Add 26mL of absolute ethanol, 50mL of toluene and 50mL of water into a 200mL three-necked flask, start stirring, and add 19.5g of 4-[1-(3,4,5-trifluorophenoxy)difluoromethyl]-3,5-difluoromethyl]-3,5-difluoromethyl Fluorophenylboronic acid (compound 4), 15.2 g 2-(4-bromophenyl)-5-(3-fluoropropyl)-[1,3]dioxane (compound 3) and 11.7 g anhydrous sodium carbonate. The nitrogen gas was substituted three times, and 0.25 g of tetrakis(triphenylphosphine)palladium was added. When heating to the liquid phase at 60°C, slowly heat to reflux and react at reflux for 6 hours. After the reflux was completed, 40 mL of water was added to the reaction kettle, stirred for 10 minutes, left to stand for liquid separation, and the organic phase was washed twice with 40 mL×2 water. Add 3 times of petroleum ether and heat to dissolve, and perform column chromatography. The solvent was spin-dried and recrystallized three times by freezing with 4 times ethanol, and then filtered and air-dried to obtain a white solid.

所得产物:The resulting product:

理论产量26.6g,实际产量21.5g,收率80.8%;The theoretical yield is 26.6g, the actual yield is 21.5g, and the yield is 80.8%;

气相纯度(GC)99.9%;Gas phase purity (GC) 99.9%;

熔点:80.0℃;Melting point: 80.0°C;

清亮点:109.1℃;Clearing point: 109.1°C;

Δn:0.144;Δn: 0.144;

Δε:33.46;Δε: 33.46;

γ1:125mPa·s;γ1: 125mPa s;

质谱分析碎片:239、267、385、532(分子离子峰);Mass spectrometry fragments: 239, 267, 385, 532 (molecular ion peak);

H-NMR核磁谱图(CDCl,300MHz):δH:0.90-2.60(m,5H),3.50-5.90(m,7H),6.20-7.50(m,8H)。H-NMR spectrum (CDCl, 300MHz): δH: 0.90-2.60 (m, 5H), 3.50-5.90 (m, 7H), 6.20-7.50 (m, 8H).

依据实施例1的技术方案,取代含有相应基团的原料可合成如下化合物:According to the technical scheme of Example 1, the following compounds can be synthesized by substituting raw materials containing corresponding groups:

实施例2Example 2

以下组合物中使用的液晶单体全部由北京八亿时空液晶科技股份有限公司提供。除特殊说明外,实施例中各组分的含量均表示重量百分比。The liquid crystal monomers used in the following compositions were all provided by Beijing Bayi Space-Time Liquid Crystal Technology Co., Ltd. Unless otherwise specified, the contents of each component in the examples represent percentages by weight.

取以下重量份数的液晶化合物并配制液晶组合物,具体的配比及所得的液晶组合物的性能参数参见表1和表2。Take the following liquid crystal compounds in parts by weight and prepare a liquid crystal composition. See Table 1 and Table 2 for the specific proportion and performance parameters of the obtained liquid crystal composition.

表1:含有本发明所述化合物的液晶组合物各组分及性能参数Table 1: Each component and performance parameter of the liquid crystal composition containing the compound of the present invention

表2:不含本发明所述化合物的液晶组合物各组分及性能参数Table 2: Components and performance parameters of the liquid crystal composition not containing the compound of the present invention

对比表1和表2可知:加入了本发明提供的化合物的液晶组合物,介电向异性显著增大,由4.86增加到7.72,光学各向异性和清亮点稍有增加,旋转粘度和电荷保持率基本保持不变。Comparing Table 1 and Table 2, it can be seen that: the liquid crystal composition added with the compound provided by the present invention significantly increases the dielectric anisotropy from 4.86 to 7.72, slightly increases the optical anisotropy and clearing point, and the rotational viscosity and charge retention rate remained essentially unchanged.

除试验例所例举的组合物外,添加本发明提供的其它具有二噁烷环和二氟甲氧基桥键结构的液晶化合物的其他液晶组合物能得到同样优良的光学和电学性能。In addition to the compositions exemplified in the test examples, other liquid crystal compositions provided by the present invention with the addition of other liquid crystal compounds having a dioxane ring and a difluoromethoxy bridge structure can obtain the same excellent optical and electrical properties.

虽然,上文中已经用一般性说明、具体实施方式及试验,对本发明作了详尽的描述,但在本发明基础上,可以对之作一些修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。Although, the present invention has been described in detail with general description, specific implementation and test above, but on the basis of the present invention, some modifications or improvements can be made to it, which will be obvious to those skilled in the art . Therefore, the modifications or improvements made on the basis of not departing from the spirit of the present invention all belong to the protection scope of the present invention.

Claims (10)

1.一种含有二噁烷环的液晶化合物,其特征在于,所述液晶化合物具有如式I所示的结构:1. A liquid crystal compound containing a dioxane ring, characterized in that the liquid crystal compound has a structure as shown in formula I: 其中,in, A1和A2各自独立地代表1,4-苯基,其中一个或多个H原子可被F原子取代;A 1 and A 2 each independently represent 1,4-phenyl, wherein one or more H atoms may be replaced by F atoms; X选自F、OCF3、OCHF2、CF3、CF2H、Cl、OCH=CF2或OCF2CF=CF2X is selected from F, OCF 3 , OCHF 2 , CF 3 , CF 2 H, Cl, OCH=CF 2 or OCF 2 CF=CF 2 ; Y1和Y2各自独立地代表H或F;Y 1 and Y 2 each independently represent H or F; n为2~10。n is 2-10. 2.根据权利要求1所述的化合物,其特征在于,A1和A2各自独立地代表1,4-苯基,其中一个或多个H原子可被F原子取代;X选自F、OCF3、OCHF2或CF3;Y1和Y2各自独立地代表H或F,并且不同时为H;n为2、3或4。2. The compound according to claim 1, wherein A1 and A2 each independently represent 1,4-phenyl, wherein one or more H atoms can be replaced by F atoms; X is selected from F, OCF 3. OCHF 2 or CF 3 ; Y 1 and Y 2 each independently represent H or F, and are not H at the same time; n is 2, 3 or 4. 3.根据权利要求2所述的化合物,其特征在于,A1和A2各自独立地代表1,4-苯基,其中一个或多个H原子可被F原子取代;X选自F或OCF3;Y1和Y2各自独立地代表H或F,并且不同时为H;n为2、3或4。3. The compound according to claim 2, wherein A1 and A2 each independently represent 1,4-phenyl, wherein one or more H atoms can be replaced by F atoms; X is selected from F or OCF 3 ; Y 1 and Y 2 each independently represent H or F, and are not H at the same time; n is 2, 3 or 4. 4.根据权利要求3所述的化合物,其特征在于,所述液晶化合物选自如下通式结构化合物:4. compound according to claim 3, is characterized in that, described liquid crystal compound is selected from following general formula structure compound: 其中,X选自F或OCF3;n为2,3或4。Wherein, X is selected from F or OCF 3 ; n is 2, 3 or 4. 5.根据权利要求4所述的化合物,其特征在于,所述化合物的结构为:5. the compound according to claim 4, is characterized in that, the structure of described compound is: 6.制备权利要求1~5任意一项所述液晶化合物的方法,其特征在于,该方法包括如下步骤:6. The method for preparing the liquid crystal compound according to any one of claims 1 to 5, characterized in that the method comprises the steps of: 1)起始原料化合物II和III,以甲苯为溶剂,以对甲苯磺酸为脱水催化剂,加热回流脱水3~9小时,得到化合物IV;1) The starting materials Compounds II and III, using toluene as a solvent and p-toluenesulfonic acid as a dehydration catalyst, heated and refluxed for 3 to 9 hours to obtain Compound IV; 2)化合物IV与化合物V,以四三苯基膦合钯为催化剂,回流反应4~12小时,得到目标化合物I;2) compound IV and compound V, using tetrakistriphenylphosphine palladium as catalyst, reflux reaction for 4 to 12 hours, to obtain the target compound I; 其中,A1、A2、X、Y1、Y2及n的指代同权利要求1~5任一项。Wherein, A 1 , A 2 , X, Y 1 , Y 2 and n refer to any one of claims 1-5. 7.权利要求1~5任一项所述液晶化合物在液晶显示领域中的应用。7. The application of the liquid crystal compound according to any one of claims 1 to 5 in the field of liquid crystal display. 8.含有权利要求1~5任一项所述液晶化合物的液晶组合物,其特征在于,液晶化合物占液晶组合物的质量百分比为1~80%。8. The liquid crystal composition containing the liquid crystal compound according to any one of claims 1 to 5, wherein the liquid crystal compound accounts for 1 to 80% by mass of the liquid crystal composition. 9.根据权利要求8所述的组合物,其特征在于,液晶化合物占液晶组合物的质量百分比为3~50%。9. The composition according to claim 8, wherein the liquid crystal compound accounts for 3-50% by mass of the liquid crystal composition. 10.权利要求8或9所述组合物在制造液晶显示装置中的应用,其特征在于,所述液晶显示装置包括TN、ADS、FFS、IPS、VA或PSVA液晶显示器。10. The application of the composition according to claim 8 or 9 in the manufacture of a liquid crystal display device, characterized in that the liquid crystal display device comprises a TN, ADS, FFS, IPS, VA or PSVA liquid crystal display.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104130781A (en) * 2014-07-03 2014-11-05 北京八亿时空液晶科技股份有限公司 Liquid crystal composition and application thereof
CN104263382A (en) * 2014-09-11 2015-01-07 北京八亿时空液晶科技股份有限公司 Liquid crystal composite containing 1,3-dioxane and difluoromethoxy bridge-bond compound and application of liquid crystal composite
CN105018108A (en) * 2015-06-10 2015-11-04 北京华科嘉泰科技有限公司 Liquid crystal composition containing 1,3-dioxane compound and application thereof
WO2016082511A1 (en) * 2014-11-27 2016-06-02 北京八亿时空液晶科技股份有限公司 Liquid crystal compound containing difluoromethoxy bridging, composite, and applications thereof
WO2016082510A1 (en) * 2014-11-27 2016-06-02 北京八亿时空液晶科技股份有限公司 Liquid crystal compound containing difluoromethoxy bridging, composite, and applications thereof
US10584086B2 (en) 2014-11-20 2020-03-10 Beijing Bayi Space Lcd Technology Co., Ltd Liquid crystal compound containing a difluormethoxy bridge and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998020006A1 (en) * 1996-11-07 1998-05-14 Chisso Corporation Fluoroalkylated dioxane derivatives, liquid crystal compositions, and liquid-crystal display elements
CN1182085A (en) * 1996-07-15 1998-05-20 智索公司 Phenyldioxane derivatives, liquid crystal compositions, and liquid crystal display elements
CN101143808A (en) * 2006-09-13 2008-03-19 默克专利股份有限公司 Fluorine phenyl compounds for liquid crystalline mixtures
CN103724168A (en) * 2014-01-17 2014-04-16 石家庄诚志永华显示材料有限公司 Difluoro methoxy bond derivative containing deuterium as well as preparation method and application of derivative
WO2014065293A1 (en) * 2012-10-23 2014-05-01 Jnc株式会社 Liquid-crystal compound, liquid-crystalline medium and optical element
CN103773386A (en) * 2014-01-27 2014-05-07 北京八亿时空液晶科技股份有限公司 Liquid crystal compound containing 1,4-dioxane and pentafluoro-allyloxy structure and liquid crystal composition thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1182085A (en) * 1996-07-15 1998-05-20 智索公司 Phenyldioxane derivatives, liquid crystal compositions, and liquid crystal display elements
WO1998020006A1 (en) * 1996-11-07 1998-05-14 Chisso Corporation Fluoroalkylated dioxane derivatives, liquid crystal compositions, and liquid-crystal display elements
CN101143808A (en) * 2006-09-13 2008-03-19 默克专利股份有限公司 Fluorine phenyl compounds for liquid crystalline mixtures
WO2014065293A1 (en) * 2012-10-23 2014-05-01 Jnc株式会社 Liquid-crystal compound, liquid-crystalline medium and optical element
CN103724168A (en) * 2014-01-17 2014-04-16 石家庄诚志永华显示材料有限公司 Difluoro methoxy bond derivative containing deuterium as well as preparation method and application of derivative
CN103773386A (en) * 2014-01-27 2014-05-07 北京八亿时空液晶科技股份有限公司 Liquid crystal compound containing 1,4-dioxane and pentafluoro-allyloxy structure and liquid crystal composition thereof

Cited By (15)

* Cited by examiner, † Cited by third party
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CN104130781B (en) * 2014-07-03 2016-05-11 北京八亿时空液晶科技股份有限公司 A kind of liquid-crystal composition and application thereof
CN104263382A (en) * 2014-09-11 2015-01-07 北京八亿时空液晶科技股份有限公司 Liquid crystal composite containing 1,3-dioxane and difluoromethoxy bridge-bond compound and application of liquid crystal composite
CN104263382B (en) * 2014-09-11 2016-04-06 北京八亿时空液晶科技股份有限公司 Containing liquid-crystal composition and the application thereof of 1,3-diox and difluoro-methoxy bridged bond compound
US10584086B2 (en) 2014-11-20 2020-03-10 Beijing Bayi Space Lcd Technology Co., Ltd Liquid crystal compound containing a difluormethoxy bridge and application thereof
WO2016082510A1 (en) * 2014-11-27 2016-06-02 北京八亿时空液晶科技股份有限公司 Liquid crystal compound containing difluoromethoxy bridging, composite, and applications thereof
WO2016082511A1 (en) * 2014-11-27 2016-06-02 北京八亿时空液晶科技股份有限公司 Liquid crystal compound containing difluoromethoxy bridging, composite, and applications thereof
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JP2017529449A (en) * 2014-11-27 2017-10-05 北京八億時空液晶科技股▲ふん▼有限公司Beijing Bayi Space Lcd Technology Co.,Ltd Liquid crystal compound having difluoromethoxy crosslink, composition and application thereof
KR20170121151A (en) * 2014-11-27 2017-11-01 베이징 바이 스페이스 엘시디 테크놀로지 컴퍼니 리미티드 Liquid crystal compound containing difluoromethoxy bridging, composite, and applications thereof
US10494569B2 (en) 2014-11-27 2019-12-03 Beijing Bayi Space Lcd Technology Co., Ltd Liquid crystal compound containing difluoromethoxy bridge, composition and application thereof
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KR102347008B1 (en) 2014-11-27 2022-01-03 베이징 바이 스페이스 엘시디 테크놀로지 컴퍼니 리미티드 Liquid crystal compound containing difluoromethoxy bridging, composite, and applications thereof
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