Patent Publication Number: US-2010127210-A1

Title: Liquid crystal compounds and liquid crystal compositions comprising the same

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
     This Application claims priority of Taiwan Patent Application No. 97145463, filed on Nov. 25, 2008, the entirety of which is incorporated by reference herein. 
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The invention relates to a liquid crystal compound, and more particularly to a liquid crystal compound containing piperazine. 
     2. Description of the Related Art 
     Liquid crystals possess dielectric and optical anisotropy, superior molecule alignment and fluidity. When stimulated by light, heat, of an electric field or magnetic field, molecule alignments of liquid crystals are easily altered to form contrast or specific optical effects. A display fabricated thereby possesses a light weight, portability, fine size and low power consumption. Thus, recently, liquid crystals have become a popular display medium for various portable electric and information products, such as digital watches, calculator and automotive instrument panels, twisted nematic (TN) LCDs, super twisted nematic (STN) LCDs, notebook computers, optical grating of components of projectors and memory cells of printers. 
     An ideal liquid crystal material possesses superior chemical properties, for example, a wide nematic liquid crystal phase, a low melting point, low fusion heat, physicochemical stability and achromatization, and simultaneously possess superior physical properties, for example, high dielectric anisotropy (Δε) and high birefringence (Δn) properties. 
     BRIEF SUMMARY OF THE INVENTION 
     One embodiment of the invention provides a liquid crystal compound of Formula (I): 
     
       
         
         
             
             
         
       
     
     wherein 
     Y1, Y2 and Y3 are, independently, hydrogen, halogen, cyano or thiocyano, and R is C1-12 alkyl or C1-12 alkoxy. 
     One embodiment of the invention provides a liquid crystal composition comprising a first liquid crystal compound of Formula (I) and a second liquid crystal compound of Formulas (Z1)-(Z9): 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     wherein 
     R 1  is C1-9 alkyl, B is halogen or cyano, and R 2 , R 3  and R 4  are, independently, C1-10 alkyl, wherein methylene is replaced by oxygen or ethylenyl and at least one hydrogen is replaced by fluorine, and R 5  and R 8  are, independently, C1-10 alkyl, wherein methylene is replaced by oxygen, and R 6 , R 7  and R 9  are, independently, C1-10 alkyl, A1, A2, A3 and A5 are, independently, trans-1,4-cyclohexylene or 1,4-phenylene, and A4 is 1,4-phenylene, wherein at least one hydrogen is replaced by fluorine, Z 1  is ethylenyl or acetylenyl, m and n are 0-2, and X 3  is hydrogen or fluorine, wherein the first liquid crystal compound and the second liquid crystal compound have a weight ratio of 0.5:99.5-35:65. 
     Note that the chemical and photoelectric properties of the modified liquid crystal molecule of the invention are improved, thus facilitating application in various liquid crystal devices. Additionally, the dipole moment of the liquid crystal compound with a piperazine structure having rich electron pairs to induce resonance is increased. Meanwhile, the dielectric anisotropy (Δε) thereof is increased by production of an electron withdrawing effect of the polar functional groups (Y1, Y2 and Y3). The birefringence (Δn) thereof is increased by conduction into a benzene or triple bond to extend the conjugated structure length of the main chain. Additionally, performance of a display cannot be interfered with due to conduction into the colorless polar functional groups (Y1, Y2 and Y3), for example, halogen, cyano or thiocyano. When the liquid crystal composition with large dipole moment, low viscosity and high dielectric anisotropy is applied in TN LCDs, cholesterol LCDs or polymer dispersed LCDs, the driving voltage thereof is reduced. In addition to high dielectric anisotropy and high birefringence, the colorless liquid crystal compound possesses high thermal stability and high compatibility. 
     A detailed description is given in the following embodiments. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The following description is of the best-contemplated mode of carrying out the invention. This description is made for the purpose of illustrating the general principles of the invention and should not be taken in a limiting sense. The scope of the invention is best determined by reference to the appended claims. 
     One embodiment of the invention provides a liquid crystal compound of Formula (I): 
     
       
         
         
             
             
         
       
     
     In Formula (I), Y1, Y2 and Y3 may be, independently, hydrogen, halogen, cyano or thiocyano. R may be C1-12 alkyl, C1-12 alkoxy or C3-6 alkyl. 
     Specifically, the liquid crystal compound is colorless. 
     Specific liquid crystal compounds, for example, Formulas (I-1)-(I-3) are disclosed in other embodiments: 
     
       
         
         
             
             
         
       
     
     The dielectric anisotropy (Δε) of the liquid crystal compound is about 18-35. The birefringence (Δn) thereof is about 0.25-0.40. The liquid crystal compound can be widely used in, for example, reflective-type cholesterol LCDs, polymer dispersed LCDs, TN LCDs, STN LCDs, TFT LCDs or IPS LCDs. 
     Note that the chemical and photoelectric properties of the modified liquid crystal molecule of the invention are improved, thus facilitating application in various liquid crystal devices. Additionally, the dipole moment of the liquid crystal compound with a piperazine structure having rich electron pairs to induce resonance is increased. Meanwhile, the dielectric anisotropy (Δε) thereof is increased by production of an electron withdrawing effect of the polar functional groups (Y1, Y2 and Y3). The birefringence (Δn) thereof is increased by conduction into a benzene or triple bond to extend the conjugated structure length of the main chain. Additionally, performance of a display cannot be interfered with due to conduction into the colorless polar functional groups (Y1, Y2 and Y3), for example, halogen, cyano or thiocyano. When the liquid crystal composition with large dipole moment, low viscosity and high dielectric anisotropy is applied in TN LCDs, cholesterol LCDs or polymer dispersed LCDs, the driving voltage thereof is reduced. In addition to high dielectric anisotropy and high birefringence, the colorless liquid crystal compound possesses high thermal stability and high compatibility. 
     One embodiment of the invention provides a liquid crystal composition comprising a first liquid crystal compound of Formula (I) and a second liquid crystal compound of Formulas (Z1)-(Z9): 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     In Formulas (Z1)-(Z9), R 1  may be C1-9 alkyl. B may be halogen or cyano. R 2 , R 3  and R 4  may be, independently, C1-10 alkyl, wherein methylene may be replaced by oxygen or ethylenyl and at least one hydrogen may be replaced by fluorine. R 5  and R 8  may be, independently, C1-10 alkyl, wherein methylene may be replaced by oxygen. R 6 , R 7  and R 9  may be, independently, C1-10 alkyl. A1, A2, A3 and A5 may be, independently, trans-1,4-cyclohexylene or, 1,4-phenylene. A4 may be 1,4-phenylene, wherein at least one hydrogen may be replaced by fluorine. Z 1  may be ethylenyl or acetylenyl. m and n may be 0-2. X 3  may be hydrogen or fluorine. 
     The first and second liquid crystal compounds have a weight ratio of about 0.5:99.5-35:65 or 5:95-10:90. 
     EXAMPLE 1  
     Preparation of the Formula (I-1) compound and dielectric anisotropy (Δε) and birefringence (Δn) thereof: 
     
       
         
         
             
             
         
       
     
     Step 1: 
     
       
         
         
             
             
         
       
     
     First, under nitrogen, 1 g of compound A (6.2 mmol), 0.9 g of bromopentane (6 mmole), 1.38 g of potassium carbonate (10 mmol) and 20 mL of dimethyl sulfoxide (DMSO) were added to a reaction bottle and heated to 100-110° C. with reflux for 16 hours. After cooling, the resulting solution was repeatedly extracted with saturated salt water and ethyl acetate until DMSO was removed. After being dried by magnesium sulfate and concentrated, the crude product was purified by column chromatography. A canary yellow liquid compound M1 was obtained, with 90% of yield. 
     Step 2: 
     
       
         
         
             
             
         
       
     
     First, under nitrogen, 1 g of compound M1 (4.2 mmol), 1.38 g of n-bromosuccinimide (NBS) (10 mmol) and 10 mL of dichloromethane were added to a reaction bottle and allowed to react at room temperature for 16 hours. The resulting solution was then repeatedly extracted with saturated salt water and ethyl acetate. After being dried by magnesium sulfate and concentrated, the crude product was purified by column chromatography. A canary yellow liquid compound M2 was obtained, with 90% of yield. 
     Step 3: 
     
       
         
         
             
             
         
       
     
     First, under nitrogen, 1 g of ethynyltrimethylsilane (10.2 mmol) and 10 mL of THF were added to a reaction bottle and cooled to −78° C. using liquid nitrogen and acetone. Next, 12 mL of n-BuLi was added and allowed to react for 20 minutes. 2.4 g of zinc chloride (18.3 mmol) dissolved in THF was then added to the reaction bottle and continuously reacted for 20 minutes in the low temperature state. After warming to 0° C., 2.1 g of compound M2 (10.2 mmol) and 0.3 g of tetrakis(triphenylphosphine) palladium (0.3 mmol) dissolved in THF were added to the reaction bottle and allowed to react at 60° C. with reflux for 12 hours. The reaction was terminated by adding NH 4 Cl. The resulting solution was then repeatedly extracted with saturated salt water and ethyl acetate. After being dried by magnesium sulfate and concentrated, the crude product was purified by column chromatography. A canary yellow solid compound M3 was obtained, with 70% of yield. 
     Step 4: 
     
       
         
         
             
             
         
       
     
     First, under nitrogen, 1 g of compound M3 (3 mmol), 10 mL of methanol/dichloromethane (1/1) and 0.4 g of potassium carbonate (4.5 mmol) were added to a reaction bottle and allowed to react at room temperature for 12 hours. The resulting solution was then repeatedly extracted with 20 mL of dichloromethane. After being dried by magnesium sulfate and concentrated, the crude product was purified by column chromatography. A canary yellow solid compound M4 was obtained, with 75% of yield. 
     Step 5: 
     
       
         
         
             
             
         
       
     
     First, under nitrogen, 1 g of compound M4 (3.9 mmol) and 5 mL of THF were added to a reaction bottle and cooled to −78° C. using liquid nitrogen and acetone. Next, 1.7 mL of n-BuLi was added and allowed to react for 20 minutes. 0.9 g of zinc chloride (7 mmol) dissolved in THF was then added to the reaction bottle and continuously reacted for 20 minutes in the low temperature state. After warming to 0° C., 0.8g of 4-bromo-2-fluorobenzonitrile (3.9 mmol) and 0.2 g of tetrakis(triphenylphosphine) palladium (0.2 mmol) dissolved in THF were added to the reaction bottle and allowed to react at 60° C. with reflux for 12 hours. The reaction was terminated by adding NH 4 Cl. The resulting solution was then repeatedly extracted with saturated salt water and ethyl acetate. After being dried by magnesium sulfate and concentrated, the crude product was purified by column chromatography. A white solid compound I-1 was obtained, with 65% of yield. The dielectric anisotropy (Δε) of compound I-1 was 31.8. The birefringence (Δn) thereof was 0.3763. The preparations of compound I-2 and compound I-3 were similar to that of compound I-1. The distinction thereamong was merely different reactants used in step 5. A person skilled in the art can simply prepare compound I-2 and compound I-3 according to Example 1. The dielectric anisotropy (Δε) of compound I-2 was 26.9. The birefringence (Δn) of compound I-2 was 0.3206. The dielectric anisotropy (Δε) of compound I-3 was 18.8. The birefringence (Δn) of compound I-3 was 0.2685. Comparison of the dielectric anisotropy (Δε) and the birefringence (Δn) between compounds I-1-I-3 and conventional liquid crystal molecules with similar structures is shown in Table 1. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                 Dielectric 
                 Bire- 
               
               
                   
                 anisotropy 
                 fringence 
               
               
                   
                 (Δε) 
                 (Δn) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 Compound I-1 
                 31.8 
                 0.3763 
               
               
                 Compound I-2 
                 26.9 
                 0.3206 
               
               
                 Compound I-3 
                 18.8 
                 0.2685 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 19.8 
                 0.146 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 15.4 
                 0.119 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 16.7 
                 0.2 
               
               
                   
               
            
           
         
       
     
     The results indicated that the dielectric anisotropy (Δε) of compounds I-1-I-3 was higher than that of the conventional liquid crystal molecules due to conduction into a piperazine group having rich unshared electron pairs capable of inducing resonance to increase molecule dipole moment. Also, the birefringence (Δn) of compounds I-1-I-3 was apparently higher than that of the conventional liquid crystal molecules due to conduction into a triple bond to extend the conjugated structure length of the liquid crystal molecule main chain. 
     EXAMPLE 2  
     Preparation of the liquid crystal composition (1) and dielectric anisotropy (Δε) and birefringence (Δn) thereof: 
     Compound I-1 and a liquid crystal mixture (YY066-042) were mixed with a ratio of 5:95 to form a liquid crystal composition. The liquid crystal mixture (YY066-042) comprised 8% of 5HBBCN, 24.1% of 5HBCN, 7.7% of 5HBEBFCN, 13.5% of 5HBF, 7% of 2HEBFCN, 6.5% of 3HHEBF, 3.5% of 5HHEBF, 1.7% of 2BBCN, 4.9% of 3HEBBCN, 15.4% of 5BEBFCN and 7.7% of 3HBEBFCN. The dielectric anisotropy (Δε) of the liquid crystal mixture (YY066-042) was 17.3. The birefringence (Δn) thereof was 0.1355. The driving voltage of the device formed by the liquid crystal mixture (YY066-042) was 1.043V. After adding compound I-1, the dielectric anisotropy (Δε) of the liquid crystal composition increased to 18.1. The birefringence (Δn) thereof increased to 0.1475. The driving voltage of the device formed by the liquid crystal mixture (YY066-042) and Compound I-1 was reduced to 1.023V. Note that for each component of the liquid crystal mixture (YY066-042), each code name was corresponded to various chemical formulas, for example, code name 2 represents C 2 H 5 —, code name 3 represents C 3 H 7 —, code name 5 represents C 5 H 11 —, code name H represents 
     
       
         
         
             
             
         
       
     
     code name B represents 
     
       
         
         
             
             
         
       
     
     code name CN represents CN, code name E represents —COO—, and code name F represents —F. 
     EXAMPLE 3  
     Preparation of the liquid crystal composition (2) and dielectric anisotropy (Δε) and birefringence (Δn) thereof: 
     Compound I-2 and a liquid crystal mixture (DH0381-110) were mixed with a ratio of 5:95 to form a liquid crystal composition. The liquid crystal mixture (DH0381-110) comprised 10.3% of 5HBBCN, 7.2% of 3HBO2, 12.6% of 2BBCN, 31.9% of 5BBCN, 10% of 3HEBBCN, 21.8% of 7BBCN and 6.2% of 5BEBBCN. The dielectric anisotropy (Δε) of the liquid crystal mixture (DH0381-110) was 13.49. The birefringence (Δn) thereof was 0.0987. The driving voltage of the device formed by the liquid crystal mixture (DH0381-110) was 1.862V. After adding compound I-2, the dielectric anisotropy (Δε) of the liquid crystal composition increased to 14.27. The birefringence (Δn) thereof increased to 0.1112. The driving voltage of the device formed by the liquid crystal mixture (DH0381-110) and Compound I-2 was reduced to 1.434V. Note that for each component of the liquid crystal mixture (DH0381-110), each code name was corresponded to various chemical formulas, for example, code name 2 represents C 2 H 5 —, code name 3 represents C 3 H 7 —, code name 5 represents C 5 H 11 —, code name 7 represents C 7 H 15 —, code name H represents 
     
       
         
         
             
             
         
       
     
     code name B represents 
     
       
         
         
             
             
         
       
     
     code name CN represents CN, code name F represents —F, code name O represents —O—, and code name E represents —COO—. 
     EXAMPLE 4  
     Preparation of the liquid crystal composition (3) and dielectric anisotropy (Δε) and birefringence (Δn) thereof: 
     Compound I-3 and a liquid crystal mixture (LOT3) were mixed with a ratio of 10:90 to form a liquid crystal composition. The liquid crystal mixture (LOT3) comprised 2.5% of 5HBF, 2.5% of 6HBF, 2.5% of 7HBF, 9.6% of 3HHB(F)F, 2.5% of 3HBEB(FF)F, 2% of 4HBEB(FF)F, 6.2% of 3HHEB(FF)F, 4.9% of 3HHB(FF)F, 9.6% of 3HBB(FF)F, 9.7% of 5HBB(FF)F, 5.2% of 4HHB(FF)F, 4.5% of 5HHB(FF)F, 9.9% of 3HHV, 4.7% of 3HBB(F)F, 9.8% of 3HH2B(F)F, 9.1%   1BHHV and 4.8% of 2BB(F)B3. The dielectric anisotropy (Δε) of the liquid crystal mixture (LOT3) was 7.38. The birefringence (Δn) thereof was 0.0987. The driving voltage of the device formed by the liquid crystal mixture (LOT3) was 1.862V. After adding compound I-3, the dielectric anisotropy (Δε) of the liquid crystal composition increased to 8.545. The birefringence (Δn) thereof increased to 0.1158. The driving voltage of the device formed by the liquid crystal mixture (LOT3) and Compound I-3 was reduced to 1.802V. Note that for each component of the liquid crystal mixture (LOT3), each code name was corresponded to various chemical formulas, for example, code name 1 represents CH 3 —, code name 3 represents C 3 H 7 —, code name 4 represents C 4 H 9 —, code name 5 represents C 5 H 11 —, code name 6 represents C 6 H 13 —, code name 7 represents C 7 H 15 —, code name H represents 
     
       
         
         
             
             
         
       
     
     code name B represents 
     
       
         
         
             
             
         
       
     
     code name B(F) represents 
     
       
         
         
             
             
         
       
     
     code name B(FF) represents 
     
       
         
         
             
             
         
       
     
     code name F represents —F, code name E represents —COO—, and code name V represents CH 2 ═CH—. 
     While the invention has been described by way of example and in terms of preferred embodiment, it is to be understood that the invention is not limited thereto. To the contrary, it is intended to cover various modifications and similar arrangements (as would be apparent to those skilled in the art). Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements.