Liquid crystal composition and liquid crystal display element

Abstract

Provided are a polymerizable compound represented by formula I and a liquid crystal composition formed by combining such a polymerizable compound with a specific liquid crystal component, particularly a PSVA liquid crystal composition for displays or TV applications and a PSA-IPS liquid crystal composition for an IPS mode; in particular, the polymerizable compound has a faster polymerization rate, and a “material system” formed from the selected polymerizable component and liquid crystal component has a low rotary viscosity and good photoelectric properties, and has a high VHR after (UV) photoradiation, this avoiding the problem of the occurrence of residual images to final displays. ##STR00001##

Claims

1. A polymerizable liquid crystal compound represented by formulas I-1 to I-18: ##STR00122## ##STR00123## ##STR00124## ##STR00125## wherein each S independently represents H, a C1-C5 alkyl group, a C1-C5 alkoxy group, a fluorine-substituted C1-C5 alkyl group, a fluorine-substituted C1-C5 alkoxy group, F or Cl, wherein any one CH.sub.2 or several CH.sub.2 that are not adjacent may be independently replaced by —O—, —S—, —CO—, —CH.sub.2O—, —OCH.sub.2—, —COO—, —OOC— or an acrylate group or a methacrylate group; each P independently represents ##STR00126## each Sp independently represents a single bond, a C1-C5 alkyl group, a C1-C5 alkenyl group, wherein any one CH.sub.2 or several CH.sub.2 that are not adjacent may be replaced by —O—, —S—, —CO—, —CH.sub.2O—, —OCH.sub.2—, —COO—, —OOC— or an acrylate group; and each o independently represents 0, 1, 2 or 3.

2. The liquid crystal compound according to claim 1, wherein the compound represented by formula I-1 to I-18 is a compound represented by formulas I-1-1 to I-17-6 below: ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178##

Description

DETAILED DESCRIPTION OF EMBODIMENTS

(1) The present invention is further described in conjunction with particular examples below, but the present invention is not limited to the following examples. Said methods are all conventional methods, unless otherwise specified. Said raw materials are all commercially available, unless otherwise specified.

(2) The reaction process is generally monitored through TLC, and the post-treatments after the reaction is completed are generally water washing, extracting, combining organic phases and then drying, evaporating and removing the solvent under a reduced pressure, recrystallization and column chromatographic separation; and a person skilled in the art would be able to achieve the present invention according to the following description.

(3) In the present specification, the percentages are mass percentages, the temperatures are in degree Celsius (° C.), and the specific meanings of other symbols and the test conditions are as follows:

(4) Cp represents the clearing point (° C.) of the liquid crystal measured by a DSC quantitative method;

(5) S—N represents the melting point (° C.) for the transformation of a liquid crystal from a crystal state to a nematic phase;

(6) Δn represents optical anisotropy, n.sub.o is the refractive index of an ordinary light, n.sub.e is the refractive index of an extraordinary light, with the test conditions being: 25±2° C., 589 nm and using an abbe refractometer for testing;

(7) Δε represents dielectric anisotropy, Δε=ε//−ε⊥, wherein ε// is a dielectric constant parallel to a molecular axis, and ε⊥ is a dielectric constant perpendicular to the molecular axis, the test conditions are 25±0.5° C., a 20 micron parallel cell, and INSTEC: ALCT-IR1 for testing;

(8) γ1 represents a rotary viscosity (mPa.Math.s), with the test conditions being 25±0.5° C., a 20-micron parallel cell, and INSTEC: ALCT-IR1 for testing; and

(9) ρ represents electrical resistivity (Ω.Math.cm), with the test conditions being: 25±2° C., and the test instruments being a TOYO SR6517 high resistance instrument and an LE-21 liquid electrode.

(10) VHR represents a voltage holding ratio (%), with the test conditions being: 20±2° C., a voltage of ±5 V, a pulse width of 10 ms, and a voltage holding time of 16.7 ms. The test equipment is a TOYO Model 6254 liquid crystal performance comprehensive tester.

(11) τ represents a response time (ms), with the test instrument being DMS-501 and the test conditions being: 25±0.5° C., a test cell that is a 3.3-micron IPS test cell, an electrode spacing and an electrode width, both of which are 10 microns, and an included angle between the frictional direction and the electrode of 10°.

(12) T (%) represents a transmittance, wherein T (%)=100%*bright state (Vop) luminance/light source luminance, with the test instrument being DMS501, and the test conditions being: 25±0.5° C., a test cell that is a 3.3-micron IPS test cell, an electrode spacing and an electrode width, both of which are 10 microns, and an included angle between the frictional direction and the electrode of 10°.

(13) The conditions for the ultraviolet photopolymerization of the polymerizable compound involve using ultraviolet light with a wavelength of 313 nm and an irradiation light intensity of 0.5 Mw/cm.sup.2

(14) In the examples of the invention of the present application, liquid crystal monomer structures are represented by codes, and the codes for ring structures, end groups and linking groups of liquid crystals are represented as in Tables (I) and (II) below

(15) TABLE-US-00001 TABLE (I) Corresponding code for ring structure Ring structure Corresponding code C P G Gi Y Sa Sb 0 Sc

(16) TABLE-US-00002 TABLE (II) Corresponding code for end group and linking group End group and linking group Corresponding code C.sub.nH.sub.2n+1.sup.- n- C.sub.nH.sub.2n+1O— nO- —OCF.sub.3 -OT —CF.sub.2O— -Q- —CH.sub.2O— -O- —F -F —CN -CN —CH.sub.2CH.sub.2— -E- —CH═CH— -V- —C≡C— -W- —COO— -COO- —CH═CH—C.sub.nH.sub.2n+1 Vn- C(5)- C(3)-

EXAMPLES

(17) ##STR00093##

(18) The following specific embodiments are used to illustrate the present invention:

Preparation of Polymerizable Compound

Example 1

(19) The structural formula of the polymerizable compound is as represented by the following formula I-1-1:

(20) ##STR00094##

(21) the route of the preparation thereof is as follows:

(22) ##STR00095##

Specific Operation Procedures of the Preparation

Intermediate 2

(23) To a 2 L three-necked flask, 0.1 mole of raw material 1, 0.5 L of tetrahydrofuran, and 0.02 L of water are added, the temperature is reduced to 0° C., 0.15 moles of potassium borohydride is added in portions, the temperature is controlled at 0° C. for a reaction for 3 h, and the temperature is naturally raised to room temperature (about 25° C.), and the reaction is carried out for 8 hours at room temperature. 100 L of water is added to the system, the pH is then adjusted to 6-7 with dilute acid, the system is subjected to liquid separation, and the aqueous phase is subjected to extraction with ethyl acetate, dried over anhydrous sodium sulfate and subjected to rotary drying to give intermediate 2.

Intermediate 3

(24) To a 1 L three-necked flask, intermediate 2 from the above step, 5 g of p-toluenesulfonic acid, and 0.5 L of toluene are added, and the system is stirred and warmed to reflux for water separation for 2 hours. The system is poured into a column containing 20 g of silica gel, and rinsed with 0.5 L of toluene, and the eluent is washed three times with water to neutral, and subjected to rotary drying to give intermediate 3.

Intermediate 4

(25) To a 2 L three-necked flask, intermediate 3 from the above step, 0.5 L of toluene, 0.1 L of anhydrous ethanol, and 10 g of palladium on carbon (5%) are added, evacuation is carried out 5 times with nitrogen gas and 3 times with hydrogen gas, hydrogenation is carried for 3 hours, the system is poured into a column containing 20 g of silica gel, and rinsed with 0.5 L of toluene, and the eluent is washed three times with water to neutral, and subjected to rotary drying to give intermediate 4.

Intermediate 5

(26) To a 2 L three-necked flask, intermediate 4 from the above step and 0.5 L of dichloromethane are added, the mixture is cooled to 0° C. under stirring, 4.5 folds by mole of boron tribromide is dropwise added, the temperature is controlled at 0° C. or less, the dropwise addition is completed within 1 h, the temperature is controlled at 0° C. for a reaction for 12 h, the reaction liquid is poured to 1 kg of water, stirred for 15 minutes and subjected to liquid separation to separate out most (about 0.5 L) of the dichloromethane, 0.5 L of ethyl acetate is added to the aqueous phase, the aqueous phase is stirred until the solid is completely dissolved, and is subjected to liquid separation, the aqueous phase is subjected to extraction with 0.2 L×2 of ethyl acetate, the organic phases are combined, washed with water and subjected to liquid separation, 0.5 kg of anhydrous sodium sulfate is added for drying for 4 hours, the solvent is removed by means of rotary drying, and recrystallization is carried out using 5 folds of petroleum ether to give intermediate 5.

Product I-1-1

(27) To a 1 L three-necked flask, 0.02 moles of intermediate 5, 0.07 moles of methacrylic acid and 0.5 L of toluene are added, the temperature is reduced to 0° C. under the protection of nitrogen, the temperature is controlled at 0-5° C., 0.09 moles of DCC is added, and after the addition is complete, the temperature is naturally raised to room temperature (about 25° C.) for reactions for 8 hours. 500 ml of water is added, liquid separation is carried out, the aqueous phase is subjected to extraction with 100 ml×2 of toluene, the organic phases are combined and washed with 500 ml×2 of a saline solution, after the washing is complete, the organic phase is dried over anhydrous sodium sulfate and evaporated to dryness, 30 g of silica gel and 3 folds of petroleum ether (90-120° C.) are taken for passing a column, the column is rinsed with 2 folds of petroleum ether (90-120° C.), and after evaporation, 2 folds of ethanol is used for recrystallisation to give product I-1-1.

(28) By using a similar synthesis method,

(29) ##STR00096## ##STR00097##
are synthesized.

Example 2

(30) The structural formula of the polymerizable compound is as represented by the following formula I-1-8:

(31) ##STR00098##

Intermediate 7

(32) To a 2 L three-necked flask, 0.1 mole of raw material 6 and 0.8 L of dichloromethane are added, the mixture is cooled to 0° C. under stirring, 3 folds by mole of boron tribromide is dropwise added, the temperature is controlled at 0° C. or less, the dropwise addition is completed within 1 h, the temperature is controlled at 0° C. for reaction for 12 h, the reaction liquid is poured to 1 kg of water, stirred for 15 minutes and subjected to liquid separation to separate out most (about 0.8 L) of the dichloromethane, 0.5 L of ethyl acetate is added to the aqueous phase, the aqueous phase is stirred until the solid is completely dissolved, and is subjected to liquid separation, the aqueous phase is subjected to extraction with 0.2 L×2 of ethyl acetate, the organic phases are combined, washed with water and subjected to liquid separation, 0.5 kg of anhydrous sodium sulfate is added for drying for 4 hours, the solvent is removed by means of rotary drying, and recrystallization is carried out using 5 folds of petroleum ether to give intermediate 7.

Product I-1-8

(33) To a 1 L three-necked flask, 0.05 moles of intermediate 7, 0.2 moles of methacrylic acid and 0.5 L of toluene are added, the temperature is reduced to 0° C. under the protection of nitrogen, the temperature is controlled at 0-5° C., 0.25 moles of DCC is added, and after the addition is complete, the temperature is naturally raised to room temperature (about 25° C.) for reactions for 12 hours. 500 ml of water is added, liquid separation is carried out, the aqueous phase is subjected to extraction with 100 ml×2 of toluene, the organic phases are combined and washed with 500 ml×2 of a saline solution, after the washing is complete, the organic phase is dried over anhydrous sodium sulfate and evaporated to dryness, 30 g of silica gel and 3 folds of petroleum ether (90-120° C.) are taken for passing a column, the column is rinsed with 2 folds of petroleum ether (90-120° C.), and after evaporation, 2 folds of ethanol is used for recrystallisation to give product I-1-8.

(34) By using a similar method,

(35) ##STR00099##

Example 3

(36) The structural formula of the polymerizable compound is as represented by the following formula I-3-10:

(37) ##STR00100##

Intermediate 9

(38) To a 2 L three-necked flask, 0.1 mole of raw material 8 and 0.8 L of dichloromethane are added, the mixture is cooled to 0° C. under stirring, 3 folds by mole of boron tribromide is dropwise added, the temperature is controlled at 0° C. or less, the dropwise addition is completed within 1 h, the temperature is controlled at 0° C. for reaction for 12 h, the reaction liquid is poured to 1 kg of water, stirred for 15 minutes and subjected to liquid separation to separate out most (about 0.8 L) of the dichloromethane, 0.5 L of ethyl acetate is added to the aqueous phase, the aqueous phase is stirred until the solid is completely dissolved, and is subjected to liquid separation, the aqueous phase is subjected to extraction with 0.2 L×2 of ethyl acetate, the organic phases are combined, washed with water and subjected to liquid separation, 0.5 kg of anhydrous sodium sulfate is added for drying for 4 hours, the solvent is removed by means of rotary drying, and recrystallization is carried out using 5 folds of petroleum ether to give intermediate 9.

Product I-3-10

(39) To a 1 L three-necked flask, 0.05 moles of intermediate 9, 0.2 moles of methacrylic acid, and 0.5 L of toluene are added, the temperature is reduced to 0° C. under the protection of nitrogen, the temperature is controlled at 0-5° C., 0.25 moles of DCC is added, and after the addition is complete, the temperature is naturally raised to room temperature (about 25° C.) for reaction for 12 hours. 500 ml of water is added, liquid separation is carried out, the aqueous phase is extracted with 100 ml×2 of toluene, the organic phases are combined and washed with 500 ml×2 of a saline solution, after the washing is complete, the organic phase is dried over anhydrous sodium sulfate and evaporated to dryness, 30 g of silica gel and 3 folds of petroleum ether (90-120° C.) are taken for passing a column, the column is rinsed with 2 folds of petroleum ether (90-120° C.), and after evaporation, 2 folds of ethanol is used for recrystallisation to give product I-3-10.

(40) By using a similar synthesis method, a product of

(41) ##STR00101##
is synthesized.

Example 4

(42) The structural formula of the polymerizable compound is as represented by the following formula I-9-1:

(43) ##STR00102##

(44) the route of the preparation thereof is as follows:

(45) ##STR00103##

Specific Operation Procedures of the Preparation

Intermediate 11

(46) To a 2 L three-necked flask, 0.1 mole of raw material 10, 0.5 L of tetrahydrofuran, and 0.02 L of water are added, the temperature is reduced to 0° C., 0.15 moles of potassium borohydride is added in portions, the temperature is controlled at 0° C. for reaction for 3 h, and the temperature is naturally raised to room temperature (about 25° C.) for a reaction at room temperature for 8 hours. 100 L of water is added to the system, the pH is then adjusted to 6-7 with dilute acid, the system is subjected to liquid separation, and the aqueous phase is subjected to extraction with ethyl acetate, dried over anhydrous sodium sulfate and subjected to rotary drying to give intermediate 11.

Intermediate 12

(47) To a 2 L three-necked flask, intermediate 11 from the above step and 0.5 L of dichloromethane are added, the mixture is cooled to 0° C. under stirring, 4.5 folds by mole of boron tribromide is dropwise added, the temperature is controlled at 0° C. or less, the dropwise addition is completed within 1 h, the temperature is controlled at 0° C. for a reaction for 12 h, the reaction liquid is poured to 1 kg of water, stirred for 15 minutes and subjected to liquid separation to separate out most (about 0.5 L) of the dichloromethane, 0.5 L of ethyl acetate is added to the aqueous phase, the aqueous phase is stirred until the solid is completely dissolved, and is subjected to liquid separation, the aqueous phase is subjected to extraction with 0.2 L×2 of ethyl acetate, the organic phases are combined, washed with water and subjected to liquid separation, 0.5 kg of anhydrous sodium sulfate is added for drying for 4 hours, the solvent is removed by means of rotary drying, and recrystallization is carried out using 5 folds of petroleum ether to give intermediate 12.

Product I-9-1

(48) To a 1 L three-necked flask, 0.02 moles of intermediate 12, 0.07 moles of methacrylic acid, and 0.5 L of toluene are added, the temperature is reduced to 0° C. under the protection of nitrogen, the temperature is controlled at 0-5° C., 0.09 moles of DCC is added, and after the addition is complete, the temperature is naturally raised to room temperature (about 25° C.) for reaction for 8 hours. 500 ml of water is added, liquid separation is carried out, the aqueous phase is extracted with 100 ml×2 of toluene, the organic phases are combined and washed with 500 ml×2 of a saline solution, after the washing is complete, the organic phase is dried over anhydrous sodium sulfate and evaporated to dryness, 30 g of silica gel and 3 folds of petroleum ether (90-120° C.) are taken for passing a column, the column is rinsed with 2 folds of petroleum ether (90-120° C.), and after evaporation, 2 folds of ethanol is used for recrystallisation to give product I-9-1.

(49) By using a similar synthesis method, products of

(50) ##STR00104## ##STR00105##
are obtained.

Example 5

(51) The structural formula of the polymerizable compound is as represented by the following formula I-9-14:

(52) ##STR00106##

(53) Specific Operation Procedures of the Preparation:

Intermediate 13

(54) To a 5 L three-necked flask, 0.1 mole of a chloromethyl ether triphenylphosphine salt and 0.8 L of tetrahydrofuran are added, the mixture is cooled to 0° C. under stirring, 0.11 moles of potassium tert-butoxide is added in portions, and after the addition is complete, the temperature is controlled at 0-5° C. for reaction for 2 h. Raw material 10 is dissolved in 10 folds of tetrahydrofuran, the tetrahydrofuran is dropwise added to a reaction flask, the temperature is controlled at 0-5° C., and after the dropwise addition for reaction is completed in 3 hours, the temperature is naturally raised to room temperature (about 25° C.) for a reaction at room temperature for 8 hours. 1 L of water is added to the system, the system is subjected to liquid separation, the aqueous phase is subjected to extraction with ethyl acetate, washed with aqueous ethanol three times, dried over anhydrous sodium sulfate, and subjected to rotary drying, and recrystallization is carried out with anhydrous ethanol to give intermediate 13.

Intermediate 14

(55) To a 2 L three-necked flask, intermediate 13 from the above step, 0.5 L of dichloromethane and 0.5 L of acetone are added, the mixture is cooled to 0° C. under stirring, an aqueous hydrochloric acid solution is dropwise added, the temperature is controlled at 0-10° C. or less, the dropwise addition is completed within 1 h, the temperature is controlled at 0° C. for reaction for 12 h, the reaction liquid is poured to 1 kg of water, stirred for 15 minutes and subjected to liquid separation to separate out most (about 0.5 L) of the dichloromethane, 0.5 L of dichloromethane is added to the aqueous phase, the aqueous phase is stirred until the solid is completely dissolved, and is subjected to liquid separation, the aqueous phase is subjected to extraction with 0.2 L×2 of dichloromethane, the organic phases are combined, washed with water and subjected to liquid separation, 0.5 kg of anhydrous sodium sulfate is added for drying for 4 hours, the solvent is removed by means of rotary drying, and recrystallization is carried out using 5 folds of petroleum ether to give intermediate 14.

Intermediate 15

(56) To a 2 L three-necked flask, 0.05 moles of intermediate 14, 0.5 L of tetrahydrofuran, and 0.02 L of water are added, the temperature is reduced to 0° C., 0.1 mole of potassium borohydride is added in portions, the temperature is controlled at 0° C. for reaction for 3 h, and the temperature is naturally raised to room temperature (about 25° C.) for reaction at room temperature for 8 hours. 100 L of water is added to the system, the pH is then adjusted to 6-7 with dilute acid, the system is subjected to liquid separation, and the aqueous phase is subjected to extraction with ethyl acetate, dried over anhydrous sodium sulfate and subjected to rotary drying to give intermediate 15.

Intermediate 16

(57) To a 2 L three-necked flask, intermediate 15 from the above step and 0.5 L of dichloromethane are added, the mixture is cooled to 0° C. under stirring, 4.5 folds by mole of boron tribromide is dropwise added, the temperature is controlled at 0° C. or less, the dropwise addition is completed within 1 h, the temperature is controlled at 0° C. for reaction for 12 h, the reaction liquid is poured to 1 kg of water, stirred for 15 minutes and subjected to liquid separation to separate out most (about 0.5 L) of the dichloromethane, 0.5 L of ethyl acetate is added to the aqueous phase, the aqueous phase is stirred until the solid is completely dissolved, and is subjected to liquid separation, the aqueous phase is subjected to extraction with 0.2 L×2 of ethyl acetate, the organic phases are combined, washed with water and subjected to liquid separation, 0.5 kg of anhydrous sodium sulfate is added for drying for 4 hours, the solvent is removed by means of rotary drying, and recrystallization is carried out using 5 folds of petroleum ether to give intermediate 16.

Product I-9-14

(58) To a 1 L three-necked flask, 0.02 moles of intermediate 16, 0.07 moles of methacrylic acid, and 0.5 L of toluene are added, the temperature is reduced to 0° C. under the protection of nitrogen, the temperature is controlled at 0-5° C., 0.09 moles of DCC is added, and after the addition is complete, the temperature is naturally raised to room temperature (about 25° C.) for reaction for 8 hours. 500 ml of water is added, liquid separation is carried out, the aqueous phase is extracted with 100 ml×2 of toluene, the organic phases are combined and washed with 500 ml×2 of a saline solution, after the washing is complete, the organic phase is dried over anhydrous sodium sulfate and evaporated to dryness, 30 g of silica gel and 3 folds of petroleum ether (90-120° C.) are taken for passing a column, the column is rinsed with 2 folds of petroleum ether (90-120° C.), and after evaporation, 2 folds of ethanol is used for recrystallisation to give product I-9-14.

(59) By using a similar synthesis method, products of

(60) ##STR00107## ##STR00108##
are obtained.

Example 6

(61) The structural formula of the polymerizable compound is as represented by the following formula I-3-1:

(62) ##STR00109##
are synthesized.

(63) ##STR00110##

Intermediate 18

(64) To a 2 L three-necked flask, 0.1 mole of raw material 17 and 0.8 L of dichloromethane are added, the mixture is cooled to 0° C. under stirring, 3 folds by mole of boron tribromide is dropwise added, the temperature is controlled at 0° C. or less, the dropwise addition is completed within 1 h, the temperature is controlled at 0° C. for reaction for 12 h, the reaction liquid is poured to 1 kg of water, stirred for 15 minutes and subjected to liquid separation to separate out most (about 0.8 L) of the dichloromethane, 0.5 L of ethyl acetate is added to the aqueous phase, the aqueous phase is stirred until the solid is completely dissolved, and is subjected to liquid separation, the aqueous phase is subjected to extraction with 0.2 L×2 of ethyl acetate, the organic phases are combined, washed with water and subjected to liquid separation, 0.5 kg of anhydrous sodium sulfate is added for drying for 4 hours, the solvent is removed by means of rotary drying, and recrystallization is carried out using 5 folds of petroleum ether to give intermediate 18.

Product I-3-1

(65) To a 1 L three-necked flask, 0.05 moles of intermediate 18, 0.2 moles of methacrylic acid, and 0.5 L of toluene are added, the temperature is reduced to 0° C. under the protection of nitrogen, the temperature is controlled at 0-5° C., 0.25 moles of DCC is added, and after the addition is complete, the temperature is naturally raised to room temperature (about 25° C.) for reaction for 12 hours. 500 ml of water is added, liquid separation is carried out, the aqueous phase is extracted with 100 ml×2 of toluene, the organic phases are combined and washed with 500 ml×2 of a saline solution, after the washing is complete, the organic phase is dried over anhydrous sodium sulfate and evaporated to dryness, 30 g of silica gel and 3 folds of petroleum ether (90-120° C.) are taken for passing a column, the column is rinsed with 2 folds of petroleum ether (90-120° C.), and after evaporation, 2 folds of ethanol is used for recrystallisation to give product I-3-1.

(66) By using a similar synthesis method, a product of

(67) ##STR00111##
is synthesized.

Example 7

(68) The structural formula of the polymerizable compound is as represented by the following formula I-9-8:

(69) ##STR00112##
are obtained.

(70) ##STR00113##

(71) Specific Operation Procedures of the Preparation:

Intermediate 19

(72) To a 1 L three-necked flask, 0.1 mole of intermediate 16, 0.22 moles of methacryloyl chloride, 0.15 L of triethylamine and 0.5 L of toluene are added, and the reaction is carried out at room temperature (about 25° C.) for 12 hours. 500 ml of water is added, liquid separation is carried out, the aqueous phase is extracted with 100 ml×2 of toluene, the organic phases are combined and washed with 500 ml×2 of a saline solution, after the washing is complete, the organic phase is dried over anhydrous sodium sulfate and evaporated to dryness, 30 g of silica gel and 3 folds of petroleum ether (90-120° C.) are taken for passing a column, the column is rinsed with 2 folds of petroleum ether (90-120° C.), and after evaporation, 2 folds of ethanol is used for recrystallisation to give intermediate 19.

Product I-9-8

(73) To a 1 L three-necked flask, 0.05 moles of intermediate 19, 0.06 moles of acrylic acid, and 0.5 L of toluene are added, the temperature is reduced to 0° C. under the protection of nitrogen, the temperature is controlled at 0-5° C., 0.25 moles of DCC is added, and after the addition is complete, the temperature is naturally raised to room temperature (about 25° C.) for reaction for 12 hours. 500 ml of water is added, liquid separation is carried out, the aqueous phase is extracted with 100 ml×2 of toluene, the organic phases are combined and washed with 500 ml×2 of a saline solution, after the washing is complete, the organic phase is dried over anhydrous sodium sulfate and evaporated to dryness, 30 g of silica gel and 3 folds of petroleum ether (90-120° C.) are taken for passing a column, the column is rinsed with 2 folds of petroleum ether (90-120° C.), and after evaporation, 2 folds of ethanol is used for recrystallisation to give product I-9-8.

(74) By using a similar synthesis method, a product of

(75) ##STR00114##
are obtained.

(76) ##STR00115##
are synthesized.

Comparative Example 1 (RM-1)

(77) ##STR00116##

Comparative Example 2 (RM-2)

(78) ##STR00117##

Comparative Example 3 (RM-3)

(79) ##STR00118##

Comparative Example 4 (RM-4)

(80) ##STR00119##

Comparative Example 5 (RM-5)

(81) ##STR00120##

Comparative Example 6 (RM-6)

(82) ##STR00121##

Comparative Example 7

(83) TABLE-US-00003 Category Liquid crystal monomer code Content (%) III CY-C(5)-O4 11 III PY-C(5)-O2 9 III COY-3-O2 12 III CCOY-3-O2 8 III CY-5-O2 10 II CC-3-V 20 II CC-3-2 29.75 RM RM-1 0.25

Example 1

(84) TABLE-US-00004 Category Liquid crystal monomer code Content (%) III CY-C(5)-O4 11 III PY-C(5)-O2 9 III COY-3-O2 12 III CCOY-3-O2 8 III CY-5-O2 10 II CC-3-V 20 II CC-3-2 29.75 I I-1-1 0.25

Example 2

(85) TABLE-US-00005 Category Liquid crystal monomer code Content (%) III CY-5-O4 11 III PY-3-O2 9 III COY-3-O2 12 III CCOY-3-O2 8 II PP-5-1 10 II CC-3-V1 15 II CC-3-2 10 IV Sa-C(5)1O-O2 5 V CCP-3-1 10 V CPP-3-2 9 I I-1-8 1

Example 3

(86) TABLE-US-00006 Category Liquid crystal monomer code Content (%) III CCY-C(5)-O4 11 III CPY-C(5)-O2 9 III CCY-3-O2 12 IV Sa-C(3) 1O-O4 8 II PP-1-2V 10 II CC-3-V1 25 II CP-3-O2 5 V CLP-3-1 12 V CPP-3-O2 7.8 I I-1-10 0.2

Example 4

(87) TABLE-US-00007 Category Liquid crystal monomer code Content (%) III CCY-3-O2 11 III CPY-3-O2 9 III PYP-3-O2 12 III CLY-5-O2 10 IV Sb-C(5) 1O-O4 8 II PP-5-1 10 II CC-3-V 25 II CC-3-2 5 V CCP-3-1 4.8 VI CPGIP-5-2 5 I I-9-1 0.2

Example 5

(88) TABLE-US-00008 Category Liquid crystal monomer code Content (%) III CCY-3-O2 11 III CPY-3-O2 9 III PYP-3-O2 10 III CCOY-5-O2 10 III COY-3-O2 10 IV Sb-C(5) 1O-O4 10 II CC-3-V 20 V CCP-3-1 4.9 V CPP-1V-2 5 VI CGPC-3-1 10 I I-12-1 0.1

Example 6

(89) TABLE-US-00009 Category Liquid crystal monomer code Content (%) III CY-C(5)-O4 11 III PY-C(3)1-O2 9 III COY-3-O2 12 III CCOY-3-O2 8 III CY-5-O2 10 II CC-3-V 20 II CC-3-2 29.75 I I-9-14 0.25

Example 7

(90) TABLE-US-00010 Category Liquid crystal monomer code Content (%) III CY-C(5)-O4 11 III PY-C(5)-O2 9 III COY-3-O2 12 III CCOY-3-O2 8 II PP-5-1 10 II CC-3-V1 15 II CC-3-2 10 IV Sa-C(5)1O-O2 5 V CCP-3-1 10 V CPP-3-2 9 I I-3-1 1

Example 8

(91) TABLE-US-00011 Category Liquid crystal monomer code Content (%) III CY-5-O4 11 III CPY-C(3)1-O2 9 III CCY-3-O2 12 IV Sa-C(3) 1O-O4 8 II PP-1-2V 10 II CC-3-V1 25 II CP-3-O2 5 V CLP-3-1 12 V CPP-3-2V1 7.8 I I-9-8 0.2

Example 9

(92) TABLE-US-00012 Category Liquid crystal monomer code Content (%) III CCY-3-O2 11 III CPY-3-O2 9 III PYP-3-O2 12 III CLY-5-O2 10 IV Sb-C(5) 1O-O4 8 II PP-5-1 10 II CC-3-V 25 II CC-3-2 5 V CCP-3-1 4.8 VI CPGIP-5-2 5 I I-1-10 0.2

Example 10

(93) TABLE-US-00013 Category Liquid crystal monomer code Content (%) III CCY-3-O2 11 III CPY-3-O2 9 III PYP-3-O2 10 III CCOY-5-O2 10 III COY-3-O2 10 IV Sb-C(5) 1O-O4 10 II CC-3-V 20 V CCP-3-1 4.9 V CPP-V-1 5 VI CGPC-3-1 10 I I-15-7 0.1

(94) 1. Conversion Rate of Polymerizable Compound

(95) Determination of the Rate of Polymerization of a Liquid Crystal Medium Prepared from a Polymerizable Compound in a Liquid Crystal Display Device:

(96) to a mixture in Comparative Example 6, from which RM-1 is omitted, as parent MUTY, polymerizable compound RMs of Examples 1-7 are respectively added thereto in an amount of 2500 ppm; for comparison, equivalent amounts of the RMs of Comparative Examples 1-6 are respectively added to the MUTY, liquid crystal media are prepared by means of the above-mentioned liquid crystal medium preparation method, the liquid crystal media are injected into liquid crystal cells, the PSA panel process is simulated, and the rate of polymerization thereof is determined, with the specific conditions being: UV1: 80 mW/cm.sup.2@365 nm, 200 s; and UV2: 5 mW/cm.sup.2@365 nm, 120 min, and the liquid crystal cells are further cut open for HPLC analysis, with the results being as shown in the following table.

(97) TABLE-US-00014 Addition Residual Conversion Tilt angle Sample composition amount amount rate after UV (Comparative Exam- 2500 478 81% 81.2 ple 1) RM-1 (Comparative Exam- 2500 617 75% 83.1 ple 2) RM-2 (Comparative Exam- 2500 125 95% 78 ple 3) RM-3 (Comparative Exam- 2500 400 84% 88.1 ple 4) RM-4 (Comparative Exam- 2500 120 95% 78.2 ple 5) RM-5 (Comparative Exam- 2500 110 96% 78.1 ple 6) RM-6 I-1-1 2500 102 96% 82.1 I-1-4 2500 100 96% 83.5 I-1-8 2500 105 96% 85.2 I-1-10 2500 107 96% 84.8 I-3-10 2500 110 96% 84.5 I-3-11 2500 111 96% 84.9 I-9-1 2500 106 96% 83.3 I-7-1 2500 105 96% 83.1 I-9-14 2500 109 96% 86.3 I-3-1 2500 113 95% 85.2 I-3-6 2500 98 96% 84.2 I-9-8 2500 101 96% 84.5 I-1-10 2500 95 96% 83.2 I-8-8 2500 97 96% 83.3 I-15-7 2500 103 96% 83.4

(98) As can be seen from the above table, with respect to Comparative Examples 1, 2, and 4, the polymerizable compounds provided by the present invention have a rapid reaction rate and achieve a higher conversion rate in the same time.

(99) However, due to the reaction time being too fast, Comparative Examples 3, 5, and 6 result in the formed particles being larger and uneven and the formed pretilt angle being too large, causing a phenomenon of light leakage. The polymerizable compound provided by the present invention results in the formed particles being uniform and an appropriate pretilt angle while maintaining a faster reaction time, the technical advantages being obvious.

(100) 2. Response Time

(101) Mixtures prepared from various polymerizable compounds and liquid crystal compounds are injected into devices. After the polymeric compounds are polymerized by means of irradiation with ultraviolet light, the response times of the devices are measured. Where a mixture of a polymeric compound and a liquid crystal compound is not added, the response time is slow. Therefore, it can be concluded that the combination of the polymeric compound and the liquid crystal compound, referred to in the present invention, has an obvious effect in shortening the response time.

(102) TABLE-US-00015 Example Response time (ms) Comparative Example 5 15.1 Example 1 11.1 Example 2 7.3 Example 3 9.7 Example 4 8.2 Example 5 9.3 Example 6 10.1 Example 7 9.3 Example 8 9.5 Example 9 8.7 Example 10 9.2

(103) 3. Reliability

(104) Mixtures prepared from various polymerizable compounds and liquid crystal compounds are injected into test cells. After the polymeric compound is polymerized by means of irradiation with ultraviolet light, the voltage holding ratio (VHR) is measured under the conditions of ultraviolet light, high temperature, etc., and a highly reliable liquid crystal, i.e., having a high VHR (16.7 ms), is preferred. The data of the examples are obviously preferred.

(105) TABLE-US-00016 Example VHR (16.7 ms) (%) Comparative Example 5 99.0 Example 1 99.87 Example 2 99.83 Example 3 99.86 Example 4 99.91 Example 5 99.82 Example 6 99.85 Example 7 99.91 Example 8 99.87 Example 9 99.91 Example 10 99.85