CN110551078A - Compound, optically anisotropic body, and liquid crystal display device - Google Patents
Compound, optically anisotropic body, and liquid crystal display device Download PDFInfo
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Abstract
The invention relates to a compound, an optical anisotropic body and a liquid crystal display device, wherein the invention discloses a compound with a polymerizable group shown as a formula I, , A 1 and A 2 respectively and independently represent alkyl with 3-10 carbon atoms, alkenyl with 4-10 carbon atoms or alkoxy with 3-10 carbon atoms, wherein any-CH 2 -is optionally substituted by-O-, and any hydrogen is optionally substituted by F, Z 1 and Z 2 respectively and independently represent-COO-, -CO-, -CH 2 COO-, -COOCH 2 -, -CH 2 CH 2 COO-or-COOCH 2 CH 2 -, and n and m are respectively and independently 1, 2 or 3.
Description
Technical Field
The present invention relates to the field of liquid crystal compounds, and more particularly to a liquid crystal compound having a polymerizable group, an optically anisotropic body, and a liquid crystal display device.
Background
Compounds having a polymerizable group (polymerizable compounds) have been used in various optical materials; for example, a polymerizable composition containing a polymerizable compound is aligned in a liquid crystal state and polymerized to produce a polymer having a uniform orientation, and such a polymer can be used for a polarizing plate, a retardation plate, or the like required for a display. In many cases, a polymerizable composition containing two or more polymerizable compounds is used in order to satisfy the required optical properties, polymerization rate, solubility, melting point, glass transition temperature, transparency of the polymer, mechanical strength, surface hardness, heat resistance, and light resistance. In this case, it is required that the polymerizable compound used has good physical properties for the polymerizable composition without adversely affecting other properties.
In order to increase the viewing angle of a liquid crystal display, it is required that the wavelength dispersion of the birefringence of the retardation film is small or reverse wavelength dispersion is obtained. As a material for this purpose, various polymerizable liquid crystal compounds having reverse wavelength dispersibility or low wavelength dispersibility have been developed. However, the existing material synthesis method is complex, the synthesis period is long, toxic and harmful raw materials are used in the synthesis process, the synthesis cost is high, and large-scale production and application are difficult. The prior art also has the defects of low stability, easy deterioration and self-polymerization in the production, storage and transportation processes, and unfavorable production, storage and transportation.
Patent document
Patent document 1: CN 107108473A
Disclosure of Invention
The present invention has been made to solve the problem of providing a polymerizable compound which has excellent optical properties and good miscibility and does not cause crystal precipitation when added to a polymerizable composition.
in addition, the polymeric compound of the invention has good stability, is not easy to deteriorate and polymerize in the production and storage processes, and has low cost, simple production and convenient large-scale commercial application.
In order to solve the above problems, the present invention provides a compound represented by formula I:
Wherein A is1、A2each independently represents an alkyl group having 3 to 10 carbon atoms, an alkenyl group having 4 to 10 carbon atoms, or an alkoxy group having 3 to 10 carbon atoms, wherein any of-CH2-optionally substituted by-O-, any hydrogen being optionally substituted by F; z1、Z2Each independently represents-COO-, -CO-, -CH2COO-、-COOCH2-、-CH2CH2COO-, or-COOCH2CH2-; n and m each independently represent 0, 1, 2 or 3.
P representsor H;
Sp represents a single bond, a C1-C20 alkyl group, or a C2-C20 alkenyl group, any one or more of which are not linked2Optionally substituted by-O-, -S-, -CO-, -CH2O-、-OCH2-, -COO-, -OOC-or acrylate group.
Optionally, the compound shown in the formula I is any one or more of a compound shown in a formula I-a, a compound shown in a formula I-b or a compound shown in a formula I-c:
Optionally, the compound shown in the formula I-a is one or more of compounds shown in formulas I-a-1 to I-a-6; the compound shown in the formula I-b is one or more of the compounds shown in the formulas I-b-1 to I-b-6: the compound shown in the formula I-c is one or more of compounds shown in formulas I-c-1 to I-c-6;
In a second aspect of the invention, there is provided a composition comprising a compound as hereinbefore described.
In a third aspect of the present invention, there is provided a liquid crystal composition comprising the aforementioned compound.
In a fourth aspect of the invention, there is provided a polymer obtainable by polymerisation of a compound as hereinbefore described or obtainable by polymerisation of a composition as hereinbefore described. The aforementioned compounds can be polymerized by a method generally used in the art, such as UV ultraviolet irradiation, heating, or addition of a radical initiator.
In a fifth aspect of the present invention, there is provided an optically anisotropic body formed of the aforementioned polymer.
In a sixth aspect of the present invention, there is provided a liquid crystal display device comprising the compound, or the polymer, or the optically anisotropic body.
the compound does not cause crystal precipitation when added into the polymerizable composition, is a polymerizable compound with high storage stability, adopts non-toxic and low-cost starting materials, and effectively reduces the synthesis cost.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The progress of the reaction is generally monitored by TLC, and the post-treatment after the completion of the reaction is generally water washing, extraction, combination of organic phases, drying, evaporation of the solvent under reduced pressure, recrystallization, and column chromatography, and those skilled in the art can implement the present invention as described below.
A compound of formula I-a, and when A1And A2when m is the same as n and P is not H, the synthesis method is as follows:
The method specifically comprises the following eight steps 1-8:
1-1) mixingdissolving in DMF, adding into three-neck flask, adding potassium carbonate, heating to 80 deg.C, reacting for 3 hr, cooling, filtering the reaction solution, adding toluene into the filter cake, passing through silica gel column to obtain light yellow liquid, evaporating to remove solvent, and pulping with petroleum ether to obtain the final product
1-2) mixingDissolving in tetrahydrofuran, adding into three-neck flask, adding lithium hydroxide, heating to reflux, reflux reacting for 2 hr, cooling, pouring the reaction solution into dilute hydrochloric acid water solution, extracting with ethyl acetate, washing with water, and removing anhydrous sulfurDrying sodium acid, spin-drying to obtain yellow solid, and pulping with petroleum ether to obtain the final product;1-3) mixing p-hydroxybenzoic acid and HOA1Adding Cl, sodium hydroxide, potassium iodide and water into a three-neck flask, heating to reflux, carrying out reflux reaction for 4 hours, cooling, adding hydrochloric acid into the reaction solution, filtering the reaction solution, and recrystallizing the filter cake with ethyl acetate for 2 times to obtain the compound
1-4) mixingDissolving in toluene, adding into three-neck flask, adding p-toluenesulfonic acid and acrylic acid, heating to reflux, reflux reacting for 4 hr, cooling, pouring the reaction solution into water, extracting with dichloromethane, washing with water, spin-drying, and recrystallizing with ethanol twice to obtain the final product
1-5) mixingDissolving DMAP in dichloromethane, adding into a three-neck flask, keeping the temperature at 0-10 ℃, dropwise adding a dichloromethane mixed solution of DCC, heating to room temperature for 4 hours after the completion of adding for half an hour, reacting for 4 hours, filtering the reaction solution, spin-drying, adding toluene to dissolve the product, carrying out column chromatography to obtain a light yellow liquid, spin-drying the reaction solution, recrystallizing the product isopropanol and toluene for 1 time to obtain the product
1-6) mixingDissolving in DMF, adding into three-neck flask, adding potassium carbonate, heating to 80 deg.C, reacting for three hours while maintaining the temperature, cooling, pouring the reaction solution into ice water, filtering the reaction solution, and filtering to obtain filter cake tolueneRecrystallizing with ethanol to obtain the product
1-7) mixing(±) -10-camphorsulfonic acid, tetrahydrofuran, ethanol andAdding into three-neck bottle, heating to 60 deg.C, reacting for 6 hr, cooling, rotary evaporating to remove solvent, pulping with isopropanol, and performing column chromatography to obtain the final product
1-8) mixingDissolving in toluene, adding into three-neck flask, adding P-toluenesulfonic acid and PH, heating to reflux, reflux reacting for 4 hr, cooling, pouring the reaction solution into water, extracting with dichloromethane, washing with water, spin-drying, performing toluene column chromatography, recrystallizing with toluene and ethanol to obtain I-a, and P represents
The synthesis method of the compounds shown in the formulas I-b and I-c is similar to that of I-a, and the starting materials are prepared fromChange to
a compound of formula I-a, and when A1And A2When m is n and P is H, the synthesis method is as follows:
The method specifically comprises seven steps from the following step 1-1 to step 1-7:
1-1) mixingDissolving in DMF, adding into three-neck flask, adding potassium carbonate, heating to 80 deg.C, reacting for 3 hr, cooling, filtering the reaction solution, adding toluene into the filter cake, passing through silica gel column to obtain light yellow liquid, evaporating to remove solvent, and pulping with petroleum ether to obtain the final product
1-2) mixingdissolving in tetrahydrofuran, adding into a three-neck flask, adding lithium hydroxide, heating to reflux, carrying out reflux reaction for 2 hours, cooling, pouring the reaction solution into a dilute hydrochloric acid aqueous solution, extracting the reaction solution with ethyl acetate, washing with water, drying with anhydrous sodium sulfate, and carrying out spin drying to obtain a yellow solid, and pulping with petroleum ether to obtain a product;1-3) mixing p-hydroxybenzoic acid and HOA1Adding Cl, sodium hydroxide, potassium iodide and water into a three-neck flask, heating to reflux, carrying out reflux reaction for 4 hours, cooling, adding hydrochloric acid into the reaction solution, filtering the reaction solution, and recrystallizing the filter cake with ethyl acetate for 2 times to obtain the compound
1-4) mixingDissolving in toluene, adding into three-neck flask, adding p-toluenesulfonic acid and acrylic acid, heating to reflux, reflux reacting for 4 hr, cooling, pouring the reaction solution into water, extracting with dichloromethane, washing with water, spin-drying, and recrystallizing with ethanol twice to obtain the final product
1-5) mixingDissolving DMAP in dichloromethane, adding into a three-neck flask, keeping the temperature at 0-10 ℃, dropwise adding a dichloromethane mixed solution of DCC, heating to room temperature for 4 hours after the completion of adding for half an hour, reacting for 4 hours, filtering the reaction solution, spin-drying, adding toluene to dissolve the product, carrying out column chromatography to obtain a light yellow liquid, spin-drying the reaction solution, recrystallizing the product isopropanol and toluene for 1 time to obtain the product
1-6) mixingDissolving in DMF, adding into three-neck flask, adding potassium carbonate, heating to 80 deg.C, reacting for three hours while maintaining the temperature, cooling, pouring the reaction solution into ice water, filtering the reaction solution, and recrystallizing the filter cake with toluene and ethanol to obtain the final product
1-7) mixing(±) -10-camphorsulfonic acid, tetrahydrofuran, ethanol andAdding into a three-neck bottle, heating to 60 ℃, keeping the temperature for reaction for 6 hours, cooling, removing the solvent by rotary evaporation, pulping with isopropanol, and carrying out column chromatography to obtain a product I-a;
The synthesis method of the compounds shown in the formulas I-b and I-c is similar to that of I-a, and the starting materials are prepared fromchange to
example 1
Preparing a compound shown as a formula I-a-4, wherein the structural formula is as follows,
The synthetic route is as follows:
Specifically, the method comprises the following eight steps of I-a-4-1 to I-a-4-8, wherein I-a-4-1) is to carry out (9.5g, 38mmol)And (2.34g, 17mmol)dissolving in 100mL DMF, adding into three-neck flask, adding (5.6g, 41mmol) potassium carbonate, heating to 80 deg.C, keeping the temperature for reaction for 3 hr, cooling, filtering the reaction solution, adding toluene into the filter cake, passing through silica gel column to obtain light yellow liquid, evaporating to remove solvent, and pulping with petroleum ether to obtain (4.5g, 11mmol)Yield: 65 percent;
I-a-4-2) coupling (5g, 11.2mmol)Dissolving in 100mL of tetrahydrofuran and 25mL of water, adding into a three-neck flask, adding (0.67g, 17mmol) of lithium hydroxide, heating to reflux, carrying out reflux reaction for 2 hours, cooling, pouring the reaction solution into a dilute hydrochloric acid aqueous solution, extracting the reaction solution with ethyl acetate, washing with water, drying with anhydrous sodium sulfate, and carrying out spin drying to obtain a yellow solid, and pulping with petroleum ether to obtain a product; (2.9g, 8mmol)The yield thereof was found to be 71%. I-a-4-3) Synthesis of p-hydroxybenzoic acid (6g, 43mmol), (7.1g,52mmol) of chlorohexanol, (3.44g, 86mmol) of sodium hydroxide, (0.7g, 4.3mmol) of potassium iodide and 50mL of water were put in a three-necked flask, heated to reflux, reacted under reflux for 4 hours, cooled, added with hydrochloric acid to the reaction solution, filtered, and recrystallized from ethyl acetate cake for 2 times to obtain (6.1g, 26mmol)The yield is 60 percent; i-a-4-4) coupling (6g, 25mmol)Dissolving in 100mL toluene, adding into a three-neck flask, adding (0.43g, 2.5mmol) p-toluenesulfonic acid and (3.6g, 50mmol) acrylic acid, heating to reflux, refluxing for 4 hours, cooling, pouring the reaction solution into water, extracting with dichloromethane, washing with water, spin-drying, and recrystallizing the product with ethanol twice to obtain (5.84g, 20mmol)The yield is 80%;
I-a-4-5) mixing (10g, 34mmol)(0.38g, 3.1mmol) DMAP and (5.6g, 15.4mmol)Dissolving in 100mL dichloromethane, adding into a three-neck flask, keeping the temperature at 0-10 ℃, dropwise adding (7g, 34mmol) DCC dichloromethane mixed solution, adding for half an hour, heating to room temperature, reacting for 4 hours, filtering the reaction solution, spin-drying, adding toluene to dissolve the product, performing column chromatography to obtain light yellow liquid, spin-drying the reaction solution, recrystallizing the product isopropanol and toluene for 1 time to obtain (9.7g, 10.7mmol)The yield is 70%; i-a-4-6) mixing (5g,30mmol)And (4.5g, 36mmol)Dissolving in 50mL DMF, adding into three-neck flask, adding (4.9g, 36mmol) potassium carbonate, heating to 80 deg.C, maintaining the temperature for reaction for three hours, cooling, pouring the reaction solution into ice water, filtering the reaction solution, and recrystallizing the filter cake with toluene and ethanol to obtain the product (5.8g, 23mmol)The yield is 77%;
I-a-4-7) preparation (7.6g, 30mmol)(1.4g, 6mmol) (+ -) -10-Camphorsulfonic acid, tetrahydrofuran 100mL, ethanol 100mL and (22.8g, 25mmol)Adding into three-neck bottle, heating to 60 deg.C, reacting for 6 hr, cooling, rotary evaporating to remove solvent, pulping with isopropanol, and performing column chromatography to obtain product (18.8g, 16mmol)
The yield is 64 percent; i-a-4-8) coupling (11.7g, 10mmol)dissolving in 100mL of toluene, adding into a three-necked flask, adding (0.17g, 1mmol) of p-toluenesulfonic acid and (1.44g, 20mmol) of acrylic acid, heating to reflux, carrying out reflux reaction for 4 hours, cooling, pouring the reaction solution into water, extracting with dichloromethane, washing with water, spin-drying, carrying out toluene column chromatography on a product, and recrystallizing with toluene and ethanol to obtain (7.2g, 6mmol) of the compound shown in the formula I-a-4 with the yield of 60%.
Using a synthesis procedure analogous to that of example 1, compounds I-b-4, I-c-4 were obtained by simply changing the starting materials for the synthesis,change of starting material for synthesis
The synthesis of the compounds I-a-3, I-b-3 and I-c-3 is similar to example 1, starting from the respective starting materialsHowever, it is necessary to exchange chlorohexanol for chloropropanol in step I-a-4-3).
Example 2
Preparing a compound shown as a formula I-b-2, wherein the structural formula is shown as follows,
The synthetic route is as follows:
Specifically, the method comprises the following eight steps of I-b-2-1 to I-b-2-8, wherein I-b-2-1) is (10g, 38mmol)And (2.34g, 17mmol)Dissolving in 100mL DMF, adding into three-neck flask, adding (5.6g, 41mmol) potassium carbonate, heating to 80 deg.C, keeping the temperature for reaction for 3 hr, cooling, filtering the reaction solution, adding toluene into the filter cake, passing through silica gel column to obtain light yellow liquid, evaporating to remove solvent, and pulping with petroleum ether to obtain (5.7g, 12mmol)Yield: 76%;
i-b-2-2) coupling (5g, 10.5mmol)dissolving in 100mL tetrahydrofuran and 25mL water, adding into three-neck flask, adding (0.4g, 15.8mmol) lithium hydroxide, heating to reflux, reflux reacting for 2 hr, cooling, and reactingPouring the reaction solution into a dilute hydrochloric acid aqueous solution, extracting the reaction solution with ethyl acetate, washing with water, drying with anhydrous sodium sulfate, and spin-drying to obtain a yellow solid, and pulping with petroleum ether to obtain a product; (3.35g, 8.6mmol)The yield thereof was found to be 90%.
I-b-2-3) p-hydroxybenzoic acid (6g, 43mmol), (7.1g, 52mmol) Chlorohexanol, (3.44g, 86mmol) sodium hydroxide, (0.7g, 4.3mmol) Potassium iodide and 50mL water were added to a three-necked flask, heated to reflux, refluxed for 4 hours, cooled, hydrochloric acid was added to the reaction solution, the reaction solution was filtered, and the cake was recrystallized from ethyl acetate 2 times to give (6.1g, 26mmol)The yield is 60 percent; i-b-2-4) coupling (6g, 25mmol)Dissolving in 100mL toluene, adding into a three-neck flask, adding (0.43g, 2.5mmol) p-toluenesulfonic acid and (3.6g, 50mmol) acrylic acid, heating to reflux, refluxing for 4 hours, cooling, pouring the reaction solution into water, extracting with dichloromethane, washing with water, spin-drying, and recrystallizing the product with ethanol twice to obtain (5.84g, 20mmol)The yield is 80%;
I-b-2-5) coupling (10g, 34mmol)(0.38g, 3.1mmol) DMAP and (6g, 15.4mmol)Dissolving in 100mL of dichloromethane, adding into a three-neck flask, keeping the temperature at 0-10 ℃, dropwise adding (7g, 34mmol) of dichloromethane mixed solution of DCC, adding for half an hour, heating to room temperature, reacting for 4 hours, filtering the reaction solution, spin-drying, adding toluene to dissolve the product, performing column chromatography to obtain light yellow liquid, spin-drying the reaction solution, and obtaining isopropanol and toluene productsrecrystallize 1 time to give (10.1g, 10.7mmol)The yield is 70%;
I-b-2-6) coupling (5g,30mmol)And (4.9g, 36mmol)Dissolving in 50mL DMF, adding into three-neck flask, adding (4.9g, 36mmol) potassium carbonate, heating to 80 deg.C, maintaining the temperature for reaction for three hours, cooling, pouring the reaction solution into ice water, filtering the reaction solution, and recrystallizing the filter cake with toluene and ethanol to obtain the product (6.7g, 22.5mmol)The yield is 75%; i-b-2-7) coupling (8.9g, 30mmol)(+ -) -10-Camphorsulfonic acid (1.4g, 6mmol), tetrahydrofuran 100mL, ethanol 100mL and (23.4g, 25mmol)Placing into a three-necked bottle, heating to 60 deg.C, reacting for 6 hr, cooling, removing solvent by rotary evaporation, pulping with isopropanol, and performing column chromatography to obtain product (18.3g, 15mmol)
The yield is 60%;
I-b-2-8) coupling (12.2g, 10mmol)dissolving in 100mL of toluene, adding into a three-neck flask, adding (0.17g, 1mmol) of p-toluenesulfonic acid and (1.44g, 20mmol) of acrylic acid, heating to reflux, refluxing for 4 hours, cooling, pouring the reaction solution into water, extracting with dichloromethane, washing with water, spin-drying, performing toluene column chromatography, and performing toluene ethanol extractionRecrystallization afforded (6.36g, 5mmol) of the compound of formula I-b-2 in 50% yield.
Using a synthesis similar to that of example 2, compounds I-a-2, I-c-2 were obtained by simply changing the starting materials for the synthesis,change of starting material for synthesis
The synthesis of the compounds I-a-1, I-b-1 and I-c-1 is similar to that of example 2, starting from the respective starting materialsHowever, it is necessary to exchange chlorohexanol for chloropropanol in step I-b-4-3).
Example 3
Preparing a compound shown as a formula I-c-6, wherein the structural formula is as follows,
The synthetic route is as follows:
specifically, the method comprises seven steps including the following step I-c-6-1 to step I-c-6-7, wherein I-c-6-1) is to carry out (10.5g, 38mmol)And (2.34g, 17mmol)Dissolving in 100mL DMF, adding into three-neck flask, adding (5.6g, 41mmol) potassium carbonate, heating to 80 deg.C, reacting for 3 hr, cooling, filtering the reaction solution, adding toluene into the filter cake, passing through silica gel column,To give a pale yellow liquid, evaporate the solvent to dryness, and slurry the product with petroleum ether to give (6g, 12mmol)yield: 70 percent;
I-c-6-2) coupling (5.6g, 11.2mmol)Dissolving in 100mL of tetrahydrofuran and 25mL of water, adding into a three-neck flask, adding (0.67g, 17mmol) of lithium hydroxide, heating to reflux, carrying out reflux reaction for 2 hours, cooling, pouring the reaction solution into a dilute hydrochloric acid aqueous solution, extracting the reaction solution with ethyl acetate, washing with water, drying with anhydrous sodium sulfate, and carrying out spin drying to obtain a yellow solid, and pulping with petroleum ether to obtain a product; (3.3g, 7.8mmol)The yield thereof was found to be 71%. I-c-6-3) p-hydroxybenzoic acid (6g, 43mmol), (7.1g, 52mmol) Chlorohexanol, (3.44g, 86mmol) sodium hydroxide, (0.7g, 4.3mmol) Potassium iodide and 50mL water were added to a three-necked flask, heated to reflux, refluxed for 4 hours, cooled, hydrochloric acid was added to the reaction solution, the reaction solution was filtered, and the cake was recrystallized from ethyl acetate 2 times to give (6.1g, 26mmol)The yield is 60 percent; i-c-6-4) coupling (6g, 25mmol)Dissolving in 100mL toluene, adding into a three-neck flask, adding (0.43g, 2.5mmol) p-toluenesulfonic acid and (3.6g, 50mmol) acrylic acid, heating to reflux, refluxing for 4 hours, cooling, pouring the reaction solution into water, extracting with dichloromethane, washing with water, spin-drying, and recrystallizing the product with ethanol twice to obtain (5.84g, 20mmol)The yield is 80%;
I-c-6-5) mixing (10g, 34mmol)(0.38g, 3.1mmol) DMAP and (6.4g, 15.4mmol)Dissolving in 100mL dichloromethane, adding into a three-neck flask, keeping the temperature at 0-10 ℃, dropwise adding (7g, 34mmol) DCC dichloromethane mixed solution, adding for half an hour, heating to room temperature, reacting for 4 hours, filtering the reaction solution, spin-drying, adding toluene to dissolve the product, performing column chromatography to obtain light yellow liquid, spin-drying the reaction solution, recrystallizing the product isopropanol and toluene for 1 time to obtain (9.67g, 10mmol)The yield is 65%;
I-c-6-6) coupling (5g,30mmol)And (5g, 36mmol)dissolving in 50mL DMF, adding into three-neck flask, adding (4.9g, 36mmol) potassium carbonate, heating to 80 deg.C, maintaining the temperature for reaction for three hours, cooling, pouring the reaction solution into ice water, filtering the reaction solution, and recrystallizing the filter cake with toluene and ethanol to obtain the product (5.87g, 22mmol)the yield is 73%;
I-c-6-7) coupling (8g, 30mmol)(+ -) -10-Camphorsulfonic acid (1.4g, 6mmol), tetrahydrofuran 100mL, ethanol 100mL and (24.1g, 25mmol)Adding into a three-neck flask, heating to 60 deg.C, reacting for 6 hr, cooling, removing solvent by rotary evaporation, pulping with isopropanol, and performing column chromatography to obtain product (19.4g, 16mmol) with yield of I-c-6 of 64%;
Use ofSynthesis procedures similar to those of example 3 were carried out by changing only the starting materials for the synthesis to give the compounds I-a-6 and I-b-6,change of starting material for synthesis
the synthesis of the compounds I-a-5, I-b-5 and I-c-5 is analogous to example 3, starting from the respective starting materialsHowever, it is necessary to exchange chlorohexanol for chloropropanol in step I-a-4-3).
Maximum solubility evaluations were carried out for the compounds R-1, R-2, R-3 shown in patent document 1, and the compounds represented by the formulae I-a-4, formula I-b-2, and formula I-c-6 in examples 1 to 3.
The method for evaluating the maximum solubility is as follows: a liquid crystal composition is selected as a mother liquid crystal, 5 to 25% of the compound of formula I-a-4 is added as example 4, the compound of formula I-b-2 is added as example 5, the compound of formula I-c-6 is added as example 6, the compound of formula R-1 is added as comparative example 1, the compound of formula R-2 is added as comparative example 2, and the compound of formula R-3 is added as comparative example 3 in a mass percent amount of 5% respectively, and the mixture is uniformly mixed to be used as an evaluation object of the maximum solubility. The maximum solubility evaluation objects of examples 4-6 and comparative examples 1-3 after being uniformly mixed are respectively placed in an environment of 20 +/-3 ℃ for 30 days, and the mass percentage content of the evaluation object without crystal precipitation is the maximum solubility of the compound.
The mother liquid crystal comprises 30 percent of the compound of the formula Y-1, 30 percent of the compound of the formula Y-2 and 40 percent of the compound of the formula Y-3 by mass percent respectively.
TABLE 1
| evaluating an object | Maximum solubility | |
| Example 4 | Compounds of formula I-a-4 | 25％ |
| Example 5 | Compounds of formula I-b-2 | 25％ |
| Example 6 | compounds of formula I-c-6 | 25％ |
| Comparative example 1 | compounds of formula R-1 | 20％ |
| Comparative example 2 | Compounds of formula R-2 | 25％ |
| Comparative example 3 | compounds of formula R-3 | 20％ |
As is apparent from Table 1, the maximum solubility of examples 4 to 6 comprising the compounds represented by the formulae I-a-4, I-b-2 and I-c-6, respectively, was the same or higher than that of comparative examples 1 to 3 comprising the compounds represented by the formulae R-1, R-2 and R-3, respectively.
A coating solution was prepared by adding 20% of the compound of formula I-a-4 as example 7, 20% of the compound of formula I-b-2 as example 8, 20% of the compound of formula I-c-6 as example 9, 20% of the compound of formula R-1 as comparative example 4, 20% of the compound of formula R-2 as comparative example 5, 20% of the compound of formula R-3 as comparative example 6, and the photopolymerization initiators Irgacure907 (manufactured by BASF corporation) 1%, 4-methoxyphenol 0.1% and chloroform 80% to the above mother liquid crystal. The coating liquid was applied to the rubbed glass substrate by a spin coating method. After drying at 80 ℃ for 1 minute, further drying at 120 ℃ for 1 minute was carried out. Then, the test piece was irradiated with ultraviolet light at an intensity of 40mW/cm2 for 25 seconds using a high-pressure mercury lamp to prepare a test piece showing unevenness.
For the obtained polymer, the degree of unevenness was evaluated by observation with a polarization microscope. 10 films each containing a compound showing the unevenness to be evaluated were prepared, and the number of the unevenness was counted. The number of display unevenness observed in 10 sheets of films was counted, and the number of display unevenness was 0, B, C, D, E, and F, respectively, when the number of display unevenness was not 0, not 1, not 5 or less, not 10, not 11 to 20, and not 21 or more. The evaluation results are shown in Table-2.
| evaluating an object | Display unevenness | |
| Example 7 | Compounds of formula I-a-4 | A |
| Example 8 | Compounds of formula I-b-2 | A |
| Example 9 | Compounds of formula I-c-6 | A |
| Comparative example 4 | Compounds of formula R-1 | A |
| comparative example 5 | Compounds of formula R-2 | A |
| Comparative example 6 | Compounds of formula R-3 | A |
As can be seen from Table 2, examples 7 to 9 showed comparable degrees of unevenness as compared with comparative examples 4 to 6.
The compound provided by the embodiment of the present invention is a polymerizable compound having high solubility without causing crystal precipitation when added to a polymerizable composition, and a film-like polymer obtained by polymerizing a polymerizable composition containing the polymerizable compound is less likely to show unevenness. The compounds of the formulae R-1, R-2 and R-3 provided in patent document 1 are prepared from starting materials for synthesisThe compound provided by the embodiment of the invention adopts The compound provided by the embodiment of the invention adopts the starting raw materials for synthesis, which are large in consumption in large-scale industrial production, so that the raw materials are easier to obtain and lower in acquisition cost, and the synthesis cost of the compound is effectively reduced by selecting the starting raw materials with low cost.
Claims (8)
1. A compound represented by formula I,
Wherein A is1、A2Each independently represents an alkyl group having 3 to 10 carbon atoms, an alkenyl group having 4 to 10 carbon atoms, or an alkoxy group having 3 to 10 carbon atoms, wherein any of-CH2-optionally substituted by-O-, any hydrogen being optionally substituted by F; z1、Z2Each independently represents-COO-, -CO-, -CH2COO-、-COOCH2-、-CH2CH2COO-, or-COOCH2CH2-; n and m are each independently 0, 1, 2 or 3.
P represents:Or H;
Sp represents a single bond, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, wherein any one or more of CH are not linked2Optionally substituted by-O-, -S-, -CO-, -CH2O-、-OCH2-, -COO-, -OOC-or acrylate group.
2. The compound of claim 1, wherein: the compound shown in the formula I is a compound shown in a formula I-a, a formula I-b or a formula I-c:
wherein A is1、A2Each independently represents an alkyl group having 3 to 10 carbon atoms, an alkenyl group having 4 to 10 carbon atoms, or an alkoxy group having 3 to 10 carbon atoms, wherein any of-CH2-optionally substituted by-O-, any hydrogen being optionally substituted by F; z1、Z2Each independently represents-COO-, -CO-, -CH2COO-、-COOCH2-、-CH2CH2COO-, or-COOCH2CH2-; n and m are each independently 0, 1, 2 or 3.
P represents:or H;
sp represents a single bond, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, any one or more of which are not connected to each other2May be substituted by-O-, -S-, -CO-, -CH2O-、-OCH2-, -COO-, -OOC-or acrylate group.
3. The compound of claim 2, wherein: the compound shown in the formula I-a is one or more of compounds shown in formulas I-a-1 to I-a-6; the compound shown in the formula I-b is one or more of the compounds shown in the formulas I-b-1 to I-b-6: the compound shown in the formula I-c is one or more of compounds shown in formulas I-c-1 to I-c-6;
4. A composition comprising a compound of any one of claims 1 to 3.
5. a liquid crystal composition containing the compound according to any one of claims 1 to 3.
6. a polymer obtained by polymerizing the composition of claim 4 or the liquid crystal composition of claim 5.
7. An optically anisotropic body formed from the polymer of claim 6.
8. A display device comprising a compound according to any one of claims 1 to 3, or comprising a polymer according to claim 6, or comprising an optically anisotropic body according to claim 7.
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|---|---|---|---|---|
| US20130023637A1 (en) * | 2010-03-31 | 2013-01-24 | Zeon Corporation | Polymerizable chiral compound, polymerizable liquid crystal compound, liquid crystal polymer and optically anisotropic body |
| JP2015078282A (en) * | 2013-10-16 | 2015-04-23 | Jnc株式会社 | Polymerizable compound, polymerizable composition and liquid crystal display element |
| CN107108473A (en) * | 2015-01-16 | 2017-08-29 | Dic株式会社 | Polymerizable compound and optically anisotropic body |
| CN108070386A (en) * | 2017-12-20 | 2018-05-25 | 石家庄诚志永华显示材料有限公司 | Liquid-crystal composition and liquid crystal display element |
| CN108084029A (en) * | 2017-12-20 | 2018-05-29 | 石家庄诚志永华显示材料有限公司 | Liquid-crystal composition and liquid crystal display element |
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| US20130023637A1 (en) * | 2010-03-31 | 2013-01-24 | Zeon Corporation | Polymerizable chiral compound, polymerizable liquid crystal compound, liquid crystal polymer and optically anisotropic body |
| JP2015078282A (en) * | 2013-10-16 | 2015-04-23 | Jnc株式会社 | Polymerizable compound, polymerizable composition and liquid crystal display element |
| CN107108473A (en) * | 2015-01-16 | 2017-08-29 | Dic株式会社 | Polymerizable compound and optically anisotropic body |
| CN108070386A (en) * | 2017-12-20 | 2018-05-25 | 石家庄诚志永华显示材料有限公司 | Liquid-crystal composition and liquid crystal display element |
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Application publication date: 20191210 |