JPH0457693B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel liquid crystal polymer. More specifically, the present invention is applicable to the field of optoelectronics, particularly display elements for calculators and watches, electro-optical shutters, electro-optical apertures, optical modulators, optical communication optical path switching switches, memories, liquid crystal printer heads, variable focal length lenses, etc. It is useful as a variety of electro-optical devices.It exhibits ferroelectricity even at room temperature, has a fast response speed to external factors, and is capable of displaying moving images, and can be advantageously used as a cover element for large screens and curved screens. The present invention relates to a polymer having liquid crystallinity that can be used. [Prior Art] Conventionally, display elements using low-molecular liquid crystals have been widely used for digital displays in calculators, watches, and the like. In these fields of application, conventional low-molecular liquid crystals are usually used by sandwiching them between two glass substrates whose spacing is controlled on the order of microns. However, such time adjustment has not been possible with large screens and curved screens. As a means to solve this difficulty, attempts have been made to polymerize liquid crystals and make them moldable (J. Polym. Sci, Polym. Lett., Ed. 13 , 243 (1975),
Polym.Bull., 6 6, 309 (1982), Japanese Patent Application Publication No. 1986-
21479, etc.). However, in these liquid crystal polymers, the response speed of changes in the amount of transmitted light, etc. to changes in external factors such as electric field is generally slow, and a satisfactory product has not yet been obtained. Furthermore, the liquid crystal polymer disclosed in the above-mentioned publication has the disadvantage that the polymer itself does not exhibit liquid crystal properties at room temperature and must be crystallized by heating in a temperature range above the glass transition temperature and below the transparency temperature. have. Furthermore, although the synthesis of ferroelectric polymer liquid crystals is reported in Liquid Crystal, 2 , 83 (1987), there is no description of response speed. Additionally, the polymer is colored and is not suitable for full color display. [Problems to be Solved by the Invention] The present invention is colorless and exhibits ferroelectricity even at room temperature, has a fast response to external factors, is capable of displaying moving images, and can be used as a display element for large screens and bendable screens. The object of the present invention is to provide a liquid crystal polymer that can be advantageously used as a liquid crystal polymer. [Means for solving the problem] As a result of extensive studies, the present inventors discovered that a polyether type polymer having a specific structure is colorless and exhibits ferroelectricity at around room temperature. The present invention has now been completed. That is, the present invention provides a liquid crystal polymer having the following general formula, having repeating units, and having a number average molecular weight of 1000 to 2000. (In the formula, k is an integer from 1 to 30, and R ¹ is

【formula】

【formula】

[expression] or

[Formula], X is -COO- or -OCO-, R ² is -COOR ³ , -OCOR ³ or -OR ³ , and R ³ is

[Formula], R ⁴ and R ⁵ are respectively -CH ₃ , a halogen atom,
or -CN, m and n are integers from 0 to 10, provided that when ^R4 is _-CH3 , n is not 0, P is 0 or 1, and C with * is It is an asymmetric carbon atom. ) The number average molecular weight of the liquid crystal polymer of the present invention is from 1000 to
It is 2000. A number average molecular weight of 1,000 to 2,000 is advantageous in that a good alignment state can be easily obtained by applying it to a substrate with electrodes in a liquid crystal state.
Further, in such a liquid crystal polymer, there is little decrease in response speed due to polymerization. A general method for synthesizing the liquid crystal polymer of the present invention is shown below. The polymer of the present invention has the following general formula: (Here, k, X, R ¹ , R ² , R ³ , R ⁴ , m, and n have the same meanings as defined above.) be able to. These monomers can be obtained, for example, as follows. (1) R ₁ is

[Formula] As shown in the reaction formula below, an alkenol () is halogenated with a halogenating agent such as thionyl chloride in the presence of pyridine to obtain an alkene halide (). An alkene halide () and a compound () are reacted in a suitable solvent such as 2-butanone in the presence of an alkali such as potassium carbonate to obtain an ether (). Next, the desired monomer (2) is obtained by oxiranizing this ether (2) with a peracid such as m-chloroperbenzoic acid in a suitable solvent such as dichloromethane. (In the formula, Y is a halogen.) As the alkenol (), for example, 9-
Decen-1-ol, 11-dodecen-1-ol, 7-octen-1-ol, 5-hexen-1-ol and the like are preferred. Here, the above compound ()

【formula】 is synthesized as follows. [

Synthesis of [Formula]] As shown in the reaction formula below, 4'-hydroxybiphenyl-4-carboxylic acid and an optically active alcohol () are mixed in a suitable solvent such as benzene, and an esterification catalyst, e.g. This ester compound () is obtained by reacting at a desired temperature in the presence of concentrated sulfuric acid, p-toluenesulfonic acid, or the like. Examples of the optically active alcohol () include (+)-2-methylbutanol, (-)-2-methylbutanol, (+)-2-chlorobutanol,
(-)-2-chlorobutanol, (+)-2-methylpentanol, (-)-2-methylpentanol, (+)-3-methylpentanol, (-)-3
-methylpentanol, (+)-4-methylhexanol, (-)-4-methylhexanol,
(+)-2-chloropropanol, (-)-2-chloropropanol, (+)-5-methylheptanol, (-)-5-methylheptanol, (+)-
6-methyloctanol, (-)-6-methyloctanol, (+)-2-cyanobutanol,
(-)-2-cyanobutanol, (-)-2-butanol, (+)-2-butanol, (-)-2-pentanol, (+)-2-pentanol, (-)-
2-octanol, (+)-2-octanol,
(-)-2-fluorooctanol, (+)-2-
Fluorooctanol, (+)-2-fluorohexanol, (-)-2-fluorohexanol, (+)-2-fluorononanol, (-)-2
-Fluorononanol, (+)-2-chloro-3
-methylpentanol, (-)-2-chloro-3
-Methylpentanol etc. are used. Preferably (-)-2-methylbutanol,
(+)-2-butanol, (-)-2-pentanol, (-)-2-octanol, (-)-2-fluorooctanol, and (-)-2-chloro-3-methylpentanol were used. It will be done. [

Synthesis of [Formula]] As shown in the reaction formula below, biphenyl-4,
This ester compound () is obtained by reacting 4'-diol with an optically active carboxylic acid (). Examples of the optically active carboxylic acid () include (+)-2-methylbutanoic acid, (-)-2-methylbutanoic acid, (+)-2-chlorobutanoic acid,
(-)-2-chlorobutanoic acid, (+)-2-methylpentanoic acid, (-)-2-methylpentanoic acid,
(+)-3-methylpentanoic acid, (-)-3-methylpentanoic acid, (+)-4-methylhexanoic acid,
(-)-4-methylhexanoic acid, (+)-2-chloropropanoic acid, (-)-2-chloropropanoic acid,
(+)-6-methyloctanoic acid, (-)-6-methyloctanoic acid, (+)-2-cyanobutanoic acid,
(-)-2-cyanobutanoic acid, (+)-2-fluorooctanoic acid, (-)-2-fluorooctanoic acid, (+)-2-fluorohexanoic acid, (-)-2
-fluorohexanoic acid, (+)-2-fluorononanoic acid, (-)-2-fluorononanoic acid, (+)-
2-chloro-3-methylpentanoic acid, (-)-2
-chloro-3-methylpentanoic acid and the like. [

Synthesis of [Formula]] As shown in the reaction formula below, the optically active alcohol [ ] is tosylated, and this is reacted with biphenyl-4,4'-diol to obtain the ether form ( ). (2) R ¹ is As shown in the reaction formula below, an alkene halide () and p-hydroxybenzoic acid ethyl ester are reacted in a suitable solvent such as acetone in the presence of an alkali such as potassium carbonate to obtain an ether. Next, the protective group for the carboxyl group in this ether form is removed with an aqueous potassium hydroxide solution, hydrochloric acid, etc. to obtain a carboxylic acid form. A halogenating agent such as thionyl chloride is added to this carboxylic acid, and the mixture is heated in a solvent such as toluene to form an acid halide. Next, this acid halide and the compound () are reacted in the presence of pyridine in a solvent such as toluene to obtain the ester compound (), and then m-chloroperbenzoic acid, etc. is reacted in a suitable solvent such as dichloromethane. The desired monomer () is obtained by oxirane conversion using a peracid. (3) R ¹ is As shown in the reaction formula below, an alkene halide () and hydroquinone are reacted in the presence of an alkali such as potassium carbonate to form an ether (
). The following compound () is converted into acid chloride using thionyl chloride or the like. The obtained acid chloride and the ether () are reacted in the presence of pyridine to obtain the ester (). Thereafter, oxirane conversion is performed in the same manner as in (1) to obtain the desired monomer (). Here, the above compound ()

[Formula] is as follows. It can be obtained by [

Synthesis of [Formula]] Optically active alcohol () and biphenyl-
4,4'-dicarboxylic acid is reacted in a solvent such as toluene in the presence of an esterification catalyst to obtain the above ester (2). [

Synthesis of [Formula]] The optically active carboxylic acid () is converted into acid chloride using thionyl chloride or the like, and then reacted with 4'-hydroxybiphenyl-4-carboxylic acid in the presence of pyridine to obtain the above ester (). [

Synthesis of [Formula]] Obtained by tosylating 4'-hydroxybiphenyl-4-carboxylic acid ethyl ester and optically active alcohol ()

[Formula] is reacted in the presence of potassium carbonate etc. to obtain an ether form. This ether form is reacted with an aqueous alkali solution etc. to hydrolyze the ester of the protective group,
The above compound () is obtained. (4) R ¹ is

[Formula] If R ¹ in (2) above is In the method of synthesizing a monomer, the compound ()

instead of [expression] Compound()

Using [Formula] and reacting in the same manner as above, the following desired monomer () is obtained. Here, the above compound () can be obtained as follows. [

Synthesis of [Formula]] In the synthesis of compound () in (1) above, p-hydroxybenzoic acid was used instead of 4'-hydroxybiphenyl-4-carboxylic acid, and the same reaction was carried out to obtain the above ester form. (
). [

Synthesis of [Formula]] In the synthesis of compound () in (1) above, hydroquinone was used instead of biphenyl-4,4'-diol, and the same reaction was carried out,
The above ester compound () is obtained. [

Synthesis of [Formula]] In the synthesis of compound () in (1) above, hydroquinone was used instead of biphenyl-4,4'-diol, and the same reaction was carried out,
The above ether form () is obtained. (5) R ¹ is

[Formula] As shown in the reaction formula below, R ¹ in (3) above is In the synthesis of a monomer, the compound (
)

compound () instead of [formula]

A similar reaction is carried out using [Formula], and the desired monomer of the following general formula (
). Here, the above compound () can be obtained as follows. [

Synthesis of [Formula]] In the synthesis of compound () in (3) above, a similar reaction is carried out using terephthalic acid instead of biphenyl-4,4'-dicarboxylic acid,
The above ester compound () is obtained. [

Synthesis of [Formula]] In the synthesis of compound () in (3) above, p-hydroxybenzoic acid was used instead of 4'-hydroxybiphenyl-4-carboxylic acid to carry out the same reaction, and the above ester form ( )
get. R ₃ COOH () → R ³ COCl [

Synthesis of [Formula]] In the synthesis of compound () in (3) above, a similar reaction is carried out using p-hydroxybenzoic acid ethyl ester instead of 4'-hydroxybiphenyl-4-carboxylic acid ethyl ester, The above ether form () is obtained. (6) R ¹ is If R ¹ in (2) above is In the synthesis of the monomer, 4'-hydroxybiphenyl-4-carboxylic acid ethyl ester was used instead of p-hydroxybenzoic acid ethyl ester, and the compound ()

The above instead of [formula] Compound ()

A similar reaction is carried out using [Formula] to obtain the desired monomer () of the following general formula. (7) R ¹ is If R ¹ in (3) above is In the synthesis of the monomer, biphenyl-4,4'-diol is used instead of hydroquinone, and the compound ()

before instead of [expression] Compound ()

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the scope of the present invention is not limited in any way by these Examples. The structure of the obtained polymer was determined by NMR, IR,
This was confirmed by elemental analysis, and the phase transition temperature was measured and the phase was confirmed by DSC and polarized light microscopy, respectively. (glass: glass state, Cry: crystalline state, S ₁ : unidentified smectic phase (liquid crystal phase but does not respond to electrolysis), SmC ^* : chiral smectic phase C phase, SmA: smectic A phase, N : nematic phase, N ^* : chiral nematic phase, Iso: isotropic phase, the number of phase transition behavior represents the phase transition temperature in °C.) The electric field response speed was measured as follows. Measurement of electric field response speed: Sandwich the polymer between two 20 x 10 mm ITO substrates, adjust the thickness to 25 μm with a spacer, apply an AC electric field E = 2 x 10 ⁶ V/m, and measure the amount of transmitted light at that time. The response time of the change (0→90%) was measured. Example 1 (1) Synthesis of 4'-hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester 4'-hydroxybiphenyl-4-carboxylic acid
93 mmol (20 g) and (S)-(-)-2-
467 mmol (41 g) of methylbutanol was refluxed in 150 ml of benzene in the presence of 2 ml of concentrated sulfuric acid for 25 hours while removing water. After concentrating the reaction solution,
Recrystallized from a toluene-hexane mixed solvent to obtain 26.0 g of the desired ester [mp116-117.8,
[α] ²³ _D = +4.35° (CHCl ₃ )] was obtained. (Yield 98%) (2) Synthesis of 10-chloro-1-decene Add 10 pyridine to 26.0 g of 9-decen-1-ol.
Added drops and placed in an eggplant flask. 24.0 g of thionyl chloride was added dropwise under ice cooling. After dropping, at 70℃
The reaction was carried out for 8.5 hours. After the reaction, the mixture was diluted with dichloromethane and washed with an aqueous potassium carbonate solution.
After drying over magnesium sulfate, it was concentrated under reduced pressure. The residue was purified by column chromatography to obtain 27.7 g of 10-chloro-1-decene.
(Yield 95%) (3) 4'-(9-decenyloxy)biphenyl-4
-Synthesis of carboxylic acid 2-methylbutyl ester 2.5 g of 10-chloro-1-decene obtained in (2) and 6.5 g of sodium iodide were dissolved in 2-butanone and stirred at 80°C for 17 hours. After the reaction, it was diluted with dichloromethane and washed with water. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure. to the residue
4.8 g of 4'-hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester obtained in (1) and 2.4 g of potassium carbonate were added, and the mixture was heated to 80°C in 2-butanone.
The reaction was carried out for 20 hours. After the reaction, inorganic substances were removed by filtration, concentrated under reduced pressure, and purified by column chromatography to obtain 4.6 g of the desired biphenyl derivative. (Yield 76%) (4) Oxiranization 3.0 g of the biphenyl derivative obtained in (3) and 1.5 g of m-chloroperbenzoic acid were dissolved in dichloromethane, the system was purged with argon, and then stirred at room temperature for 1 day. After the reaction, the mixture was washed with an aqueous potassium carbonate solution and further washed with water. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 3.0 g of the desired monomer represented by the following formula. (yield 97%) (5) Polymerization Add 0.5 g of the monomer obtained in (4) to 5 ml of dichloromethane.
ml and the system was purged with argon. 0.03 g of stannic chloride was added, and a polymerization reaction was carried out at room temperature for 6 days. After the reaction, the reaction solution was poured into methanol. The resulting precipitate is purified by repeating reprecipitation,
0.4 g of the desired polyoxirane (Mn=1700) having a repeating unit represented by the following formula was obtained.
(yield 80%) Number average molecular weight, phase transition behavior, and
The electric field response speed is shown in the table, and the chart of ¹ H-NMR analysis is shown in Figure 1. Example 2 (1) Synthesis of 12-chloro-1-dodecene Same as Example 1 (2) except that 6.0 g of 11-dodecen-1-ol was used instead of 9-decen-1-ol. By performing the above operation, 5.2 g of 12-chloro-1-dodecene was obtained. (Yield 79%) (2) 4′-(11-dodecenyloxy)biphenyl-
Synthesis of 4-carboxylic acid 2-methylbutyl ester Obtained in (1) instead of 10-chloro-1-decene
The same operation as in Example 1 (3) was performed except that 5.2 g of 12-chloro-1-dodecene was used.
8.8 g of the desired biphenyl derivative was obtained. (Yield 76%) (3) Oxiranization 8.8 g of the biphenyl derivative obtained in (2) was subjected to the same operation as in (4) of Example 1 to obtain 8.8 g of a monomer represented by the following formula. . (Yield 95%) (4) Polymerization 2.3 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane (Mn= 1500) 1.5g was obtained. (yield 65%) Number average molecular weight, phase transition behavior, and
The electric field response speed is shown in the table, and the chart of ¹ H-NMR analysis is shown in Figure 2. Example 3 (1) 4'-(7-octenyloxy)biphenyl-
Synthesis of 4-carboxylic acid 2-methylbutyl ester 8-bromo-1-octene 5.0 g, Example 1
8.2 g of 4'-hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester obtained in (1) and 4.0 g of potassium carbonate were refluxed in acetone for 20 hours. After the reaction, add dichloromethane to dilute,
Inorganics were removed by filtration. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 7.5 g of the desired biphenyl derivative. (Yield 73%) (2) Oxiranization 7.4 g of the biphenyl derivative obtained in (1) was subjected to the same operation as in (4) of Example 1 to obtain 7.6 g of a monomer represented by the following formula. . (Yield 99%) (3) Polymerization 2.05 g of the monomer obtained in (2) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane (Mn= 1600) 1.4g was obtained. (yield 68%) Number average molecular weight, phase transition behavior, and
The electrolytic response speed is shown in the table, and the chart of ¹ H-NMR analysis is shown in Figure 3. Example 4 (1) Synthesis of p-(9-decenyloxy)benzoic acid 10-chloro-1-decene obtained in Example 1 10.0
g and 25 g of sodium iodide were reacted in 2-butanone at 80° C. for 10 hours to iodize. After washing with water, drying, and removing the solvent, 11.5 g of p-hydroxybenzoic acid ethyl ester and 9.6 g of potassium carbonate were added, and the mixture was refluxed in absolute ethanol for 15 hours. An aqueous potassium hydroxide solution (containing 4.0 g of potassium hydroxide) was added, and the mixture was further heated at 80° C. for 5 hours. After the reaction, the mixture was acidified with hydrochloric acid and concentrated under reduced pressure. Add water to the residue to suspend it, collect the insoluble matter and dry it to obtain p-(9-decenyloxy)
9.5 g of benzoic acid was obtained. (Yield 60%) (2) Synthesis of 4'-[p-(9-decenyloxy)benzoyloxy]biphenyl-4-carboxylic acid 2-methylbutyl ester p-(9-decenyloxy)benzoin obtained in (1) Toluene was added to the acid and cooled on ice. Thionyl chloride
5.0g was dropped. The reaction was carried out at 80°C for 7 hours. After the reaction, the reaction mixture was concentrated under reduced pressure to obtain crude p-decenyloxybenzoic acid chloride. 12.0 g of 4'-hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester obtained in (1) of Example 1 and 3.3 g of pyridine were dissolved in toluene and cooled on ice.
The above toluene solution of crude p-decenyloxybenzoic acid chloride was added dropwise thereto. The reaction was carried out at 50°C for 5 hours. After the reaction, the mixture was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 9.3 g of the desired ester.
(Yield 50%) (3) Example 1 was added to 9.0 g of the ester obtained in oxirane formation (2).
The same operation as in (4) was performed to obtain 8.5 g of a monomer represented by the following formula. (Yield 92%) (4) Polymerization 5.6 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane (Mn= 1800) 3.1g was obtained. (yield 55%) Number average molecular weight, phase transition behavior, and
The electrolytic response speed is shown in the table, and the chart of ¹ H-NM8 analysis is shown in Figure 4. Example 5 (1) Synthesis of p-hydroxybenzoic acid 2-methylbutyl ester 40 g of p-hydroxybenzoic acid and (-)-
125 g of 2-methylbutanol in the presence of sulfuric acid,
It was refluxed in toluene for 6 hours while removing water. Next, the reaction solution was washed with water to remove sulfuric acid. After that, drying, concentration, and purification by column chromatography are performed to obtain the desired ester.
50g [Liquid at room temperature, [α] ²³ _D = +4.9° (CHCl ₃ )]
I got it. (Yield 83%) (2) Synthesis of 4-[4'-(9-decenyloxy)benzoyloxy]benzoic acid 2-methylbutyl ester p-(9- Toluene was added to 19 g of decenyloxybenzoic acid and cooled on ice. Furthermore, 13 g of thionyl chloride was added dropwise under ice cooling. After the dropwise addition, the reaction was carried out at 80°C for 7 hours. After the reaction, the reaction solution was concentrated to remove the acid chloride. On the other hand, 18 g of 4-hydroxybenzoic acid 2-methylbutyl ester obtained in (1) and 7 g of pyridine were dissolved in toluene and cooled on ice. A toluene solution of the above acid chloride was added dropwise thereto. After the dropwise addition, the reaction was carried out at 50°C for 5 hours. After the reaction, the product is washed with water, dried over magnesium sulfate, and purified by column chromatography to obtain the desired ester.
23.5g was obtained. (Yield 72%) (3) For 15 g of the ester obtained in oxirane formation (2), the
The same operation as in (4) was performed to obtain 14.7 g of a monomer represented by the following formula. (Yield 94%) (4) Polymerization 14.7 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane (Mn= 1600) 7.3g was obtained. (yield 50%) Number average molecular weight, phase transition behavior, and
The electrolytic response speed is shown in the table, and the chart of ¹ H-NMR analysis is shown in Figure 5. Example 6 (1) Synthesis of p-hydroxybenzoic acid 1-methylpropyl ester 25 g of p-acetoxybenzoic acid was suspended in toluene and cooled on ice. There, 22g of thionyl chloride
was dripped. The mixture was reacted at 80°C for 4 hours. After the reaction, the mixture was concentrated under reduced pressure to obtain an acid chloride. 8.0 g of (+)-2-butanol and 12 g of pyridine were dissolved in toluene and cooled on ice. The toluene solution of the acid chloride obtained earlier was added dropwise thereto. The mixture was reacted at 50°C for 8 hours. After the reaction, the mixture was washed with water, dried, and concentrated under reduced pressure. The residue was dissolved in ether and cooled on ice. 9.5 g of benzylamine was added thereto, and the mixture was stirred at room temperature for 2 hours. After the reaction, the reaction solution was washed with water, dried, and concentrated under reduced pressure. The residue was purified by column chromatography to obtain the desired ester.
14.2g [Liquid at room temperature, [α] ²³ _D = +29.6° (CHCl ₃ )]
I got it. (Yield 68%) (2) Synthesis of 4-[4'-(9-decenyloxy)benzoyloxy]benzoic acid 1-methylpropyl ester p-(9- Toluene was added to 13.5 g of decenyloxybenzoic acid and cooled on ice. 9 g of thionyl chloride was added dropwise thereto. The reaction was carried out at 80°C for 7 hours. After the reaction, the reaction solution was concentrated to obtain an acid chloride. On the other hand, 10 g of 4-hydroxybenzoic acid 1-methylpropyl ester obtained in (1) and 4 g of pyridine were dissolved in toluene and cooled on ice. A toluene solution of the above acid chloride was added dropwise thereto. Next, the reaction was carried out at 50°C for 5 hours. After the reaction,
After washing the product with water and drying over magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 14.4 g of the desired ester. (Yield 65%) (3) Example 1 was added to 14.4 g of the ester obtained in oxirane formation (2).
The same operation as in (4) was performed to obtain 13.4 g of a monomer represented by the following formula. (yield 90%) (4) Polymerization 13.4 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane (Mn= 1700) 7.5g was obtained. (yield 56%) Number average molecular weight, phase transition behavior, and
The electrolytic response speed is shown in the table, and the chart of ¹ H-NMR analysis is shown in Figure 6. Example 7 (1) Synthesis of p-hydroxybenzoic acid 1-methylbutyl ester Thionyl chloride was added to 25 g of p-acetoxybenzoic acid.
25g was dropped. The mixture was heated to 80°C and reacted for 3 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride. This acid chloride was dissolved in toluene and cooled on ice. There, (-)-2-pentanol 10.2g, pyridine
A toluene solution containing 11 g was added dropwise. Then,
Stir overnight at room temperature. After the reaction, the solution was washed with water, dried, and concentrated under reduced pressure. The residue was dissolved in ether. 18 g of benzylamine was added dropwise thereto.
The mixture was stirred for 1 hour at room temperature. After the reaction, the product was washed with water, dried, and concentrated under reduced pressure. The residue was purified by column chromatography to obtain the desired ester [liquid at room temperature, [α] ²³ _D = −
20.3 g of 27.3° (CHCl ₃ ) was obtained. (Yield 86%) (2) Synthesis of 4-[4'-(9-decenyloxy)benzoyloxy]benzoic acid 1-methylbutyl ester p-(9- Toluene was added to 6.3 g of decenyloxybenzoic acid and cooled on ice. 4.0 g of thionyl chloride was added dropwise thereto. The reaction was carried out at 80°C for 7 hours. After the reaction, the reaction solution was concentrated to obtain an acid chloride. On the other hand, 5.0 g of 4-hydroxybenzoic acid 1-methylbutyl ester obtained in (1) and 1.9 g of pyridine were dissolved in toluene and cooled on ice. A toluene solution of the above acid chloride was added dropwise thereto. 50
The reaction was carried out at ℃ for 5 hours. After the reaction, the product was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 8.0 g of the desired ester. (Yield 75%) (3) Example 1 was added to 8.0 g of the ester obtained in oxirane formation (2).
The same operation as in (4) was performed to obtain 7.8 g of a monomer represented by the following formula. (Yield 94%) (4) Polymerization 7.8 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane (Mn= 1600) 4.7g was obtained. (yield 60%) Number average molecular weight, phase transition behavior, and
The electrolytic response speed is shown in the table, and the chart of ¹ H-NMR analysis is shown in Figure 7. Example 8 (1) Synthesis of p-hydroxybenzoic acid 1-methylheptyl ester Thionyl chloride was added to 32 g of p-acetoxybenzoic acid.
32g was dropped. The mixture was heated to 80°C and reacted for 3 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride. This acid chloride was dissolved in toluene and cooled on ice. There, 25 g of (-)-2-octanol, 16 g of pyridine
A toluene solution containing g was added dropwise. The mixture was stirred at room temperature overnight. After the reaction, the solution was washed with water, dried, and concentrated under reduced pressure. The residue was dissolved in ether. 21 g of benzylamine was added dropwise thereto. The mixture was stirred for 1 hour at room temperature. After the reaction, the product was washed with water, dried, and concentrated under reduced pressure. The residue was purified by column chromatography to obtain 39.3 g of the desired ester [liquid at room temperature, [α] ²³ _D = -33.8° (CHCl ₃ )]. (yield
(83%) (2) Synthesis of 4-[4'-(9-decenyloxy)benzoyloxy]benzoic acid 1-methylheptyl ester p-(9-decenyloxy)benzoic acid obtained in the same manner as in Example 4 (1) Toluene was added to 9.4 g of acid and cooled on ice. 6.0 g of thionyl chloride was added dropwise to the mixture. Next, the reaction was carried out at 80°C for 7 hours. After the reaction, the product was concentrated to obtain an acid chloride. On the other hand, 7.7 g of 4-hydroxybenzoic acid 1-methylheptyl ester obtained in (i) and 2.7 g of pyridine were dissolved in toluene and cooled on ice.
A toluene solution of the above acid chloride was added dropwise thereto. Next, the reaction was carried out at 50°C for 5 hours. After the reaction, the product was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 10.5 g of the desired ester. (yield
67%) (3) Example 1 was added to 10.5 g of the ester obtained in oxirane formation (2).
The same operation as in (4) was performed to obtain 9.7 g of a monomer represented by the following formula. (yield 90%) (4) Polymerization 9.7 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane (Mn= 1750) 6.8g was obtained. (yield 70%) Number average molecular weight, phase transition behavior, and
The electric field response speed is shown in the table, and the chart of ¹ H-NMR analysis is shown in Figure 8. Example 9 (1) Synthesis of 4-[4'-(9-decenyloxy)biphenyl-4-carbonyloxy]benzoic acid 2-methylbutyl ester 4'-(9-decenyloxy)biphenyl-4
-Toluene was added to 5.0 g of carboxylic acid and cooled on ice. 2.6 g of thionyl chloride was added dropwise to the mixture.
Next, the reaction was carried out at 80°C for 7 hours. After the reaction, the product was concentrated to obtain an acid chloride. 4-hydroxybenzoic acid 2- obtained in Example 5 (1)
3.1g methylbutyl ester and 1.5g pyridine
g was dissolved in toluene and cooled on ice. There,
A toluene solution of the above acid chloride was added dropwise. Next, the reaction was carried out at 50°C for 5 hours. After the reaction, the product was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 5.5 g of the desired ester. (Yield 72%) (2) Oxirane formation Example 1 was added to 5.5 g of the ester obtained in (1).
The same operation as in (4) was performed to obtain 5.2 g of a monomer represented by the following formula. (Yield 91%) (3) Polymerization 5.2 g of the monomer obtained in (2) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane (Mn= 1570) 3.6g was obtained. (yield 70%) Number average molecular weight, phase transition behavior, and
The electric field response speed is shown in the table, and the chart of ¹ H-NMR analysis is shown in Figure 9. Example 10 (1) Synthesis of p-hydroxybenzoic acid 2-fluorooctyl ester 11 g of thionyl chloride was added dropwise to 5.4 g of p-acetoxybenzoic acid. Heat the mixture to 80℃ and
Allowed time to react. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride. This acid chloride was dissolved in toluene and cooled on ice. There, 4.4 g of (-)-2-fluorooctanol,
A toluene solution containing 3 g of pyridine was added dropwise.
The mixture was stirred at room temperature overnight. After the reaction, the solution was washed with water, dried, and concentrated under reduced pressure. The residue was dissolved in ether. There, benzylamine 10
g was added dropwise. The mixture was stirred for 5 hours at room temperature. After the reaction, the product was washed with water, dried, and concentrated under reduced pressure. The residue was purified by column chromatography to obtain 4.9 g of the desired ester. (Yield 73%) (2) Synthesis of 4-[4'-(9-decenyloxy)benzoyloxy]benzoic acid 2-fluorooctyl ester p-(9- Toluene was added to 3.0 g of decenyloxybenzoic acid and cooled on ice. 2.0 g of thionyl chloride was added dropwise to the mixture. Next, a reaction was carried out at 80°C for 3 hours. After the reaction, the product was concentrated to obtain an acid chloride. On the other hand, 1.7 g of 4-hydroxybenzoic acid 2-fluorooctyl ester obtained in (1) and 0.9 g of pyridine were dissolved in toluene and cooled on ice.
A toluene solution of the above acid chloride was added dropwise thereto. Next, the reaction was carried out at room temperature for 15 hours. After the reaction, the product was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 2.9 g of the desired ester. (yield 88
%) (3) Example 1 was added to 2.9 g of the ester obtained in oxirane conversion (2).
The same operation as in (4) was performed to obtain 2.7 g of a monomer represented by the following formula. (Yield 91%) (4) Polymerization 2.7 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane (Mn= (1960) obtained 2.1 g. (yield 78%) Number average molecular weight, phase transition behavior, and
The electric field response speed is shown in the table, and the chart of ¹ H-NMR analysis is shown in Figure 10. Example 11 (1) 4'-(5-hexenyloxy)biphenyl-
Synthesis of 2-methylbutyl 4-carboxylate 4.7 g of 6-bromo-1-hexene, 6.3 g of 2-methylbutyl 4'-hydroxybiphenyl-4-carboxylate, and 3.1 g of potassium carbonate.
g was refluxed in 2-butanone for 20 hours. After the reaction, inorganic salts were removed by washing with water. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 6.4 g of the desired ester. (Yield 79%) (2) Oxirane conversion Example 1 was added to 2.0 g of the ester obtained in (1).
The same operation as in (4) was performed to obtain 2.0 g of a monomer represented by the following formula. (yield 95%) (3) Polymerization 2.0 g of the monomer obtained in (2) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane (Mn= 1700) 1.0g was obtained. (yield 50%) Number average molecular weight, phase transition behavior, and
The electric field response speed is shown in the table, and the chart of ¹ H-NMR analysis is shown in Figure 11. Example 12 (1) Synthesis of p-(7-octenyloxy)benzoic acid 9.4 g of 8-bromo-1-octene, 9.0 g of ethyl p-hydroxybenzoate, and 7.6 g of potassium carbonate were refluxed in ethanol for 10 hours. did.
After the reaction, an aqueous solution containing 2.4 g of sodium hydroxide was added thereto, and the mixture was further refluxed for 10 hours. After the reaction, dilute with water and add hydrochloric acid dropwise to adjust the pH to 2.
And so. The resulting precipitate was collected, thoroughly washed with water, and then dried to obtain 10.8 g of the desired ether. (Yield 89%) (2) Synthesis of 4-[p-(7-octenyloxy)benzoyloxy]biphenyl-4-carboxylic acid 2-methylbutyl ester 1.8 g of oxy)benzoic acid was suspended in toluene and cooled on ice.
1.3 g of thionyl chloride was added dropwise thereto. After dripping,
The temperature was raised and the reaction was carried out at 80°C for 3 hours. After the reaction,
The acid chloride compound was obtained by concentration under reduced pressure. Toluene was added thereto to make a toluene solution, which was cooled on ice. A toluene solution containing 2.0 g of 4'-hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester and 0.7 g of pyridine was added dropwise to the above toluene solution of acid chloride. After the dropwise addition, the temperature was raised and the mixture was reacted at 50°C for 8 hours. After the reaction, the product was washed with water, dried over magnesium sulfate, and then concentrated under reduced pressure. The residue was recrystallized from ethanol to obtain 2.5 g of the desired ester. (Yield: 69) (3) Oxiranization 2.5 g of the ester obtained in (2) was oxidized with 1.0 g of m-chloroperbenzoic acid in the same manner as in (4) of Example 1, resulting in a compound expressed by the following formula. 2.4 g of monomer was obtained. (yield 95%) (4) Polymerization 2.4 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane (Mn= 1920) 1.5g was obtained. (yield 62%) Number average molecular weight, phase transition behavior, and
The electric field response speed is shown in the table, and the chart of ¹ H-NMR analysis is shown in Figure 12. Example 13 (1) Synthesis of p-hydroxybenzoic acid 2-chloro-3-methylpentyl ester 32 g of thionyl chloride was added dropwise to 24 g of p-acetoxybenzoic acid. Heat the mixture to 80℃ and
Allowed time to react. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride. This acid chloride was dissolved in toluene and cooled on ice. A toluene solution containing 13.7 g of (-)-2-chloro-3-methylpentanol and 14 g of triethylamine was added dropwise thereto. The mixture was stirred at room temperature overnight. After the reaction, the solution was washed with water, dried, and concentrated under reduced pressure. The residue was dissolved in ether. 17 g of benzylamine was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. After the reaction, washing with water, drying, and concentration were performed. The residue was purified by column chromatography to obtain 20.3 g of the desired ester.
[[α] ²³ _D = +11.6° (CHCl ₃ )] was obtained. (yield 79
%) (2) Synthesis of 4-[4'-9-decenyloxy)benzoyloxy]benzoic acid 2-chloro-3-methylpentyl ester p-(9-decenyloxy) obtained in the same manner as in Example 4 (1) ) Toluene was added to 4.1 g of benzoic acid and cooled on ice. 6.0 g of thionyl chloride was added dropwise.
The reaction was carried out at 80°C for 7 hours. After the reaction, the reaction solution was concentrated to obtain an acid chloride. p− obtained in (1)
3.8 g of hydroxybenzoic acid 2-chloro-3-methylpentyl ester and 2.5 g of pyridine were dissolved in toluene and cooled on ice. A toluene solution of the above acid chloride was added dropwise thereto. The reaction was carried out at room temperature for 15 hours. After the reaction, the reaction solution was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 5.9 g of the desired ester. (Yield 77%) (3) Example 1 was added to 2.6 g of the ester obtained in oxirane formation (2).
The same operation as in (4) was performed to obtain 2.5 g of a monomer represented by the following formula. (yield 93%) (4) Polymerization 2.5 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane (Mn= 1300) 2.1g was obtained. (yield 88%) Number average molecular weight, phase transition behavior, and
The electric field response speed is shown in the table, and the chart of ¹ H-NMR analysis is shown in Figure 13. Example 14 (1) 4'-(9-decenyloxy)biphenyl-4
-Synthesis of carboxylic acid 2-chloro-3-methylpentyl ester 4'-(9-decenyloxy)biphenyl-4
-Toluene was added to 4.0 g of carboxylic acid and cooled on ice. Thereto, 2.0 g of thionyl chloride was added dropwise.
The reaction was carried out at 80°C for 7 hours. After the reaction, the reaction solution was concentrated to obtain an acid chloride. 2-chloro-
1.7g of 3-methylpentanol and pyridine
1.0g was dissolved in toluene and cooled on ice. A toluene solution of the above acid chloride was added dropwise thereto. The reaction was carried out at room temperature for 15 hours. After the reaction,
The reaction solution was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 4.1 g of the desired ester. (Yield 76%) (2) Oxirane formation Example 1 was added to 4.1 g of the ester obtained in (1).
The same operation as in (4) was performed to obtain 4.0 g of a monomer represented by the following formula. (yield 95%) (3) Polymerization 4.0 g of the monomer obtained in (2) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane (Mn= 1570) 3.2g was obtained. (yield 80%) Number average molecular weight, phase transition behavior, and
The electric field response speed is shown in the table, and the chart of ¹ H-NMR analysis is shown in Figure 14.

【table】

【table】

[Table] Explanation of abbreviations
glass: glass state SmA: smectic A phase
Cry: Crystalline state N ^* : Chiral nematic phase
S ₁ : Unidentified smektic phase N:
nematic phase
SmC ^* : Chiral smectic C phase Iso: Isotropic phase [Effects of the invention] The liquid crystal polymer of the present invention is colorless, exhibits ferroelectricity even at room temperature, and has a fast response speed to external factors. It is possible to display moving images, and it can also be advantageously used as a display element for large screens or curved screens, and is useful as various electro-optical biases in the field of optoelectronics, and has great industrial value.

[Brief explanation of drawings]

Figures 1 to 14 represent charts of ¹ H-NMR analysis of the liquid crystal polymers obtained in Examples 1 to 14, respectively.

[Claims]

1 (A) A polymer having a repeating unit consisting of the following general formula and having a number average molecular weight of more than 2,000 and less than 400,000 (In the formula, k is an integer from 1 to 30, and R ¹ is

【formula】

【formula】

[expression] or

[Formula], X is -COO- or -OCO-, R ² is -COOR ³ , -OCOR ³ or -OR ³

Claims (1)

R ³ is [Formula], R ⁴ and R ⁵ are each -CH ₃ , a halogen atom, or -CN, m and n are integers from 0 to 10, provided that R ⁴
When is _-CH3 , n is not 0, p is 0 or 1, and C marked with * is an asymmetric carbon atom. )