JP2765942B2 - Liquid crystalline polymer and epoxy compound used for its production - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel liquid crystalline polymer and an epoxy compound which is a monomer used for producing the same. More specifically, the present invention relates to the field of optoelectronics, in particular, display devices such as calculators and watches, electro-optical shutters, electro-optical apertures, optical modulators, optical communication optical path switching switches, memories, liquid crystal printer heads, focal length variable lenses, and the like. Useful as various electro-optical devices,
In addition to exhibiting ferroelectricity even at around room temperature, it has a high response speed to external factors, can display moving images, and can be used advantageously as a display element for large screens and curved screens, and is used for the production thereof. The present invention relates to an epoxy compound as a monomer to be obtained.

[Conventional technology]

Conventionally, display devices using low-molecular liquid crystals have been widely used for digital displays such as calculators and watches. In these applications, the conventional low-molecular liquid crystal is usually used between two glass substrates whose interval is controlled on the order of microns. However, such a gap adjustment cannot be realized on a large screen or a curved screen. One way to solve this difficulty is to polymerize the liquid crystal so that it can be molded (J.
Polym.Sci., Polym.Lett., Ed. 13, 243 (1975), Polym.Bul
l, 6 , 309 (1982), JP-A-55-21479, etc.).

However, these liquid crystalline polymers have the disadvantage that the polymers themselves do not exhibit liquid crystal properties at room temperature and must be heated to a liquid crystal temperature above the glass transition temperature and below the clearing temperature to form a liquid crystal. .

Japanese Patent Application Laid-Open No. 63-99204 reports the synthesis of a polyacrylate-based ferroelectric liquid crystal polymer, and it has been clarified that the polyacrylate exhibits higher performance than the above liquid crystal polymer. However, even with these liquid crystalline polymers, problems still remain in the response speed and the usable temperature range.

[Problems to be solved by the invention]

An object of the present invention is to provide a liquid crystalline polymer which exhibits ferroelectricity in a wide temperature range including a room temperature range and which responds rapidly to an external factor, particularly an electric field, in a wide temperature range. . That is, an object of the present invention is to provide a novel liquid crystalline polymer which enables display of moving images and production of large and curved screens when used as a display element.

A second object of the present invention is to provide an epoxy compound which is a monomer used for producing such a liquid crystalline polymer.

[Means for solving the problem]

The present inventors have conducted intensive studies, and as a result, have found that a polyether polymer having a specific structure exhibits ferroelectricity near room temperature, and have completed the present invention.

That is, the present invention provides a liquid crystalline polymer having a repeating unit represented by the following general formula.

(Where k is an integer of 2 to 30, R ¹ is In, X is -COO- or -OCO-, R ² is -COOR ^3, a -OCOR ³ or -OR ^3, R ³ is R ⁴ and R ⁵ are each —CH ₃ , a halogen atom, or —CN; m and n are each an integer of 0 to 10, provided that R ⁴ is —
In the case of CH ₃ , n is not 0, p is 0 or 1, and C marked with * is an asymmetric carbon atom. The number average molecular weight of the liquid crystalline polymer of the present invention is preferably 1,000 to 400,000. If it is less than 1,000, the formability as a liquid crystalline polymer film or coating film may be hindered. On the other hand, if it exceeds 400,000, undesired effects such as a slow response speed may appear. The particularly preferred range of number average molecular weight type of R ^1, the value of k, can not generally be defined since it depends on the optical purity of R ^3, it is usually 1,000 to 200,000.

k is an integer of 2 to 30, more preferably 4 to 20. m and n are each an integer of 0 to 10, more preferably 0 to 6.

Hereinafter, a general method for synthesizing the liquid crystalline polymer of the present invention will be described.

For example, the liquid crystalline polymer of the present invention can be synthesized using the epoxy compound according to the second aspect of the present invention. That is, the liquid crystalline polymer of the present invention has the following general formula: (Where k, X, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , m, n, and p
Has the same meaning as defined above. ) Can be obtained by polymerizing a monomer that is an epoxy compound represented by the formula (1) by a known method.

The epoxy compound as the above monomer can be obtained, for example, as follows.

(1) R ¹ As shown in the following reaction formula, allyl alcohol and α, ω-dihaloalkane (I) are dissolved in a solvent such as hexane, and a 50% aqueous sodium hydroxide solution or a phase transfer catalyst such as tetrabutylammonium bromide is used. And etherification is performed to obtain ω-haloalkylallyl ether (II). Alternatively, ω-haloalkyl allyl ether (II) is obtained by dissolving allyl alcohol and α, ω-dihaloalkane (I) in a solvent such as tetrahydrofuran (THF) and adding sodium hydride to carry out etherification. Obtained ω-
Haloalkyl allyl ether (II) and compound (III) are reacted in a suitable solvent such as 2-butanone in the presence of an alkali such as potassium carbonate to obtain an allyl ether compound (IV). Then, the allyl ether compound (IV) is epoxidized with a peracid such as m-chloroperbenzoic acid in a suitable solvent such as dichloromethane to obtain the desired epoxy compound (V).

(In the formula, Y is a halogen.) As α, ω-dihaloalkane (I), for example, 1,4
-Dibromobutane, 1,6-dibromohexane, 1,8-dibromooctane, 1,10-diiododecane, 1,12-dibromododecane, 1,14-dibromotetradecane and the like are preferably used.

Here, the compound (III) Can be synthesized as follows.

As shown in the following reaction formula, 4'-hydroxybiphenyl-4-carboxylic acid and an optically active alcohol (VI) are converted into an esterification catalyst such as concentrated sulfuric acid or p-toluene in a suitable solvent such as benzene. The ester compound (VII) is obtained by reacting at a desired temperature in the presence of sulfonic acid or the like.

Examples of the optically active alcohol (VI) 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, (+)-1-methylheptanol, (-)-1-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 or the like is used.

Preferably, (-)-2-methylbutanol, (+)
-2-butanol, (-)-2-pentanol, (-)
-2-octanol, (-)-2-fluorooctanol, (-)-2-fluorohexanol, and (-)-
2-Chloro-3-methylpentanol is used.

As shown in the following reaction formula, this ester compound (IX) can be obtained by reacting biphenyl-4,4'-diol with an optically active carboxylic acid (VIII).

As the optically active carboxylic acid (VIII), for example,
(+)-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-chloro-3-methylpentanoic acid, (−)-2-chloro-3
-Methylpentanoic acid and the like are used.

As shown in the following reaction formula, the above-mentioned optically active alcohol [VI] is tosylated, and biphenyl-4,4'-
The ether compound (X) is obtained by reacting with a diol.

(2) R ¹ As shown in the following reaction formula, ω-haloalkyl allyl ether (II) 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 form an ether. Get the body. Then
The protecting group of the carboxyl group in this ether compound is eliminated with an aqueous solution of potassium hydroxide, hydrochloric acid or the like to obtain a carboxylic acid compound. A halogenating agent such as thionyl chloride is added to the carboxylic acid compound, and the mixture is heated in a solvent such as toluene to obtain an acid halide. Next, the acid halide and the compound (II
I) is reacted with a solvent such as toluene in the presence of pyridine to obtain an allyl ether compound (XI), and then using a peracid such as m-chloroperbenzoic acid in a suitable solvent such as dichloromethane. Epoxidation gives the desired epoxy compound (XII).

(3) R ¹ As shown in the following reaction formula, the ω-haloalkyl allyl ether (II) is reacted with hydroquinone in the presence of an alkali such as potassium carbonate to obtain an ether compound (XIII).

The following compound (XIV) is acid chlorided with thionyl chloride or the like. The obtained acid chloride is reacted with the ether form (XIII) in the presence of pyridine to give an allyl ether form (XV)
Get. Thereafter, epoxidation is carried out in the same manner as in (1) to obtain the desired epoxy compound (XVI).

Here, the compound (XIV) Is obtained as follows.

The optically active alcohol (VI) is reacted with biphenyl-4,4'-dicarboxylic acid in a solvent such as toluene in the presence of an esterification catalyst to obtain the ester (XVII).

After optically active carboxylic acid (VIII) is acid chlorided with thionyl chloride or the like, 4'-hydroxybiphenyl-4
And reacting with carboxylic acid in the presence of pyridine to obtain the ester (XVIII).

Obtained by tosylating 4'-hydroxybiphenyl-4-carboxylic acid ethyl ester and optically active alcohol (VI). Is reacted in the presence of potassium carbonate or the like to obtain an ether compound. The ether compound is reacted with an aqueous alkali solution or the like to hydrolyze the ester of the protecting group to obtain the above compound (XIX).

(4) R ¹ When R ^{1 in the} above (2) is In the method for synthesizing an epoxy compound which is
I) Instead of compound (XX) And the other reactions are carried out in the same manner to obtain the following epoxy compound (XXI).

Here, the compound (XX) is obtained as follows.

In the synthesis of compound (VII) in the above (1),
The same reaction is carried out by using p-hydroxybenzoic acid instead of 4'-hydroxybiphenyl-4-carboxylic acid to obtain the above ester (XXII).

In the synthesis of compound (VIII) in the above (1),
The same reaction was carried out using hydroquinone instead of biphenyl-4,4'-diol, and the above ester (XXII
I get.

In the synthesis of compound (X) in the above (1), the same reaction is carried out using hydroquinone instead of biphenyl-4,4'-diol, and the above ether compound (XXIV)
Get.

(5) R ¹ As shown in the following reaction formula, R ^{1 in the} above (3) is Compound (XIV) in the synthesis of the epoxy compound Instead of the compound (XXV) To obtain the desired epoxy compound (XXVI) of the following general formula.

Here, the compound (XXV) is obtained as follows.

In the synthesis of compound (XVII) in the above (3),
The same reaction was carried out using terephthalic acid instead of biphenyl-4,4'-dicarboxylic acid, and the above ester product (XXVI
I get.

In the synthesis of compound (XVIII) in the above (3), the same reaction is carried out using p-hydroxybenzoic acid instead of 4'-hydroxybiphenyl-4-carboxylic acid to obtain the above ester (XXVIII).

In the synthesis of compound (XIV) in the above (3),
The same reaction was carried out by using p-hydroxybenzoic acid ethyl ester instead of 4'-hydroxybiphenyl-4-carboxylic acid ethyl ester, and the above ether (XXIX)
Get.

(6) R ¹ When R ^{1 in the} above (2) is In the synthesis of the epoxy compound of formula (III), 4'-hydroxybiphenyl-4-carboxylic acid ethyl ester is used instead of p-hydroxybenzoic acid ethyl ester, and the compound (III) In place of the above compound (XX) To obtain the desired epoxy compound (XXX) of the following general formula.

(7) R ¹ If R ^{1 in} (3) above is In the synthesis of an epoxy compound, biphenyl-4,4'-diol is used in place of hydroquinone, and compound (XIV) In place of the above compound (XXV) To obtain the desired epoxy compound (XXXI) of the following general formula.

Specific examples of the epoxy compound which is a monomer according to the present invention include those represented by the following structural formula.

Next, one or more monomers thus obtained are polymerized to synthesize the liquid crystalline polymer of the present invention. At this time, a known cationic polymerization method or the like may be employed as the polymerization method. it can.

Various catalysts are known as catalysts for cationic polymerization. Protonic acids such as sulfuric acid, phosphoric acid, and perchloric acid, boron trifluoride, aluminum chloride, titanium tetrachloride, and Lewis such as stannic chloride Acids, boron trifluoride etherate, etc., among which stannic chloride are preferably used.

It is also possible to carry out coordination polymerization using an organic aluminum complex or the like. In this case, the number average molecular weight is 30,0
A liquid crystalline polymer of 00 or more is obtained.

Various polymerization methods such as bulk polymerization, slurry polymerization, and solution polymerization are known, and any of these methods may be used, but solution polymerization is preferred.

The polymerization temperature depends on the type of catalyst and is not uniform,
Usually, 0 to 30 ° C is appropriate.

The polymerization time depends on other factors such as polymerization temperature,
Usually several hours to 6 days.

The molecular weight can be adjusted by adding a known molecular weight modifier and / or adjusting the concentration of the catalyst with respect to the monomer.

In the bulk polymerization method, the monomer and the initiator are sufficiently mixed, the mixture is sufficiently degassed, and introduced between two substrates, for example, a glass substrate, and heated, whereby the liquid crystalline polymer is heated. It can also be directly fixed in a state of being in close contact between the substrates.

As the solvent in the case of slurry polymerization or solution polymerization,
Known inert solvents can be used, and among them, hexane, dichloromethane, or aromatic solvents such as benzene, toluene, and xylene are preferably used.

In addition, in the polymerization reaction and the epoxidation reaction, it is preferable, but not essential, that the system be replaced with an inert gas such as argon or nitrogen.

The liquid crystalline polymer thus obtained can be formed into a film by a known film forming method, for example, a casting method, a T-die, an inflation method, a calendar method, a stretching method, and the like. The liquid crystal polymer in the form of a film is sandwiched between two ordinary glass substrates, a large glass substrate, a curved glass substrate, a polyester film, etc., and is used for liquid crystal displays, electro-optical shutters, electro-optical diaphragms, etc. It can be used in various optoelectronic fields.

Alternatively, a polymer solution dissolved in an appropriate solvent is applied to a substrate surface such as a glass substrate, and the solvent is evaporated, whereby a film can be formed in a state directly adhered to the substrate surface.

Measurement of the phase transition temperature of the liquid crystalline polymer of the present invention confirmed that the chiral smectic C phase liquid crystal state was realized in a wide temperature range including around normal temperature. Also,
It was also confirmed that the response time to an electric field near room temperature was extremely fast, several milliseconds. This indicates that the liquid crystalline polymer of the present invention is a very useful material having a possibility to be used in a wide temperature range including room temperature.

Further, in the liquid crystalline polymer of the present invention, since the properties of the smectic phase liquid crystal and the properties of a typical polymer that are easy to mold are combined, there are many applications in the fields of integrated optics, optoelectronics, and information storage. There is a possibility of application. For example, a liquid crystal display such as a digital display of various shapes, an electro-optical shutter, an electro-optical switch such as an optical path switch for optical communication, an electro-optical aperture, a memory element,
It can be used as various electronic optical devices such as a light modulator, a liquid crystal printer head, and a variable focal length lens.

In addition, if necessary, the liquid crystal polymer of the present invention may be mixed with other polymers, mixed with other low-molecular liquid crystal, various inorganics, including stabilizers, plasticizers, etc. Improvements can be made by a number of processing methods well known in the art, such as the addition of additives.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the scope of the present invention is not limited to these examples.

The structures of the obtained polymer and epoxy compound were confirmed by NMR, IR, and elemental analysis, and the measurement of the phase transition temperature and the confirmation of the phase were performed by DSC and a polarizing microscope, respectively. (Glass: glassy state, Cry: crystalline state, S: unidentified smectic phase, SmC ^* : chiral smectic C phase, SmA: smectic A phase, N: nematic phase, Ch: cholesteric phase, Iso: isotropic phase, phase The numbers of the transition behavior represent the phase change temperature in ° C.) The electric field response speed and the spontaneous polarization value were measured as follows.

Measurement of electric field response speed A polymer is sandwiched between two 20 × 10 mm ITO substrates, the thickness is adjusted to 25 μm with a spacer, and an AC electric field E = 2 × 10 ⁶ V
/ m, and the response time of the change in the amount of transmitted light (0 → 90%) at that time was measured.

Measurement of spontaneous polarization value The polymer was sandwiched between glass substrates with an ITO circular transparent electrode having an area of 0.2 cm ² , and the thickness was adjusted to 10 μm with a spacer. A triangular waveform voltage with a peak value of 200 V was applied, and a spontaneous polarization value was obtained from the signal of the polarization reversal current observed at this time.

Example 1 Synthesis of Monomer 1. Synthesis of 6-bromohexyl allyl ether 5.0 g of allyl alcohol and 65 g of 1,6-dibromohexane
Was dissolved in 80 ml of hexane. Thereto, 110 g of a 50% aqueous sodium hydroxide solution and 1.5 g of tetrabutylammonium bromide were added, and the mixture was refluxed for 17 hours. After the reaction, the hexane layer was collected, washed with water, and dried over magnesium sulfate. Next, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 12.6 g of the target ω-haloalkylallyl ether compound. (Yield 66%) 1. Synthesis of 4- (6-allyloxyhexyloxy) benzoic acid 6.0 g of 6-bromohexyl allyl ether obtained in 1.
4.4 g of methyl p-hydroxybenzoate and 2.0 g of potassium hydroxide were dissolved in 50 ml of ethanol and refluxed for 12 hours. Subsequently, 150 ml of an aqueous potassium hydroxide solution (containing 6.0 g of potassium hydroxide) was added, and the mixture was further refluxed for 12 hours.
After the reaction, hydrochloric acid was added dropwise to adjust the pH to 2, and the resulting precipitate was collected. The obtained precipitate was sufficiently washed with water, and then dried by heating under reduced pressure to obtain 6.5 g of the desired carboxylic acid compound. (Yield 87%) 1. Synthesis of 4- (6-allyloxyhexyloxy) benzoic acid 4 '-(2-methylbutyloxycarbonyl) phenyl ester Two drops of pyridine were added to 2.8 g of the carboxylic acid obtained in 1. Was added as a catalyst. Thereto, a large excess of thionyl chloride, that is, 20 ml of thionyl chloride is added as a solvent, and the mixture is added
Stirred for hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride.

p-hydroxybenzoic acid 2-methylbutyl ester 2.
A toluene solution containing 2 g and 1.0 g of pyridine was added dropwise to the toluene solution of the above acid chloride. Then, the reaction was performed at room temperature for one day. 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 2.5 g of the desired phenylbenzoate. (Yield: 53%) The phenylbenzoate derivative exhibited a liquid crystal state at room temperature.

1. Epoxidation 2.5 g of the phenylbenzoate obtained in 1 was dissolved in dichloromethane, and the system was replaced with argon. 1.0 g of m-chloroperbenzoic acid was added and reacted at room temperature for 1 day. After the reaction, the resultant was washed with an aqueous solution of potassium carbonate, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 2.6 g of a monomer which was an epoxy compound represented by the above structural formula. The obtained product was used for the next reaction without further purification.

FIG. 1 shows the NMR chart and the assignment of hydrogen of this epoxy compound, and the results of elemental analysis are shown below.

Elemental analysis value C (%) H (%) Calculated value 69.40 7.49 Actual value 70.9 7.6 [Polymerization] 2.6 g of the monomer obtained in 1. was dissolved in dichloromethane, and the system was replaced with argon. There, stannic chloride 20
μ (3 mol% of monomer) was added. Polymerization was performed at room temperature for 3 days. After the reaction, the reaction solution was concentrated and purified by column chromatography to obtain 1.0 g of a desired polymer having a repeating unit represented by the following formula. (38% yield) FIG. 2 shows the NMR chart and the assignment of hydrogen of the obtained polymer, and Table 1 shows the number average molecular weight, phase transition behavior, spontaneous polarization value, and electric field response speed.

Example 2 [Synthesis of monomer] 2. Synthesis of 4 '-(6-allyloxyhexyloxy) biphenyl-4-carboxylic acid 2-methylbutyl ester 6.6 g of 6-bromohexyl allyl ether obtained in 1. of Example 1, 4-hydroxybiphenyl- 8.5 g of 4-carboxylic acid 2-methylbutyl ester and potassium carbonate
4.2 g was heated and stirred in 2-butanone at 80 ° C. for 12 hours.
After the reaction, inorganic substances were removed by filtration, and then the solvent was distilled off under reduced pressure. The residue was recrystallized from methanol to obtain 4.6 g of the desired biphenyl derivative. 2. Epoxidation 2.5 g of the biphenyl derivative obtained in 2. was dissolved in dichloromethane, and the system was replaced with argon. Then, 1.2 g of m-chloroperbenzoic acid was added, and the mixture was stirred at room temperature for 2 days. After the reaction, the reaction solution was washed with an aqueous solution containing 2.5 g of potassium carbonate. Next, after drying over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 2.0 g of the desired monomer, which is the epoxy compound represented by the above structural formula. (Yield 77%) The obtained monomer was a liquid having a high viscosity at room temperature. The obtained monomer was used for the next reaction without further purification.

FIG. 3 shows the NMR chart and the assignment of hydrogen of this epoxy compound, and the results of elemental analysis are shown below.

Elemental analysis value C (%) H (%) Calculated value 73.61 8.24 Actual value 73.8 8.35 [Polymerization] 2.0 g of the monomer obtained in 2. was dissolved in dichloromethane, and the system was replaced with argon. There, stannic chloride 16
μ (3 mol% of monomer) was added. Polymerization was carried out at room temperature for 4 days. After the reaction, the reaction solution was concentrated and then reprecipitated in methanol. The precipitate was collected and purified by column chromatography to obtain 0.5 g of a desired polymer having a repeating unit represented by the following formula. (Yield 25%) FIG. 4 shows the NMR chart and the assignment of hydrogen of the obtained polymer, and Table 1 shows the number average molecular weight, phase transition behavior, spontaneous polarization value, and electric field response speed.

Example 3 [Synthesis of monomer] 3. Synthesis of p-hydroxybenzoic acid 2-fluorooctyl ester Take 7.6 g of p-acetoxybenzoic acid into an eggplant flask,
20 ml of thionyl chloride were added. Next, the mixture was heated and stirred at 80 ° C. for 4 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride.

A toluene solution containing 6.4 g of (-)-2-fluoro-1-octanol and 3.5 g of pyridine was added dropwise to the toluene solution of the above acid chloride. The resulting mixture was stirred at room temperature for one day. Then, the reaction solution was washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was dissolved in ether, and 15 ml of benzylamine was added dropwise. Then, the mixture was stirred at room temperature for 3 hours. The obtained reaction solution was washed with dilute hydrochloric acid, then with water, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 8.0 g of the desired ester. (Yield 71%) 3. Synthesis of 4- [4 '-(6-allyloxyhexyloxy) benzoyloxy] benzoic acid 2-fluorooctyl ester 4- (6-allyloxyhexyloxy) benzoic acid 1.
Take 0 g in an eggplant flask, add 5 ml of thionyl chloride, and add
C. and reacted for 3 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride.

A toluene solution of 1.0 g of 2-fluorooctyl p-hydroxybenzoate and 0.4 g of pyridine was added dropwise to the toluene solution of the above acid chloride. The resulting mixture was stirred at room temperature for one day. 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 the desired phenylbenzoate derivative (0.8 g). (Yield 42%) 3. Epoxidation 0.8 g of the phenylbenzoate derivative obtained in 2. was dissolved in dichloromethane, and the system was replaced with argon. Then m
0.3 g of chloroperbenzoic acid was added, and the mixture was stirred at room temperature for 1 day. After the reaction, the reaction solution was washed with an aqueous potassium carbonate solution.
Next, after drying over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 0.6 g of a desired monomer, which is an epoxy compound represented by the above structural formula. (Yield: 75%) The NMR chart and the assignment of hydrogen of this epoxy compound are shown in FIG. 5, and the results of elemental analysis are shown below.

Elemental analysis value C (%) H (%) F (%) Calculated value 68.36 7.59 3.49 Actual value 69.1 7.7 3.5 [Polymerization] 0.6 g of the monomer obtained in 3. was dissolved in dichloromethane, and the system was replaced with argon. There, stannic chloride 4
was added, and the mixture was polymerized at room temperature for 2 days. After the reaction, the reaction solution was concentrated and then purified by column chromatography to obtain 0.4 g of a desired polymer having a repeating unit represented by the following formula. (67% yield) The NMR chart and the assignment of hydrogen of the obtained polymer are shown in FIG. 6, and the number average molecular weight, phase transition behavior, spontaneous polarization value, and electric field response speed are shown in Table 1.

Example 4 Synthesis of Monomer 4. Synthesis of 8-bromooctyl allyl ether 3.5 g of allyl alcohol was dissolved in 50 ml of THF. There, 60% sodium hydride (a mixture of sodium hydride and mineral oil, the content of sodium hydride is 60% by weight
2.5 g) was added little by little. After stirring at room temperature for 30 minutes, a solution consisting of 33 g of 1,8-dibromooctane and 100 ml of THF was added dropwise. After the completion of the dropwise addition, the temperature was raised and the mixture was refluxed for 12 hours. After the reaction, a small amount of water was added to decompose the remaining sodium hydride. Next, THF was distilled off under reduced pressure, dichloromethane and water were added, and the mixture was shaken. The dichloromethane layer was collected and dried over magnesium sulfate. After concentration under reduced pressure, the residue was purified by column chromatography, and the target ω-haloalkyl allyl ether 8.6 g
(57% yield) 4. Synthesis of 4- (8-allyloxyoctyloxy) benzoic acid 8-bromooctylallyl ether obtained in 4.
7 g was used in place of 6-bromohexyl allyl ether used in 1. of Example 1, and the same operation as in 1. of Example 1 was performed to obtain 7.3 g of the desired carboxylic acid compound. (Yield 80
%) 4. Synthesis of p-hydroxybenzoic acid 2-fluorohexyl ester (-)-2-fluoro-1- used in 3. of Example 3
The same operation as in 3. of Example 3 was performed using 4.0 g of (-)-2-fluoro-1-hexanol instead of octanol to obtain 5.4 g of the desired product. (Yield: 74%) 4. Synthesis of 4- [4 '-(8-allyloxyoctyloxy) benzoyloxy] benzoic acid 2-fluorohexyl ester 4.4 g of the carboxylic acid obtained in 4. Compound 3.
The same operation as in 3. of Example 3 was performed using 6 g to obtain 4.2 g of the desired phenylbenzoate. (Yield 58
%) 4. Epoxidation 4.1 g of the phenylbenzoate derivative obtained in 4 was dissolved in dichloromethane, and the system was replaced with argon. Then m
2.0 g of chloroperbenzoic acid was added, and the mixture was stirred at room temperature for 1 day. After the reaction, the reaction solution was washed with an aqueous potassium carbonate solution.
Next, after drying over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 4.1 g of a desired monomer, which is an epoxy compound represented by the above structural formula. (Yield 97%) The NMR chart and hydrogen assignment of this epoxy compound are shown in FIG. 7, and the results of elemental analysis and the phase transition behavior are shown below.

Elemental analysis C (%) H (%) F (%) Calculated 68.36 7.59 3.49 Actual 68.2 7.6 3.45 Phase transition behavior [Polymerization] 2.0 g of the monomer obtained in 4 was dissolved in dichloromethane, and the system was replaced with argon. There, stannic chloride 13
was added, and the mixture was polymerized at room temperature for 3 days. After the reaction, the reaction solution was concentrated and then purified by column chromatography to obtain 1.5 g of a desired polymer having a repeating unit represented by the following formula. (75% yield) FIG. 8 shows the NMR chart and the assignment of hydrogen of the obtained polymer, and Table 1 shows the number average molecular weight, the phase transition behavior, the spontaneous polarization value, and the electric field response speed.

Example 5 [Synthesis of monomer] 5. 4- (8-allyloxyoctyloxy) -4 '
Synthesis of -Hydroxybiphenyl 5.0 g of 8-bromooctyl allyl ether, 12 g of 4,4'-diphenol, and 9.0 g of potassium hydroxide obtained in the same manner as in 4. of Example 4 were refluxed in ethanol for 20 hours. After the reaction, the inorganic substances were removed by hot filtration. After the ethanol was distilled off under reduced pressure, the residue was dissolved in a water: acetone mixed solvent. Dilute hydrochloric acid was added to the resulting solution to adjust the pH to 2. The solution was then heated to evaporate the acetone, the insolubles were collected by filtration while hot, and then recrystallized from ethanol to give 3.5 g of the desired biphenyl derivative (49% yield). 8-allyloxyoctyloxy) -4 '
Synthesis of-(2-chloro-3-methylpentanoyloxy) biphenyl 1.5 g of the biphenyl derivative obtained in 5. and 2-chloro-3
-1.0 g of methylpentanoic acid was dissolved in dichloromethane. Dicyclohexylcarbodiimide 1.
3 g and 0.1 g of 4-pyrrolidinopyridine were added, and the mixture was stirred at room temperature for 1 day. After the reaction, insolubles were removed by filtration and then washed with water. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 1.0 g of the desired biphenyl derivative. (Yield 48%) 5. Epoxidation 1.0 g of the biphenyl derivative obtained in 5. was dissolved in dichloromethane, and the system was replaced with argon. Then, 0.5 g of m-chloroperbenzoic acid was added, and the mixture was stirred at room temperature for 1 day. After the reaction, the reaction solution was washed with an aqueous potassium carbonate solution, and further washed with water. Then, after drying over magnesium sulfate,
The solvent was distilled off under reduced pressure to obtain 0.8 g of the desired epoxy compound monomer represented by the above structural formula. (Yield 77%) The NMR chart and hydrogen assignment of this epoxy compound are shown in FIG. 9, and the results of elemental analysis are shown below.

Elemental analysis value C (%) H (%) Cl (%) Calculated value 69.24 7.81 7.05 Actual value 70.2 7.7 6.6 [Polymerization] 0.8 g of the monomer obtained in 5. was dissolved in dichloromethane, and the system was replaced with argon. There, stannic chloride 6
was added, and the mixture was polymerized at room temperature for 2 days. After the reaction, the reaction solution was concentrated and then purified by column chromatography to obtain 0.5 g of a desired polymer having a repeating unit represented by the following formula. (63% yield) The NMR chart of the obtained polymer and the assignment of hydrogen
FIG. 0 shows the number average molecular weight, phase transition behavior, spontaneous polarization value, and electric field response speed in Table 1.

Example 6 [Synthesis of monomer] 6. 4 '-[4 "-(8-allyloxyoctyloxy) benzoyloxy] biphenyl-4-carboxylic acid 2
Synthesis of -Methylbutyl ester 2.8 g of the carboxylic acid compound obtained in 4. of Example 4 and 4 '
The same operation as in 3. of Example 3 was carried out using 2.6 g of 2-hydroxybutyl-carboxylic acid 2-methylbutyl ester to obtain 3.0 g of the desired biphenylbenzoate. 6. Epoxidation 1.5 g of the biphenylbenzoate obtained in 6. was dissolved in dichloromethane, and the system was replaced with nitrogen. 0.6 g of m-chloroperbenzoic acid was added, and the mixture was stirred at room temperature for 7 hours. After the reaction, the reaction solution was washed with an aqueous potassium carbonate solution. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 1.5 g of the desired epoxy compound monomer represented by the above structural formula. (Yield 97%) The NMR chart and hydrogen assignment of this epoxy compound are shown in FIG. 11, and the results of elemental analysis are shown below.

Elemental analysis value C (%) H (%) Calculated value 73.44 7.53 Actual value 73.6 7.5 [Polymerization] 1.5 g of the monomer obtained in 6. was dissolved in dichloromethane, and the system was replaced with nitrogen. There, stannic chloride 15μ
Was added and polymerized at room temperature for 30 hours. After the reaction, the reaction solution is concentrated and then purified by column chromatography.
0.9 g of the desired polymer having a repeating unit represented by the following formula was obtained. (60% yield) The NMR chart of the obtained polymer and the assignment of hydrogen
FIG. 2 shows the number average molecular weight, phase transition behavior, spontaneous polarization value, and electric field response speed in Table 2.

Example 7 [Synthesis of monomer] 7. Synthesis of 10-iododecyl allyl ether 2.0 g of allyl alcohol, 1.5 g of 60% sodium hydride,
The same reaction and operation as in 4. of Example 4 were carried out using 33.0 g of 1,10-diiododecane to obtain 8.2 g of the desired ω-haloalkyl allyl ether. (Yield 53%) 7. Synthesis of 4 '-(10-allyloxydecyloxy) biphenyl-4-carboxylic acid 10-iododecyl allyl ether obtained in 7.
g, 4'-hydroxybiphenyl-4-carboxylic acid 4.8
g, 3.3 g of potassium hydroxide and 5.0 g of water were refluxed in 50 ml of methanol for 24 hours, and after adding 500 ml of water, hydrochloric acid was added dropwise to adjust the pH to 2. The precipitate was collected and dried under reduced pressure. The crude product was recrystallized from acetic acid to obtain 4.3 g of the desired carboxylic acid compound. (Yield 53%) 7. Synthesis of 4-hydroxybenzoic acid 1-methylbutyl ester To 5.7 g of 4-acetoxybenzoic acid, 3 drops of pyridine were added as a catalyst. There, toluene 50ml and thionyl chloride 10
A solution consisting of ml was added and stirred at 80 ° C. for 3 hours. After the reaction, toluene and excess thionyl chloride were distilled off under reduced pressure to obtain an acid chloride.

The toluene solution of the above acid chloride was added dropwise to a toluene solution containing 2.5 g of (R)-(−)-2-pentanol and 3.4 g of triethylamine, and the mixture was stirred at room temperature for 5 hours. After the reaction, the mixture was washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain an ester.

The ester was dissolved in ether, and 4.0 g of benzylamine was added. After reacting by stirring at room temperature for 3 hours,
The extract was washed with diluted hydrochloric acid, washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 4.8 g of the desired ester.
(Yield 73%) 7. Synthesis of 4 ″-(1-methylbutyloxycarbonyl) phenyl 4 ′-(10-allyloxydecyloxy) biphenyl-4-carboxylate 4.3 g of the carboxylic acid compound obtained in 7. Then, 3 drops of pyridine and 5.0 g of thionyl chloride were added thereto, and the mixture was stirred for 4 hours at 90 ° C. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride. The toluene solution of the above acid chloride was added dropwise to a toluene solution containing 0.9 g of pyridine and 0.9 g of pyridine, and the mixture was stirred at room temperature for 1 day, washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The product was recrystallized from to give 5.4 g of the desired phenylbiphenylcarboxylate (86% yield) 7. Epoxidation 2.7 g of the phenylbiphenylcarboxylate obtained in 7. was dissolved in dichloromethane to form a system. Al After adding 1.0 g of m-chloroperbenzoic acid and stirring at room temperature for 7 hours, the reaction solution was washed with aqueous potassium carbonate solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. As a result, 2.5 g of the desired epoxy compound monomer represented by the above structural formula was obtained (yield: 90%). The NMR chart and hydrogen assignment of this epoxy compound are shown in FIG. Is shown below.

Elemental analysis value C (%) H (%) Calculated value 74.00 7.84 Actual value 74.2 7.8 [Polymerization] 2.5 g of the monomer obtained in 7. was dissolved in dichloromethane, and the system was replaced with argon. There, stannic chloride 24
was added, and the mixture was polymerized at room temperature for 30 hours. After the reaction, the reaction solution was concentrated and then purified by column chromatography to obtain 2.1 g of a desired polymer having a repeating unit represented by the following formula. (Yield 84%) The NMR chart of the obtained polymer and the assignment of hydrogen
FIG. 4 shows the number average molecular weight, phase transition behavior, spontaneous polarization value, and electric field response speed in Table 2.

Example 8 [Synthesis of monomer] 8. Synthesis of 4- [4 '-(8-allyloxyoctyloxy) phenyl] phenol 7.0 g of 8-bromooctyl allyl ether, 11.0 g of 4,4'-diphenol and 8.0 g of potassium hydroxide were dissolved in methanol for 20 minutes. Refluxed for hours. After methanol was distilled off under reduced pressure, acetone was added, and hydrochloric acid was added dropwise. After removing insoluble matter by filtration, the solvent was distilled off under reduced pressure. The residue was recrystallized from ethanol to obtain 7.2 g of the desired phenol compound. (Yield 72%) 8. Synthesis of 4- (2-methylbutyloxy) benzoic acid 10.0 g of S-(−)-2-methylbutanol was added to pyridine 1
It was dissolved in 00 ml and cooled on ice. Thereto, 26.0 g of p-toluenesulfonyl chloride was added, and the mixture was stirred at room temperature for 6 hours. Add ether, wash with water, dry over magnesium sulfate,
The solvent was distilled off under reduced pressure to obtain a tosyl compound.

To the tosyl compound, 17.0 g of 4-hydroxybenzoic acid and 7.4 g of potassium hydroxide were added, and the mixture was refluxed for 14 hours in 50 ml of methanol. Potassium hydroxide aqueous solution (potassium hydroxide 18.0
g) and refluxed for an additional 5 hours. Water 1 was added and then hydrochloric acid was added dropwise to pH = 2. The resulting precipitate was collected and dried by heating to obtain 13.3 g of the desired carboxylic acid compound. (Yield 56%) 8. Synthesis of 4 ″-(8-allyloxyoctyloxy) biphenyl-4′-yl 4- (2-methylbutyloxy) benzoate 2.4 g of the carboxylic acid obtained in 8. was added to thionyl chloride. 8.0g
Was added and stirred at 80 ° C. for 3 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride.

4.0 g of the phenol obtained in step 8 and triethylamine 1.
The THF solution of the above acid chloride was added dropwise to 3 g of the THF solution, and the mixture was stirred at room temperature for 1 day. Then, ether was added, washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was recrystallized from methanol to obtain 5.0 g of the desired ester. (80% yield) 8. Epoxidation 1.2 g of the ester obtained in 8. was dissolved in dichloromethane, and the system was replaced with argon. Then, 0.5 g of m-chloroperbenzoic acid was added, and the mixture was stirred at room temperature for 7 hours. After the reaction, the reaction solution was washed with an aqueous potassium carbonate solution. After drying over magnesium sulfate, the solvent is distilled off under reduced pressure, and the desired monomer which is an epoxy compound represented by the above structural formula
1.0 g was obtained. (Yield 81%) The NMR chart and hydrogen assignment of this epoxy compound are shown in FIG. 15, and the results of elemental analysis are shown below.

Elemental analysis value C (%) H (%) Calculated value 74.97 7.91 Actual value 75.0 7.9 [Polymerization] 1.0 g of the monomer obtained in 8. was dissolved in dichloromethane, and the system was replaced with argon. There, stannic chloride 10
was added, and the mixture was polymerized at room temperature for 30 hours. After the reaction, the reaction solution was concentrated and purified by column chromatography to obtain 0.6 g of a desired polymer having a repeating unit represented by the following formula. (60% yield) The NMR chart of the obtained polymer and the assignment of hydrogen
FIG. 6 shows the number average molecular weight, phase transition behavior, spontaneous polarization value, and electric field response speed in Table 2.

Example 9 [Synthesis of monomer] 9. Synthesis of 4- (2-fluorohexyloxy) phenol 6.0 g of 2-fluorohexanol was dissolved in pyridine, 10.0 g of p-toluenesulfonyl chloride was added thereto, and the mixture was stirred at room temperature for 10 hours. Ether was added, washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a tosyl compound.

16.5 g of hydroquinone and 10.0 g of potassium hydroxide were added to the tosyl compound, and the mixture was refluxed in methanol in an argon atmosphere for 16 hours. Hydrochloric acid was added, insolubles were removed by filtration, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 7.6 g of the desired phenol compound. (Yield 72%) 9. Synthesis of 4- (8-allyloxyoctyloxy) benzoic acid 4 '-(2-fluorohexyloxy) phenyl ester 4- (8-allyloxyoctyloxy) benzoic acid 3.
3 g, 3 drops of pyridine and 8 g of thionyl chloride were heated and stirred at 80 ° C. for 3 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride.

1.9 g of the phenol obtained in step 9 and triethylamine 1.
The toluene solution of the above acid chloride was added dropwise to a toluene solution containing 2 g, and the mixture was stirred at room temperature for 8 hours. Then, it was washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 2.7 g of the desired ester. (Yield 60%) 9. Epoxidation 2.7 g of the ester obtained in 9. was dissolved in dichloromethane, and the system was replaced with nitrogen. Then, 1.2 g of m-chloroperbenzoic acid was added, and the mixture was stirred at room temperature for 7 hours. After the reaction, the reaction solution was washed with an aqueous potassium carbonate solution. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure, and 2.4 g of a monomer, which is an epoxy compound represented by the above-mentioned structural formula of interest.
I got (Yield: 86%) The NMR chart and hydrogen assignment of this epoxy compound are shown in FIG. 17, and the results of elemental analysis are shown below.

Elemental analysis value C (%) H (%) F (%) Calculated value 69.74 8.00 3.68 Observed value 69.8 7.9 3.6 [Polymerization] 2.0 g of the monomer obtained in 9. was dissolved in dichloromethane, and the system was replaced with nitrogen. There, stannic chloride 23μ
Was added and polymerized at room temperature for 30 hours. After the reaction, the reaction solution is concentrated and then purified by column chromatography.
1.8 g of the desired polymer having a repeating unit represented by the following formula was obtained. (Yield 90%) The NMR chart of the obtained polymer and the assignment of hydrogen
FIG. 8 shows the number average molecular weight, phase transition behavior, spontaneous polarization value, and electric field response speed in Table 2.

Example 10 Synthesis of Monomer 10. Synthesis of 4- (2-fluorohexyloxy) phenol 7.4 g of 2-fluorooctanol was dissolved in pyridine, 10.0 g of p-toluenesulfonyl chloride was added thereto, and the mixture was stirred at room temperature for 10 hours. Ether was added, washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a tosyl compound.

The above tosyl compound, 16.5 g of hydroquinone and 10.0 g of potassium hydroxide were refluxed in methanol in an argon atmosphere for 16 hours. Hydrochloric acid was added, insolubles were removed by filtration, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 6.5 g of the desired phenol compound. (Yield 54
%) 10. Synthesis of 4- (8-allyloxyoctyloxy) benzoic acid 4 '-(2-fluorooctyloxy) phenyl ester 4- (8-allyloxyoctyloxy) benzoic acid 5.
5 g, 3 drops of pyridine and 7 g of thionyl chloride at 80 ° C.
The mixture was heated and stirred for an hour. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride.

3.0 g of the phenol obtained in step 10 and triethylamine
The toluene solution of the above acid chloride was added dropwise to a toluene solution containing 2.0 g, and the mixture was stirred at room temperature for 8 hours. Then wash with water,
After drying over magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 3.4 g of the desired ester. (Yield 51%) 10. Epoxidation 3.4 g of the ester obtained in step 10 was dissolved in dichloromethane, and the system was replaced with nitrogen. Next, 1.6 g of m-chloroperbenzoic acid was added, and the mixture was stirred at room temperature for 7 hours. After the reaction, the reaction solution was washed with an aqueous potassium carbonate solution. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure, and the desired monomer, an epoxy compound represented by the above structural formula, 3.
0 g was obtained. (Yield: 86%) The NMR chart and hydrogen assignment of this epoxy compound are shown in FIG. 19, and the results of elemental analysis are shown below.

Elemental analysis value C (%) H (%) F (%) Calculated value 70.56 8.33 3.49 Actual value 70.7 8.2 3.4 [Polymerization] 3.0 g of the monomer obtained in 10. was dissolved in dichloromethane, and the system was replaced with nitrogen. There, stannic chloride 30μ
Was added and polymerized at room temperature for 30 hours. After the reaction, the reaction solution was concentrated and purified by column chromatography to obtain 1.9 g of a desired polymer having a repeating unit represented by the following formula. (63% yield) The NMR chart of the obtained polymer and the assignment of hydrogen
FIG. 0 shows the number average molecular weight, phase transition behavior, spontaneous polarization value, and electric field response speed in Table 2.

Example 11 (Synthesis of monomer) 11. Synthesis of 14-bromotetradecyl allyl ether 2.0 g of allyl alcohol, 1.7 g of 60% sodium hydride,
Using 30 g of 1,14-dibromotetradecane,
The same reaction and operation as in 4 were performed to obtain 7.9 g of the desired ω-haloalkyl allyl ether. (Yield 69%) 11. 4- (14-allyloxytetradecyloxy)
Synthesis of benzoic acid Using 7.9 g of the allyl ether compound obtained in 11., 3.6 g of p-hydroxybenzoic acid methyl ester and 1.6 g of potassium hydroxide, the same reaction and operation as in 1. of Example 1 were carried out, 6.8 g of the following carboxylic acid compound was obtained. (Yield 74%) 11. 4- (14-allyloxytetradecyloxy)
Synthesis of 4 '-(2-fluorohexyloxy) phenyl benzoate 4- (14-allyloxytetradecyloxy) benzoic acid (3.9 g), pyridine (3 drops) and thionyl chloride (5.0 g) were heated and stirred at 80 ° C. for 3 hours. did. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride.

2.4 g of 4- (2-fluorohexyloxy) phenol
And the toluene solution of the above acid chloride compound was dropped into a toluene solution containing 1.1 g of triethylamine and stirred at room temperature for 8 hours. Then, it was washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 3.5 g of the desired ester. (yield
58%) 11. Epoxidation 3.5 g of the ester obtained in 11 was dissolved in dichloromethane, and the system was replaced with nitrogen. Then, 1.2 g of m-chloroperbenzoic acid was added, and the mixture was stirred at room temperature for 7 hours. After the reaction, the reaction solution was washed with an aqueous potassium carbonate solution. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure, and the desired monomer, an epoxy compound represented by the above structural formula, 3.
4 g were obtained. (Yield 95%) The NMR chart and hydrogen assignment of this epoxy compound are shown in FIG. 21, and the results of elemental analysis are shown below.

Elemental analysis value C (%) H (%) F (%) Calculated value 73.97 8.89 3.16 Actual value 74.0 8.9 3.0 [Polymerization] 3.4 g of the monomer obtained in 11. was dissolved in dichloromethane, and the system was replaced with nitrogen. There, stannic chloride 30μ
Was added and polymerized at room temperature for 30 hours. After the reaction, the reaction solution was concentrated and then purified by column chromatography to obtain 1.8 g of a desired polymer having a repeating unit represented by the following formula. (54% yield) The NMR chart of the obtained polymer and the assignment of hydrogen
FIG. 2 shows the number average molecular weight, phase transition behavior, spontaneous polarization value, and electric field response speed in Table 2.

Example 12 2.0 g of the monomer synthesized in Example 1 and 3.6 g of the monomer synthesized in Example 6 were dissolved in dichloroethane, and the system was replaced with argon. Thereto, boron trifluoride (1 mol% of the monomer) was added, and polymerized at room temperature for 8 hours. After the reaction, the reaction solution was concentrated and then purified by column chromatography to obtain 4.2 g of a desired copolymer having a repeating unit represented by the following formula (yield: 75%). The NMR chart of the obtained polymer and the assignment of hydrogen
FIG. 3 shows the number average molecular weight, phase transition behavior, spontaneous polarization value, and electric field response speed in Table 2.

[Effects of the Invention] According to the present invention, a chiral smectic C phase liquid crystal state is obtained in a wide temperature range including a room temperature range, and when an optical display device is used, the response speed to external factors is remarkably fast, and the contrast ratio is high. Therefore, it is possible to provide a liquid crystalline polymer having remarkably excellent practical advantages, for example, it can be suitably used for a moving image display element, a large screen, a curved screen, and the like.

[Brief description of the drawings]

FIG. 1 is an NMR chart of the epoxy compound obtained in Example 1, and FIG. 2 is an NMR chart of the liquid crystalline polymer obtained in Example 1. FIG. 3 is an NMR chart of the epoxy compound obtained in Example 2, and FIG. 4 is an NMR chart of the liquid crystalline polymer obtained in Example 2. FIG. 5 is an NMR chart of the epoxy compound obtained in Example 3, and FIG. 6 is an NMR chart of the liquid crystalline polymer obtained in Example 3. FIG. 7 is an NMR chart of the epoxy compound obtained in Example 4, and FIG. 8 is an NMR chart of the liquid crystalline polymer obtained in Example 4. FIG. 9 is an NMR chart of the epoxy compound obtained in Example 5, and FIG. 10 is an NMR chart of the liquid crystalline polymer obtained in Example 5. FIG. 11 is an NMR chart of the epoxy compound obtained in Example 6, and FIG. 12 is an NMR chart of the liquid crystalline polymer obtained in Example 6. FIG. 13 is an NMR chart of the epoxy compound obtained in Example 7, and FIG. 14 is an NMR chart of the liquid crystalline polymer obtained in Example 7. FIG. 15 is an NMR chart of the epoxy compound obtained in Example 8, and FIG. 16 is an NMR chart of the liquid crystalline polymer obtained in Example 8. FIG. 17 is an NMR chart of the epoxy compound obtained in Example 9, and FIG. 18 is an NMR chart of the liquid crystalline polymer obtained in Example 9. FIG. 19 is an NMR chart of the epoxy compound obtained in Example 10, and FIG. 20 is an NMR chart of the liquid crystalline polymer obtained in Example 10. FIG. 21 is an NMR chart of the epoxy compound obtained in Example 11, and FIG. 22 is an NMR chart of the liquid crystalline polymer obtained in Example 11. FIG. 23 is an NMR chart of the liquid crystalline polymer obtained in Example 12.

Continuation of the front page (56) References JP-A-62-190208 (JP, A) JP-A-62-190223 (JP, A) JP-A-62-201419 (JP, A) JP-A-59-199649 (JP, A) JP-A-63-264629 (JP, A) JP-A-1-156971 (JP, A) JP-A-1-131234 (JP, A) JP-A-1-284522 (JP, A) 63-113526 (JP, A) JP-A-2-60924 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 65/00-65/48 C09K 19/00-19 / 60 REGISTRY (STN) CA (STN)

Claims (2)

(57) [Claims] 1. A liquid crystalline polymer having a repeating unit represented by the following general formula. (Where k is an integer of 2 to 30, R ¹ is In, X is -COO- or -OCO-, R ² is -COOR ^3, a -OCOR ³ or -OR ^3, R ³ is Wherein R ⁴ and R ⁵ are each —CH ₃ , a halogen atom or —CN, m and n are each an integer of 0 to 10, provided that R ⁴ is-
In the case of CH ₃ , n is not 0, p is 0 or 1, and C marked with * is an asymmetric carbon atom. ) 2. An epoxy compound having a structure represented by the following general formula. (Where k is an integer of 2 to 30, R ¹ is In, X is -COO- or -OCO-, R ² is -COOR ^3, a -OCOR ³ or -OR ^3, R ⁴ and R ⁵ are each —CH ₃ , a halogen atom or —CN, m and n are each an integer of 0 to 10, provided that R ⁴ is —
In the case of CH ₃ , n is not 0, p is 0 or 1, and C marked with * is an asymmetric carbon atom. )