JPH0699555B2 - Liquid crystalline polymer and its intermediate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel liquid crystalline polymer and an epoxy compound which is an intermediate used in its production. More specifically, the present invention is in the field of optoelectronics, particularly calculators, display devices such as watches, electro-optical shutters, electro-optical apertures, optical modulators, optical communication optical path selector switches, memories, liquid crystal printer heads, variable focal length lenses, etc. The present invention relates to a liquid crystalline polymer used as a base liquid crystal of a liquid crystalline polymer material useful as various electro-optical devices, and an epoxy compound which is an intermediate used in the production thereof.

[Prior Art] As a means for obtaining a ferroelectric liquid crystal material, a method of adding an optically active compound to a host liquid crystal exhibiting an SmC phase and preparing it is currently being actively studied. (For example, JPLe Pesant, JNPe
rbet, B.Mourey, M.Hareng, G.Decobert, JC Dubois, Mol.C
ryst.Liq.Cryst., 1985 , 129 , 61-74, or Sadao Takehara, Tadao Tokaibayashi, Hiroshi Ogawa, Masashi Osawa, Nobu Fujisawa, 14th LCD Symposium Lectures, 18-19 etc.) Advantages of this method The characteristics of the host liquid crystal such as spontaneous polarization value, response speed, and phase transition temperature can be changed by adding a small amount of optically active compound to the host liquid crystal, and it is easy to optimize the characteristics required for practical use. That is the point. However, the liquid crystal material obtained by this method has a narrow temperature range showing the SmC ^* phase, and phase separation due to crystallization easily occurs.
There is a problem that the film forming property is poor.

[Problems to be Solved by the Invention] The present invention exhibits ferroelectricity in a wide temperature range including room temperature by blending with an optically active compound such as a low molecular weight ferroelectric liquid crystal compound or a non-liquid crystalline optically active compound. Another object of the present invention is to provide a liquid crystalline polymer which is a novel matrix liquid crystal capable of obtaining a ferroelectric liquid crystal material excellent in film forming property and fast response to an electric field.

Another object of the present invention is to provide an epoxy compound which is an intermediate used in the production of such a liquid crystalline polymer.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have found that a polyether type liquid crystalline polymer having a specific structure is blended with an optically active compound at room temperature. It was found that a liquid crystalline polymer material exhibiting ferroelectricity can be obtained in a wide temperature range including a range, and the present invention has been completed based on this finding.

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

(In the formula, k is an integer of 2 to 30, 1 is an integer of 1 to 10, X is -COO- or -OCO-, R ² is -COOR ^3, -OCOR ^3, an -OR ³ or R ^3, R ³ is an alkyl group having no asymmetric carbon. ) The number average molecular weight of the liquid crystalline polymer of the present invention is preferably 1,
It is 000 to 400,000. If it is less than 1,000, the film of the liquid crystalline polymer, the moldability as a coating film, that is, the film forming property may be impaired, while if it exceeds 400,000, unfavorable effects such as slow response speed may appear. is there. A particularly preferable range of the number average molecular weight depends on the kind of R ¹ , the value of k 1 and the like, and therefore cannot be specified, but it is usually 1,000 to 200,000. k is an integer of 2 to 30, more preferably 4 to 20. 1 is an integer of 1 to 10, more preferably an integer of 1 to 6.

R ³ is an alkyl group having no asymmetric carbon, specifically, a linear alkyl group having preferably 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, 2,2,2- Trifluoroethyl group, 2,2,3,3,4,4,4-heptafluorobutyl group,
Linear polyhaloalkyl such as 2,2,3,3-tetrafluoropropyl group, 1H, 1H, 7H-dodecafluoroheptyl group, trifluoromethyl group, perfluoropropyl group, perfluorooctyl group, perfluoroheptyl group Group, isopropyl group, isobutyl group, tert-butyl group, isopentyl group, branched alkyl group such as neopentyl group, 1,1,1,
Examples thereof include branched polyhaloalkyl groups such as 3,3,3-hexafluoropropyl group.

The general method for synthesizing the liquid crystalline polymer of the present invention is shown below.

For example, the liquid crystalline polymer of the present invention can be synthesized using the following epoxy compounds.

(In the formula, 1, k, X, R ¹ , R ² and R ³ have the same meanings as defined above), which is obtained by polymerizing a monomer which is an epoxy compound by a known method. it can.

As shown in the following reaction formula, allyl alcohol, 3
Ω-alkenyl alcohol such as butene-1-ol and α, ω-dihaloalkane (I) are dissolved in a solvent such as hexane, and a 50% aqueous sodium hydroxide solution and a phase transfer catalyst such as tetrabutylammonium bromide are added, Etherification, ω-haloalkylalkenyl ether (II)
To get Alternatively, alkenyl alcohol and α, ω-dihaloalkane (I) are dissolved in a solvent such as tetrahydrofuran (THF) and sodium hydride is added to carry out etherification to obtain ω-haloalkylalkenyl ether (II).
The obtained ω-haloalkylalkenyl ether (II) is reacted with the compound (III) in the presence of an alkali such as potassium carbonate in a suitable solvent such as 2-butanone to obtain an alkenyl ether (IV). Then, the alkenyl ether (IV) is epoxidized with a peracid such as m-chloroperbenzoic acid in a suitable solvent such as dichloromethane to obtain the target epoxy compound (V).

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

Here, the above compound (III) It can be synthesized as follows.

As shown in the following reaction formula, 4'-hydroxybiphenyl-
The 4-carboxylic acid and the alcohol (VI) having no asymmetric carbon are mixed with each other in a suitable solvent such as benzene in the presence of an esterification catalyst such as concentrated sulfuric acid or p-toluenesulfonic acid. The ester compound (VII) is obtained by reacting at a desired temperature.

Examples of the alcohol (VI) include n-butyl alcohol, n-pentyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl alcohol,
sec-Butyl alcohol, t-butyl alcohol, etc. are used.

As shown in the following reaction formula, the ester compound (IX) is obtained by reacting biphenyl-4,4'-diol with a carboxylic acid (VIII) having no asymmetric carbon.

Examples of the carboxylic acid (VIII) include n-butanoic acid,
n-Pentanoic acid, n-hexanoic acid, etc. are used.

As shown in the following reaction formula, the alcohol (VI) is tosylated, and biphenyl-4,4'-diol is reacted with this to obtain the ether compound (X).

As shown in the following reaction formula, ω-haloalkylalkenyl ether (II) is reacted with ethyl p-hydroxybenzoate in a suitable solvent such as acetone in the presence of an alkali such as potassium carbonate to obtain an ether body. . Then, the protective group of the carboxyl group in the ether is eliminated with an aqueous solution of potassium hydroxide, hydrochloric acid or the like to give a carboxylic acid. To this carboxylic acid compound, a halogenating agent such as thionyl chloride is added and heated in a solvent such as toluene to obtain an acid halide. Then, the acid halide and the compound (III) are reacted in a solvent such as toluene in the presence of pyridine to obtain an alkenyl ether compound (XI), and then m-chloroperoxide is added in a suitable solvent such as dichloromethane. The desired epoxy compound (XII) is obtained by epoxidizing with a peracid such as benzoic acid.

As shown in the following reaction formula, the ω-haloalkylalkenyl ether (II) and hydroquinone are reacted in the presence of an alkali such as potassium carbonate to obtain an ether body (XIII).

The following compound (VIV) is converted to an acid chloride with thionyl chloride or the like. The obtained acid chloride is reacted with an ether form (XIII) in the presence of pyridine to give an alkenyl ether form (XIII).
V) get. Thereafter, epoxidation is carried out in the same manner as in the case of (1) to obtain the desired epoxy compound (XVI).

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

The 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 above ester (XVII).

Carboxylic acid (VIII) is converted to acid chloride with thionyl chloride or the like, and then reacted with 4'-hydroxybiphenyl-4-carboxylic acid in the presence of pyridine to give the above ester compound (XVII
I) get.

4'-Hydroxybiphenyl-4-carboxylic acid ethyl ester is reacted with p-toluenesulfonic acid ester obtained by torching alcohol (VI) in the presence of potassium carbonate or the like to obtain an ether form. This ether is reacted with an alkaline aqueous solution to hydrolyze the ester of the protective group,
The above compound (XIX) is obtained.

R ^{1 in} (2) above is In the method of synthesizing the epoxy compound, the compound (II
I) Instead of compound (XX) And using the same procedure as above, to obtain the following target 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 performed using p-hydroxybenzoic acid instead of 4'-hydroxybiphenyl-4-carboxylic acid to obtain the above ester form (XXII).

In the synthesis of the compound (VIII) in the above (1), hydroquinone was used instead of biphenyl-4,4'-diol, and the same reaction was performed to obtain the above ester compound (XXII
I) get.

In the synthesis of the compound (X) in the above (1), hydroquinone was used instead of biphenyl-4,4'-diol, and the same reaction was performed to obtain the above ester body (XXIV).
To get

As shown in the following reaction formula, R ^{1 in} (3) above is In the synthesis of the epoxy compound, the compound (XIV> Instead of compound (XXV) The same reaction is carried out using to obtain the desired epoxy compound (XXVI) of the following general formula.

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

In the synthesis of the 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 form (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 form (XXVIII).

In the synthesis of compound (XIX) in the above (3),
The same reaction was carried out using p-hydroxybenzoic acid ethyl ester instead of 4'-hydroxybiphenyl-4-carboxylic acid ethyl ester to give the above ether compound (XXI
X) get.

R ^{1 in} (2) above is In the synthesis of the epoxy compound, 4′-hydroxybiphenyl-4-carboxylic acid ethyl ester was used in place of p-hydroxybenzoic acid ethyl ester,
Compound (III) Instead of the compound (XX) The same reaction is carried out using to obtain the desired epoxy compound (XXX) of the following general formula.

R ^{1 in} (3) above is In the synthesis of the epoxy compound, the compound (XIV) was prepared by using biphenyl-4,4-diol instead of hydroquinone. In place of the above compound (XXV) A similar reaction is carried out using to obtain the desired epoxy compound (XXXI) of the following general formula.

Specific examples of the epoxy compound that is the monomer according to the present invention include those represented by the following structural formulas.

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 can be adopted as the polymerization method.

Various kinds of catalysts for cationic polymerization are known, but protonic acids such as sulfuric acid, phosphoric acid and perchloric acid, boron oxyfluoride, aluminum chloride, titanium tetrachloride, Lewis such as stannic chloride. Examples thereof include acids and boron trifluoride etherate, among which stannic chloride is preferably used.

It is also possible to carry out coordination polymerization using an organoaluminum complex or the like. In this case, the number average molecular weight 300,
More than 000 liquid crystalline polymers can be obtained.

As a polymerization method, various methods such as bulk polymerization, slurry polymerization and solution polymerization are known, and any of these methods may be used, but solution polymerization is preferable.

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

Although the polymerization time varies depending on other factors such as the polymerization temperature, it is usually several hours to 6 days.

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

In the bulk polymerization method, the monomer and the initiator are thoroughly mixed, the mixture is sufficiently degassed, and two substrates,
For example, the liquid crystalline polymer can be directly immobilized in a state in which the liquid crystalline polymer is in close contact between the substrates by being introduced between glass substrates and heated.

A known inert solvent can be used as a solvent in the case of slurry polymerization or solution polymerization, and among them, hexane, dichloromethane, or an aromatic solvent such as benzene, toluene, or xylene is preferably used.

In the polymerization reaction and the epoxidation reaction,
Although not essential, it is preferable to replace the system with an inert gas such as argon or nitrogen.

The liquid crystalline polymer thus obtained is blended with an optically active compound, and known film forming methods such as casting method, T-die method, inflation method, calendar method,
It can be used after being formed into a film by a stretching method or the like. The film-shaped liquid crystalline polymer is not only two ordinary glass substrates, but also a large glass substrate, curved glass substrate, polyester film, etc., and is used for liquid crystal displays, electronic optical shutters, electronic optical diaphragms, etc. Can be used in various fields of optoelectronics.

In addition, by applying a polymer solution dissolved in an appropriate solvent to the surface of a substrate such as a glass substrate and evaporating the solvent,
It is also possible to form a film in a state where it is directly adhered to the substrate surface.

It has been confirmed that the liquid crystalline polymer of the present invention blended with an optically active compound exhibits ferroelectricity in a wide temperature range including around room temperature. It was also confirmed that the response speed to the electric field was fast.

Further, the ferroelectric liquid crystal material blended with the liquid crystalline polymer of the present invention is also excellent in film forming property, so that it has many potential applications in the fields of integrated optics, optoelectronics, and information storage. For example, liquid crystal displays such as digital displays of various shapes, electro-optical shutters, electro-optical switches such as optical path switching switches for optical communication, electro-optical apertures, memory elements,
It can be used as various electro-optical devices such as a light modulator, a liquid crystal printer head, and a variable focal length lens.

Among the optically active compounds used by blending with the liquid crystalline polymer of the present invention, as the ferroelectric low molecular weight liquid crystal compound,
For example, Schiff base type ferroelectric low molecular weight liquid crystal compound, azo and azoxy base type ferroelectric low molecular weight liquid crystal compound, biphenyl and aromatics ester type ferroelectric low molecular weight liquid crystal compound, halogen, cyano group and other ring substituents Examples include the introduced ferroelectric low-molecular liquid crystal compound and the ferroelectric low-molecular compound having a heterocycle.

Examples of the Schiff base ferroelectric low-molecular liquid crystal compound include compounds (1) to (4) shown below.

Examples of the azo and azoxy ferroelectric low-molecular liquid crystal compounds include the following (5) and (6).

As the biphenyl and aromatic ester-based ferroelectric low-molecular liquid crystal compounds, for example, the following (7),
(8) is mentioned.

Examples of the ferroelectric low molecular weight liquid crystal compound having a ring substituent such as halogen or cyano group include the following compounds (9) to (11).

Examples of the ferroelectric low molecular weight liquid crystal compound having a heterocycle include the following compounds (12) and (13).

The above compounds are typical compounds of the ferroelectric low molecular weight liquid crystal compound, and the ferroelectric low molecular weight liquid crystal compound of the present invention is not limited to those having these structural formulas.

The non-liquid crystal optically active compound is not particularly limited, but examples thereof include the compounds shown below.

The liquid crystalline polymer of the present invention can be used as a ferroelectric liquid crystal by blending the above-mentioned optically active compound. The compounding amount of the optically active compound is preferably more than 0 and 90 mol% or less with respect to the entire composition. When the optically active compound is non-liquid crystalline, it is usually
It is used by blending more than 0 and 30 mol% or less, preferably 10 to 20 mol%. When the optically active compound has liquid crystallinity, it is usually more than 0 and 90 mol% or less, preferably,
Used by blending 20 to 80 mol%.

If necessary, the liquid crystalline polymer of the present invention can be used as a mixture of polymer liquid crystals, or as a mixture with another polymer. In addition, various inorganic, organic, and metal additives including stabilizers and plasticizers can be added and used.

[Examples] 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 are NM
Confirmation by R, IR, and elemental analysis, and measurement of phase transition temperature and confirmation of phase were performed by DSC and polarizing microscope, respectively. (Glass: glass state, SmC ^* : chiral smectic C phase, SmA: Snackuccic A phase, Iso: isotropic phase, the numbers of phase transition behavior are the phase change temperatures in ° C.) Example 1 [ Monomer synthesis] 1. Synthesis of 6-bromohexyl allyl ether 5.0 g of allyl alcohol and 65 g of 1,6-dibromohexane were dissolved in 80 ml of hexane. There, 110 g of 50% aqueous sodium hydroxide solution and 1.5 g of tetrabutylammonium bromide
Was 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. Then, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 12.6 g of a desired 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 ethyl hydroxybenzoate and 2.0 g of potassium hydroxide were dissolved in 50 ml of ethanol and refluxed for 12 hours. Then, 150 ml of an aqueous potassium hydroxide solution (containing 6.0 g of potassium hydroxide) was added, and the mixture was refluxed for 12 hours. After the reaction, hydrochloric acid was added dropwise to adjust the pH to 2, and the generated precipitate was collected. The precipitate obtained is washed thoroughly with water, then heated under reduced pressure to dryness and the desired carboxylic acid derivative (6.5 g)
Got (Yield 87%) 1. Synthesis of 4 '-(n-butoxycarbonyl) phenyl ester of 4- (6-allyloxyhexyloxy) benzoic acid 2 g of carboxylic acid obtained in 1. was catalyzed by 2 drops of pyridine Added as. To this, a large excess of thionyl chloride, that is, 20 ml of thionyl chloride was added as a solvent, and the mixture was stirred at 80 ° C. for 4 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride form.

A toluene solution containing 1.9 g of p-hydroxybenzoic acid n-butyl ester and 1.0 g of pyridine was added dropwise to the toluene solution of the above acid chloride form. Then, the reaction was carried out at room temperature for 1 day. After the reaction, it was washed with water and dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 3.7 g of the target phenylbenzoate compound. (Yield 81%) 1. Epoxidation 1.8 g of the phenylbenzoate compound 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 product was washed with an aqueous potassium carbonate solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 1.7 g of a monomer which is an epoxy compound represented by the above structure. The obtained product was used for the next reaction without further purification.

[Polymerization] 1.7 g of the monomer obtained in 1. was dissolved in dichloromethane, and the system was replaced with argon. There, stannic chloride 21μ
1 (5 mol% of monomer) was added. Polymerization was carried out at room temperature for 3 days. After the reaction, the reaction solution was concentrated and purified by column chromatography to obtain 1.2 g of a target polymer having a repeating unit represented by the following formula. (Yield 71%) The δ (ppm) of ¹ H-NMR (CDCl ₃ ) of this polymer is shown below. The molecular weight and phase transition behavior are shown in Table 1.

δ (ppm) 0.8-2.0 (m, 15H), 3.2-3.5 (m, 7
H), 3.7 (t, 2H), 4.0 (t, 2H), 6.8 (d, 2H),
7.2 (d, 2H), 8.0 (d, 4H) Example 2 [Synthesis of Monomer] Synthesis of 2.4 '-(6-allyloxyhexyloxy) biphenyl-4-carboxylic acid n-butyl ester 6.6 g of 6-bromohexyl allyl ether obtained in 1 of Example 1, 4-hydroxybiphenyl-4 -8.1 g of carboxylic acid n-butyl ester and 4.2 g of potassium carbonate,
The mixture was heated and stirred in 2-butanone at 80 ° C for 12 hours. After the reaction
The inorganics were removed by filtration, then the solvent was removed under reduced pressure.
The residue was recrystallized from methanol to obtain 13.5 g of the target biphenyl derivative. (Yield 95%) 2. Epoxidation 13.5 g of the biphenyl derivative obtained in 2. was dissolved in dichloromethane and the system was replaced with argon. Then, 7.4 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 11.8 g of potassium carbonate. Then, after drying over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 11.8 g of a desired epoxy compound monomer represented by the above structural formula. (Yield 85%) The obtained monomer was a liquid having high viscosity at room temperature.
The obtained monomer was used in the next reaction without further purification.

[Polymerization] 11.8 g of the monomer obtained in 1. was dissolved in dichloromethane, and the system was replaced with argon. There, stannic chloride 14
0 μl (5 mol% of monomer) was added. Polymerization was carried out at room temperature for 4 days. After the reaction, the reaction solution was concentrated and reprecipitated in methanol. The precipitate was collected and purified by column chromatography to obtain 7.7 g of a target polymer having a repeating unit represented by the following formula.

The δ (ppm) of ¹ H-NMR (CDCl ₃ ) of this polymer is shown below. The molecular weight and phase transition behavior are shown in Table 1.

δ (ppm) 0.8-2.1 (m, 15H), 3.2-3.8 (m, 7
H), 3.9 (t, 2H), 4.1 (t, 2H), 6.8 (d, 2H),
7.4 (d, 4H), 8.0 (d, 2H) Example 3 Synthesis of 1,10 in place of 1,6-dibromohexane in Example 1
-Dibromodecane was synthesized similar to Example 1 by substituting 4-hydroxybiphenyl-4'-carboxylic acid n-butyl ester for p-hydroxybenzoic acid 2-methylbutyl ester.

The chart of ¹ H-NMR (CDCl ₃ ) of this polymer is shown in FIG. 1, and δ (ppm) is shown below. The molecular weight and phase transition behavior are shown in Table 1.

δ (ppm) 0.8-2.1 (m, 23H), 3.3-3.7 (m, 7
H), 3.8 (t, 2H), 4.1 (t, 2H), 6.8 (d, 2H),
7.1 (d, 4H), 7.7 (2d, 4H), 8.1 (2d, 4H) Example 4 [Synthesis of Monomer] 7. Synthesis of 10-iododecyl allyl ether 2.0 g of allyl alcohol was dissolved in 50 ml of THF. There, 2.5 g of 60% sodium hydride (a mixture of sodium hydride and mineral oil with a sodium hydride content of 60% by weight)
Was added little by little. After stirring for 30 minutes at room temperature, 1,10-
A solution consisting of 33.0 g of diiododecane and 10 ml of THF was added dropwise. 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 to obtain the desired ω-haloalkyl allyl ether 8.
2g was obtained. (Yield 53%) 4. Synthesis of 4 '-(10-allyloxydecyloxy) biphenyl-4-carboxylic acid 10-iododecyloxyallyl ether obtained in 4.
8.2g, 4'-hydroxybiphenyl-4-carboxylic acid 4.
8g, potassium hydroxide 3.3g and water 5.0g methanol 50
After refluxing in ml for 24 hours to react, 500 ml of water was added, and then 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%) 4. Synthesis of 4 ″-(n-butyloxycarbonyl) phenyl 4 ′-(10-allyloxydecyloxy) biphenyl-4-carboxylate To 4.3 g of the carboxylic acid compound obtained in 4. Pyridine (2 drops) and thionyl chloride (5.0 g) were added, 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 body p-hydroxybenzoic acid n-butyl ester 2.0 g
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. . After the reaction, it was washed with water and dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was recrystallized from methanol to obtain the desired phenylbiphenylcarboxylate compound. (Yield 85%) 4. Epoxidation Phenylbiphenylcarboxylate obtained in 4.
5.2 g was dissolved in dichloromethane and the system was purged with argon. 2.3 g of m-chloroperbenzoic acid was added and reacted at room temperature for 7 hours. After the reaction, the product was washed with an aqueous solution of potassium carbonate, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 4.8 g of an epoxy compound monomer represented by the above structure. The obtained product was used for the next reaction without further purification.

[Polymerization] 4.8 g of the monomer obtained in 1. was dissolved in dichloromethane, and the system was replaced with argon. There, stannic chloride 46μ
1 (5 mol% of monomer) was added. Polymerization was carried out at room temperature for 3 days. After the reaction, the reaction solution was concentrated and purified by column chromatography to obtain 3.3 g of a target polymer having a repeating unit represented by the following formula.

The chart of ¹ H-NMR (CDCl ₃ ) of this polymer is shown in FIG. 2, and δ (ppm) is shown below. The molecular weight and phase transition behavior are shown in Table 1.

δ (ppm) 0.8-2.0 (m, 23H), 3.4-3.7 (m, 7
H), 3.8 (t, 2H), 4.1 (t, 2H), 6.8 (d, 2H),
7.1 (d, 2H), 7.6 (2d, 4H), 8.1 (2d, 4H) Example 5 [Synthesis of monomer] 5. 4- (8-allyloxyoctyloxy) -4 '
-Hydroxybiphenyl synthesis 8-bromooctyl allyl ether 5.0 g, 4,4'-diphenol 12 g and potassium hydroxide 9.0 g in ethanol 2
Refluxed for 0 hours. After the reaction, inorganic substances were removed by hot filtration. After ethanol was distilled off under reduced pressure, the residue was dissolved in a water: acetone mixed solvent. Dilute hydrochloric acid was added to the obtained solution to adjust the pH to 2. Then, this solution was heated to evaporate acetone, insoluble matter was collected by filtration while hot, and then recrystallized from ethanol to obtain 3.5 g of a desired biphenyl derivative. (Yield 49%) 5. 4- (8-allyloxyoctyloxy) -4 '
Synthesis of-(pentanoyloxy) biphenyl 1.5 g of the biphenyl derivative obtained in 5. and 0.4 g of pentanoic acid were dissolved in dichloromethane. To the obtained solution, 1.3 g of dicyclohexylcarbodiimide and 0.1 g of 4-pyrrolidinopyridine were added, and the mixture was stirred at room temperature for 1 day. After the reaction, insoluble materials 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 1.5 g of the target biphenyl derivative. (Yield 82%) 5. 1.5 g of the phenyl derivative obtained in 5. epoxidation was dissolved in dichloromethane and the system was replaced with argon. 0.9 g of m-chloroperbenzoic acid was added and reacted at room temperature for 1 day. After the reaction, it was washed with an aqueous potassium carbonate solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 1.5 g of a monomer which is an epoxy compound represented by the above structure. The obtained product was used for the next reaction without further purification.

[Polymerization] 1.5 g of the monomer obtained in 5. was dissolved in dichloromethane, and the system was replaced with argon. There, stannic chloride 19μ
1 (5 mol% of monomer) was added. Polymerization was carried out at room temperature for 3 days. After the reaction, the reaction solution was concentrated and purified by column chromatography to obtain 0.9 g of a target polymer having a repeating unit represented by the following formula.

The δ (ppm) of ¹ H-NMR (CDCl ₃ ) of this polymer is shown below. The molecular weight and phase transition behavior are shown in Table 1.

δ (ppm) 0.8-1.9 (m, 19H), 2.1 (t, 2H), 3.3
-3.7 (m, 7H), 4.1 (t, 2H), 6.8-7.4 (m, 8H) Example 6 [Synthesis of monomer] 6. 4- [4- (8-allyloxyoctyloxy)
Synthesis of phenyl] phenol 8-bromooctyl allyl ether 7.0 g, biphenyl-
1,4 g of 4,4'-diol and 8.0 g of potassium hydroxide were refluxed in methanol for 20 hours. After methanol was distilled off under reduced pressure, acetone was added and hydrochloric acid was added dropwise. The insoluble material was removed by filtration, and the solvent was evaporated under reduced pressure. The residue was recrystallized from ethanol to obtain the desired phenol. (Yield 72%) 6. Synthesis of 4- [4- (8-allyloxyoctyloxy) phenyl] phenyl-4'-butoxybenzoate 8.0 g of thionyl chloride was added to 3.9 g of 4-butoxybenzoic acid,
The mixture was 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 form.

7.1 g of phenol obtained in 6. and 2.0 g of triethylamine
The THF solution of the above acid chloride form was added dropwise to the THF solution of, and the mixture was stirred at room temperature for 1 day. Then, ether was added, the mixture was washed with water, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was recrystallized from methanol to obtain 9.0 g of the target ester.
(Yield 85%) 6. 9.0 g of the ester compound obtained in epoxidation 6 was dissolved in dichloromethane, and the system was replaced with argon. Then, 4.4 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 objective monomer that is an epoxy compound represented by the above structural formula 8.
6g was obtained.

[Polymerization] 8.6 g of the monomer obtained in 6. was dissolved in dichloromethane, and the system was replaced with argon. There, stannic chloride 19μ
1 (5 mol% of monomer) was added. Polymerization was carried out at room temperature for 30 hours. After the reaction, the reaction solution was concentrated and purified by column chromatography to obtain 4.8 g of a target polymer having a repeating unit represented by the following formula.

The δ (ppm) of ¹ H-NMR (CDCl ₃ ) of this polymer is shown below. The molecular weight and phase transition behavior are shown in Table 1.

δ (ppm) 0.8-2.0 (m, 19H), 3.4-3.6 (m, 7
H), 3.8 (t, 2H), 3.9 (t, 2H), 6.8 (2d, 4H),
7.3 (m, 6H), 8.0 (d, 2H) Example 7 [Synthesis of Monomer] 7. Synthesis of 14-bromotetradecyl allyl ether 2.0 g allyl alcohol, 1.7 g 60% sodium hydride, 1,
30 g of 14-dibromotetradecane, 4.
The same reaction and operation as described in (1) above were carried out to obtain 7.9 g of the desired ω-haloalkylaryl ether compound. (Yield 69%) 7. Synthesis of 4- (14-allyloxytetradecyloxy) benzoic acid 7.9 g of the allyl ether obtained in 7., 3.6 g of p-hydroxybenzoic acid methyl ester and 1.6 g of potassium hydroxide were added. The same reaction and operation as in Example 1 were carried out to obtain 6.8 g of the desired carboxylic acid compound. (Yield 74%) 7. Synthesis of 4- (14-allyloxytetradecyloxy) benzoic acid (hexyloxy) phenyl ester 4- (14-allyloxytetradecyloxy) benzoic acid
6.8 g, 3 drops of pyridine and 6.2 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 form.

A toluene solution of the acid chloride was added dropwise to a toluene solution containing 3.4 g of 4-hexyloxyphenol and 1.8 g of triethylamine, and the mixture was stirred at room temperature for 8 hours. Then, it was washed with water and dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 7.1 g of the target ester. (Yield 72%) 7. 7.1 g of the ester obtained in 7. epoxidation was dissolved in dichloromethane and the system was replaced with nitrogen. Then m-chloroperbenzoic acid
3.2 g 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 6.7 g of a desired monomer which is an epoxy compound represented by the above structural formula. (Yield 92%) [Polymerization] 6.7 g of the monomer obtained in 7. was dissolved in dichloromethane, and the system was replaced with argon. There, stannous chloride 67μ
1 was added. Polymerization was carried out at room temperature for 30 hours. After the reaction, the reaction solution is concentrated and purified by column chromatography to obtain a target polymer having a repeating unit represented by the following formula.
Obtained 3.8 g.

The δ (ppm) of ¹ H-NMR (CDCl ₃ ) of this polymer is shown below. The molecular weight and phase transition behavior are shown in Table 1.

δ (ppm) 0.8-2.0 (m, 35H), 3.4 (m, 7H), 3.8
(T, 2H), 3.9 (t, 2H), 6.9 (m, 6H), 8.0
(D, 2H) Example 8 In Example 1, 3-buten-1-ol was used instead of allyl alcohol, and 1,6-dibromohexane was used instead of 1,6-dibromohexane.
1,10-dibromodecane, p-hydroxybenzoic acid 2-
It can be synthesized by using 4-hydroxybiphenyl-4'-carboxylic acid n-butyl ester instead of methyl butyl ester. ¹ H of the obtained polymer
-Δ (ppm) of NMR (CDCl ₃ ) is shown below. The molecular weight and phase transition behavior are shown in Table 1.

δ (ppm) 0.8-2.1 (m, 23H), 3.2-3.7 (m, 9
H), 3.8 (t, 2H), 4.1 (t, 2H), 6.8 (d, 2H),
7.1 (d, 2H), 7.7 (2d, 4H), 8.1 (2d, 4H) Example 9 Synthesis of 1.9 g of the monomer of Example 1 and 3.6 g of the monomer of Example 3 were dissolved in dichloroethane, and the system was replaced with argon. Boron trifluoride (1 mol% of the monomer) was added thereto and polymerized at room temperature for 8 hours. After the reaction, the product was purified by column chromatography to obtain 3.9 g of the above copolymer. (Yield 70
%) Δ (ppm) value and peak intensity ratio of the obtained polymer are shown below. The molecular weight and phase transition behavior are shown in Table 1.

δ (ppm) Peak intensity ratio 0.8−2.1 5.0 3.2−3.7 1.8 3.7−4.1 1 6.8−8.1 2.6 Example 10 (Mn = 1700) [Polymer of Example 1] A liquid crystal composition having a SmC ^* phase with a content of the low molecular weight liquid crystalline compound (B) of 20 mol% or more was obtained in the above mixed system. When the response time was examined, the content of the low-molecular liquid crystal compound was 70.
With a composition of mol% or more, the response speed was almost the same as the response speed of the low molecular weight liquid crystal compound alone.

That is, the response speed of the composition in which the molar ratio of (A) and (B) was 3: 7 was 210 μsec at the measurement temperature of 5 ° C., and the response speed of (B) alone was 200 μsec at the measurement temperature of 5 ° C.

The phase transition behavior of this liquid crystal composition was as follows.

However, the response speed here was measured as follows.

That is, a liquid crystal was sandwiched between two ITO glass substrates, and an alignment cell having a thickness of about 2 μm was produced by a shearing method.
Further, an electric field of ± 20 MV / m was applied under crossed Nicols, and the time required for the change in the light transmittance at that time to reach 0 to 90% was measured.

Example 11 The liquid crystal of the mixed system shown in Example 10 was melted at 50 ° C. for 15 μm.
m film, sandwiched between two pairs of rollers with different surface speeds (front: 3 m / min, back: 2 m / min) via two PET films (thickness 100 μm) and uniaxially stretched (5 times) ) Was carried out and the SmA phase was gradually cooled at 5 ° C./min, and it was confirmed by observation with a polarizing microscope that a good oriented film was obtained.

Comparative Example 1 (Mn = 1800) Phase transition behavior When the response time and the phase transition behavior when the content of the low molecular weight liquid crystalline compound (B) was 70 mol% in the above mixed system were examined,
The response speed of the composition in which the molar ratio of (A) and (B) was 3: 7 was 270 μsec at the measurement temperature of 5 ° C., and the response speed of (B) alone was 200 μsec at the measurement temperature of 5 ° C.

The phase transition behavior of this liquid crystal composition was as follows.

Phase transition behavior The compound A of Comparative Example 1 was synthesized as follows.

4- (9-decenyloxy) benzoic acid 30 mmol (8.3
g) and a solution of thionyl chloride (60 mmol, 7.4 g) in toluene (50 ml) were stirred at 80 ° C. for 3 hours and then concentrated under reduced pressure to obtain an acid chloride. A solution of the acid chloride in THF (5 ml) was added dropwise to a solution of 4-hydroxybenzoic acid butyl ester (25 mmol, 4.6 g) and triethylamine (5 ml) in THF (50 ml), and the mixture was stirred at room temperature for 5 hours. The reaction mixture was concentrated, water was added, and the mixture was extracted with ether. The extract was dried, concentrated, and purified by column chromatography to obtain 10.1 g (yield 90%) of a monomer precursor.

A solution of 10 mmol (4.5 g) of the monomer precursor and 15 mmol (2.6 g) of m-chloroperbenzoic acid in 50 ml of methylene chloride was replaced with argon and then stirred at room temperature for 5 hours. The reaction solution was washed with an aqueous potassium carbonate solution and water, dried, and filtered. After substituting the filtrate with argon, 0.5 mmol of stannic chloride was added and reacted at room temperature for 4 days. The reaction liquid was concentrated and then purified by column chromatography to obtain a target polymer.

Example 12 [Compound of Example 2] B is Mol.Cryst.Liq.Cryst., 1985,129,61-74 JPLe Pes
ant, JNPerbet, B.Monrey, M.Hareng, G.Decobert, JCDu
Synthesized according to bois. The phase transition behavior of this compound is as follows.

In the above mixed system, the content of the non-liquid crystalline optically active substance (B) is 5
A liquid crystal composition having an SmC ^* phase was obtained at ˜20 mol%. When the response time was examined when the content of (B) was 10 mol%, the response speed was 2 msec at the measurement temperature of 25 ° C.

The phase transition behavior of this liquid crystal composition was as follows.

Phase transition behavior Comparative example 2 (Mn = 1700) In the above mixed system, the content of the non-liquid crystalline optically active substance (B) is 5
A liquid crystal composition having an SmC ^* phase was obtained at ˜20 mol%. When the response time when the content of (B) was 10 mol% was examined, the response speed was 3 msec at a measurement temperature of 25 ° C.

The phase transition behavior of this liquid crystal composition was as follows.

Phase transition behavior The polymer (A) is a compound 4- (9-decenyloxy) obtained by reacting 4-hydroxy-4′-biphenylcarboxylic acid n-butyl ester with 9-decenyl bromide under Williamson reaction conditions. ) -4'-biphenylcarboxylic acid n-butyl ester was obtained by epoxidizing and further polymerizing according to the method shown in the synthesis of the compound (A) in Comparative Example 1. The phase transition behavior was as follows.

[Effects of the Invention] The liquid crystalline polymer obtained by the present invention is blended with an optically active compound such as a low-molecular-weight ferroelectric liquid crystal compound or a non-liquid crystalline optically active substance so that it can be strengthened in a wide temperature range including room temperature The ferroelectric liquid crystal material that exhibits dielectric properties and is excellent in film-forming property and high-speed response to an electric field has an extremely great industrial value.

Further, the intermediate of the present invention is preferably used for producing the above liquid crystalline polymer.

[Brief description of drawings]

1 and 2 are NMR charts of the polymers obtained in Examples 3 and 4.

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Claims (2)

[Claims] 1. A liquid crystalline polymer having a repeating unit represented by the following general formula. (In the formula, k is an integer of 2 to 30, l is an integer of 1 to 10, X is -COO- or -OCO-, R ² is -COOR ^3, -OCOR ^3, an -OR ³ or R ^3, R ³ is an alkyl group having no asymmetric carbon. ) 2. An epoxy compound having a structure represented by the following general formula. (In the formula, k is an integer of 2 to 30, l is an integer of 1 to 10, X is -COO- or -OCO-, R ² is -COOR ^3, -OCOR ^3, an -OR ³ or R ^3, R ³ is an alkyl group having no asymmetric carbon. )