JPH0386846A - Liquid crystal compound and liquid crystal polymer therefrom - Google Patents

Abstract

NEW MATERIAL:A liquid crystal compound of formula I [(j) is 1-10; (k) is 1-30; (m) is 0-5; R is of formula II, formula III (X is COO or OCO), formula IV, etc.]. EXAMPLE:1-ethoxycarbonylethyl 4-{4'-[4''-(10allyloxydecyloxy) phenyl]benzoyloxy}benzoate. USE:A raw material for the synthesis of a liquid crystal polymer made up of recurring unit of formula V. Giving ferroelectricity at near normal temperature as well as quick in response to external factors, thus capable of moving picture image display, and useful as a display element for large-sized pictures or curved pictures. PREPARATION:A compound of formula VI ((q)is 1 or 2) is halogenated and reacted with an alkyl lactate into a compound of formula VII, which is then reacted with benzylamine into a compound of formula VIII. This compound is then reacted with a compound of formula IX (p) is 1 or 2), thus obtaining the corresponding compound of the formula I (of formula X).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a liquid crystal compound and a liquid crystal polymer synthesized from the compound. More specifically, the present invention is applicable to the field of optoelectronics, particularly display elements for calculators and watches, electro-optical shutters, electro-optical apertures, optical modulators, optical communication optical path switching switches, memories, liquid crystal printer heads, variable focal length lenses, etc. Liquid crystal polymers that are useful as various electro-optical devices such as those that exhibit ferroelectricity even at room temperature, have a fast response speed to external factors, and are capable of displaying moving images, and liquid crystals that are suitable for use in the synthesis of these polymers. It concerns compounds.

In particular, the liquid crystal polymer of the present invention has high practicality as a display element for large screens and curved screens.

[Conventional technology]

Conventionally, display elements using low molecular weight liquid crystals have been widely used in digital displays such as calculators and watches. In these fields of application, conventional low-molecular-weight liquid crystals are usually used by sandwiching them between two glass substrates whose spacing is controlled on the order of 5 microns. However, such adjustment of the gap has not been possible with large screens and curved screens. As one means of solving this difficulty, attempts have been made to polymerize liquid crystals and make them moldable. For example, JP-A No. 55-21479, JP-A No. 63-992
04 and EP-0184482 disclose various polyacrylate-based ferroelectric polymer liquid crystals, but these polymer liquid crystals exhibit ferroelectricity in a high temperature range and are not practical. It was difficult to say that the results were necessarily satisfactory. Furthermore, these polymer liquid crystals have the disadvantage that their response speed to changes in the amount of transmitted light, etc. to changes in external factors such as electric fields is generally slow.

[Problem to be solved by the invention]

An object of the present invention is to provide a device that exhibits ferroelectricity in a wide temperature range including around room temperature, has a fast response to external factors, is capable of displaying moving images, and is advantageously used as a display element for large screens and curved screens. The objective is to provide a liquid crystal polymer that can

Another object of the present invention is to provide a liquid crystal compound that can be suitably used for the bottom of a liquid crystal polymer.

[Means to solve the problem]

As a result of intensive studies to solve the above problems, the present inventors have found that a liquid crystal polymer obtained by polymerizing a specific epoxy type compound having an alkyl lactate structure exhibits high-speed response in a wide temperature range around room temperature. Furthermore, the inventors have discovered that a specific vinyl compound having an alkyl lactate structure is suitable as a raw material for the above-mentioned liquid crystal polymer, leading to the completion of the present invention.

That is, the present invention is based on the following general formula (1) [However, in formula (1), j represents an integer of 1 to 10, k represents an integer of 1 to 30, and m represents an integer of 0 to 5. , where X is -COO- or -oco-teal.

The present invention also provides the following general formula %) () [However, j in formula (II) is 1 to 10, preferably 1 to
k represents an integer of 1 to 30, preferably 6 to 12, m represents an integer of O to 5, where X is -
The present invention provides a liquid crystal polymer having a repeating unit represented by COO- or -0CO-teal.

The liquid crystal polymer of the present invention can be obtained by polymerizing an epoxy compound represented by the following formula (III) obtained by epoxidizing the liquid crystal compound represented by the above formula (I) alone or in combination.

CI[I) [However, j, m, and R in formula (Ill) have the same meanings as above. ] Furthermore, other epoxy compounds, such as non-liquid crystal epoxy compounds, may be copolymerized as long as there is no problem in achieving the object of the present invention.

The number average molecular weight of the polymer of the present invention is preferably 1,0
00 to 500,000. If it is less than 1,000, the moldability of the copolymer as a film or coating may be impaired, while if it exceeds 5oo or ooo, undesirable effects such as slow response speed may appear. . A particularly preferable range of the number average molecular weight cannot be unconditionally defined because it depends on the type of R, the values of j and k, the value of -, etc., but it is 1,000 to 100,000.

The liquid crystal compound (I) used as a raw material for the liquid crystal polymer of the present invention can be prepared, for example, by the following method.

C) 13C00+C00H 1) 5octz (1) 2)　　　　C)I.

(2) As shown in the above reaction formula, acetoxy aromatic carboxylic acid (1) (q is 1 or 2) is halogenated with a halogenating agent such as thionyl chloride to form an acid chloride, and this is reacted with an alkyl lactate. Ester form (2) is obtained.

This is reacted with benzylamine etc. to form a hydroxyl form (3
).

1) SOCl2 2) (3) HI -COOCRCOO(CHz) -CHs (5
) Next, as shown in the above reaction formula, the aromatic carboxylic acid (4) having a terminal double bond (p is 1 or 2) and the hydroxy compound (3) are reacted to form the desired liquid crystal compound (5).
get.

When the liquid crystal compound of the present invention is epoxidized using a peracid such as m-chloroperbenzoic acid in a suitable solvent such as dichloromethane, an epoxy monomer is obtained. Next, one or more of the epoxy monomers thus obtained are polymerized or copolymerized with other epoxy compounds to synthesize the liquid crystal polymer of the present invention. As a method, a known cationic polymerization method or the like can be employed.

Various catalysts are known as catalysts for cationic polymerization, including protonic acids such as sulfuric acid, phosphoric acid, and perchloric acid, boron trifluoride, aluminum chloride, titanium tetrachloride, and Lewis catalysts such as tin chloride. Examples include acids, boron trifluoride etherate, and among these, stannic chloride is 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 molecule is 1130,
000 or more can be obtained.

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

Although the polymerization temperature varies depending on the type of catalyst, 0 to 30°C is usually suitable.

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

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

In the bulk polymerization method, the seven polymers and an initiator are sufficiently mixed, the mixture is sufficiently degassed, and two substrates,
For example, by introducing the polymer between glass substrates and heating, it is also possible to directly immobilize the polymer 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.

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

The polymer thus obtained can be formed into a film by a known film forming method, such as a casting method, a T-die method, an inflation method, a calender method, or a stretching method. Film-like polymers can be sandwiched between not only two ordinary glass substrates, but also large glass substrates, curved glass substrates, polyester films, etc., and used in various applications such as liquid crystal displays, electro-optical shutters, electro-optical apertures, etc. It can be used in the field of optoelectronics. Alternatively, a copolymer solution dissolved in a suitable solvent can be applied to the surface of a substrate such as a glass substrate, and the solvent can be evaporated to form a film in direct contact with the substrate surface.

The liquid crystal polymer of the present invention can be determined by measuring its phase transition temperature.
It was confirmed that the chiral smectic C-phase liquid crystal state is realized in a wide temperature range including around room temperature. It was also confirmed that the response time at around room temperature was fast.

The polymers of the present invention combine the properties of smectic phase liquid crystals with the properties of typical polymers, such as easy moldability, and therefore have many applications in the fields of integrated optics, optoelectronics, and information storage. There is sex. For example, liquid crystal displays such as digital display displays of various shapes, electro-optical switches such as electro-optic shutters and optical path switching switches for optical communication, electro-optic apertures, memory elements, optical modulators, liquid crystal optical printer heads, variable focal length lenses, etc. can be used as various electro-optical devices.

If necessary, the above polymers may be mixed with each other, mixed with other polymers, and various inorganic, organic, and metal additives may be added, including other liquid crystal compounds, adhesives, stabilizers, plasticizers, etc. Improvements can be made by a number of processing methods well known in the art, such as addition.

〔Example〕

Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.

The structure of the obtained liquid crystal compound and liquid crystal polymer is as follows:
It was confirmed by NMR2IR1 elemental analysis, and the phase transition temperature was measured and the phase was confirmed by DSC and polarizing microscope, respectively.

The NMR charts of the liquid crystal compounds obtained in Examples 1 to 5 and the liquid crystal polymers obtained in Examples 6 to 13 are shown in the first column.
5 and 6 to 12.

Further, the phase transition behavior and electric field response speed of each liquid crystal compound and liquid crystal polymer are shown in the table. (G glass state, Cry: crystalline state, SmC": chiral smectic C phase, Sm
A: Smectic A phase, N9: Chiral nematic phase, Iso: Isotropic phase, The number of phase transition behavior indicates the phase change temperature in °C
It is expressed as ) The electric field response speed was measured as follows.

-"Place a liquid crystal compound or liquid crystal polymer between two 20x10m ITO substrates, adjust the thickness to 25μ with a spacer, apply an alternating current electric field E = 2x10'V/m, and the amount of transmitted light at that time. The response time of the change (0→90%) was measured.

Example 1 1-ethoxycarbonylethyl 4-[4'(4'-(
10-allyloxydecyloxy) phenyl) benzoyloxy] 52ξ mol (3.0 g) of benzoate allyl alcohol was dissolved in 50 d of tetrahydrofuran (THF).

2.3 g of 60% sodium hydride was added little by little. After stirring for 10 minutes at room temperature, 127 mmol (50,0 g) of 1.10-jododecane and THFloo
After the completion of the dropwise addition, the resulting mixture was refluxed for 12 hours.Next, a small amount of water was added to the reaction solution to decompose the remaining sodium hydride. After THF was distilled off under reduced pressure, water and dichloromethane were added to the residue and the mixture was shaken.

The dichloromethane layer was collected and dried over magnesium sulfate. The dried dichloromethane layer was concentrated under reduced pressure, and the residue was purified by column chromatography to obtain the desired ω
-13.1 g of haloalkyl allyl ether was obtained. (
Yield: 78%) 1, ■ 25 mmol of 4'-10-allyloxydecyloxylether (8.2 g), 22 mmol of 4'-hydroxybiphenyl-4-carboxylic acid (4.8 g)
), potassium hydroxide 50 mmol (3.3 g) and water 5
．． After refluxing and reacting 0 g in 50 d of methanol for 24 hours, 500 d of water was added and hydrochloric acid was added dropwise to adjust the pH.
-2. The precipitate was collected and dried under reduced pressure. The obtained crude product was recrystallized from acetic acid to obtain the desired carboxylic acid form 4.
．． 3g was obtained.

(Yield 53%) 30 ξ rimoles (5.4 g) of 4-acetoxybenzoic acid and 90 ξ rimoles (10.8 g) of thionyl chloride in toluene 5
After stirring the 0d solution at 80°C for 2 hours, the reaction solution was concentrated under reduced pressure to obtain an acid chloride.

The THF solution of the above acid chloride was added dropwise to a 30d solution of 20 mol (2.4 g) of L-ethyl lactate and triethylamine 5111, and the mixture was stirred for 10 hours. After concentrating the reaction solution, water was added and extracted with ether. . The extract concentrate was purified by column chromatography to obtain 9 g of the desired acetoxy compound a. (Yield 63%) 12.5-1 mol (3,5 mol) of the acetoxy compound obtained in 1.
70 mmol (6.4 g) of benzylamine was added to the ether 200 M1 solution of g) and stirred for 5 hours.

After washing the reaction solution with water, it was purified by column chromatography to obtain 1.2 g of the desired hydroxy compound. (Yield 42%) Sifenino ν benzoyloxybenzonyhen 3 sushi 1, 8 mmol (3.3 g) of the carboxylic acid compound obtained in ① and 24ξ mol (2.9 g) of thionyl chloride in toluene 30
- After stirring the solution at 80°C for 2 hours, the resulting reaction solution was concentrated under reduced pressure to obtain an acid chloride. 1. A THF 3-m solution of the above acid chloride was added dropwise to a THF 10 m solution of 4 mmol (0.95 g) of the hydroxyl compound obtained in step (2) and triethylamine 1111, and the solution was stirred for 10 hours. After concentrating the reaction solution, water was added. The mixture was extracted with ether. After the extract was condensed with -a, it was purified by column chromatography to obtain 2.0 g of the desired liquid crystal compound. (yield
79%) Table 2 shows the phase transition behavior and response speed to electric field of the obtained liquid crystal compound.

Example 2 1-ethoxycarbonylethyl 4- (4-(10-
Allyloxydecyloxy)benzoyloxy)penzoate CH3 10-iododecyl allyl ether 70 mmol (22
, 7g), p-hydroxybenzoic acid methyl ester 70
ξ Limol (10,6 g) and 70 mmol (9,6 g) of potassium carbonate were refluxed in absolute ethanol for 15 hours.
Potassium hydroxide aqueous solution (potassium hydroxide 4.
After the reaction was heated at 80''C for 5 hours, the reaction solution was acidified with hydrochloric acid and concentrated under reduced pressure.

Add water to the residue to suspend it, collect the insoluble matter and dry it,
-(10-allyloxydecyloxy)benzoic acid 18.
7g was obtained. (Yield 80%) Next, a solution of 1049 moles (3.3 g) of 4-(10-allyloxydecyloxy)benzoic acid and 18 [rimole (2.2 g) of thionyl chloride] in 30 M of toluene was heated at 80°C.
After stirring for an hour, the mixture was concentrated under reduced pressure to obtain an acid chloride.

Next, a THF5IIIt solution of the acid chloride was added dropwise into a THFIO solution of 8 mmol (2.0 g) of 1-ethoxycarbonylethyl 4-hydroxybenzoate and triethylamine 1-, and the reaction was stirred at room temperature for 10 hours. After concentrating the liquid, water was added and extracted with ether. The extract was dried and subjected to fA condensation, and then purified by column chromatography to obtain the desired liquid crystal compound 3.2.
I got g. (Yield 73%) Table 2 shows the phase transition behavior and response speed to electric field of the obtained liquid crystal compound.

Example 3 1-ethoxycarbonylethyl 4'-[4"-(8
-(3-Butenyloxy)octyloxy)benzoyloxycopyphenyl-4-carboxylate & 27,2g) and 60
1 of Example 1 using 1.7 g of sodium hydride.
The same operation as in (2) was carried out to obtain 8.4 g of the desired ω-haloalkyl alkenyl ether. (Yield 76%) 3. 30 mmol (7.9 g) of the ether obtained in ①, 30 mmol (4.9 g) of methyl 4-hydroxybenzoate.
6g) and potassium carbonate 30 also rimole (4.

2g), perform the same operation as Z■ in Example 2,
8.1 g of the target benzoic acid derivative was obtained (yield: 84
%) 3, ■ 1-ethoxycarbonyl 4'-hydroxybiphenyl-4-carboxylate 30 main mols of 4'-hydroxybiphenyl-4-carboxylic acid (7.7 g)
, 20 mmol (5.4 g) of L-ethyl lactate and 77049 mol (6.4 g) of benzylua were used in Example 1.
1, ■, 1. The same operation as (2) was performed to obtain 3.2 g of the desired hydroxyl compound. (Yield 51%) 10 mmol (3.2 g) of the benzoic acid derivative obtained in 3.
After adding 30 M1 of thionyl chloride to the mixture and stirring at 80°C for 2 hours, the reaction solution was concentrated under reduced pressure to obtain an acid chloride.

Next, 3. 8ξ rimole of hydroxy compound obtained in (2.5 g
) and triethylamine ld into THF10di solution,
A THF5d solution of the acid chloride was added dropwise, and the mixture was stirred at room temperature for one day.

After concentrating the reaction solution, it was purified by column chromatography to obtain 3.5 g of the desired liquid crystal compound. (Yield 71%) Table 2 shows the phase transition behavior and response speed to electric field of the obtained liquid crystal compound.

Example 4 1-ethoxycarbonylethyl 4'-[4'-(8
-(5-hexenyloxy)octyloxy)benzoyloxy]biphenyl-4-carboxylate 5-hexen-1-ol 30 mmol (3.0 g),
Example 1 Using 80ξ rimole of 1.8-dibromooctane (2L 8g) and 1.2g of 60% sodium hydride
1. Perform the same operation as in (2), and add the desired ω-haloalkylalkenyl ether 6 (yield 75%).
0 g) and 20 mmol (2.0 g) of potassium carbonate.

2.8g) of Example 2. Perform the same operation as ■,
5.6 g of the desired benzoic acid derivative was obtained.

(Yield 80%) 10 mmol (3.5 g) of the benzoic acid derivative obtained in 4.
After adding 30 m of thionyl chloride to the solution and stirring at 80°C for 2 hours, the reaction solution was concentrated under reduced pressure to obtain an acid chloride. Next, 3 of Example 3. 8ξ rimole of the hydroxyl compound obtained in ■ (
2.5 g) and triethylamine III11 in THFI
The THF5-solution of the acid chloride was added dropwise into the OI11 solution, and the mixture was stirred at room temperature for one day. After concentrating the obtained reaction solution, it was purified by column chromatography to obtain 4.1 g of the desired liquid crystal compound. (Yield 79
%) Table 2 shows the phase transition behavior and response speed to electric field of the obtained liquid crystal compound.

Example 5 1-Butoxycarbonylethyl 4-(4'(8-allyloxyoctyloxy)phenyl)benzoate 52 mmol (3.0 g) of allyl alcohol, 2.3 g of 60% sodium hydride and 110 a of 1,8-dibromooctane 1 of Example 1 using Rimol (30.0 g)
．． The same operation as in (2) was carried out to obtain 8.3 g of the desired ω-haloalkyl allyl ether.

(Yield 64%) 25 mmol of allyl ether obtained in 5.
1.2g) of Example 1 using 22ξ mol (4.8g) of 4'-hydroxybiphenyl-4-carboxylic acid and 60 mmol (3.4g) of potassium hydroxide. The same operation as in (2) was performed to obtain 5.5 g of the desired carboxylic acid compound. (
Yield: 66%) 85 mol (3.1 g) of the carboxylic acid obtained in 5. and 20Id of thionyl chloride were stirred at 80° C. for 3 hours, and the reaction solution was concentrated under reduced pressure to obtain the acid chloride. The T)IF solution of the above acid chloride was added dropwise to a THF 30d solution of 1019 mol (1.5 g) of butyl L-lactate and 3 ml of triethylamine, and after stirring for 8 hours, the reaction solution was concentrated, water was added, and acetic acid was added. Extracted with ethyl. After concentrating the extract, it was purified by column chromatography to obtain 2.9 g of the desired liquid crystal compound. (Yield: 72%) Table 2 shows the phase transition behavior and response speed to electric field of the obtained liquid crystal compound.

The elemental analysis values of the liquid crystal compounds obtained in Examples 1 to 5 are shown in Table 1 below.

Table 1 Example 6 Poly[1-ethoxycarbonylethyl 4-[4' -
(4'-(10-glycidyldecyloxy)phenyl)benzoyloxy]benzoate] 6, ■; 1.0 mmol (6
30 mg) and 1.5 mmol m-chloroperbenzoic acid (
After substituting 260 mg) of a 10M 1:4 solution of methylene chloride with argon, it was stirred at room temperature for 5 hours, and the reaction solution, which was kept overnight, was washed with an aqueous potassium carbonate solution and water, dried, and concentrated. 510 mg of epoxy monomer was obtained. (Yield 94%) After replacing the methylene chloride 10I11 solution containing 0.94 mmol of the epoxy monomer obtained in 6.
After concentrating the reaction solution, which was stirred at room temperature for 5 days, it was purified by column chromatography to obtain 320 mg of a polymer having a repeating unit represented by the following formula.
I got it. (Conversion rate 52%, Mn=3200) The phase transition behavior of the obtained polymer and the response speed to electric field were
Shown in the table.

Example 7 Poly[1-ethoxycarbonylethyl 4-(4'-(
10-glycidyldecyloxy)bency, ruoxy)
Benzoate J 7, ■ E' □□□ B position 1.0 mmol (55
6.0 mg) of Example 6. The same operation as in (2) was performed to obtain an epoxy heptanomer represented by the following formula.

(Yield 94%) 0.94 mmol (5
6.40s+g) of Example 6. A polymer having a repeating unit represented by the following formula was obtained. (Conversion rate: 85%, Mn=2700) Table 2 shows the phase transition behavior of the obtained polymer and the response speed to an electric field.

Example 8 Poly[l-ethoxycarbonylethyl 4'[4'~(
8-(3,4-epoxybutyloxyoctyloxy)
Benzoyloxy 1-biphenyl-4-carboxylate] 8. 3. 1.049 mol (6 mol) of the liquid crystal compound obtained in
20 mg) of Example 6. The same operation as (2) was performed to obtain an epoxy monomer represented by the following formula.

(Yield 94%) 0.94 mmol (59 mmol) of the epoxy monomer obtained in step a
6.0mg) of Example 6. A polymer having a repeating unit represented by the following formula was obtained. (
Conversion rate: 75%, Mn-5600) Table 2 shows the phase transition behavior and response speed to electric field of the obtained polymer.

Example 9 Poly[1-ethoxycarbonylethyl 4'[4'-
(8-(5,6-epoxyhexyloxy)octyloxy)benzoyloxy 1-biphenyl-4-carboxylate] 9.011 Yoni Z position Example 4, 4. 1.0 mmol (6
6.40 g) of Example 6. The same operation as (2) was performed to obtain an epoxy monomer represented by the following formula. (Yield 93%) 0.93 mmol (6
6.10mg) of Example 6. A polymer having a repeating unit represented by the following formula was obtained by combining in the same manner as in (2).

(Conversion rate 0) 86%, Mn=540 Table 2 shows the phase transition behavior and response speed to electric field of the obtained polymer.

Example ■0 Poly[1-butoxycarbonylethyl 4(4'-(
8-glycidyloctyloxy)phenyl)benzoate] 10, ■ 5. of Example 5. 1.0a mol (5 mol) of the liquid crystal compound obtained in
10 mg) of Example 6. The same operation as (2) was performed to obtain an epoxy monomer represented by the following formula.

(Yield 97%) 10. 0.97ξ mol of the epoxy monomer obtained in ② (
510 mg) in 6. of Example 6. A polymer having a repeating unit represented by the following formula was obtained. (Conversion rate: 77%, Mn=2900) Table 3 shows the phase transition behavior of the obtained polymer and the response speed to an electric field.

Example 11 [1-ethoxycarbonylethyl 4-[4'-(4
'-(10-glycidyldecyloxy)phenyl)penzoyloxycopenzoate]-[1-ethoxycarbonylethyl 4-(4'(10-glycidyldecyloxy)benzoyloxy]benzoate] copolymer 11, ■ Polymer base Example 6 was prepared using a mixture of 0.4 mmol (260 mg) of the epoxy monomer obtained in 6.■ of Example 6 and 0.6 mmol (340 mg) of the epoxy monomer obtained in 7.■ of Example 7. A copolymer having a repeating unit represented by the following formula was obtained in the same manner as in 6.■.(Conversion rate: 81%, Mn-3800) The phase transition behavior and response speed to electric field of the obtained copolymer were determined. It is shown in Table 3.

Example 12 [1-Ethoxycarbonylethyl 4-[4'-(4'-(10-glycidyldecyloxy)phenyl)penzoyloxycobenzoate]-[(R)-s
ec-pentyl 4-(4'-(9゜10-epoxydecyloxy)benzoyloxy)benzoate] copolymer 12.1. (2) Ten drops of pyridine were added to 26.0 g of 10-chloro-1-decen-1-ol, and the mixture was placed in an eggplant flask. Under water cooling, thionyl chloride 24.
0 g was added dropwise. After the dropwise addition, the reaction was carried out at 70° C. for 8.5 hours, and then diluted with dichloromethane and washed with an aqueous potassium carbonate solution. After drying over magnesium sulfate, it was concentrated under reduced pressure.

The residue was purified by column chromatography to obtain 10-
27.7 g of chloro-1-decene was obtained. (Yield 95%
) 12.1. ■ -9-1゛cenyloxy 6-12.
1. 10.0 g of 10-chloro-1-decene obtained in step (2) and 25 g of sodium iodide were heated at 80°C in 2-butanone.
The mixture was reacted for 10 hours and iodinated. After washing with water, drying, and removing the solvent, 11.5 g of p-hydroxybenzoic acid ethyl ester and 9.6 g of potassium carbonate were added, and the mixture was refluxed in absolute ethanol for 15 hours. Potassium hydroxide aqueous solution (
After 6 reactions, the mixture was acidified with hydrochloric acid and concentrated under reduced pressure. Water was added to the residue to suspend it, and the insoluble matter was collected and dried to give p-(9-decenyloxy)benzoic acid 9.5
I got g. (yield 60%) p-acetoxybenzoic acid 2
25 g of thionyl chloride was added dropwise to 5 g. Mixture at 80℃
The mixture was heated to a temperature of 100.degree. C. and reacted for 3 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride. This acid chloride was dissolved in toluene and cooled on ice. There (-)-2
- A toluene solution containing 10.2 g of pentanol and 11 g of pyridine was added dropwise. It was then stirred at room temperature overnight.

After the reaction, the solution was washed with water, dried, and concentrated under reduced pressure, and the residue was dissolved in ether. 18 g of benzilane was added dropwise thereto. After the reaction, the mixture was stirred for 1 hour at room temperature, the product was washed with water, dried, and concentrated under reduced pressure. The residue was purified by column chromatography to obtain the desired ester [liquid at room temperature, [α]η=-27.3° (CHCIs)1
20.3g was obtained. (Yield 86%) 12.1. Toluene was added to 12.7 g of p-(9-decenyloxy)benzoic acid obtained in step (2), and the mixture was cooled on ice.

8.2 g of thionyl chloride was added dropwise thereto. The reaction was carried out at 80°C for 7 hours. After the reaction, the reaction solution was condensed to obtain an acid chloride. On the other hand, 12.1. 10.0 g of p-hydroxybenzoic acid 1-methylbutyl ester obtained in
and 3.8 g of pyridine were dissolved in toluene and cooled on ice. A toluene solution of the above acid chloride was added dropwise thereto. After 5 hours of reaction at 50° C., the product 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 15.1 g of the desired ester. (
Yield 71%) 12, i ■ E'Top 12.1. 6. of Example 6 was added to 15.1 g of the ester obtained in step (2). The same operation as in (2) was carried out to obtain 14.7 g of an epoxy monomer represented by the following formula. (Yield 94%) 12, II 11! = 0.3 mmol (190 mg) of the epoxy monomer obtained in step (3) of Example 6 and 12. (R)-sec- obtained in ■
6 of Example 6 using a mixture of 0.7 mmol (340+ g) of pentyl 4-(4'-(9,10-epoxydecyloxy)benzoyloxy)benzoate. ■
A copolymer having a repeating unit represented by the following formula was obtained. (Conversion rate 80%, Mn=360
0) Table 3 shows the phase transition behavior and response speed to electric field of the obtained copolymer.

Example 13 [1-ethoxycarbonylethyl 4′-[4-(4“
-(10-glycidyldecyloxy)phenyl)benzoyloxy 1 benzoate]-[Propylene oxide 1 copolymer 13, 6. Using a mixture of 0.6 mmol (380 mg) of the epoxy monomer obtained in step ① and 0.4 mmol (23+sg) of propylene oxide, 6.
A copolymer having a repeating unit represented by the following formula was obtained by combining in the same manner as in (2). (Conversion rate 83%, Mn=420
0) CH.

Table 3 shows the phase transition behavior and response speed to electric field of the obtained copolymer.

〔Effect of the invention〕

The liquid crystal polymer of the present invention exhibits ferroelectricity even at room temperature, has a quick response to external factors, and is capable of displaying moving images, and can be advantageously used as a display element for large screens and curved screens. and its industrial value is extremely large.

[Brief explanation of drawings]

Figures 1 to 5 show charts of NMR spectra of liquid crystal compounds obtained in Examples 1 to 5, and Figures 6 to 13 show charts of liquid crystal polymers obtained in Examples 6 to 13. This shows a chart of the NMR spectrum of .

Claims (1)

[Claims] 1. The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [However, j in formula (1) represents an integer from 1 to 10, and k represents an integer from 1 to 30. Represents an integer, m represents an integer from 0 to 5, R represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc.▼, where X is -COO- or -OCO-. ]
A liquid crystal compound represented by 2. The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [However, in formula (II), j represents an integer from 1 to 10, k represents an integer from 1 to 30, and m represents Represents an integer from 0 to 5, R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲Mathematical formulas, chemical formulas, tables, etc. There is ▼, where X is -COO- or -OCO-. ]
A liquid crystal polymer having a repeating unit represented by