JPH0269522A - Copolymer of liquid crystal - Google Patents

Abstract

PURPOSE:To obtain a liquid crystal copolymer useful as display element of large scope and bent scope, showing ferroelectricity even in the neighborhood of low temperature, rapidly responding, capable of exhibiting a moving scope comprising an oxyethylene polymer containing a specific aromatic group- containing group and a straight-chain alkyl at the side chain. CONSTITUTION:An epoxy compound {e.g., 4-[4'-(9-decenyloxy)biphenyl-4- carbonyloxy]benzoic acid 2-methylbutyl ester} shown by formula I {R<1> is group shown by formula II [k is 1-30; R<3> is group shown by formula III (X is single bond, COO, etc.; p and q are 1 or 2; A and B are halogenated biphenylene; R<4> is ester, alkoxy, etc.)]} is combined and copolymerized with an epoxy compound (e.g., propylene oxide) shown by formula IV [R<2> is H or group shown by formula (CH2)nCH3 (n is 0-9)] in the presence of stannic chloride catalyst to give the aimed liquid crystal copolymer having repeating unit shown by formula V and formula VI in the molar ratio of (99:1)-(10:90).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel liquid crystal copolymer. 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. The present invention relates to a liquid crystal copolymer that is useful as various electro-optical devices such as those that exhibit ferroelectricity even at room temperature, has a fast response speed to external factors, and is capable of displaying moving images. In particular, the liquid crystal copolymer of the present invention has high practicality as a display element for large screens and curved screens.

Attempts are being made to make it moldable. for example,
JP-A-55-21479, JP-A-63-9920
4 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.

[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 liquid crystals are usually used by being sandwiched between two glass substrates whose spacing is controlled on the order of microns. However, such adjustment of the gap has not been possible with large screens and curved screens. One way to solve this difficulty is to make liquid crystal into a polymer, which itself [the problem to be solved by the invention].The present invention exhibits ferroelectricity even at room temperature, and has a fast response to external factors. The object of the present invention is to provide a liquid crystal copolymer that is capable of displaying images and can be used advantageously as a display element for large screens and curved screens.

[Means to solve the problem]

As a result of intensive studies to solve the above problems, the present inventors have discovered that a liquid crystal copolymer obtained by copolymerizing an epoxy type compound having a specific structure in a specific ratio can be used in a wide temperature range around room temperature. The present invention was completed based on the discovery that the present invention exhibits a high-speed response.

That is, the present invention provides a liquid crystal copolymer having repeating units represented by the following general formulas [1] and [2], and in which the molar ratio of [1] and [2] is 99:1 to tor9o. It is.

-CHzCHO-(1) R-CHzCHO-(2) [In the formula, 91 is a group represented by -(C1h)h-OR', k is an integer from 1 to 30, R3 is -A, -X-BQ-R"?' is a group shown,
X is a single bond, -COO- or 10CO-, pSq
are 1 or 2, respectively, and may be the same or different from each other, Y is a halogen atom, and may be the same or different from each other, and A and B are the same or different from each other. R4 is -COOR', -0COR' or -
OR', and R& and Rff are C1, halogen atom, and CN, respectively.
or CF, where R and T are each integers from 0 to 10 (however, when is CHI, T is not O), and S
is 0 or l, 1tt is H or -(CHg)nCH
, where n is an integer of 0 to 9, and C with * is an asymmetric carbon atom. ] In the above formula, specific examples of A and B include groups represented by the following formula.

In the above formula, a and b are each independently an integer of 0 to 4, and specific examples of the optically active group R% include, for example:
For example, 2-methylbutyl group, 2-fluorooctyl group,
2-chloro-3-methylpentyl group, 2-chloro-1-
Examples include methylpropyl group, 2-cyabutyl group, 1-(trifluoromethyl)hebutyl group, and 1-methylpropyl group.

The liquid crystal copolymer of the present invention is obtained by combining epoxy compounds represented by the following formulas [3] and [4] so that the molar ratio of the repeating units of [1] and [2] is 99:1 to 10:90, preferably 90: It is obtained by copolymerizing at a ratio of 10 to 20:80.

If the molar ratio is outside this range, high-speed response will be insufficient.

(R', R'' have the same meanings as above.) The number average molecular weight of the copolymer of the present invention is preferably I, 000 to 5.
00,000. 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 a slow response speed may appear. . A particularly preferable range of the number average molecular weight cannot be unconditionally defined because it depends on the types of R1 and R2, the value of k, the value of n, the optical purity of R5, etc., but it is between 2,000 and 100°000.
It is.

A general method for synthesizing the epoxy compound [3] used as a monomer of the liquid crystal copolymer of the present invention is shown below.

= 1) As shown in the reaction formula below, altenol (I) is halogenated with a halogenating agent such as thionyl chloride in the presence of pyridine to obtain an alkene halide (n). Alkene halide (II) and compound (III) are reacted in the presence of an alkali such as potassium carbonate in a suitable solvent such as 2-butanone to obtain ether (IV). Next, the desired monomer (V) is obtained by epoxidizing this ether (IV) with a peracid such as m-chloroperbenzoic acid in a suitable solvent such as dichloromethane.

11□C=C1 ((CHz) hOH-→H, C engineering C1
l (CHz) hY(1) (I
I) 11□C=CH(C1lz)hY + IO! R'
(n) U) 10ZC=CB(Coz)ko, @)@;/-R'(I
V) (V) (In the formula, Y is a halogen.) As artenol (1), for example, 9-decene-1
-ol, 11-dodecen-1-ol, 7-octen-1-ol and the like are preferred.

Here, the above compound (III) IO()(>R
' is synthesized as follows.

[Synthesis of HO COOR5] As shown in the reaction formula below, 4'-hydroxybiphenyl-
4-carboxylic acid and optically active alcohol (Vl) are mixed in a suitable solvent such as benzene in the presence of an esterification catalyst such as concentrated sulfuric acid or p-)luenesulfonic acid at a desired temperature. By reacting, this ester compound (■) is obtained.

(■) (■) As the optically active alcohol (Vl), for example, (R)-
2-methylbutanol, (S)-2-methylbutanol, (R)-4-methylhexanol, (S)-4-methylhexanol, (R)-2-70 lobulanol, (
S)-2-chloropropanol, (R)-2-cyatuburobanol, (S)-2-cyatuburobanol, (R)
-4-chloropentanol, (S)-4-chloropentanol, (R)-2-butanol, (S)-2-butanol, (S)-2-pentanol, (R)-2-pentanol , (S)-2-octatool, (R)-2-octatool, (S)-2-fluorooctatool, (R)
-2-fluorooctatool, (S)-2-fluorononanol, (R)-2-fluorononanol, (2S,
3S)-2chloro-3-methyl-1-pentanol, (
2S,33)-2-fluoro-3-methyl-1-pentanol, (2S,3S)-2-bromo-3-methyl-1
-pentanol, (33,43) -3-chloro-4-
Methyl-1-hexanol, (4S,53)-4-chloro-5-methyl-1-heptatool, (53,6S)
-5-chloro-6-methyl-1-octatool, (6S
, 73) -6-chloro-7-methyl-1-nonanol, (R)-(+)-1,1,1-)lifluoro-2-octatool, 3-chloro-2-butanol, and the like are used.

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

■0℃X wings OH+R'C0OH→no(X wings 0COR'
(■) (■) As the optically active carboxylic acid (■), for example, (R)-
2-Methylbutanoic acid, (S)-2-methylbutanoic acid, (
23,33)-2-chloro-3-methylpentanoic acid, (
2S,3S)-2-fluoro-3-methylpentanoic acid,
(R)-2-methylpentanoic acid, (S)-2-methylpentanoic acid, (R)-3-methylpentanoic acid, (S)-3
-methylpentanoic acid, (R)-4-methylhexanoic acid,
(S)-4-methylhexanoic acid, (R)-2-chloropropanoic acid, (S)-2-chloropropanoic acid, (R)-6
-methyloctanoic acid, (S)-6-methyloctanoic acid,
(R)-2-cyanobutanoic acid, (S)-2-cyanobutanoic acid, (R)-2-cyanopropanoic acid, and (S)-
2-cyanopropanoic acid is mentioned.

(Synthesis of HO()()-OR') As shown in the reaction formula below, the optically active alcohol (Vl) is tosylated, and bipheni)Li-4,
This ether (X) is obtained by reacting 4'-diol.

(X) to form a carboxylic acid form. A halogenating agent such as thionyl chloride is added to this carboxylic acid, and the mixture is heated in a solvent such as toluene to form an acid halide.

Next, this acid halide and the compound (III) are reacted in a solvent such as toluene in the presence of pyridine to obtain an ester (X I), and then m-chlorofiltration is performed in a suitable solvent such as dichloromethane. By epoxidizing using a peracid such as benzoic acid, the desired monomer (X I
).

, q-2) As shown in the reaction formula below, an alkene halide (■) and p-
Ethyl hydroxybenzoate is reacted with hydroxybenzoic acid ethyl ester in a suitable solvent such as acetone in the presence of an alkali such as potassium carbonate to obtain an ether.Next, the protecting group of the carboxyl group in this ether is converted into an aqueous solution of potassium hydroxide, Hydrochloric acid, etc. (I[) (III) (XI) (XIV) (XI[) When Q = 2) As shown in the reaction formula below, an alkene halide (■) and hydroquinone are combined in the presence of an alkali such as potassium carbonate. The reaction is carried out below to obtain the ether compound (XII[).

The following compound (XIV) is converted into acid chloride using thionyl chloride or the like. The obtained acid chloride and ether form (XI[r
) in the presence of pyridine to form the ester (XV)
get. Thereafter, oxirane conversion is performed in the same manner as in (1) to obtain the desired monomer (XVI).

Here, the above compound (X TV ) HOOCk Ra
is obtained as follows.

(Synthesis of cooR5) Optically active alcohol (Vl) and biphenyl-4゜4'-dicarboxylic acid are reacted in a solvent such as toluene in the presence of an esterification catalyst to obtain the above ester (X■) .

Synthesis of CHooc@-@)-ocoa5] After converting the optically active carboxylic acid (■) into acid chloride using thionyl chloride or the like, it was reacted with 4'-hydroxybiphenyl-4-carboxylic acid in the presence of pyridine to obtain the above ester ( Obtain X■).

R5COCl + l100c(?ΣΣGOH1
In the case of q = 1) In Chizuma's synthesis method, compound (III) CHOO
Synthesis of C@@-OR'] 4'-hydroxybiphenyl-4-carboxylic acid ethyl ester and R' 03 S @ CH3 obtained by tosylating an optically active alcohol (Vl) are reacted in the presence of potassium carbonate, etc. , obtain the etheric body. This ether form is reacted with an aqueous alkaline solution or the like to hydrolyze the ester of the protecting group to obtain the above compound (XIX).

-nooc@@-oRs(x■) The following desired monomer (XX I) is obtained.

Here, the above compound (XX) can be obtained as follows.

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

(Synthesis of 80@-0COR') In the synthesis of compound (■) in (1) above, hydroquinone was used instead of biphenyl-4,4'-diol, and a similar reaction was carried out, and the above ester form (XXI
Get [[).

(Synthesis of 110@ORS) In the synthesis of compound (X) in (1) above, hydroquinone was used instead of biphenyl-4,4'-diol, a similar reaction was carried out, and the above ether form (XXT
V) is obtained.

, q=1) As shown in the reaction formula below, R3 in (3) above is (XXVI
).

HOOC@-R'CIC0eR' (XXV) (XXVI) Here, the above compound (XXV'') can be obtained as follows.

[Synthesis of H00C@C00RS] In the synthesis of compound (X
■) Obtain.

Perform the reaction to obtain the desired monomer of the following general formula - + l
100C@C0OR' (XX■) In the synthesis of compound (X■) in (3) above, a similar reaction was carried out using p-hydroxybenzoic acid instead of 4'-hydroxybiphenyl-4-carboxylic acid, and the above Ester body (XX
■) Obtain.

(XX■) When q=l) In the synthesis of a monomer in which R3 in the above (2) is −
In the synthesis of compound (XIV) in (3) above, using carboxylic acid ethyl ester, p
A similar reaction is carried out using -hydroxybenzoic acid ethyl ester to obtain the above ether (XXIX).

The desired monomer (XXX) of the following general formula is obtained.

When q=1) In the monomer synthesis, biphenyl-4,4'-diol is used in place of hydroquinone, and the desired monomer (XXXI) shown below is obtained.

Further, an epoxy compound in which the aromatic rings of A and B are substituted with halogens is also synthesized according to the above method.

Examples of the epoxy compound [4] include ethylene oxide, propylene oxide, and 1,2-epoxyhexane.

Next, the thus obtained epoxy compound represented by formula [3] and the epoxy compound represented by formula [4] are copolymerized to synthesize the copolymer 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 stannic 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 organoaluminum complex or the like. In this case, the number average molecular weight is 30.0
00 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 appropriate.

The polymerization time varies depending on other factors such as the polymerization temperature, but is usually 1 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 monomer and 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 Hensen, 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 copolymer 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 used not only on two ordinary glass substrates, but also on large glass substrates, d
By sandwiching it between planar glass substrates, polyester films, etc., it can be used in various optoelectronic fields such as liquid crystal displays, electro-optical shutters, and electro-optical apertures. Furthermore, by applying a copolymer solution dissolved in a suitable 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 direct contact with the substrate surface.

It was confirmed from measurements of the phase transition temperature that the copolymer of the present invention achieves a chiral smectic C-phase liquid crystal state over a wide temperature range including around room temperature. It was also confirmed that the response time at around room temperature was fast.

The copolymers 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. Possible application. 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.

In addition, if necessary, the above-mentioned copolymers may be mixed together, mixed with other polymers, and added with various inorganic, organic, and metal additives including stabilizers, plasticizers, etc., according to those skilled in the art. can be improved by a number of well-known processing methods.

〔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 polymer was confirmed by NMR and IR1 elemental analysis, and the phase transition temperature was measured and the phase was confirmed by DSC and polarizing microscope, respectively.

NMR charts of the copolymers obtained in Examples 1 to 8 are shown in FIGS. 1 to 8.

In addition, the phase transition behavior and electric field response speed of each copolymer are shown in the table below. , the number of phase transition behavior is the phase change temperature expressed in °C.) The electric field response speed was measured as follows.

・Sandwich the polymer between two 1゛20×10゛ITO substrates, adjust the thickness to 25μl with a spacer, and apply an AC electric field E=
Apply 2XIO”V/m and change the amount of transmitted light at that time (0
→90%) response time was measured.

Example 1 -(CHzCIhO)-- 4.0 g of p-hydroxybenzoic acid and 12.5 g of (-)-2-methylbutanol were refluxed in toluene in the presence of sulfuric acid for 6 hours while removing water.

Next, the reaction solution was washed with water to remove sulfuric acid. Then dry,
Concentration and purification by column chromatography yielded 5.0 g of the desired ester (liquid at room temperature, [α)]
231=+4.9° (CHClx)) was obtained. (
Yield 83%) 10-chloro-1-decene10. Og and 25 g of sodium iodide were reacted in 2-butanone at 80° C. for 10 hours to iodize. After washing with water, drying, and removing the solvent, 11.5 g of p-hydroxybenzoic acid ethyl ester,
Add 9.6 g of potassium carbonate and dissolve in absolute ethanol for 15 min.
Refluxed for an hour. After adding an aqueous potassium hydroxide solution (containing 4.0 g of potassium hydroxide) and heating at 80° C. for 5 hours, the mixture was acidified with hydrochloric acid and concentrated under reduced pressure. Water is added to the residue to suspend it, the insoluble matter is collected and dried, and 4-(
9-decenyloxy)benzoic acid 9.5 g (yield 60%)
I got it. Toluene was added to 4.5 g of the obtained 4-(9-decenyloxy)benzoic acid, and the mixture was cooled on ice.

Furthermore, 3.5 g of thionyl chloride was added dropwise under water cooling.
After the dropwise addition, the reaction was carried out at 80°C for 7 hours. After the reaction, the reaction solution was concentrated to obtain an acid chloride. - way, 4- obtained from ■
Hydroxybenzoic acid 2-methylbutyl ester 4.5g
and 1.8 g of pyridine were dissolved in toluene and cooled with water. After the toluene solution of the above acid chloride was added dropwise thereto, the reaction was carried out at 50°C for 5 hours. After the reaction, the product was washed with water and dried over magnesium sulfate.
The product was purified by column chromatography to obtain 5.5 g (yield: 72%) of the desired alkene compound.

■ 101 d of methylene chloride containing 3 mmol (0.52 g) of m-chloroperbenzoic acid to 5.5 g of the alkene obtained from the reaction ■
The solution was purged with argon and stirred for 10 hours.

After washing the reaction solution with an aqueous potassium carbonate solution, it was dried and concentrated.
5.2 g (yield: 92%) of Shitsummer shown by the following formula was obtained.

2.0 mmol (0.96 g) of methylene chloride 1011, the monomer synthesized in step (2)! i! After the solution was purged with argon, 0.5 mmol (22 cm) of ethylene oxide and 0.25 mmol of stannic chloride were added and left at room temperature for 5 days. After concentrating the reaction solution, it was purified by column chromatography to obtain 0.70 g of polymer (conversion rate 71%, Mn = 22
00, copolymerization ratio man is 77:
23) was obtained.

■ ±Uni≧≦Needle color 2.0 mmol (0,
After replacing the methylene chloride 10 relative solution of 96 g) with argon,
2.0 mmol (0.09 g) of ethylene oxide and 0.40 mmol of stannic chloride were added, and the mixture was left at room temperature for 5 days. After concentrating the reaction solution, it was purified by column chromatography to obtain 0.64 g of polymer (conversion rate 64%, Mn
= 1700, and the copolymerization ratio man was 54:46) from the NMR spectrum.

Example 3 Example 2 (CH2CHtO).

-(CHzCHO), 1-Hs ■ lUj≧S needle 1 bottom 2.0 mmol of the monomer synthesized in Example 1 (■) (0,
96 g) of methylene chloride 10 solution in 1 m of argon.
After that, 2.0 mmol (0.12 g) of propylene oxide
) and 0.40 mmol of stannic chloride at room temperature.
I left it for days. After concentrating the reaction solution, it was purified by column chromatography to obtain 0.71 g of polymer (conversion rate 72%).
, Mn=1600, and the copolymerization ratio man was 60=40) from the NMR spectrum.

After dropping a solution of 1 g) of water (3 tni ) + n-butanol (10 d), the mixture was stirred at 120° C. for 8 hours. After adding water to the reaction solution and extracting with ether, the dried and concentrated product was purified by column chromatography to obtain 4.8 g of ether (yield: 72%).
) was obtained.

Example 4 -(CHzCHtO)-- ■ 4-2-Methylbutoxy 37 mmol of p-toluenesulfonic acid 2-methylbutyl ester obtained by tosylation of S-(-)-2-methylbutanol, a relative of phenol. (9.0 g) and 74 mmol (8.2 g) of hydroquinone in n-butanol suspension with 50 mmol of sodium hydroxide (2°10-chloro-1-decene 1
0. Og and 25 g of sodium iodide were reacted in 2-butanone at 80°C for 10 hours to iodinate. 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. Add potassium hydroxide aqueous solution (containing 4°Og of potassium hydroxide),
Heated at 80°C for an additional 5 hours. After the reaction, the mixture was acidified with hydrochloric acid and concentrated under reduced pressure. Add water to the residue and suspend it.
Insoluble materials were collected and dried to obtain 9.5 g (yield: 60%) of 4-(9-decenyloxy)benzoic acid.

Next, 10 mmol (2,8 g) of 4-(9-decenyloxy)benzoic acid, 30 mmol (3,6 g) of thionyl chloride
) was reacted at 100° C. for 3 hours, and then concentrated under reduced pressure to obtain an acid chloride. 8 mmol (1.4 g) of the ether obtained in step (2), TH of triethylamine 2d
After dropping a THF5d solution of the above acid chloride into the F20m solution and stirring for 10 hours, water was added to the reaction mixture and extracted with ether. The dried and concentrated product was purified by column chromatography to obtain 2.2 g of the alkene (yield 63%).

■ A 10 d methylene chloride solution containing 2 mmol (0.84 g) of the alkene obtained from ``D'' and 3 mmol (0.52 g) of m-chloroperbenzoic acid was replaced with argon and stirred for 10 hours. The solution was washed with an aqueous potassium carbonate solution, then dried and concentrated to obtain 0.82 g (yield: 90%) of a monomer represented by the following formula.

Monomer synthesized in H3 ■ 2.0 mmol (0.91 g) of methylene chloride 10#d! After replacing the solution with argon, 0.5 mmol (22 mmol) of ethylene oxide and 0.25 mmol of tin chloride were added, and the 0 reaction solution was left at room temperature for 5 days. .59g (conversion rate 63%, Mn=2600
, the copolymerization ratio m:n is 88:12 from the NMR spectrum.
) was obtained.

Example 5 11 g of thionyl chloride was added dropwise to 5.4 g of CI mountain CH3 -hydroxy -fluoro-p-acetoxybenzoic acid. After the mixture was heated to 80°C and reacted for 3 hours, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride. This acid chloride was dissolved in toluene and cooled with water.

There, 4.4 g of (-)-2-fluorooctatool,
A toluene solution containing 3 g of pyridine was added dropwise. After the reaction, the mixture was stirred at room temperature overnight, the solution was washed with water, dried, and concentrated under reduced pressure. The residue was dissolved in ether. 10 g of benzylamine was added dropwise thereto. After the reaction, the mixture was stirred for 5 hours at room temperature, the product was washed with water, dried, and concentrated under reduced pressure. The residue was purified by column chromatography to obtain 4.9 g of the desired ester. (yield 7
3%) 4-(9-decenyloxy)benzoic acid obtained in the same manner as in Example 1.3. Toluene was added to Og and cooled on ice. 2.0 g of thionyl chloride was added dropwise to the mixture, and the reaction was then carried out at 80° C. for 3 hours. After the reaction, the product was concentrated to obtain an acid chloride.

On the other hand, 1.7 g of 4-hydroxybenzoic acid 2-fluorooctyl ester obtained in step (2) and 0.9 g of pyridine were dissolved in toluene and cooled on ice. A toluene solution of the above acid chloride was added dropwise thereto.Next, the reaction was carried out at room temperature for 15 hours.After the reaction, the product was washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. . The residue was purified by column chromatography to obtain 2.8 g of the desired ester. (Yield: 85%) (2) 2.8 g of the ester obtained from Meng JI iodine (2) was subjected to the same operation as in Example 1 (2) to obtain 2.6 g of a monomer represented by the following formula. (Yield: 91%) After replacing a solution of 2.0 mmol (1.08 g) of the monomer synthesized with 4'-9--cenyloxy biphenyl-■ in 10 d of methylene chloride with argon, 1.2 - 0.5 mmol (50 μ) of epoxyhexane and 0.5 mmol of stannic chloride.
25 mmol was added and left at room temperature for 5 days. After concentrating the reaction solution, it was purified by column chromatography to obtain 0.88 g of polymer (conversion rate 78%, Mn=2400, copolymerization ratio m:n 82=18 from NMR spectrum).

Example 6 4'-(9-decenyloxy)biphenyl-4-calyHn M4. Toluene was added to Og and cooled on ice.

2.0 g of thionyl chloride was added dropwise thereto. The reaction was carried out at 80°C for 7 hours. After the reaction, the reaction solution was concentrated to obtain an acid chloride. 1.7 g of 2-chloro-3-methylpentanol and 1.0 g of pyridine were dissolved in toluene and cooled with water. A toluene solution of the above acid chloride was added dropwise thereto. After 15 hours of reaction at room temperature, the reaction solution was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 4.3 g of the desired ester (
A yield of 80% was obtained.

(CHzCHO) 11 ■) The same operation as in Example 1 (■) was carried out on 4.3 g of the ester obtained from the "Katsu" Usanie Chemical ■, and 4.2 g of the monomer represented by the following formula (yield: 95 %) was obtained.

A solution of 2.0 mmol (0.97 g) of the monomer synthesized in step (2) in methylene chloride 101n1 was replaced with argon, and 0.5 mmol (22 ■) of ethylene oxide and 0.25 mmol of tin chloride were added thereto for 5 days at room temperature. I left it alone. After concentrating the reaction solution, it was purified by column chromatography to obtain 0.58 g of polymer (conversion rate 58%, Mn = 2400
, the copolymerization ratio m:n is 84:16 from the NMR spectrum.
) was obtained.

Example 7 (CHzCHO)ll- ■　　　　　-7-ocunyloxy　6　4 precepts.

9.4 g of 8-bromo-1-octene, 9.4 g of ethyl p-hydroxybenzoate. Og and 7.6 g of potassium carbonate were refluxed in ethanol for 10 hours. An aqueous solution containing 2.4 g of sodium hydroxide was added thereto, and the mixture was further refluxed for 10 hours. After the reaction, dilute with water and add hydrochloric acid dropwise to adjust the pH.
was set to 2. The resulting precipitate was collected, thoroughly washed with water, and then dried to obtain 10.8 g of the desired ether. (Yield: 89%) 9 g of P-(7-octynyloxy)benzoic acid obtained in ① was suspended in toluene and cooled on ice. 6 g of thionyl chloride was added dropwise thereto. After the dropwise addition, the temperature was raised and the mixture was reacted at 80°C for 6 hours. After the reaction, the mixture was concentrated under reduced pressure to obtain an acid chloride. Toluene was added thereto to make a toluene solution, which was cooled on ice.

A toluene solution containing 10 g of 4'-hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester and 3 g of pyridine was added dropwise to the toluene solution of the above acid chloride. After the addition, the temperature was raised and the temperature was raised to 50°C for 8 hours. Reacted 0
After the reaction, the product was washed with water, dried over magnesium sulfate, and then concentrated under reduced pressure. The residue was recrystallized from ethanol to obtain 8.2 g of the desired ester (yield: 45%).
I got it.

After adding 2.0 mmol (0.09 g) of ethylene oxide and 0.40 mmol of stannic chloride and allowing it to stand at room temperature for 5 days, the reaction solution was concentrated and purified by column chromatography. 64%, Mn
= 2200, and the copolymerization ratio man was 80:20) from the NMR spectrum.

Example 8 ■ 7.2 g of the ester obtained from the difference ■ - Otsu conversion ■ was mixed with m-chloroperbenzoic acid 3
6.3 g of a monomer represented by the following formula was obtained. (Yield 85%) -(CIICl, O), + 2.0 mmol (1,06 g) of methylene chloride 10j11 of the monomer synthesized with ①! After replacing the solution with argon, 4'
Toluene was added to 5.0 g of -(9-decenyloxy)biphenyl-4-carboxylic acid, and the mixture was cooled on ice.

2.6 g of thionyl chloride was added dropwise to the mixture. Then 8
The reaction was carried out at 0°C for 7 hours. After the reaction, the product was concentrated to obtain an acid chloride. 3.1 g of 4-hydroxybenzoic acid 2-methylbutyl ester obtained in the same manner as in Example 1 (2) and 1.5 g of pyridine were dissolved in toluene and cooled on ice. A toluene solution of the above acid chloride was added dropwise thereto.Next, the reaction was carried out at 50°C for 5 hours.After the reaction, the product was washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. I left. The residue was purified by column chromatography to obtain the desired ester 5.
゜2g was obtained. (Yield 68%) After replacing the methylene chloride 10Id solution of g) with argon, 2.0 mmol (0.09 g) of ethylene oxide and 0.40 mmol of stannic chloride were added, and the solution was left at room temperature for 5 days. After concentrating, it was purified by column chromatography to obtain 0.73 g of polymer (conversion rate 60%, Mn-
2100, the copolymerization ratio m:n is 7 from the NMR spectrum.
8:22) was obtained.

Example 9 (1) 5.2 g of the ester obtained in (1) was subjected to the same operation as (2) in Example 1 to obtain 4.9 g of a monomer represented by the following formula. (Yield 92%) -(CHICHO), -CHl Monomer 2.0 mmol (1,124-acetoxy-2-fluorobenzoic acid 20 mmol (4,0
A solution of 60 mmol (7.2 g) of thionyl chloride in 100 m of toluene was stirred at 80° C. for 2 hours and then concentrated under reduced pressure to obtain an acid chloride.

R-(+)-1,1,1-1 refluoro-2-octatool 15 mmol (2,8 g) and triethylamine 5
Add the above acid chloride to ml of THF30 relative solution in THF.
After adding the 10d solution dropwise, the mixture was stirred for 10 hours. After concentrating the reaction solution, water was added and extracted with ether. After concentrating the extract, it was made into an ether 200d solution, to which benzylamine 20- was added and stirred for 5 hours. After washing the reaction solution with water, it was purified by column chromatography to obtain 15 g of the desired hydroxy compound.
(yield 52%).

A toluene solution of crude p-decenyloxybenzoic acid chloride was added dropwise. The reaction was carried out at 50°C for 5 hours. After the reaction, the mixture was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 2.0 g of the desired alkene (yield 69%).
I got it.

(2) Active' I-Supportation Using 2.0 mmol (1.16 g) of the alkene obtained in (1), a monomer represented by the following formula was synthesized in the same manner as in (2) of Example 1. (Yield: 86%) Toluene was added to 2.8 g of p-(9-decenyloxy)benzoic acid obtained in the same manner as in Example 1, and the mixture was cooled on ice. 5.0 g of thionyl chloride was added dropwise. The reaction was carried out at 80°C for 7 hours. After the reaction, the reaction mixture was concentrated under reduced pressure to obtain crude p-decenyloxybenzoic acid chloride.

1.6 g of the hydroxy compound obtained in step (2) and 3.3 g of pyridine were dissolved in toluene and cooled on ice. Then, using 1.0 mmol (600 ■) of heptamine obtained in the above (■) and 0.5 mmol (29 ■) of propylene oxide,
The polymer was synthesized in the same manner.

(Conversion rate 78%, Mn=2000.man is 10:30 from NMR spectrum) Example 10 (CH2Cl(0), - (CLC)to).

CH.

15 mmol (5.0 g) and hydroxy compound 10 obtained in ①
An alkene compound was synthesized from mmol (1.9 g) in the same manner as in Example 4 (2). (Yield: 80%) ■ A monomer was synthesized in the same manner as in Example 4 (■) using 2.0 mmol (1.0 g) of the alkene compound obtained in the process (2).

(Yield 93%) S-(+)-2-methylbutanoic acid 50 mmol (5,
1 g), hydroquinone 100 mmol (11,0 g
) Toluene 150III! , concentrated sulfuric acid llR to fJ solution
1 was added, and the mixture was stirred under reflux for 3 hours. After concentration, the residue was purified by column chromatography to obtain 7.1 g of a hydroxy compound (yield: 73%).

■ 1.0 mmol (510 ■) of the monomer obtained in polymer synthesis ■ and the
A polymer was synthesized in the same manner as in Example 3 (2) using 0.5 mmol (29) of lopylene oxide.

(Conversion rate 78%, Mn=2200.m: n is NMR
According to the spectrum, 72:2B) 4-(13-tetradecenyloxy)benzoic acid [Effects of the invention] The liquid crystal copolymer of the present invention not only exhibits ferroelectricity even at room temperature, but also exhibits excellent response to external factors. It is possible to quickly display moving images, and it can be advantageously used as a display element for large screens and curved screens, and its industrial value is extremely large.

[Brief explanation of the drawing]

1 to 8 are NMR spectra of the liquid crystal copolymers obtained in Examples 1 to 8, respectively.

Claims (1)

[Claims] 1. It has repeating units represented by the following general formulas [1] and [2], and the molar ratio of [1] and [2] is 99:1 to 10.
:90 liquid crystal copolymer. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [1] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [2] [In the formula, R^1 is a group represented by -(CH_2)_k-OR^3, k is an integer from 1 to 30, R^3 is a group represented by -A_p-X-B_q-R^4, X is a single bond, -COO- or -OCO-, p, q are 1 or 2 respectively, A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and B is ▲
There are mathematical formulas, chemical formulas, tables, etc.▼, where a and b are each independently an integer of 0 to 4 and may be the same or different from each other, Y is a halogen atom, may be the same or different from each other, A and B may be the same or different from each other, R^4 is -COOR^5, -OCOR^5 or -OR^5, R^5 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^6 and R^7 are CH_3, halogen atom, and C, respectively.
N or CF_3, R and T are each integers from 0 to 10 (however, when R^7 is CH_3, T is not 0), S is 0 or 1, and R^2 is H or A group represented by -(CH_2)nCH_3, where n is an integer from 0 to 9, and C marked with * is an asymmetric carbon atom.]