JPH0439326A - Liquid crystal polymer and epoxy compound useful as monomer for production of the polymer - Google Patents

Abstract

PURPOSE:To provide the subject polymer containing recurring units having a specific optically active aromatic group, having excellent response to electric field, etc., suitably working within a broad temperature range including a relatively low temperature range such as room temperature and useful for large- sized display element, etc. CONSTITUTION:The objective polymer contains the recurring unit of formula I {K is 1-10; j is 2-30; R<1> is optically active aromatic group of formula II to formula V [R<2> is optically active alkyl group of formula VI (m is 0-10; n is 1-10; C labeled with * is asymmetric carbon atom)]}. The polymer can be produced e.g. by the ring-opening polymerization of an epoxy compound of formula VII in the presence of a catalyst for the ring-opening polymerization of epoxy group such as stannic chloride.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an epoxy compound useful as a liquid crystal polymer and a monomer for producing the same, and more particularly, the present invention relates to an epoxy compound useful as a liquid crystal polymer and a monomer for producing the same. Liquid crystalline polymers, which are novel ferroelectric liquid crystal polymers that can be realized in liquid crystal display devices, liquid crystal memory devices, etc., and can be suitably used in various liquid crystal application fields including optoelectronics fields. The present invention relates to an epoxy compound that is a novel optically active compound useful as a monomer for producing liquid crystalline polymers. [Prior Art] Low-molecular ferroelectric liquid crystal compounds generally have excellent properties such as high-speed response to external factors such as electric fields, contrast ratio, etc., and can operate even in a relatively low temperature range such as room temperature. Because many of them have this, they are used in various optoelectronic fields as materials for liquid crystal display elements, liquid crystal memory elements, etc. However, low-molecular liquid crystal compounds have drawbacks such as difficulty in producing large-area or curved liquid crystal elements such as large-screen or curved-screen display elements. Therefore, in recent years, ferroelectric liquid crystals have been made into polymers in order to realize large-area or curved liquid crystal elements such as liquid crystal display elements with large screens or curved screens. liquid crystalline polymers have been proposed. However, in general, when liquid crystals are made into polymers, they tend to have the disadvantage of reduced responsiveness, and are often unsuitable for liquid crystal elements that require high-speed responsiveness for displaying moving images and the like. Further, not only polymer liquid crystals but also liquid crystals in general have a wide operating temperature range, and preferably operate in a relatively low temperature range such as room temperature. However, all of the ferroelectric liquid crystalline polymers proposed so far do not necessarily satisfy high-speed response and operating temperature characteristics. Among the ferroelectric liquid crystal polymers that have been proposed in the past, examples of ferroelectric liquid crystal polymers that satisfy this performance include polysiloxane-based ferroelectric liquid crystal polymers (Japanese Patent Application Laid-Open No. 63-28074
2, etc.) and polyoxirane-based ferroelectric liquid crystalline polymers consisting of repeating units represented by the following general formula % (Japanese Patent Application Laid-Open No. 6.3-264629, Japanese Patent Application Laid-Open No. 1-131234) etc. The above-mentioned conventional polysiloxane-based ferroelectric liquid crystal polymers and polyoxirane-based ferroelectric liquid crystal polymers have excellent responsiveness to electric fields, and have a chiral smectic C phase (Sm
It is a liquid crystal polymer that exhibits excellent performance such that the temperature range in which it exhibits C” phase is in a relatively low temperature range near room temperature, and it also extends over a relatively wide temperature range. However, the applications of liquid crystal polymers are In view of the increasing popularity of ferroelectric liquid crystal polymers, it is desired to develop a new ferroelectric liquid crystalline polymer having the above-mentioned excellent performance or even better performance. [Problems to be solved by the invention] The present invention has been made in view of the above circumstances.One object of the present invention is to provide a device that has excellent high-speed response to electric fields, etc., and is suitable for use in a wide temperature range including relatively low temperature ranges such as room temperature. It is a ferroelectric liquid crystal polymer that has the advantage of being able to operate, and can be suitably used not only for normal planar devices but also for various large-area or curved liquid crystal devices. It is an object of the present invention to provide a novel liquid crystalline polymer which, when used as a display element, can easily realize a liquid crystal display element with a large screen, a curved screen, and even a moving image display. One objective is to provide an epoxy compound that is a novel optically active compound that is useful as a monomer for producing the liquid crystalline polymer of the present invention. [Means for Solving the Problems] The present inventors have As a result of intensive research to achieve the above objective, we have developed a polyoxirane system consisting of repeating units having a specific optically active alkyloxycarbonyl group-containing aromatic group in the side chain via a spacer consisting of an oxyethylene unit and a methylene unit. Ferroelectric liquid crystalline polymer
They discovered that it is a liquid crystalline polymer with excellent operating temperature characteristics such as exhibiting SmC1 phase in a wide temperature range including relatively low temperature ranges such as room temperature, and has excellent performance such as high responsiveness to electric fields etc. We have discovered that various optically active epoxy compounds corresponding to the above-mentioned specific repeating units are also novel compounds, and are useful as 7mers for the production of liquid crystalline polymers, and based on these findings, we have completed the present invention. reached. That is, the present invention is based on the following general formula % formula % [However, k in formula (1] is an integer from 1 to 10, and j
is an integer from 2 to 30, R1 is the following general formula (herein, formula Ha) ~l:Id), and R2 is the following general formula (wherein, m is 0). is an integer of ~10, n is an integer of 1 to 10, and C with an umbrella represents an asymmetric carbon atom. ) is an optically active alkyl group represented by ) is an optically active aromatic group represented by ] It provides a liquid crystalline polymer characterized by having a repeating unit represented by the following. Furthermore, the present invention relates to a novel compound useful as a monomer for producing the above-mentioned liquid crystalline polymer, that is, a compound represented by the following general formula % [wherein 1 j and R1 in the formula (I[l] are respectively, It has the same meaning as that of formula [1]. ] It also provides an epoxy compound represented by: The liquid crystalline polymer of the present invention is a ferroelectric liquid crystalline polymer comprising at least one repeating unit represented by the general formula (1), and as described below, the optically active polymer corresponding to the repeating unit - can be obtained by polymerizing the epoxy compound of the present invention, that is, the epoxy compound represented by the above general formula [111]. In the general formula [1] and general formula [■], k is an integer of 1 to 10, preferably an integer of 1 to 6. Also,
j is an integer of 2 to 30, preferably an integer of 4 to 20. R1 in the general formula (1) and general formula CI[I] represents the general formula [1a], [1b], (I c) or (Id)
represents an optically active aromatic group represented by the following, and R1 in the optically active aromatic group represents an optically active alkyl group represented by the general formula (II). In general formula (II), m is an integer of 0 to 10, preferably an integer of 0 to 6. Further, n is an integer of 1 to 10, preferably an integer of 1 to 6. Optically active alkyl group (R”
Specific examples and preferred examples of ) are exemplified by the optically active alcohol ()10-R2) described below (the same applies hereinafter). The repeating unit represented by the general formula (I) is k and j
There are many different types depending on the values of and the type of R1. These repeating units have the general formula [I[[]
Since the epoxy compound of the present invention represented by corresponds to an epoxy ring-opened (polymerized) monomer unit, specific examples include the return units of each epoxy compound exemplified later. The liquid crystalline polymer of the present invention may be a homopolymer consisting of any one type of repeating unit represented by the various general formulas [I], or may be a homopolymer consisting of any two or more types of repeating units represented by the various general formulas [I]. It may be a copolymer consisting of repeating units, or a mixture thereof. Furthermore, the liquid crystalline polymer of the present invention may contain the repeating unit represented by the general formula [I] and other repeating units as long as the object of the present invention is not adversely affected. . The molecular weight of the liquid crystalline polymer of the present invention is not particularly limited, but the number average molecular weight is preferably 1,000 to 400,000, mainly from the viewpoint of moldability and electric field responsiveness.
It is preferable that it is in the range of . Its number average molecular weight is 1,
If it is less than 000, the moldability of the liquid crystal polymer as a film or coating may be impaired;
If it exceeds 0.000, the response speed may decrease. Particularly preferable ranges of this number average molecular weight include the type of R1,
Since it depends on the values of k and j, the optical purity of R2, etc., it cannot be defined unconditionally, but it is usually 1.000 to 20.
,000. The liquid crystalline polymer of the present invention is produced using an epoxy compound corresponding to the repeating unit represented by the general formula CI), which constitutes the liquid crystalline polymer, although there are no particular restrictions on the manufacturing method thereof. The epoxy compound of the present invention represented by can be suitably synthesized by epoxy ring-opening polymerization using a known method. The reaction formula for the polymerization can be formally expressed as follows. C)1. -CH CLOnCtlzCLO□CH, -Sword OR'→ -(
OCHICH) - CHzO-GCHzCFIzObr4CHzh-OR'
Any polymerization method may be used as long as a liquid crystalline polymer having a predetermined repeating unit as described above can be obtained, but cationic polymerization using an appropriate catalyst is usually preferably employed. The catalyst to be used is not particularly limited, and various known catalysts for epoxy ring-opening polymerization can be used. Particularly preferred catalysts include, for example, stannic chloride (SnC
I, b), etc., but are not necessarily limited to these. Further, although there is no particular restriction on the polymerization method, a solution polymerization method using an appropriate solvent is usually suitably employed. The solvent to be used is not particularly limited and may be appropriately selected from known solvents used in epoxy ring-opening polymerization.
Particularly preferred solvents include, for example, methylene chloride. Reaction conditions such as reaction temperature may be selected appropriately depending on the type of catalyst used and the composition of the reaction system, but the polymerization reaction should be carried out under as mild conditions as possible to prevent racemization of the optically active alkyl group. For example, in the case of solution polymerization using stannic chloride as a catalyst and methylene chloride as a solvent, the desired polymerization reaction can be easily achieved by reacting at around room temperature for several hours to 6 days. be able to. The epoxy compound (
The epoxy compound of the present invention) can be synthesized using various reactions such as known synthesis techniques, and the synthesis method is not particularly limited. It can be suitably synthesized according to various reaction routes. However, in the following, k, j and R2 each represent the same meaning as above, X represents a halogen atom, and Me represents a methyl group. Osamu'L Fire:'2L a, CHz=CHCHJr + HO(CHtC
HzO)J [1] That is, allyl bromide and diol form [1] are reacted in the presence of potassium hydroxide in dioxane to obtain ether form [2]. b, X-7 monomer (2) + X (CH2)j , obtain the ether body [5]. Next, the carboxyl group protecting group (M
e) is eliminated with a water-methanol mixed solution of potassium hydroxide to obtain carboxylic acid form [6]. [4] That is, compound [4] is obtained by reacting ether [2] with α,ω-dihaloalkane [3] in the presence of sodium hydride in THF. CH, CI. [7] Pyridine, toluene CB! = CI CHzO(CHzCHzO)m(CHz)Jo

[9] That is, carboxylic acid form [6] is treated with thionyl chloride in dichloromethane to obtain acid halide form [7]. Next, the acid halide [7] was reacted with the 4'-hydroxybiphenyl-4-carboxylic acid ester (8) containing optically active alkyl 4R1 in toluene in the presence of pyridine to form the optically active ester.

Obtain [9]. That is, ester

[9] with m-chloroperbenzoic acid (
m-CPBA) to obtain the desired epoxy compound [10]. Jisei' 6 Nihi I (Synthesis of compound [4] is the same as the synthesis route 1 above) [11] That is, compound [4] and 4'-hydroxybiphenyl-4-carboxylic acid in the presence of potassium hydroxide, A reaction is carried out in a methanol-water mixed solution to obtain carboxylic acid form [11]. (JI2CIt [10] CHz=CH [12] Pyridine, toluene CB! = CH CH2O(C)lICH!0)k(CIrijO-[14
] That is, carboxylic acid form [11] in dichloromethane,
Treatment with thionyl chloride to obtain acid halide [12] Next, the acid halide [12] is reacted with 4-hydroxybenzoic acid ester [13] containing an optically active alkyl group R2 in toluene in the presence of pyridine. , to obtain an optically active ester [14]. [15] That is, the ester form [14] is m-black benzoin!
(m-CPBA) to obtain the desired optically active epoxy compound [15]. In the manner described above, epoxy compound [10] and epoxy compound [15], which are examples of the epoxy compound of the present invention, can be suitably obtained. Other epoxy compounds of the present invention [16] and [17] can be obtained by modification of the above synthesis route 1 or 2. For example, epoxy compound [16] can be obtained by g of synthesis route 2, It can be easily obtained by reacting the acid halide [12] with optically active alcohol (HO-Rt) (1B) and esterifying it, and then epoxidizing the obtained optically active ester as described above. On the other hand, epoxy compound [17] is, for example, 4'-hydroxybiphenyl-4 in d of synthetic route 1.
It can be easily obtained by reacting P-hydroxybenzoic acid ester [13] with compound [7] instead of -carboxylic acid ester [8] and following the same procedure. In addition, the diol used in the above synthetic route [
Specific examples of 1) include ethylene glycol,
Diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol and the like can be mentioned. It is usually preferable to use one of these various diols in order to improve the purity of the obtained epoxy compound or the uniformity of the liquid crystalline polymer, but if necessary, they may interfere with the purpose of the present invention. Two or more types may be used in combination as a mixture, etc., as long as there is no exception. Further, specific examples of the α,ω-dihaloalkane include:
For example, 1.4-dibromobutane, 1゜5-dibromopentane, 1.6-dibromohexane, 1.8-dibromooctane, 1.10-dibromodecane, 1.12-dibromododecane, 1゜14-dibromotetradecane. , 1.
4-short butane, 1,6-short hexane, 1.
Examples include 8-short octane and 1,10-jododecane. These various α,ω-dihaloalkanes are usually preferably used alone in order to improve the purity of the obtained epoxy compound or the uniformity of the liquid crystalline polymer, but if necessary, they may be used in the present invention. Two or more types may be used in combination as a mixture, etc., within a range that does not interfere with the purpose. The ester [8] used in the above synthetic route can be synthesized using, for example, 4'-hydroxybifuyny-4-carboxylic acid and various optically active alcohols [18] as exemplified later.
] That is, HO-R" can be easily obtained by reacting it in an appropriate solvent such as benzene using concentrated sulfuric acid, P-)luenesulfonic acid, etc. as a catalyst. Ester body [13]
can be easily synthesized by using P-hydroxybenzoic acid in place of 4'-hydroxybiphenyl-4-carboxylic acid in the above. The optically active alcohol [18], i.e. 110-R1
Specific examples include (+ or -)-methylpentanol (where the methyl group is at the 2 or 3 position), (
+ or -) -4-methylhexanol, (+ or -) -
1-methylheptatool, (+ or -)-2-methylbutanol, (+ or -)-6-methyloctatool, (
Examples include + or -)-2-butanol, (+ or -)-2-pentanol, (10 or -)-2-octatool, and the like. Among these, (-)-2-methylbutanol, (+)-2-butanol, (-)-2
Preferred examples include -pentanol and (-)-2-octatool. It should be noted that these various optically active alcohols are usually preferably used alone in order to improve the optical purity of the obtained epoxy compound or the uniformity of the liquid crystalline polymer, but they may be used as needed. Two or more types may be used in combination as a mixture, etc., as long as the optical purity is maintained sufficiently and the purpose of the present invention is not adversely affected. Specifics of Rt in the repeating unit represented by the general formula CI) constituting the liquid crystalline polymer of the invention and e in the epoxy compound of the invention represented by the general formula (I [l) corresponding to the repeating unit] Examples and preferred examples can be exemplified by various optically active alkyl groups (R'') in the above-mentioned optically active alcohol (110-R di). There are a wide variety of specific examples of epoxy compounds depending on the values of k and j and the type of R1 (that is, the values of m and n and the type of R2), but the following are typical examples: , (R2- CH. CHiCHCJs, etc.) C) I. ) zcL, etc.) (R2-, etc.) /\ C) 12-CH (R2- O ttz (Rt--CHCJs, etc.) [However, the carbon atom with this mark in R2 in these epoxy compounds is asymmetric Each epoxy compound has D-unit and L-unit optical isomers depending on the steric structure of the optically active alkyl group R2. It can be obtained as a (10) monomer and a (−) monomer of various optical purity depending on the optical purity of the liquid crystalline polymer of the present invention. The optically active epoxy compounds exemplified above can be obtained by epoxy ring-opening polymerization as described above. At that time, it is usually preferable to polymerize one type of epoxy compound with the highest possible optical purity, but It is not necessarily limited to this, and it can also be synthesized by polymerizing one or more optically active epoxy compounds of various optical purity within a range that does not impede the purpose of the present invention, and further, It can also be obtained by copolymerizing with other epoxy compounds.The liquid crystalline polymer of the present invention suitably produced as described above has specific properties in the side chain via a smoother composed of an oxyethylene unit and a methylene unit. It is a polyoxirane-based ferroelectric liquid crystal polymer with a novel structure consisting of repeating units having an optically active alkyloxycarbonyl group-containing aromatic group. It exhibits excellent phase transition behavior such as , and has excellent liquid crystal properties such as a fast response speed to electric fields and the like. Furthermore, since it is a liquid crystalline polymer with excellent moldability such as film-forming properties, it can be suitably used not only for ordinary flat devices but also for various large-area or curved liquid crystal devices. When used as an element, it is possible to realize a liquid crystal display element with a large screen, a curved surface, and even a moving image display. As described above, the liquid crystalline polymer of the present invention is a liquid crystalline polymer that is extremely useful in practice, and can be used not only in various liquid crystal display elements and liquid crystal memories, but also in a wide range of liquid crystal application fields, including various optical devices and electronics fields. It can be suitably used. In addition, when manufacturing a liquid crystal element such as a liquid crystal display element using the liquid crystalline polymer of the present invention, there are no particular restrictions on the manufacturing method. It may be used as a liquid crystal element for a desired purpose by forming it into a coating film, sandwiching it between predetermined conductive substrates, or the like. Furthermore, the epoxy compound of the present invention is a novel optically active compound, and can be widely used in various fields of use including as a monomer for producing the liquid crystalline polymer of the present invention. [Example] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. The structure of the obtained polymer was confirmed by NMR. In addition, measurement of phase transition temperature and confirmation of phase are performed using DS.
(glass state, SmC": chiral smectic C phase, SmA:
Chiral smectic physiognomy, N": chiral nematic phase, Iso: isoyoshi phase, the number of phase transition behavior is the phase transition temperature expressed in °C). The electric field response speed is The polymer was sandwiched between two glass substrates with circular ITO, and the thickness was adjusted to 1Jm using a spacer.
When a square wave of ±IOMV/m is applied, the amount of transmitted light changes (
1 (190%). Example 1 (Synthesis of 1,000 units) HzC-CtlCHzOCHzCHzO(CHz) s
0 sodium hydride 1.8 g tetrahydrofuran 10
4. Add ethylene glycol monoallyl ether to the 0di solution.
7g and 1. After simultaneously dropping 25 g of 8-dibromooctane, the mixture was refluxed for 8 hours. After filtering off the solid matter, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 4.4 g of compound (1) (yield: 32%). 1.0 g of rum was dissolved in 25M1 of methanol and refluxed for 19 hours. After filtering off the solid matter, the solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate. This was washed with aqueous potassium carbonate solution, dried over magnesium sulfate, and then the solvent was removed under reduced pressure. The residue was purified by column chromatography to obtain 3.2 g of compound (2) (yield 64%). 3.2 g of compound (2) obtained in 1. (2) and 1.8 g of potassium hydroxide were dissolved in a mixed solution of 20 d of methanol and 40 ml of water and refluxed for 5 hours. After the reaction, the mixture was acidified with hydrochloric acid and the resulting precipitate was collected. The obtained precipitate was washed with water and then heated and dried under reduced pressure to obtain 2.9 g of the desired carboxylic acid compound (3) (yield 93%). 2.3 g of compound (1) 4, Ig, p-hydroxybenzoic acid methyl ester obtained in 1.■ and potassium hydroxide 1.
4'-4"-8-2-allyloxyethoxy octyloxy benzoyloxybiphenyl-4-carvone
Compound (3) obtained with 2-methylbutyl ether 1, 0.
85 g and 3 dl of thionyl chloride were mixed with methylene chloride 5IIi
and refluxed for 4 hours. After the reaction, excess thionyl chloride and the solvent were distilled off under reduced pressure to obtain an acid chloride. 4'-Hydroxybiphenyl-4-carboxylic acid (-)-
0.67 g 2-methylbutyl ester and 0 pyridine
．． A toluene solution containing 23 g was added dropwise to the toluene solution of the above acid chloride, and after the reaction was stirred at room temperature for 15 hours, the solid matter was removed, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain compound (4).
) 0.83 g was obtained (yield 56%). 0.46 g of chloroperbenzoic acid was dissolved in 10 d of methylene chloride and stirred at room temperature for 10 hours. The reaction mixture was washed with aqueous potassium carbonate solution, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 0.54 g of monomer (5), which is the epoxy compound of the present invention (yield 64%). The NMR chart of this compound and the assignment of hydrogen are shown in FIG. (Polymerization) 0.47 g of the monomer (5) obtained in 1. was added and polymerized for 4 days at room temperature. After adding methanol, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain the desired polymer 0.11, which is a liquid crystalline polymer of the present invention having a repeating unit represented by the following formula.
g (yield 23%). 1. 0.83 g of compound (4) obtained in ① and m-ic
H,cB← CHzOChCHzO(CHz) so -80ae and stirred at 55°C for 8 hours. After removing the solid matter, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 4.8 g of compound (6).
was obtained (yield 39%). The NMR chart and hydrogen assignment of the obtained polymer are shown in FIG. 2, the number average molecular weight is shown in Table 1, and the phase transition behavior and electric field response speed are shown in Table 2. Example 2 (Synthesis of monomer) HaHzC-CHCToO(CHzCthO) t (CH
z) 6.7 g of compound (6) obtained in 5O-2■ was added to Example 1-1. 1. of Example 1 was used in place of the ethylene glycol monoallyl ether used in (2). Repeating the same procedure as in (2) yielded 5.0 g of compound (7) (yield 32%).
. Allyl bromide 10g, diethylene glycol 8.8
1 of Example 1 using 4.9 g of compound (7) obtained by dioxane Z2 and 2.1 g of p-hydroxybenzoic acid methyl ester, and 5.5 g of potassium hydroxide. The same operation as (2) was performed to obtain 1.2 g of compound (8) (yield: 2
1%). 0.79 g of Z■ Le Cie was obtained (yield 52%). 1.2 g of compound (8) obtained in Z■ and 0.77 g of potassium hydroxide were dissolved in a mixed solution of 20 d of methanol and 50 d of water. After one reaction under reflux for 4 hours, methanol was removed, acidified with hydrochloric acid, and extracted with ether. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 0.90 g of compound (9). (Yield 79%) Compound (10) obtained in 2. 0.79 g and m-
1゜■ of Example 1 using 53g of black perbenzoin MO.
By performing the same operation as above, 0.65 g of monomer (11), which is the epoxy compound of the present invention, was obtained (yield 80%).
The NMR chart of this compound and the assignment of hydrogen are shown in FIG. 1 of Example 1 using 0.90 g of compound (9) obtained in Z■ and 0.65 g of 4'hydroxybiphenyl-4-carboxylic acid (-)-2-methylbutyl ester. Perform the same operation as in (1) to dissolve compound (10) (polymerization) 0.60 g of monomer (11) obtained in 2 (2) in 2d of methylene chloride, add 5 μl of stannic chloride, and dissolve at room temperature. Polymerization was carried out for 2 days. After adding methanol,
The solvent was removed under reduced pressure. The residue was purified by column chromatography, and the desired polymer 0.
19 g was obtained (yield 31%). -JOCHzCHP [CHzO(CLCLO)z(CL)sO- The NMR chart and hydrogen assignment of the obtained polymer are shown in Figure 4, the number average molecular weight is shown in Table 1, and the phase transition behavior and electric field response speed are shown in Table 2. Shown below. Bromobenone 12 sodium hydride 4.4 g tetrahydrofuran 150
1 g of ethylene glycol monoallyl ether I in the di solution
and 50 g of 1,5-dibromopentane were added dropwise at the same time, and the mixture was refluxed for 11 hours. After removing the solid matter, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 7.7 g of compound (12) (yield 28%). Example 3 (Synthesis of monomer) HaHzC-CHCHJCHzCHzO(C)It) sO
- Compound (12) obtained in &■ 3.0 g and p-
1 of Example 1 using 2.0 g of hydroxybenzoic acid methyl ester. Perform the same operation as in ① to obtain compound (13) 2.
．． Obtained 0g. (Yield 52%). 3, ■ 1 (2-allyloxyethoxy-5-) 2.0 g of the compound (13) obtained in 3, ■ and 1.2 g of potassium hydroxide were dissolved in 25 m of water and refluxed for 2 hours. The resulting precipitate was collected. The resulting precipitate was washed with water and then dried by heating under reduced pressure to obtain 1.3 g of the desired carboxylic acid form (14) (yield: 68%).
). 3. Compound (15) obtained in ① 1.5 g and m-
1. of Example 1 using 0.68 g of chloroperbenzoic acid.
The same operation as in (2) was performed to obtain 0.50 g of monomer (16), which is the epoxy compound of the present invention (yield 33%).
, the NMR chart of this compound and the assignment of hydrogen are shown in FIG. 1.2 g of compound (14) obtained in 3.■ and 4'
1 of Example 1 using 1°Og of hydroxybiphenyl-4-carboxylic acid (-)2-methylbutyl ester. The same operation as in (2) was carried out to obtain 1.59 g of compound (15) (
yield 67%). (Polymerization) 3. Dissolve 0.05 g of Chitsuma (16) obtained in
was added and polymerized for 5 days at room temperature. After adding methanol, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain the desired polymer 0, which is a liquid crystalline polymer of the present invention having a repeating unit represented by the following formula.
．． 17 g was obtained (yield 34%). 2-Methylbutyl ester 16) Person-40CH,C
H4 CHzOCEzCHzO(C)Iz)sO-The NMR chart and hydrogen assignment of the obtained polymer are shown in FIG. 6, the number average molecular weight is shown in Table 1, and the phase transition behavior and electric field response speed are shown in Table 2. 4'-hydroxybiphenyl-4-carboxylic acid 3.3g
and 2.2 g of potassium hydroxide in 0.69 m of water and 40 m of methanol. wd! 0 was dissolved in a mixed solution of and refluxed for 4 hours.
After the reaction, methanol was distilled off under reduced pressure. The residue was dissolved in water and then acidified with hydrochloric acid. The resulting precipitate was collected and recrystallized from methanol to obtain the desired carboxylic acid form (17) 1.8
g (yield 34%). Example 4 (Synthesis of monomer) HaH,C-CHCHffiOCHICB! 0(C)liriS
o to 4 of Example 4. Compound (17) obtained in (1) 1.
1 of Example 1 using 8 g and 1.1 g of 4-hydroxybenzoic acid (-)-1-methylhebutyl ester. The same operation as in (2) was performed to obtain 1.6 g of compound (1B) (
yield 57%). Example 3-3. Compound (12) obtained in ■ 3.5
g, 4, ■ 4''-1-Methylhebutyloxycarbonyl phenyl 4'-5-2-23-epoxypropoxy oxy pentyloxy 4, Compound obtained in ■ (
18) 1.6 g and m-black perbenzoin M1.2 g
1 of Example 1. Perform the same operation as in (2) and add 0.35 monomer (19), which is the epoxy compound of the present invention.
(21% yield). The NMR chart of this compound and the assignment of hydrogen are shown in FIG. -(OCthCH← CHzOCHzCHzO(CHz) sO- The NMR chart and hydrogen assignment of the obtained polymer are shown in FIG. 8, the number average molecular weight is shown in Table 1, and the phase transition behavior and electric field response speed are shown in Table 2. (Polymerization) 0.35 g of the monomer (19) obtained in 4.
was added and polymerized for 6 days at room temperature. After adding methanol, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain the desired polymer 0, which is a liquid crystalline polymer of the present invention having a repeating unit represented by the following formula.
．． 11 g was obtained (yield 31%). (The following is a margin) Table 2 130: Published by Teraki [Effects of the invention] According to the present invention, it has excellent high-speed response to electric fields, etc., and operates suitably in a wide temperature range including a relatively low temperature range such as room temperature. A ferroelectric liquid crystalline polymer that has the advantages of being able to
It can be suitably used for various types of large-area or curved liquid crystal devices, and especially when used as a display device, it can easily realize a liquid crystal display device with a large screen, a curved screen, and even a moving image display. It is possible to provide a novel liquid crystalline polymer capable of Further, according to the present invention, it is possible to provide an epoxy compound which is a novel optically active compound useful as a monomer for producing the liquid crystalline polymer of the present invention. FIG. 2, FIG. 4, FIG. 6, and FIG. 8 show the NM of the liquid crystalline polymer of the present invention obtained in Examples 1 to 4, respectively.
An R chart is shown.

Claims (1)

[Claims] 1. The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] [However, the formula [I] is an integer from 1 to 10,
j is an integer from 2 to 30, and R^1 is the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I a], ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I b], ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I c ] or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I d] Here, R^2 in the formulas [ I a] ~ [ I d] is as follows. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (However, m in formula [II] is an integer from 0 to 10, and n
is an integer from 1 to 10, and C with * represents an asymmetric carbon atom. ) is an optically active alkyl group represented by ) is an optically active aromatic group represented by ] A liquid crystalline polymer characterized by having a repeating unit represented by the following. 2. The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] [However, k in formula [III] is an integer from 1 to 10,
j is an integer from 2 to 30, and R^1 is the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I a], ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I b], ▲ There are mathematical formulas, chemical formulas, tables, etc.▼[I c] or▲There are mathematical formulas, chemical formulas, tables, etc.▼[I d] {Here, R^1 in the formulas [I a] to [I d] is as follows General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (However, m in formula [II] is an integer from 0 to 10, and n
is an integer from 1 to 10, and C with * represents an asymmetric carbon atom. ) is an optically active alkyl group represented by } is an optically active aromatic group represented by ] An epoxy compound represented by