JP3246938B2 - Method for producing liquid crystal copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention can control the molecular weight easily and, in addition, can control the carbon-terminal of the polymer main chain obtained.
The present invention relates to a method for producing a liquid crystal copolymer capable of reducing the number of carbon double bonds. More specifically, the present invention has excellent long-term stability for use in liquid crystal display panels and the like, exhibits a chiral smectic C phase (SmC ^* phase) over a wide temperature range, and has a high-speed response to changes in an external electric field. The present invention also relates to a method for producing a liquid crystal copolymer having excellent contrast.

[0002]

2. Description of the Related Art Polymer liquid crystals are used to increase the size of liquid crystal display panels.
Although it is a useful liquid crystal material for forming a curved surface, a polymer liquid crystal exhibiting high-speed response to a change in an external electric field and having sufficiently satisfactory characteristics in a usable temperature range has not been obtained at present. For example, JP-A-63-990204
In the publication, the synthesis of a polyacrylate-based ferroelectric polymer liquid crystal is reported, and it is clear that it exhibits excellent performance. Problems remain in the usable temperature range.

Further, Japanese Patent Application Laid-Open No. 63-254529 discloses a polyether-based ferroelectric polymer liquid crystal obtained by polymerizing a monomer having an epoxy group. Although this side-chain type polymer liquid crystal has an advantage of responding to an external electric field stimulus in a wide temperature range including around room temperature, its response speed is slow and is still insufficient for practical use.

[0004]

SUMMARY OF THE INVENTION The present invention provides ferroelectricity over a wide temperature range including a room temperature range, responds to changes in an external electric field at high speed, and has a high contrast when used as a liquid crystal panel. It is an object of the present invention to provide a method for producing a liquid crystal copolymer, which can obtain a liquid crystal copolymer excellent in quality and can easily control the molecular weight.

The present inventors have previously reported that a novel copolymer having a chain hydrocarbon skeleton having an aromatic ring in the side chain and a siloxane skeleton as a repeating unit has been obtained over a wide temperature range including a room temperature range. SmC ^* phase) and high-speed response to electric field changes. This copolymer is composed of a diene compound having an aromatic ring in a side chain and having two carbon-carbon double bonds at a terminal and a siloxane compound having two active hydrogens at a terminal in substantially equimolar proportions of a hydrosilyl compound in a solvent. It is obtained by performing a polymerization reaction and performing addition polymerization. However, the only way to control the molecular weight of this copolymer is to change the molar ratio of the diene compound / siloxane compound, and it has been difficult to control the molecular weight. Further, according to this method, a highly reactive carbon-carbon double bond or a hydrosilane structure is left at the main chain terminal of the polymer liquid crystal, which causes a problem that the long-term stability of the liquid crystal copolymer deteriorates. An object of the present invention is to provide a method for producing a liquid crystal copolymer in which the molecular weight can be easily controlled.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, when a diene compound and a siloxane compound are subjected to addition polymerization to produce a liquid crystal copolymer, a reaction system is required. The inventors have found that the above problem can be solved by adding a compound having one olefinic double bond in the molecule to carry out a polymerization reaction, and have completed the present invention based on this finding.

That is, the present invention provides a diene compound [I] represented by the following general formula:

Embedded image (Where l and m are integers of 2 to 5, a is an integer of 1 to 20, b is an integer of 1 to 10, Z is

[0008]

Embedded image And * represents an asymmetric carbon. ) And a siloxane compound [II] represented by the following general formula:

[0009]

Embedded image

(Wherein p represents an integer of 0 to 3) to produce a liquid crystal copolymer by addition polymerization, a compound having one olefinic double bond in the reaction system [II]
A method for producing a liquid crystal copolymer, characterized by performing a polymerization reaction by adding I).

The liquid crystal copolymer obtained by the present invention has a repeating unit represented by the following general formula, and has excellent response to an external electric field and excellent contrast in a wide temperature range including a room temperature range. .

[0012]

Embedded image (In the formula, l, m, p, a, b, and Z are the same as described above.)

In the polyaddition reaction of the liquid crystal copolymer of the present invention, the diene compound [I],
Siloxane compound [II] and olefinic compound [I
II].

As the solvent used in the reaction, benzene, toluene, xylene, tetrahydrofuran, dioxane and the like are preferably used. As the catalyst, H ₂ PtC
l _6, PtCl _4, Pt, platinum acetylacetonate, P
tCl ₂ , PtBr ₂ , PtI ₂ , Pt (C ₂ H ₄ ) (PP
_{h 3) 3, [Pt (} C 2 H 2) Cl 2] Platinum and platinum compounds such as _2, RhCl (PPh _{3) 3} and the like are preferably used.

[0015] The reaction temperature is usually 40 ° C or higher, preferably 60 to 150 ° C. If the temperature is lower than 40 ° C., the reaction is slow, and if the reaction temperature is too high, a side reaction may occur. The reaction time is usually from 30 minutes to 20 hours, and is appropriately determined according to the reaction temperature.

In the synthesis of the above liquid crystal copolymer, when a compound having one olefinic double bond in the molecule as a molecular weight regulator is added to the reaction system and the reaction is carried out, the molecular weight of the resulting copolymer is reduced. Can be easily controlled. As the olefinic compound [III], a linear, branched or cyclic monoolefin having 6 to 10 carbon atoms is preferably used. Further, a compound represented by the following general formula is also used.

[0017]

Embedded image

(Wherein c is an integer of 0 to 10 and d is 1 to 2
An integer of 0, e is an integer of 1 to 10, W is

Embedded image The molar ratio of diene compound [I] / siloxane compound [II] is such that siloxane compound [II] / diene compound [I] <
4 is preferable. When the molar ratio is 4 or more, it becomes difficult to obtain a liquid crystal copolymer. Further, the olefinic compound [I
II] / diene compound [I] (molar ratio) is 0.01 to 1
The ratio is preferably 0, and is appropriately determined according to the target molecular weight. If it is less than 0.01, the effect of lowering the molecular weight is small, and if it is more than 10, polymerization hardly proceeds.

Specific examples of the olefinic compound [III] include 1-hexene, 1-octene, 2-hexene, 4-methyl-1-pentene, cyclohexene, vinylcyclohexane, 4 '-[4 "-′ 10- (2-propenyloxy) decyloxy {benzoyloxy] biphenyl-4-carboxylic acid (S)-
(+)-1-methylbutyl ester, 4 '-[4 "-
{8- (3-butenyloxy) octyloxy} biphenyl-4-carbonyloxy] benzoic acid (S)-(+)-1-methylheptyl ester and the like. In particular, a monoolefin compound exhibiting liquid crystallinity can reduce the amount of carbon-carbon double bonds at the main chain terminals without impairing liquid crystallinity.

The diene compound [I] used as a raw material for producing the above liquid crystal copolymer is, for example, Z

[0021]

Embedded image In the case of, the following general formula

[0022]

Embedded image

(Wherein l and m are the same as above) and a general formula X (CH ₂ ) _a X [V] (where a is an integer of 1 to 20, and X is -Br, -I or-
OSO ₂ C ₆ H ₄ CH ₃ . ) Is carried out in a solvent in the presence of an alkaline reagent in the presence of an alkali reagent, and the resulting reaction mixture is purified to obtain a product, which is then treated with methyl 4-hydroxybenzoate. And etherification reaction in a solvent in the presence of an alkali reagent, and then purifying the obtained reaction mixture to hydrolyze the obtained product in an alkaline aqueous solution or an alkaline water-alcohol mixed solution, thereby obtaining The reaction solution was poured into water, the pH was made acidic by adding a mineral acid, and then the compound obtained by ether extraction or filtration was reacted with an acid halogenating agent.
It can be produced by subjecting the obtained acid chloride and a hydroxy compound [VI] represented by the following formula to an esterification reaction in a solvent.

[0024]

Embedded image (Where b is the same as above.)

The reaction proceeds, for example, as follows.

[0026]

Embedded image

The alcohol [IV] and the bifunctional compound [V] are etherified in a solvent in the presence of an alkali reagent to obtain (1).

Specific examples of the alcohol [IV] include 1,4-pentadien-3-ol, 1,5-hexadien-3-ol, 1,6-heptadien-3-ol, and 1,7-octadiene. -3-ol, 1,6-heptadien-4-ol, 1,8-nonadien-5-ol, 1,10-undecadien-6-ol and the like.

Examples of the bifunctional compound [V] include dibromomethane, diiodomethane, ditosylmethane, dibromoethane, diiodoethane, ditosylethane, dibromopropane, diiodopropane, ditosylpropane, dibromobutane, diiodobutane, ditosylbutane, Dibromopentane, diiodopentane, ditosylpentane, dibromohexane, diiodohexane, ditosylhexane, dibromoheptane, diiodoheptane,
Ditosylheptane, dibromooctane, diiodooctane, ditosyloctane, dibromononane, diiodononane, ditosylnonane, dibromodecane, diiododecane, ditosyldecane, dibromoundecane, diiodoundecane, ditosylundecane, dibromododecane, diiododecane, ditosododecane, etc. .

As a solvent for the etherification reaction, an aprotic polar solvent such as tetrahydrofuran or N, N-dimethylformamide is preferably used. As a catalyst for the etherification reaction, a metal hydride such as sodium hydride or the like is used. A metal hydroxide such as potassium hydroxide or sodium hydroxide or a basic compound capable of ionizing -OH is preferably used.

In the etherification reaction, an alcohol [IV] is introduced into a mixture of an alkali reagent and a solvent, and the mixture is alkoxide-converted at room temperature (however, in the case of compounds and reagents having low reactivity, heating is performed). The reaction is carried out by introducing the active compound [V] and heating and stirring at 50 to 100 ° C.

Next, the compound (1) is subjected to an etherification reaction with methyl 4-hydroxybenzoate in a solvent in the presence of an alkali reagent to obtain a compound (2). As a solvent for the etherification reaction, for example, a ketone solvent such as acetone and 2-butanone and an ether inert solvent such as tetrahydrofuran and ether are suitably used. As the etherification reaction reagent, for example, potassium carbonate, sodium carbonate and the like Or metal hydroxides such as potassium hydroxide and sodium hydroxide are preferably used. Etherification reaction is 4
-Methyl hydroxybenzoate, compound (1) obtained by the etherification reaction, an alkali reagent, and a solvent are introduced in any order, and the mixture is heated and stirred at 50 to 100 ° C.

Next, the compound is heated in an alkaline aqueous solution or an alkaline water-alcohol mixed solution, if necessary, to carry out hydrolysis to obtain a compound (3). After making the substance, an esterification reaction is performed with the hydroxy compound [VI] and a toluene solvent or the like in the presence of pyridine or the like to obtain the desired diene compound [I].

In the hydrolysis, metal hydroxides such as potassium hydroxide and sodium hydroxide are preferably used as alkalis, and methanol and methanol are used as alcohols.
A water-soluble lower alcohol such as ethanol is preferably used. The hydrolysis reaction may be heated with only an ester, an alkali catalyst, and water. However, when an alcohol is further added, the solubility of the ester compound as a raw material is improved, and the reaction proceeds easily.

In the halogenation reaction, known acid halogenating agents such as thionyl chloride, phosphorus oxychloride, phosphorus pentachloride and the like are used. Pyridine, triethylamine or the like may be added to the reaction system. As a solvent for the esterification reaction of
For example, an ether inert solvent such as tetrahydrofuran and a hydrocarbon inert solvent such as toluene and hexane are preferably used.

The esterification reaction is carried out by introducing an acid chloride or an acid chloride dissolved in a solvent into a solution containing a phenol and a hydrogen halide acceptor such as a tertiary amine such as pyridine and triethylamine, followed by stirring. . When the reactivity is low, the mixture may be heated to 30 to 80C.

Z is

Embedded image Is also synthesized according to the above reaction.

The optically active group in the hydroxy compound [VI] is introduced using the following reaction using an optically active alcohol R ² OH. −COOH + R ² OH → −COOR ²

The optically active alcohol R ² OH used here
Include (+)-2-butanol, (-)-2-butanol, (+)-2-pentanol, (-)-2-pentanol, (+)-2-hexanol, and (-)-2 -Hexanol, (+)-2-heptanol, (-)-2-
Heptanol, (+)-2-octanol, (-)-2
-Octanol (+)-2-nonanol, (-)-2-
Nonanol, (+)-2-decanol, (-)-2-decanol, (+)-2-undecanol and (-)-2
-Undecanol.

A typical example of the diene compound [I] thus obtained is 1-methylbutyl 4'-
[4 ″-{10- (1,5-hexadien-3-yloxy) decyloxy} benzoyloxy] biphenyl-4-carboxylate, 1-methylbutyl 4-
[4 "-{8- (1,6-heptadien-4-yloxy) octyloxy} biphenyl-4'-carbonyloxy] benzoate.

Next, as the siloxane compound [II] having two Si—H bonds, which is a raw material used in the method of the present invention, those having a p value of 0, 1, and 2 have a p value of , A single compound is used, but a compound having a large value of p has a distribution in the degree of polymerization (value of p), so the value of p is represented by an average value. Therefore, the value of p in the obtained liquid crystal copolymer is also an average value. Specifically, 1,1,3,3-tetramethyldisiloxane, 1,1,
3,3,5,5-hexamethyltrisiloxane, 1,
Various α, ω-hydrogen oligodimethylsiloxanes such as 1,3,3,5,5,7,7-octamethyltetrasiloxane are used.

The liquid crystal copolymer obtained as described above has excellent long-term stability and excellent characteristics as a liquid crystal material such as responsiveness to electric field change and contrast.

When a pyrimidine compound is blended with the liquid crystal copolymer obtained according to the present invention, the resulting composition has responsiveness,
The contrast is further improved as compared with the above liquid crystal copolymer.

The compounding ratio of the liquid crystal copolymer in the above composition is usually 99 to 50% by weight, preferably 80 to 60% by weight, and the compounding ratio of the pyrimidine compound is usually 1 to 50% by weight, preferably 20 to 40% by weight. %. If the amount of the pyrimidine compound is small, the high-speed response is not sufficient, and if it exceeds 50% by weight, the tilt angle is reduced and the contrast is reduced.

As the pyrimidine compound suitably used for preparing the above composition, the following compounds may be mentioned.

Pyrimidine compound

Embedded image

[0047]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0048]

Embedded image

[0049]

Embedded image

3- (10-bromodecyloxy) -1,
Synthesis of 5-hexadiene 4.1 g of sodium hydride (content 60%) was suspended in 50 ml of tetrahydrofuran (THF), and the system was replaced with argon. 1,5-hexadien-3-ol 9.8
g of a THF solution containing 50 g was added dropwise. The mixture was stirred at room temperature until the generation of hydrogen gas stopped. 100 ml of a THF solution containing 75 g of 1,10-dibromodecane was added, and the mixture was refluxed for 7 hours. The resulting insolubles were removed by filtration, and THF was distilled off under reduced pressure. Purification by silica gel column chromatography gave 14.3 g of the desired bromo compound.
(Yield 45%)

4 '-[4 "-{10- (1,5-hexadien-3-yloxy) decyloxy} benzoyloxy] biphenyl-4-carboxylic acid
Synthesis of (S)-(+)-1-methylbutyl ester 19.0 g of the bromo compound obtained above, 9.2 g of methyl 4-hydroxybenzoate, and 3.4 g of potassium carbonate were added to 2-
Refluxed in 50 ml of butanone for 12 hours. The resulting insolubles were removed by filtration, and the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography gave a methyl ester.

The above-mentioned methyl ester, 10.0 g of potassium hydroxide and 3.0 g of water were dissolved in 20 ml of methanol in 1 ml.
Refluxed for hours. 50 ml of water was added, and the mixture was further refluxed for 1 hour. Dilute with 300 ml of water and add dilute hydrochloric acid dropwise to pH = 2
And The resulting precipitate was collected by filtration, washed with water and dried.
-{10- (1,5-hexadien-3-yloxy)
16.6 g of decyloxy dibenzoic acid was obtained.

To 8.3 g of the above carboxylic acid, 4.0 g of thionyl chloride and a catalytic amount of pyridine were added, and 85 ° C.
For 2 hours. After excess thionyl chloride was distilled off under reduced pressure, 50 ml of toluene was added to obtain an acid chloride solution. Thereto, 50 ml of a toluene solution containing 6.3 g of (S) -1-methylbutyl 4-hydroxybiphenyl-4'-carboxylate and 1.8 g of pyridine was added dropwise at room temperature, and reacted at room temperature for one day. The resulting insolubles were removed by filtration, and the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography yields the desired optically active monomer 4 ′-[4 ″-{10- (1,5-hexadiene-3).
-Yloxy) decyloxy {benzoyloxy] biphenyl-4-carboxylic acid (S)-(+)
9.7 g of -1-methylbutyl ester was obtained. (50% yield from bromide)

Synthesis of the copolymer 4 ′-[4 ″-{10- (1,5)
-Hexadien-3-yloxy) decyloxy {benzoyloxy] biphenyl-4-carboxylic acid (S)-(+)-1-methylbutyl ester 4.0
0 g (6.2 mmol), 0.26 g of 1-hexene
(3.1 mmol) and 0.84 g (6.3 mmol) of 1,1,3,3-tetramethyldisiloxane were uniformly dissolved in 40 ml of dry toluene. Next, after adding 4.2 mg of chloroplatinic acid hexahydrate, the mixture was stirred at 85 ° C. for 5 hours. The air in the reaction vessel was replaced with argon gas before starting the heating, and the reaction vessel was sealed so that moisture and air did not enter the vessel during the reaction.

The reaction mixture was cooled to room temperature and filtered.
The filtrate was concentrated using a rotary evaporator. Further, this concentrate was purified by column chromatography, and then dried under vacuum at 60 ° C. overnight to obtain 3.20 g of a white viscous substance. The structure of this substance was confirmed by ¹ H-NMR. FIG. 1 shows the molecular structure and NMR spectrum. When the molecular weight of this substance was measured by GPC, Mn =
2,410, Mw = 3,490. The characteristics as a liquid crystal are shown below.

113.4-109.1 ° C. -20 ° C. Iso → SmC ^* → G τ _10-90 = 23.6 ms (25 ° C.): 2θ = 78 ゜ (25 ° C.) Next, using methylene chloride, Polymer 6
7% by weight, pyrimidine compound P1008 manufactured by Midori Kagaku
A 33% by weight composition was prepared, and the characteristics of the liquid crystal composition were measured by the method described above. The structure of P1008 and the characteristics of the liquid crystal composition are shown below.

[0057]

Embedded image

103.5-90 ° C. 87.2 ° C.-20 ° C. Iso → SmA → SmC ^* → Gτ _10-90 = 8.5 ms (25 ° C.): 2θ = 47 ゜ (25 ° C.)

Evaluation Method The characteristics as a liquid crystal were evaluated as follows. 20 × 10m
A liquid crystal was sandwiched between two glass substrates having an ITO electrode having a thickness of 2.0 m, and a cell whose thickness was adjusted to 2.0 μm with a spacer was produced. The phase series was determined by heating the cell and observing it with a polarizing microscope while lowering the temperature of the once polymerized liquid crystal. At this time, the liquid crystal was uniaxially horizontally aligned by a shearing method by mutually shifting the substrates with a smectic A phase (SmA) or a chiral smectic C phase (SmC ^* ). The response time τ _10-90 is defined as the time required for the transmitted light intensity to change from 10% to 90% when the liquid crystal cell is arranged between the orthogonal polarizers and a step voltage of ± 10 V is applied between the electrodes. . The tilt angle 2θ was determined from the change in the extinction position that rotates according to the change in the sign of the applied voltage of 10 V.
In addition, in the formula showing the phase transition behavior, each symbol has the following meaning. G: glass phase, SmC: smectic C liquid crystal phase, SmC
^* : Chiral smectic C liquid crystal phase, SmA: smectic A liquid crystal phase, Iso: isotropic liquid

Example 2 4 '-[4 "-{10- (1,5-hexadiene-3)
-Yloxy) decyloxy {benzoyloxy] biphenyl-4-carboxylic acid (S)-(+)
1.92 g (3.00 mmol) of 1-methylbutyl ester, 4 '-[4 "-{10- (2-propenyloxy) decyloxy} benzoyloxy] biphenyl-
4-Carboxylic acid (S)-(+)-1-methylbutyl ester 0.90 g (1.50 mmol)
[See JP-A-3-64321] and 1,1,3,
0.40 g (3.00 mmol) of 3-tetramethyldisiloxane was uniformly dissolved in 30 ml of dry toluene.
Next, 2.0 mg of chloroplatinic acid hexahydrate was added.
The mixture was stirred at 5 ° C for 4.5 hours. The air in the reaction vessel was replaced with argon gas in advance, and the reaction vessel was sealed so that moisture and air did not enter the vessel during the reaction.

The reaction mixture was cooled to room temperature and filtered,
The filtrate was concentrated using a rotary evaporator. The concentrate was further purified by column chromatography,
Vacuum dried at 0 ° C. overnight to obtain 2.20 g of a white viscous substance. The structure of this substance was confirmed by ¹ H-NMR.
FIG. 2 shows the molecular structure and NMR spectrum. It can be seen that the number of carbon-carbon double bonds at the terminal of the polymer main chain is smaller than that of the liquid crystal copolymer of the comparative example. When the molecular weight of this substance was measured by GPC, Mn = 2,080,
Mw was 3,400, and the molecular weight was able to be reduced as compared with the comparative example. The characteristics as a liquid crystal were as follows.

120.9-114.7 ° C. -20 ° C. Iso → SmC ^* → G τ _10-90 = 38.8 ms (25 ° C.): 2θ = 68 ゜ (25 ° C.) Next, using methylene chloride, A composition comprising 67% by weight of a polymer and 33% by weight of a pyrimidine compound P1008 manufactured by Midori Kagaku was prepared, and the characteristics of the liquid crystal composition were measured by the method described above. The characteristics of the liquid crystal composition as a liquid crystal are shown below. 106.7-98 ℃ 87 ℃ -20 ℃ Iso → SmA → SmC ^* → Gτ _10-90 = 6.3ms (25 ℃): 2θ = 41 ゜ (25 ℃)

Comparative Example 1 4 ′-[4 ″-{10- (1,5-hexadiene-3)
-Yloxy) decyloxy {benzoyloxy] biphenyl-4-carboxylic acid (S)-(+)
15.00 g of 1-methylbutyl ester (23.40
Mmol) and 3.14 g (23.40 mmol) of 1,1,3,3-tetramethyldisiloxane in dry toluene 5
It was uniformly dissolved in 5 ml. Next, after adding 5.0 mg of chloroplatinic acid hexahydrate, the mixture was stirred at 85 ° C. for 5 hours. The air in the reaction vessel was replaced with argon gas in advance, and the reaction vessel was sealed so that moisture and air did not enter the vessel during the reaction.

The reaction mixture was cooled to room temperature and filtered.
The filtrate was concentrated using a rotary evaporator. The concentrate was further purified by column chromatography,
Vacuum dried overnight at 0 ° C. to obtain 16.02 g of a white viscous substance. The structure of this substance was confirmed by ¹ H-NMR.
FIG. 3 shows the molecular structure and NMR spectrum. When the molecular weight of this substance was measured by GPC, Mn = 3.9.
00, Mw = 8,900. The characteristics as a liquid crystal were as follows.

115.5-111 ° C. -20 ° C. Iso → SmC ^* → G τ _10-90 = 88 ms (25 ° C.): 2θ = 76 ゜ (25 ° C.)

[0066]

According to the present invention, in addition to exhibiting ferroelectricity over a wide temperature range including a room temperature range, the liquid crystal panel has a high-speed response to a change in an external electric field, and has excellent contrast when formed into a liquid crystal panel. The molecular weight of the polymer can be easily controlled. Further, according to the present invention, since the number of carbon-carbon double bonds at the terminal of the main chain can be reduced,
A liquid crystal copolymer having excellent stability can be obtained.

[Brief description of the drawings]

FIG. 1 is a molecular structure and an NMR chart of a copolymer obtained in Example 1.

FIG. 2 is a molecular structure and an NMR chart of a copolymer obtained in Example 2.

FIG. 3 is a molecular structure and an NMR chart of a copolymer obtained in Comparative Example 1.

Continuation of front page (56) References JP-A-2-180845 (JP, A) JP-A-5-132558 (JP, A) JP-A-5-170912 (JP, A) JP-A-5-194744 (JP) JP-A-5-156025 (JP, A) JP-A-4-268389 (JP, A) JP-A-4-314784 (JP, A) JP-A-5-202358 (JP, A) 4-320218 (JP, A) WO 92/1731 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 77/00-77/62 C08L 83/00-83/16 C09K 19/38-19/40 G02F 1/13 500 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A diene compound [I] represented by the following general formula: (Wherein, l and m are integers of 2 to 5, a is an integer of 1 to 20, b is an integer of 1 to 10, and Z is And * represents an asymmetric carbon. ) And a siloxane compound [II] represented by the following general formula: (Where p represents an integer of 0 to 3) to produce a liquid crystal copolymer by addition polymerization, a compound having one olefinic double bond in the molecule is added to the reaction system to carry out the polymerization reaction. A method for producing a liquid crystal copolymer. 2. An olefinic double bond having one in the molecule.
Are 1-hexene, 1-octene, 2-hexene
4-methyl-pentene-1, cyclohexene or biene
2. The liquid crystal copolymer according to claim 1, which is nylcyclohexane.
Manufacturing method. 3. An olefinic double bond is present in the molecule.
Is 4 '-[4 "-{10- (2-propenyl)
Oxy) decyloxy {benzoyloxy] biphenyl
-4-Carboxylic acid (S)-(+)-1-
Methyl butyl ester or 4 '-[4 "-{8- (3-
Butenyloxy) octyloxy Biphenyl-4-ca
Rubonyloxy] benzoic acid (S)-(+)
The liquid according to claim 1, which is -1-methylheptyl ester.
A method for producing a crystalline copolymer.