JP3075807B2 - Liquid crystal material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal material, and more particularly to a novel main chain type thermotropic liquid crystal polymer material having a metal complex.

[0002]

2. Description of the Related Art Polymer liquid crystal materials can be roughly classified into thermotropic and lyotropic materials, and can be classified into a main chain type and a side chain type in terms of chemical structure.

The main chain type polymer liquid crystal material has a mesogen group in the main chain, and this mesogen group generally comprises C, H, O, N, and halogen.

[0004] On the other hand, if a liquid crystal polymer having a metal complex functioning as a mesogen group is realized, the characteristics produced by the molecular arrangement of the liquid crystal polymer and the unique properties of the metal complex will be obtained. Various applications are expected.

Accordingly, a polymerizable liquid crystal material having a metal complex as described above can be newly obtained by obtaining a polymerizable liquid crystal material to which a metal ion can be coordinated and by coordinating the metal ion with this as a starting material. It can be obtained and is meaningful.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel liquid crystal material in which a metal can be coordinated and polymerizable.

A second object of the present invention is to provide a novel high-molecular liquid crystal material which can make use of the characteristics of a metal complex.

[0008]

This and other objects are achieved by the present invention which is defined below as (1) to (3).

(1) A liquid crystal material represented by the following formula 3:

[0010]

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In the chemical formula 3, m represents a positive integer of 1 to 20, and n represents a positive integer of 4 to 40. ]

(2) The liquid crystal material according to (1), further comprising a metal ion, wherein the metal ion is coordinated to the β-diketone segment in Chemical formula 3 to form a polymer.

(3) The liquid crystal material according to the above (2), represented by the following chemical formula 4.

[0014]

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[In the chemical formula 4, M represents a metal ion. m represents a positive integer of 1 to 20, and n represents a positive integer of 4 to 40. k represents the degree of polymerization. ]

Note that the present inventors have previously described the 39th (1.
990) Annual Meeting of the Society of Polymer Science, Japan (October 17, 1990)
Held at Nagoya University, Faculty of Engineering)
7: Synthesis of Polymer Liquid Crystal Containing β-Diketone Segment and Properties of Its Metal Complex ”(filed as Japanese Patent Application No. 2-244268). However, the metal content of the polymer of the present invention is as low as 0.2 to 2% by weight, whereas the metal content of the polymer of the present invention is 7 to 10% by weight. The present invention can be expected to exhibit various functions, and the present invention is more advantageous in terms of structure to exhibit a liquid crystal function than this.

[0017]

[Specific Configuration] Hereinafter, a specific configuration of the present invention will be described in detail.

The liquid crystal material of the present invention is a compound represented by Chemical Formula 3. The compound represented by Chemical Formula 3 has two β-diketone segments in the polyester main chain.

In the formula 3, m is 1 to 20, especially 3 to 9
And n is preferably 4 to 40, particularly preferably 6 to 20.

Specific examples of the compound represented by Formula 3 are shown below. In the following, m and n in Chemical formula 3 are shown.

(1) m = 3, n = 6 (2) m = 1, n = 12 (3) m = 3, n = 12 (4) m = 5, n = 12 (5) m = 7, n = 12

The compound represented by the formula (3) can be obtained by combining the compound (A) synthesized according to the scheme I of the formula (5) with the compound represented by the formula (I).
It is synthesized from compound (B) synthesized according to I according to Scheme III of Chemical Formula 7.

First, 4-hydroxyacetophenone and C _m H _{2m + 1} -CO-O-CO-
C _m H _{2m + 1} is stirred for about 1 hour at a temperature of about 120 ° C., and then dry BF ₃ is blown thereinto to obtain a compound (A) having a β-diketone segment. This synthesis method is described in "MEB Jones, MFLynch, DA Tho
rnton, and RFWebb, Makromol. Chem., 50, 232 (196
1) and DJSardella, DHHeinert, and BLShap
iro, J. Org. Chem., 34, 2817 (1969) ".

On the other hand, the compound (B) is prepared by reacting the compound represented by Scheme I
According to I, “WRSorenson and TWCampbell, Toshio Hoshino and Naoya Yoda, Polymer Synthesis Experimental Method (Tokyo Kagaku Doujin)
P125 "and" C. Carfagna, U. Caruso, A. Roviell
o, and A.Sirigu, Makromol.Chem., Rapid Commun. 8 345
-351 (1987) ".

Then, according to Scheme III in Chemical Formula 7, compound (A) is added with pyridine, dissolved and cooled, and then compound (B) is added. The mixture is stirred under ice cooling or at room temperature for about 2 to 3 hours. A compound of formula 3 is obtained.

[0026]

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[0027]

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[0028]

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The compound of the formula (3) has a molecular weight of about 500 to 1,000, and has an elemental analysis and an infrared absorption spectrum (IR
Spectrum).

The compound of formula (3) is a low-molecular liquid crystal compound, and although the liquid crystal phase differs depending on the values of n and m, both are thermotropic liquid crystals.

The liquid crystal material of the present invention further contains a metal ion, and the β-diketone segment in the compound of formula 3 coordinates to the metal ion to form a polymer,
It is preferably a polymer represented by Chemical Formula 4.

In the chemical formula 4, m and n are each a chemical formula 2
And the degree of polymerization k is about 6 to 12. The central metal ion M is Cu, Mn, Fe, V
And the like. When it is Mn or the like, a water molecule or the like may be further coordinated, and M is a concept including such a case.

The content of the metal in the polymer of the formula (4) is
As described above, the content is relatively high at about 7 to 10 wt%, which is advantageous in exhibiting a function caused by a high metal content.

The polymer of Chemical Formula 4 may be a homopolymer in which m and n are all the same, or a copolymer in which m and n are different for each structural unit.

Specific examples of the polymer of Chemical Formula 4 are shown in Chemical Formulas 8, 9 and 10. Here, the constituent units are shown.

[0036]

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[0037]

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[0038]

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According to the scheme of Chemical Formula 11, the polymer of Chemical Formula 4 is obtained by dissolving the compound of Chemical Formula 2 in hot dioxane, further adding triethylamine, and then adding a methanol solution of a metal salt with stirring, and stirring at room temperature for about 1 hour. Is obtained. Such a reaction is performed in air or under a nitrogen atmosphere. The compound of Chemical formula 3 may be used alone or in combination of two or more, depending on the intended product of the homopolymer or copolymer. The metal salt is CuCl _{2.
2H 2 O, MnCl 2 · 4H} 2 chlorides O or the like is used.

The polymer of Chemical Formula 4 has a number average molecular weight of 500
0 to 10,000, and can be confirmed by elemental analysis, IR spectrum, and the like.

This is a gray-green polymer, which is a thermotropic liquid crystal, and the temperature range at which the liquid crystal is displayed is 180 to 260 ° C. in many cases.

It is considered that the polymer of Chemical Formula 4 has a common liquid crystal phase unlike the low molecular weight compound of Chemical Formula 3. This is because when a low molecule forms a liquid crystal phase, the whole molecule including the terminal methylene chain contributes to it, whereas in the case of a polymer, the terminal methylene chain overlaps with the next molecule to form a complex This is because it is considered that the shape was reduced, and the influence of the terminal methylene chain on the liquid crystal phase was reduced, and all of them exhibited a common texture.

Further, some of the polymers of Chemical Formula 4 can be melt-defined to form a fibrous polymer, which is expected to expand the application.

[0044]

The present invention will be specifically described below with reference to examples.

Example 1 (1) As reagents tetrahydrofuran (THF), dimethylformamide (DMF), chloroform, ethanol, methanol and dioxane, use was made of a single-fraction product of a commercially available special grade product or a commercially available first grade product according to a conventional method. did. As silica gel for the column, Wako Shikagel C-200 was used without pretreatment. As other reagents, commercially available special grade products or commercially available first grade products were used as they were, unless otherwise specified.

(2) Low molecular weight liquid crystal compound (represented by Chemical Formula 3)
Compound (2-1) Bis- [4- (1,3-hexamethylenedi)
Nyl) phenyl] -4,4 '-(1,6-hexamethylene
Synthesis of (dioxy) dibenzoate [Compound (1)] (2-1-1) Synthesis of 4- (1,3-tetramethylenedionyl) phenyl [In Scheme I of Chemical Formula 5, m =
In case of 1]

Reference [MEB Jones, MFLynch, DA Tho
rnton, and RFWebb, Makromol. Chem., 50, 232 (196
1): DJSardella, DEHeinert, and BLShapiro, JO
rg. Chem., 34, 2817 (1969)].

In a 100 ml eggplant flask, 15:00 (0.1
10 mol) of hydroxyacetophenone and 60 ml (0.
64 mol) of acetic anhydride and stirred at 120 ° C. for 1 hour. The reaction solution was cooled, and 120 g of NaBF ₄ , 20 g of diboron trioxide and 1 part of concentrated sulfuric acid were placed in a 300 ml eggplant flask.
Dry BF ₃ gas generated by framing a mixture of 00 ml, 20% 30% fuming nitric acid was blown vigorously until saturation. As the reaction proceeded, sludge became sludge and solid gradually precipitated. After leaving for 2 hours under ice-cooling, sodium acetate (AcONa) / water (30 g / 300 ml)
And refluxed for 40 minutes. Further, 200 ml of water was added, and the mixture was sufficiently cooled and separated into an oil layer. Take out the water layer 76g
(0.9 mol) of sodium bicarbonate.
This was extracted with ether, and the oil layer was dissolved in the ether layer and washed with water. The ether layer was extracted with 400 ml of 8% NaOH and neutralized with cold concentrated hydrochloric acid. The solution was cooled, and the precipitated crystals were dried by filtration and sublimated to obtain the desired product.

Yield: 15.3 g Yield: 78% C ₁₀ H ₁₀ O ₃ (molecular weight 178.18)

(2-1-2) Synthesis of 1,6-bis (p-chloroformylphenoxy) hexane [Scheme 6]
II, when n = 6]

Reference [WR Sorenson and TWCampbell
Author, Toshio Hoshino and Naoya Yoda, Polymer Synthesis Experimental Method (Tokyo Kagaku Dojin) P125 "and" C. Carfagna, U. Caruso, A.
Roviello, and A. Sirigu, Makromol. Chem., Rapid Commu
n.8 345-351 (1987)].

Yield: 12.86 g Yield: 89% C ₂₀ H ₂₀ O ₄ Cl ₂ (molecular weight 395.28)

(2-1-3) Synthesis of Compound (1)

2.06 g (10 mol) of 4- (1,3-
Hexamethylene dionyl) phenol was placed in a 100 ml eggplant-shaped flask, 20 ml of pyridine was added, stirred, dissolved, cooled in an ice bath, and then 1.98 g (5 mol) of 1,6-
Bis- (p-chloroformylphenoxy) hexane was added little by little, and the mixture was further stirred under ice cooling for 2 hours. 1 at room temperature
After stirring for 20 hours, 20 ml of tetrahydrofuran (THF) was added, and the mixture was stirred for 1 hour. The reaction solution was refluxed once and left to return to room temperature. Petroleum ether was added, the insolubles were filtered off and extracted with ethyl acetate-water, and the aqueous layer was evaporated to obtain a precipitate. Dry this and add 2 with chloroform
The product was recrystallized twice to obtain the desired product [Compound (1)].

Yield: 1.39 g Yield: 37% Elemental analysis result: C ₄₄ H ₄₆ O ₁₀ (molecular weight 754.84)

[0056](2-2) bis- [4- (1,3-tetra
Methylenedionyl) phenyl] -4,4 '-(1,12
-Dodecamethylenedioxy) dibenzoate [compound
(2)]

Synthesis of (2-2-1) 4- (1,3-hexamethylenedionyl) phenol [in the case of m = 3 in Scheme I of Chemical Formula 5]

The compound was synthesized with reference to the synthesis method described in the above-mentioned section (2-1-1).

In a 100 ml eggplant flask, 13.6 g (0.
1 mol) of 4-hydroxyacetophenone (75 ml, 0.1 mol).
458 mol) of n-butyric anhydride was added and stirred at 120 ° C. for 1 hour. This was cooled on ice, and N in a 500 ml eggplant flask was
aBF ₅ 135 g, boron trioxide 22.5 g, concentrated sulfuric acid 1
Dry BF ₃ gas generated by 13 ml, 22.5 ml of 30% fuming nitric acid was blown in for 50 minutes. After leaving the mixture under ice cooling for 2 hours, it was added to 300 ml of water and extracted with 300 ml of ether. The ether layer was further extracted with 200 ml of cold 2N NaOH, and the ether layer was evaporated. 6g of Na
OH, 20 ml of water and 50 ml of ethanol were added and refluxed for 1 hour. Ethanol is distilled off and 200 ml of water, 200 ml
Extracted with ether. The aqueous layer was neutralized with concentrated hydrochloric acid and extracted with ether. The ether layer was evaporated and purified with Si / CHCl ₅ as a column. Further, recrystallization from benzene-n-hexane gave the desired product.

Yield: 14.5 g Yield: 70% C ₁₂ H ₁₄ O ₅ (molecular weight 206.23)

(2-2-2) Synthesis of 1,12-bis (p-chloroformylphenoxy) dodecane [When n = 12 in Scheme II of Chemical Formula 6]

The compound was synthesized according to the synthesis method described in the above-mentioned section (2-1-2).

Yield: 3.91 g Yield: 72% C ₂₆ H ₃₂ O ₄ Cl ₂ (molecular weight 497.44)

(2-2-3) Synthesis of Compound (2)

In a 100 ml eggplant flask, 1.43 g (8 mm
ol) 4- (1,3-tetramethylenedionyl) phenol was added, and 2.0 ml of pyridine was added. The mixture was stirred, dissolved, and sufficiently cooled in an ice bath. Then, 1.92 g (4 mmol) of 1,92 g
12-Bis (p-chloroformylphenoxy) dodecane was added little by little, and the mixture was stirred under ice cooling for 2 hours and at room temperature for 1 hour. 50 ml of THF was added, the mixture was refluxed once, and cooled. The precipitate was separated by filtration and washed with petroleum ether, THF, water and THF in this order. This was dried and recrystallized from chloroform to obtain the desired product [Compound (2)].

Yield: 1.53 Yield: 50% Elemental analysis result: C ₄₆ H ₅₀ O ₁₀ (Molecular weight 752.90)

[0067](2-3) bis- [4- (1,3-hexa
Methylenedionyl) phenyl] -4,4 '-(1,12
-Dodecamethylenedioxy) dibenzoate [compound
Synthesis of (3)]

1.65 g (8 mmo) in a 50 ml eggplant flask
l) 4- (1,3-Hexamethylenedionyl) phenol was added, pyridine (20 ml) was added, the mixture was stirred, dissolved, and sufficiently cooled in an ice bath. Then, 1.95 g (4 mmol) of 1,12
-Bis (p-chloroformylphenoxy) dodecane was added little by little, and the mixture was stirred under ice cooling for 2 hours and at room temperature for 1 hour.
After adding 20 ml of THF and refluxing the mixture, it was turned into a clear solution and then cooled. The precipitate was separated by filtration and washed with water and ethyl acetate-petroleum ether (1: 2). This was dried and recrystallized from chloroform to obtain the desired product [compound (3)].

Yield: 2.19 Yield: 67% Elemental analysis result: C ₅₀ H ₅₈ O ₁₀ (molecular weight 819.00)

[0070]

[0071](2-4) bis- [4- (1,3-octa
Methylenedionyl) phenyl] -4,4 '-(1,12
-Dodecamethylenedioxy) dibenzoate [compound
(4)] Synthesis

(2-4-1) Synthesis of 4- (1,3-octamethylenedionyl) phenol [When m = 5 in Scheme I of Chemical Formula 5]

The compound was synthesized by referring to the synthesis method described in the above-mentioned section (2-1-1).

10 g (0.07
34 mol) of hydroxyacetophenone and 75 g (0.
350 mol) of n-caproic anhydride, stirred at 120 ° C. for 1 hour, cooled, and cooled in a 500 ml eggplant flask.
aBF ₄ 135 g, boron trioxide 22.5 g, concentrated sulfuric acid 1
13 ml, 30% fuming nitric acid 22.5 ml and dried B
F ₃ gas was blown for about 50 minutes. After standing for 2 hours under ice-cooling, it was further left for 1 hour at room temperature, poured into 400 ml of water containing 10 g of AcONa, and refluxed for 30 hours. After cooling, the mixture was extracted with ether, and the ether layer was extracted with 2N NaOH. The aqueous layer was neutralized with concentrated hydrochloric acid, extracted with ether and evaporated, and the precipitate was purified by column with Si / CHCl ₃ to obtain 1.3 g of the desired product. And EtOH 100 ml, N
8 g of aOH and 10 ml of water were added and refluxed for 2 hours to hydrolyze. EtOH was distilled off, 200 ml of water was added, and the mixture was extracted with ether. The aqueous layer was neutralized with concentrated hydrochloric acid, extracted with ether and evaporated, and the precipitate was purified with a column of Si / CHCl ₃ . Furthermore, benzene-n-hexane (1: 5)
To give the desired product.

Yield: 6.3 g Yield: 36% C ₁₄ H ₁₈ O ₃ (molecular weight 234.28)

(2-4-2) Synthesis of Compound (4)

1.61 g (6 mmo) in a 50 ml eggplant flask
l) 4- (1,3-octamethylenedionyl) phenol was added, pyridine (20 ml) was added, the mixture was stirred, dissolved, cooled in an ice bath, and then 1.44 g (3 mmol) of 1,12-bis (p-chloroformyl) was added. (Phenoxy) dodecane was added little by little, and the mixture was stirred under ice cooling for 2 hours and at room temperature for 1 hour. TH
15 ml of F was added, and the mixture was refluxed once and cooled. The precipitate was separated by filtration, washed with a mixed solvent of THF and petroleum ether, and further washed with cold methanol. This was dried and recrystallized from chloroform to obtain the desired product [compound (4)].

Yield: 1.17 g Yield: 45% Elemental analysis: C ₅₄ H ₆₆ O ₁₀ (molecular weight 875.11)

[0079]

[0080](2-5) bis- [4- (1,3-decameme
Tylenedionyl) phenyl] -4,4 '-(1,12-
Dodecamethylenedioxy) dibenzoate [compound
(5)]

Synthesis of (2-5-1) 4- (1,3-decamethylenedionyl) phenol [In the case of m = 7 in Scheme I of Chemical Formula 3]

The compound was synthesized by referring to the synthesis method described in the above-mentioned section (2-1-1).

20 g (0.14
(7 mol) of 4-hydroxyacetophenone and n-caprylic anhydride were added and stirred at 120 ° C. for 1 hour. This was cooled on ice, and 216 g of NaBF ₄ in a 1 liter eggplant flask was added.
Dry BF ₃ gas generated from 36 g of diboron trioxide, 180 ml of concentrated sulfuric acid and 36 ml of 30% fuming nitric acid was blown in for about 50 minutes. Then, after leaving for 2 hours under ice cooling and overnight at room temperature,
400 ml of cold water was added, and 300 ml of ether was further added.
Shake well with a separatory funnel. At this time, the precipitated 4- (1,
(3-Decamethylenediniol) phenyl-n-octanoate was removed by suction. 44.1 g of this ester (0.1
13 mol) with 15 g (0.375 mol) of NaOH, Et
The mixture was refluxed overnight in 200 ml of OH and 20 ml of water. This was evaporated, water was added thereto, and the mixture was extracted with ether.
Neutralized with Cl and extracted with ether. The ether layer was evaporated, n-hexane was added and cooled, and the precipitated crystals were separated by filtration and dried. This was recrystallized from n-hexane to obtain the desired product.

Yield: 11.2 g Yield: 29% C ₁₆ H ₂₂ O ₃ (Mw 262.35)

(2-5-2) Synthesis of Compound (5)

62 g (10 mmol) in a 50 ml eggplant flask
Of 4- (1,3-decamethylenedionyl) phenol, 20 ml of pyridine was added thereto, followed by stirring and dissolving. After cooling in an ice bath, 2.40 g (5 mmol) of 1,12-bis (p-chloroformylphenoxydodecan) was added. Was added little by little, and the mixture was stirred under ice-cooling for 2 hours and at room temperature for 1 hour.15 mL of THF was added thereto, and the mixture was refluxed once and cooled.
The mixture was washed with a mixed solvent of petroleum ether and further washed with cold methanol. This was recrystallized from chloroform to obtain the desired product [Compound (5)].

Yield: 1.17 g Yield: 45% Elemental analysis: C ₅₄ H ₆₆ O ₁₀ (molecular weight 875.1)
1)

[0088]

(3) Polymer (compound represented by Chemical Formula 4)
Synthesis of

(3-1) Synthesis of (P-1) [Formula 8]

In a 50 ml eggplant flask, 163.8 mg (0.
2 mmol) of the compound (3) was dissolved in 40 ml of hot dioxane. After addition of 2 ml (27.2 mmol) of triethylamine, copper (II) chloride dihydrate 34.
A 1 mg (0.2 mmol) / 1 ml methanol solution was added little by little, and the mixture was stirred at room temperature for 1 hour. Next, the mixture was refluxed once, left to return to room temperature, and the solution was concentrated by evaporation. 60 ml of ethanol was added thereto, and the resulting precipitate was separated by filtration and washed with methanol, water and methanol in this order. After drying, this was dissolved in a few ml of THF and reprecipitated with methanol to obtain the desired product (P-1).

Yield: 160.8 mg Yield: 91% (C ₅₀ H ₅₆ O ₁₀ Cu) _k [Molecular weight (880.534)
_k ]

(3-2) Synthesis of (P-2) [Formula 8]

In a 50 ml eggplant flask, 175.0 mg (0.
2 mmol) of the compound (4) was dissolved in 40 ml of hot dioxane. After addition of 2 ml (27.2 mmol) of triethylamine, copper (II) chloride dihydrate 34.
A 1 mg (0.2 mmol) / 1 ml methanol solution was added little by little, and the mixture was stirred at room temperature for 1 hour. Next, the mixture was refluxed once, left to return to room temperature, and the solution was concentrated by evaporation. 60 ml of methanol was added thereto, and the resulting precipitate was separated by filtration and washed with methanol, water and methanol in this order. After drying, this was dissolved in a few ml of THF and reprecipitated with methanol to obtain the desired product (P-2).

Yield: 181.4 mg Yield: 97% (C ₅₄ H ₆₄ O ₁₀ Cu) _k [Molecular weight (936.644)
_k ]

(3-3) Synthesis of (P-3) [Formula 8]

In a 50 ml eggplant flask, 186.2 mg (0.
2 mmol) of compound (5) was dissolved in 40 ml of hot dioxane, and 2 ml (27.2 mmol) of triethylamine was added. Then, with stirring, copper (II) chloride dihydrate 34.1 was added.
mg (0.2 mmol) / 1 ml methanol solution was added little by little, and the mixture was stirred at room temperature for 1 hour. Next, the mixture was refluxed once, left to return to room temperature, and the solution was concentrated by evaporation. 60 ml of methanol was added thereto, and the resulting precipitate was separated by filtration, washed with methanol, water and methanol in that order, and dried. After drying, this was dissolved in a few ml of THF and reprecipitated with methanol to obtain the desired product (P-3).

Yield: 153.8 mg Yield: 90% (C ₅₈ H ₇₂ O ₁₀ Cu) _k [molecular weight (992.754)
_k ]

(3-4) Synthesis of (P-4) [Formula 9]

In a 50 ml eggplant flask, 36.74 mg (0.
052.9 mmol) of compound (1) and 122.9 mg (0.15 mm)
ol) of the compound (3), dissolved in 40 ml of hot dioxane, and added with 2 ml (27.2 mmol) of triethylamine, and then 34.1 mg of copper (II) chloride dihydrate with stirring.
(0.2 mmol) / 1 ml methanol solution was added little by little,
Stirred at room temperature for 1 hour. This was once refluxed, left to return to room temperature, and the solution was concentrated by evaporation.
60 ml of methanol was added thereto, and the resulting precipitate was separated by filtration, washed with methanol, water and methanol in that order, and dried. After drying, this was dissolved in a few ml of THF and reprecipitated with methanol to obtain the desired product (P-4).

Yield: 152.6 mg Yield: 89% [(C ₄₄ H ₄₄ O ₁₀ Cu) _{k / 4} (C ₅₀ H ₅₆ O ₁₀ C)
u) _{3k / 4} ] [Molecular weight (796.374) _{k / 4} (880.534)
_{3k / 4} ]

(3-5) Synthesis of (P-5) [Formula 9]

In a 50 ml eggplant flask, 73.48 mg (0.
1 mmol) of compound (1) and 81.90 mg (0.1 mmol)
Compound (3) is dissolved in 40 ml of hot dioxane,
After adding 2 ml (27.2 mmol) of triethylamine,
While stirring, 34.1 mg of copper (II) chloride dihydrate (0.
(2 mmol) / 1 ml methanol solution was added little by little, and the mixture was stirred at room temperature for 1 hour. Next, the solution was once refluxed, left to return to room temperature, and the solution was concentrated by evaporation. 60 ml of methanol was added thereto, and the resulting precipitate was separated by filtration, washed with methanol, water and methanol in that order, and dried. This is T
It was dissolved in several milliliters of HF and reprecipitated with methanol to obtain the desired product (P-5).

Yield: 161.1 mg Yield: 96% [(C ₄₄ H ₄₄ O ₁₀ Cu) _{k / 2} (C ₅₀ H ₅₆ O ₁₀ Cu)
_{k / 2} ) [Molecular weight (796.374) _{k / 2} (880.534)
_{k / 2} ]

(3-6) Synthesis of (P-6) [Formula 9]

110.23 mg in a 50 ml eggplant flask
(0.15 mmol) of compound (1) and 40.95 mg (0.
05 mmol) of compound (3) and 40 ml of hot dioxane
And 2 ml (27.2 mmol) of triethylamine were added thereto, followed by stirring with copper (II) chloride dihydrate.
A 1 mg (0.2 mmol) / 1 ml methanol solution was added little by little, and the mixture was stirred at room temperature for 1 hour. Next, the solution was once refluxed, left to return to room temperature, and the solution was concentrated by evaporation. 60 ml of methanol was added thereto, and the resulting precipitate was separated by filtration, washed with methanol, water and methanol in that order, and dried. This was dissolved in a few ml of THF and reprecipitated with methanol to obtain the desired product (P-6).

Yield: 135.6 mg Yield: 83% (C ₄₄ H ₄₄ O ₁₀ Cu) _{3k / 4} (C ₅₀ H ₅₆ O ₁₀ Cu) _{k / 4} ) [Molecular weight (796.374) _{3k / 4} (880) .534
_{k / 4} )]

(4) Melt spinning of polymers (P-1) to (P-6) The polymers were placed in sample bottles, placed in a mantle heater, the temperature was maintained at or above the melting point of each polymer, and the polymer was melted with a glass rod. Melt spinning was performed while pulling up into the air.

In each case, spinning could be performed without any trouble.

(5) Measurement of Polymers (P-1) to (P-6) Various measurements were performed on the polymers (P-1) to (P-6) as follows.

(5-1) Measurement of Infrared Absorption Spectra The infrared absorption spectrum was measured by a KBr pellet method using an A-320 infrared spectrophotometer manufactured by JASCO.

(5-2) Elemental analysis For elemental analysis, 240B manufactured by Perkin-Elmer was used.
A mold was used.

(5-3) Measurement of molecular weight The molecular weight was measured by GPC measurement and VPO measurement. For GPC measurement, HLC-802 manufactured by Toyo Soda Kogyo was used.
A was used, and the detector used was a differential refractometer RI-6 provided in the above apparatus. The solvent was adjusted to a sample concentration of about 1 mg / ml using THF, and STANDARD POLYSTYRENE manufactured by Toyo Soda Kogyo was used as a standard sample. The conditions for measurement were as follows: flow rate 1.0 ml / min., Liquid sending pressure 100 kg / c.
m ² was carried out in the following. For VPO measurement, use Corona Electric 11
A type 7 molecular weight measuring device was used. The solvent was prepared using chloroform, and the sample concentration was adjusted to around 2 g / l. The K value was determined using benzyl as a standard sample, and the molecular weight was calculated.

2.5.4 Differential Scanning Calorimetry (DSC) Measurement For the differential scanning calorimetry (DSC) measurement, a high performance differential scanning calorimeter DSC-10A manufactured by Rigaku Denki was used. The measurement was carried out at a heating rate of 10 ° C./min. Using an aluminum pan under the conditions of a nitrogen atmosphere and a DSC range of 1 mcal / sec. Further, the phase transition enthalpy was determined by the following equation.

1) Conversion of peak area and calorie The conversion of the peak area and calorie on the chart was performed as follows.

[0116] DSC range ^{± a [mcal -. / Sec} ] [. Mm / min] chart speed b chart paper width c [mm]

Under the above conditions, c [mm] is 2a
[Mcal / sec.].

As a result, bc [mm ² ] becomes 2a [mc
al ^- /sec.]×60[sec.]=120a[mcal ^- equivalent to]. Therefore, 1 [mm ² ] is 120 a / (bc) [mcal
^- ].

2) Calculation of enthalpy of phase transition The enthalpy of phase transition was determined by substituting each value into the following equation.

[0120] ΔH = K · A / M ΔH : phase change enthalpy [mcal / mg] A: Peak area [mcal ^-] K: apparatus constant [mcal / mcal ^-] M: mass of the sample [mg]

(5-5) ESR spectrum measurement ESR
The spectrum was measured using an X band Varian ESR spectrometer. The sample was measured by fixing a melt-spun fibrous polymer to a quartz plate for ESR and setting its fiber axis in a direction perpendicular and parallel to a magnetic field.

(5-6) Wide-angle X-ray Diffraction Measurement The wide-angle X-ray diffraction measurement was performed using an X-ray diffractometer CN4 manufactured by Rigaku Denki.
Using a 056A model, a plane camera was installed and a diffraction photograph was taken. The shooting conditions were as follows: tube current 25 mA, tube voltage 40
The exposure time was 1.5 hours using a CuKa line filtered with a kV, nickel foil. The sample was prepared by setting the angle between the fiber axis and the X-ray perpendicular and parallel to the melt-spun fibrous polymer.

Debye-Scherrer obtained from X-ray diffraction photograph
The Bragg equation of Equation 1 was applied to the ring to determine the spacing.

[0124]

(Equation 1)

(5-7) Observation with Polarizing Microscope Observation with a polarizing microscope was carried out using OPTIPHOT- made by Nikon.
Using a POL type polarizing microscope, a microphotographing device MICROFFLEX AFX-II was attached to the POL type polarizing microscope, and a photograph was taken.

For controlling the temperature of the sample, use Mettler.
Controlled by FP80 Central processer
The FP82 Hot Stage manufactured by ttler was used. In addition, a cover glass was used for all samples, and the magnification was 10
Observed at 0x.

(6) Measurement Results and Discussion The measurement results of the polymers (P-1) to (P-6) and the consideration of the results are summarized.

(6-1) Properties of Polymer The yields were all around 90%. Copper (I
I) Regarding the coordination rate of ions, from the results of elemental analysis,
Both are considered to be values close to 100%. Although no clear commonality with the liquid crystal phase was found, it is considered that the influence of the molecular terminals on the liquid crystallinity was reduced by the formation of a complex by copper (II) ions.

(6-2) Infrared spectrum measurement results In any of (P-1) to (P-6), 1740
cm ^-1 to ester (νC = 0), the 1600 cm ^-1 beta-diketones and benzene nucleus, appear in common absorption of 2850 cm ^-1 and 2925 cm ^-1 in methylene chain (νCH _2), the product was confirmed .

(6-3) Results of Elemental Analysis Table 1 shows the results of elemental analysis of each polymer. In each case, since the difference between the measured value (Found) and the calculated value (Calc.) Was within 0.4%, it was concluded that the target polymer was synthesized.

Table 1 also shows transition points observed by a polarizing microscope described later.

[0132]

[Table 1]

(6-4) Results of Molecular Weight Measurement From the molecular weight measurement, it is considered that these polymers are dissolved in a solvent to cause depolymerization in a solution to form a stable dimer [C. Carfagn]
a, et al., Makromol. Chem., Rapid Commun. 8, 345-3
51 (1987)], it is presumed that the dimer is polymerized as a unit. .

The depolymerization is expected to be in the equilibrium state shown by the equation (2).

[0135]

(Equation 2)

(6-5) Differential Scanning Calorimetry (DSC) Measurement DSC heating curves of each polymer are shown in FIG. 1 and FIG. Regarding (P-1) to (P-3), a plurality of endothermic peaks appeared, and it was confirmed that they had a liquid crystal phase. For (P-4) to (P-6), the endothermic peak corresponding to the solid-liquid crystal phase transition temperature (Tm) is broad, and the enthalpy change (ΔHm) at Tm and Tm.
Could not be determined. The transition points and transition enthalpies of each polymer are shown in Table 2.

[0137]

[Table 2]

(6-6) Results of ESR Spectrum Measurement FIGS. 3 to 6 show ESR spectra of each of the fibrous polymers produced by melt spinning. Table 3 shows the g value and the hyperfine coupling constant A // determined from the spectrum.

[0139]

[Table 3]

The measurement was performed by setting the fiber axis of the fibrous polymer in a direction perpendicular and parallel to the magnetic field. In the vertical direction, as can be seen in FIGS. 3 and 5, all polymers were reported [S. Antosik, NMD Brown, AAMc
Dornell, and ALPorte, J. Chem. Soc., (A), 545 (19
69)], it is considered that they form a plane four-coordinated structure, since they agree with the spectrum results of the β-diketone copper (II) complex. In the case of the parallel direction, as shown in FIGS. 4 and 6, g // did not appear and only g ⊥ appeared. this is,
The spinning indicates that the four-coordinated complex plane is oriented parallel to the fiber axis direction.

(6-7) Results of X-ray Diffraction Measurement FIGS. 7 to 18 show X-ray diffraction patterns of the respective fibrous polymers produced by melt spinning. Table 4 shows the spacing values.

[0142]

[Table 4]

Regarding the diffraction pattern, when the fiber axis was irradiated parallel to the X-rays, only an annular reflection appeared on the wide-angle side, whereas when the fiber axis was irradiated perpendicularly, the light reflected in the meridian direction on the small-angle side. Three to five arc-like reflections appeared, and broad reflections appeared in the equator direction on the wide-angle side.
The former reflection spacing can be attributed to higher-order reflections at a distance corresponding to the distance between the complexes in the molecule, and the inverses of (P-1), (P-2), (P-3), and (P −
4) For (P-5) and (P-6), the distance between the complexes of compound (1) was 3 because the ratio of compound (1) was increased.
Probable reflection attributed to 5A. The latter reflection spacing is 4.6 A common to all polymers and is attributed to the distance between the polymer backbones. From these results,
It is considered that the polymer main chain is oriented parallel to the fiber axis and forms a layer in the complex part. Further, the liquid crystal phase of these polymers was determined to be a smectic A phase,
The expected orientation of the fibrous polymer complex is shown in FIG.

(6-8) Observation with Polarizing Microscope Polarizing microscope photographs of each polymer are shown in FIGS. Regarding (P-1) to (P-6), a common fine granular texture was observed. In particular, for copolymers (P-4) to (P-6), schlieren patterns characteristic of a nematic phase were observed near the liquid crystal phase-isotropic liquid transition temperature (Ti).

Example 2 (1) Synthesis of (P-7) [Chemical Formula 10] A compound (3) which is a low-molecular liquid crystal compound was synthesized according to Example 1. However, here, the yield was increased to 76% by changing the reaction conditions of Example 1 and lengthening the reaction time of Scheme III in Chemical Formula 7 as a whole to 10 days in total. .

Under the condition that the compound (3) and MnCl ₂ .4H ₂ O are in a molar ratio of 1: 1, the compound (P-
(P-7) was synthesized according to the synthesis of 1). However, the reaction was performed in a nitrogen atmosphere. The yield was 85%, and the results of elemental analysis indicated that the calculated and measured values were in agreement.

With respect to the polymer (P-7), the solid state was observed by a polarizing microscope and ESR spectrum was measured.

(1) Observation by Polarizing Microscope and Results The sample was placed on a hot stage preheated to 130 ° C. and observed under a nitrogen stream. At that time, there was no change in the state, and the system was cooled.

When observed from 130 degrees, birefringence was observed at around 125 degrees. It was found to be a liquid crystal phase because it resembled schlieren texture. Then, observation was performed after annealing as it was overnight. As a result, the polarization part was slightly reduced. The temperature was further reduced to 100 ° C. and annealing was performed overnight. Thereafter, the state was such that many blurred polarization parts were scattered.

(2) Results of ESR spectrum measurement The ESR spectrum is shown in FIG. From the results shown in FIG. 26, 2250G and 2625 which are considered to be those of Mn (II)
It can be seen that there are many resonances in the vicinity.

From the above, (P-7) shows a liquid crystallinity, and a ligand occupies a plane in a plane having an octahedral structure distorted in a direction perpendicular to the plane by observation with a polarizing microscope or ESR measurement. It is likely that the structure is where water molecules are located.

[0152]

According to the present invention, a novel low-molecular liquid crystal material in which a metal can be coordinated and polymerizable can be obtained.

Further, a novel polymer (polymer) in which a metal is coordinated can be obtained by using this. Therefore, the properties of the metal complex can be utilized, and the content of the metal in the polymer can be relatively increased.

[Brief description of the drawings]

FIG. 1 is a graph showing the results of DCS measurement of the polymer of the present invention.

FIG. 2 is a graph showing the results of DCS measurement of the polymer of the present invention.

FIG. 3 is an ESR spectrum measured with the fiber axis of the polymer of the present invention perpendicular to the magnetic field.

FIG. 4 is an ESR spectrum measured when the fiber axis of the polymer of the present invention is parallel to a magnetic field.

FIG. 5 is an ESR spectrum measured with the fiber axis of the polymer of the present invention perpendicular to the magnetic field.

FIG. 6 is an ESR spectrum measured with the fiber axis of the polymer of the present invention set parallel to the magnetic field.

FIG. 7 is a photograph as a substitute of a drawing showing a particle structure, and shows X when the fiber axis of the polymer of the present invention is irradiated perpendicularly to X-rays.
FIG.

FIG. 8 is a drawing-substitute photograph showing the particle structure, and shows the X-axis when the fiber axis of the polymer of the present invention is irradiated perpendicularly to X-rays.
FIG.

FIG. 9 is a drawing-substituting photograph showing a particle structure, and shows X when the fiber axis of the polymer of the present invention is irradiated perpendicularly to X-rays.
FIG.

FIG. 10 is a drawing substitute photograph showing a particle structure, and is an X-ray diffraction diagram when a fiber axis of the polymer of the present invention is irradiated in parallel to X-rays.

FIG. 11 is a drawing substitute photograph showing a particle structure, and is an X-ray diffraction pattern when the fiber axis of the polymer of the present invention is irradiated in parallel to X-rays.

FIG. 12 is a drawing-substitute photograph showing the particle structure, and is an X-ray diffraction diagram when the fiber axis of the polymer of the present invention is irradiated in parallel to X-rays.

FIG. 13 is a drawing substitute photograph showing a particle structure, and is an X-ray diffraction diagram when the fiber axis of the polymer of the present invention is irradiated perpendicularly to X-rays.

FIG. 14 is a drawing substitute photograph showing a particle structure, and is an X-ray diffraction diagram when the fiber axis of the polymer of the present invention is irradiated perpendicularly to X-rays.

FIG. 15 is a drawing substitute photograph showing a particle structure, and is an X-ray diffraction pattern when the fiber axis of the polymer of the present invention is irradiated perpendicularly to X-rays.

FIG. 16 is a drawing-substitute photograph showing the particle structure, and is an X-ray diffraction pattern when the fiber axis of the polymer of the present invention is irradiated in parallel to X-rays.

FIG. 17 is a drawing substitute photograph showing a particle structure, and is an X-ray diffraction diagram when a fiber axis of the polymer of the present invention is irradiated in parallel to X-rays.

FIG. 18 is a drawing-substitute photograph showing the particle structure, and is an X-ray diffraction pattern when the fiber axis of the polymer of the present invention is irradiated in parallel to X-rays.

FIG. 19 is a schematic view showing the orientation of the complex of the polymer of the present invention.

FIG. 20 is a drawing substitute photograph showing a particle structure, and is a polarizing microscope photograph of the polymer of the present invention.

FIG. 21 is a drawing substitute photograph showing a particle structure, and is a polarizing microscope photograph of the polymer of the present invention.

FIG. 22 is a drawing substitute photograph showing a particle structure, and is a polarizing microscope photograph of the polymer of the present invention.

FIG. 23 is a drawing substitute photograph showing a particle structure, and is a polarizing microscope photograph of the polymer of the present invention.

FIG. 24 is a drawing substitute photograph showing a particle structure, and is a polarizing microscope photograph of the polymer of the present invention.

FIG. 25 is a drawing substitute photograph showing a particle structure, and is a polarizing microscope photograph of the polymer of the present invention.

FIG. 26 is an ESR spectrum of a polymer of the present invention.

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──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hiroyoshi Shirai 2496 Nagase, Maruko-cho, Nagano Prefecture, Nagano Prefecture 78725 (JP, A) JP-A-4-41492 (JP, A) JP-A-4-46182 (JP, A) JP-A-4-122708 (JP, A) JP-A-4-122721 (JP, A) (58) Field surveyed (Int.Cl. ⁷ , DB name) C09K 19/20 C09K 19/38 C09K 19/40 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A liquid crystal material represented by the following formula 1. Embedded image [In the chemical formula 1, m represents a positive integer of 1 to 20, and n
Represents a positive integer of 4 to 40. ] 2. The composition further comprises a metal ion, which metal ion coordinates to the β-diketone segment in the above chemical formula 1,
The liquid crystal material according to claim 1, wherein a polymer is formed. 3. The liquid crystal material according to claim 2, represented by the following chemical formula 2. Embedded image [In the chemical formula 2, M represents a metal ion. m is 1-2
Represents a positive integer of 0, and n represents a positive integer of 4 to 40.
k represents the degree of polymerization. ]