JP3054181B2 - Main chain type thermotropic liquid crystalline polymer material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel main chain type thermotropic liquid crystalline polymer material.

<Prior Art> Polymer liquid crystal materials can be broadly classified into thermotropic and lyotropic, 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 is generally C, H, O,
Consists of N and halogen.

On the other hand, if a liquid crystalline polymer having a metal complex that functions as a mesogen group is realized, the properties created by the molecular arrangement of the liquid crystalline polymer and the unique properties of the metal complex will be combined, and The use of is expected.

<Problem to be Solved by the Invention> A main object of the present invention is to provide a novel main chain type liquid crystal polymer material having both the properties of a metal complex and the properties of a liquid crystal polymer.

<Means for Solving the Problems> Such an object is achieved by the present invention described in the following (1) or (2).

(1) A main chain type thermotropic liquid crystalline polymer material having a β-diketone segment in a polyester main chain.

(2) The main-chain thermotropic liquid crystalline polymer material according to (1), further comprising a metal ion, wherein the β-diketone segment is coordinated to the metal ion.

<Function> In the present invention, the main chains having a mesogen group are bonded to each other by forming a metal complex via a β-diketone segment, and liquid crystallinity is effectively exhibited.

<Specific Configuration of the Invention> Hereinafter, the specific configuration of the present invention will be described in detail.

The polymer liquid crystal material of the present invention has a polyester derivative containing a β-diketone segment capable of coordinating with a metal as a main chain.

The main chain polyester derivative is obtained by condensing one kind of each of diol and dicarboxylic acid, condensing one or more kinds of hydroxycarboxylic acid, or condensing a combination of these. is there.

In this case, as the diol, ethylene glycol,
Any of aliphatic diols such as hexamethylene diol and aromatic diols such as hydroquinone, halohydroquinone, alkylhydroquinone and naphthoquinone can be used.

Also, aromatic dicarboxylic acids such as terephthalic acid and P, P'-diphenyldicarboxylic acid can be used.

As the hydroxycarboxylic acid, an aromatic hydroxycarboxylic acid such as hydroxybenzoic acid and P, P'-diphenylhydroxycarboxylic acid can be used.

However, in the present invention, β-diketone segment-COCH ₂ C
In order to introduce O- into the main chain, at least one of diols, dicarboxylic acids, and hydroxycarboxylic acids having the β-diketone segment in the molecule is used.

Examples of such compounds include Y ₁ -A ₁ -COCH ₂ CO-A ₂ -Y ₂ (Y ₁ and Y ₂ are each a hydroxy or carboxy group, and A ₁ and A ₂ are each an aromatic residue. A), that is, 1,3-bis (aryl) 1,3
Diols of propanedione, dicarboxylic acids or hydroxycarboxylic acids are preferred.

Then, metal coordination is performed by an oxygen atom in the β-diketone segment.

The content of the β-diketone segment in the polymer may be 10 to 50 mol%, and the degree of polymerization is about 50 to 1000.

As the polyester derivative of the polymer liquid crystal material of the present invention, a polyester derivative represented by the following formula (I) having 1,3-bis (P-hydroxyphenyl) 1,3-propanedione or the like as a basic unit is preferable.

Formula (I) OL ₁ OCOA ₃ OL ₂ OA ₄ CO _x OA ₁ COCH ₂ COA ₂ OCOA ₃ OL ₂ OA ₄ CO _{y In the} above formula (I), A _{1 to} A ₄ may be the same or different; Each represents an arylene group which may be substituted with a halogen, an alkoxy group or the like, particularly a phenylene group.

L ₁ and L ₂ each represent an alkylene group or an arylene group which may be substituted with a halogen, an alkoxy group or the like, particularly an alkylene group having 2 to 20 carbon atoms.

X + y = 100 mol%, and y is 5 to 50 mol%
The degree is preferred.

As a metal supported on such a polymer material, β-
There is no limitation as long as the diketone segment can coordinate, and examples thereof include Cu, Ni, Co, Fe, and Zn, and particularly preferably Cu and Ni.

In such a case, A _{1 to} A ₄ = phenylene, L ₁ = L ₂ = (CH
₂ ) The metal-carrying polymer in the case of ₆ is represented by the following formula (II).

In the above formula (II), Mt represents a metal atom capable of tetradentate coordination, and four oxygen atoms become ligands so that two β-diketone segments surround Mt.

In order to obtain such a metal complex-supporting liquid crystalline polymer material, first, a polyester derivative containing a β-diketone segment of the main chain is obtained according to the following scheme 1, and then the metal complex is synthesized according to the scheme 2.

In Scheme 1, x moles of diol, y moles of bisphenylalkanedione, and (x + y) moles of bisphenoxyalkane are subjected to a polycondensation reaction in tetrachloroethane under a nitrogen atmosphere, whereby a main chain type polyester derivative is formed. Obtain a molecular liquid crystal material. By reacting this polyester derivative with a methanol solution of a metal chloride as shown in Scheme 2, an intended metal complex-carrying polymer liquid crystal material is obtained.

X can be appropriately selected by selecting the addition amount of the metal chloride used here.

The polymer liquid crystal material synthesized by the above method can be identified by IR spectrum, ¹ H-NMR spectrum, elemental analysis, atomic absorption analysis, or the like.

In the above description, a synthesis example in the case of using Cu and Ni as the metal has been described. However, in the case of having another metal-carrying polymer or another skeleton, synthesis can be performed by a method according to this.

<Example> Hereinafter, the present invention will be described specifically with reference to examples.

Various measuring instruments used for identification of the compounds in this example are as follows.

Infrared absorption spectrum measurement Infrared absorption spectrum measurement was carried out using a JASCO A-320 type infrared spectrophotometer. Those that were soluble in chloroform were measured by the film method, and those that were insoluble in chloroform were measured by the KBr disk method. Was.

Elemental analysis For elemental analysis, Model 240B manufactured by Perkin-Elmer was used.

Atomic absorption measurement For atomic absorption measurement, Hitachi Zeeman atomic absorption spectrometer Hitachi
Model 170-70 was used.

ESR spectrum measurement The ESR spectrum was measured using an X band Varian ESR spectrometer.

The sample is not subjected to any special pretreatment, etc.
The measurement was performed in a quartz tube for R.

Example 1 Synthesis of polyester derivative (1-1) Polymer 1 of x: y = 4: 1 1.78 g (0.032 mol) of 1,6-hexanediol and 2.05 g
(0.008 mol) of 1,3 bis (P-hydroxyphenyl) 1,3
-Propanedione (molar ratio 4: 1) in 50 ml of tetrachloroethane (TCE) in 15.81 g (0.040 mol) of 1,6-bis (P
-Chloroformylphenoxy) hexane was added, and the mixture was heated at 140 ° C. for 48 hours under a nitrogen atmosphere to obtain a polymer 1 of the formula (I) by a polycondensation reaction. The yield was 18.1 g, which was 96%.

IR (KBr _{^{method) 1700cm -1 (β- ν C =}} 0 of diketone) 1705cm ^-1 (ν _C = 0 alkyl ester) 1740cm ^-1 (ν _C = 0 of aromatic ester) Elemental analysis C (%) H (%) Theoretical 71.32 6.80 Found 69.48 6.77 (1-2) Polymer 2: x: y = 1: 1 2.36 g (0.020 mol) of 1,6-hexanediol and 5.13 g
(0.020 mol) of 1,3-bis (p-hydroxyphenyl)
1,3-propanedione (1: 1 molar ratio) was added in 50 ml TCE
5.81 g (0.040 mol) of 1,6 bis (p-chloroformylphenoxy) hexane was added, and the mixture was heated at 140 ° C. for 48 hours under a nitrogen atmosphere to obtain a polymer 2 of the formula (I) by a polycondensation reaction. Was. The yield was 19.8 g, 97% in yield.

IR (KBr _{^{method) 1700cm -1 (β- ν C =}} 0 of diketone) 1705cm ^-1 (ν _C = 0 alkyl ester) 1740cm ^-1 (ν _C = 0 of aromatic ester) Elemental analysis C (%) H (%) Theoretical value 71.89 6.13 Actual value 71.68 6.25 (1-3) Polymer 3 of x: y = 1: 0 50 ml was added to 4.73 g (0.040 mol) of 1,6-hexanediol.
15.81 g (0.040 mol) of 1,6 bis (P-chloroformylphenoxy) hexane was added in TCE under a nitrogen atmosphere.
The polymer 3 of the formula (I) was obtained by heating at 140 ° C. for 48 hours and performing a polycondensation reaction. The yield was 16.4 g, which was 93% in yield.

IR (KBr method) 1705 cm ^-1 (ν _C = 0 of alkyl ester) Elemental analysis C (%) H (%) Theoretical value 70.89 7.32 Observed value 71.49 7.31 Example 2 Synthesis of Copper Complex-Supported Polymer (Cu-X) ( 2-1) Synthesis of [1-Cu-11] A solution of 1.17 g (0.0005 mol in terms of β-diketone unit) of polymer 1 synthesized in (1-1) of Example 1 in 40 ml TCE solution was 2.5 × 10 ^−. 10 ml of ³ M CuCl ₂・ 2H ₂ O methanol solution
(0.000025 mol), triethylamine twice as much as copper was added, and the mixture was allowed to react with the copper complex [1-Cu-11] of the formula (II).
I got The yield was 1.07 g.

(2-2) Synthesis of [1-Cu-24] 40 ml of TCE of 1.17 g (0.0005 mol in terms of β-diketone unit) of polymer 1 synthesized in (1-1) of Example 1
10 ml of a solution of 5.0 × 10 ^-3 M CuCl ₂・ 2H ₂ O in methanol
(0.00005 mol), triethylamine twice as much as copper was added and reacted to obtain a copper complex [1-Cu-24] of the formula (II). The yield was 1.03 g.

(2-3) Synthesis of [1-Cu-59] 40 ml of TCE of 1.17 g (0.0005 mol in terms of β-diketone unit) of polymer 1 synthesized in (1-1) of Example 1
2.5 × 10 ^-3 M CuCl ₂・ 2H ₂ O methanol solution 10 ml
(0.00025 mol), and triethylamine twice as much as copper was added and reacted to obtain a copper complex [1-Cu-59] of the formula (II). The yield was 1.12 g.

(2-4) Synthesis of [1-Cu-21] 40 ml of TCE of 1.02 g (0.001 mol in terms of β-diketone unit) of polymer 1 synthesized in (1-2) of Example 1
20 ml of 1.0 × 10 ^-2 M CuCl ₂・ 2H ₂ O methanol solution
(0.0002 mol) and triethylamine twice as much as copper were added and reacted to obtain a copper complex [1-Cu-21] of the formula (II). The yield was 1.05 g.

Example 3 Synthesis of Nickel Complex-Supported Polymer [Ni-X] (3-1) Synthesis of [1-Ni-14] 1.17 g (converted to β-diketone unit) synthesized in (1-1) of Example 1. 0.0005 mol) of polymer 1 in 40 ml of TCE
2.5 × 10 ^-3 M NiCl ₂・ 6H ₂ O methanol solution 10 ml
(0.000025 mol), triethylamine twice as much as nickel was added, and the mixture was reacted to produce a Ni complex of the formula (II) (1-Ni
-14]. The yield was 1.10 g.

(1) Viscosity of synthetic polymer, (2) Differential scanning calorimetry, (3)
ESR measurement and (4) X-ray diffraction measurement were performed.

(1) Viscosity measurement The logarithmic viscosity η of Polymers 1 to 4 was measured using TCE: phenol (4:
6) Measured at 25 ° C in the mixed solution. Table 1 shows the results.

(2) Differential scanning calorimetry (DSC measurement) For DSC measurement, Rigaku Denki's high performance differential scanning calorimeter DSC-
10A was used. The measurement was performed under the conditions of a heating rate of 10 ° C./min, a measurement atmosphere in the air, and a DSC range of 1 mcal / sec. Further, the phase transition enthalpy (ΔH) was obtained as in the following equation.

 ΔH = K · A / M A: peak surface area (mcal ゜) K: apparatus constant (mcal / mcal ゜) M: mass of sample (mg) Table 2 shows values of ΔH of the metal complex-carrying polymer.

As shown in Table 2, ΔH decreases as the coordination ratio x to the metal increases, but this is due to the fact that a bridge occurs between the polymer chains by the metal complex and the molecular motion is suppressed. A similar phenomenon is derived even when the content of the β-diketone segment increases. This is because the interaction between polymer chains is increased and the molecular motion is suppressed.

(3) ESR measurement Each compound was kept at a temperature immediately after the transition, stretched using a glass rod or tweezers, and melt-spun.

The melt-spun sample was subjected to ESR measurement by changing the angle of the magnetic field on the fiber axis.

FIG. 1 shows [1-Cu-5] synthesized in Example 2 (2-3).
9] shows the ESR measurement result.

When the fiber axis and the magnetic field are balanced, the parallel component of the g value (g
) Did not appear, but only the peak of the vertical component of the g value (g 値) appeared. Therefore, as shown in FIG. 2, the copper complex synthesized in this example suggests that the complex plane is oriented parallel to the fiber axis direction, which is the stretching direction.

Note that the nickel complex of Example 3 is inactive with respect to ESR measurement, suggesting that it has a planar four-coordinate structure in a low spin state.

(4) X-ray diffraction measurement For the measurement, a flat camera was attached and a diffraction photograph was taken using an X-ray diffractometer CN4056A manufactured by Rigaku Denki. At that time, the tube current was 25 mA, the tube voltage was 35 KV, and CuKα rays filtered with a nickel foil were used. The exposure time was one hour.

 The results obtained are shown in FIG.

Also in the measurement of X-ray diffraction, a remarkable difference is observed when X-rays are irradiated perpendicularly or parallel to the fiber axis due to the difference in the content of β-diketone and metal, as in the DSC measurement. In the orientation condition, in the homopolymer 3 containing no β-diketone component, only a cyclic pattern was observed and no orientation was observed. Polymers 1, 2, 4 containing a β-diketone component are:
Since a spot-like pattern is observed, the orientation is improved by introducing the β-diketone segment. The introduction of metal also affects the orientation of the fibers. For example, as shown in FIG. 3, in the case of 1-Ni-14, when an X-ray is directed parallel to the fiber axis, only an annular pattern can be seen. The pattern is visible and clearly oriented. In addition, clear spot patterns are seen in 1-Cu-11 and 1-Cu-24, indicating good orientation. This implies that non-excessive introduction of metal creates bridging between the polymer chains, and a high degree of orientation can be obtained by proper bridging.

<Effect of the Invention> The metal complex formed from a liquid crystalline polymer material containing a β-diketone segment in the main chain of the polyester derivative of the present invention exhibits liquid crystal behavior.

Further, it was confirmed that orientation was generated in the spinning direction by melt-spinning the obtained compound.

Furthermore, while a polymer containing no β-diketone segment in the main chain does not exhibit uniaxial orientation, a β-diketone segment is introduced into the main chain and is coordinated to a metal to clearly orient. It was confirmed that the performance was improved.

That is, the introduction of a metal complex into a polymer liquid crystal material can give a novel specificity to the behavior and orientation as a liquid crystal.

[Brief description of the drawings]

1A and 1B are ESR measurement diagrams of a copper complex of a main chain type thermotropic liquid crystalline polymer material of the present invention. FIG. 1A shows a case where a magnetic field is perpendicular to a fiber axis, and FIG. Shows the case parallel to. FIG. 2 is a schematic diagram illustrating a state where the metal complex of the main chain type thermotropic liquid crystalline polymer material of the present invention is coordinated in parallel with the fiber axis direction. FIG. 3 is an X-ray photograph showing a crystal structure replacing the drawing, and is an X-ray diffraction pattern image photograph of a nickel complex of the main chain type thermotropic liquid crystalline polymer material of the present invention;
(A) is a case where X-rays are irradiated perpendicular to the fiber axis, (b)
Indicates a case where X-rays are irradiated in parallel to the fiber axis.

Continuation of the front page (72) Inventor Wang Yoshi Shirai 2496 Nagase, Maruko-cho, Nagano Prefecture, Japan (56) References JP-A-4-114031 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 C09K 19/38 CA (STN)

Claims (2)

(57) [Claims] 1. A main chain type thermotropic liquid crystalline polymer material having a β-diketone segment in a polyester main chain. 2. The main chain type thermotropic liquid crystalline polymer material according to claim 1, further comprising a metal ion, wherein the β-diketone segment is coordinated to the metal ion.