JP2001172385A - Liquid-crystalline dendrimer and production method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel nematic liquid-crystalline polymer. SOLUTION: A liquid-crystalline dendrimer which is represented by formula Ia: -(-CH2-CH2-N-(-CH2-CH2-CH2-N-R2)2)2 or by formula Ib: -(CH2-CH2-N- CH2-(CH2-CH2-N-(-CH2-CH2CH2-N-R2)2)2)2 (R is a structure represented by formula II; and (n) is an integer of 2-6) and a production method thereof are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to novel liquid crystalline dendrimers. The liquid crystalline dendrimer of the present invention functions as a thermotropic liquid crystal, and orientation of mesogen occurs more easily than a side chain type liquid crystal. In addition, a nematic phase is exhibited as a liquid crystal phase.

Conventionally, a liquid crystal dendrimer in which a liquid crystal group is bonded to the terminal of a poly (propylene imine) dendrimer has been described by Ueda et al.
36) is known. Such a liquid crystal dendrimer is a smectic liquid crystal, and differs from the nematic liquid crystal of the present invention in the physical properties and application range of the liquid crystal phase.

[0003] The present inventors have conducted various studies to obtain a new nematic liquid crystal. As a result, it was found that by modifying the terminal of a dendrimer, which is a polymer having a highly branched three-dimensional structure, with p-oxybenzoic acid biphenol ester, an excellent liquid crystal dendrimer having nematic liquid crystallinity can be obtained. The present invention has been completed.

[0004]

SUMMARY OF THE INVENTION That is, the present invention provides the following:

Embedded image Or (Where R is And n is an integer of 2 to 6. ) Is provided.

Further, the present invention provides the following formula:

Embedded image Or And a polyfunctional amine compound represented by the following formula: (Wherein, n is the same as above). A method for producing a liquid crystalline dendrimer, comprising reacting a liquid crystalline acrylate derivative represented by the following formula in an organic solvent in the presence or absence of a catalyst. About.

[0006]

Detailed Disclosure of the Invention The liquid crystalline dendrimer of the present invention has a polyfunctional amine compound as a core. As such a core, a polypropylene imine dendrimer DAB-Am-
4. Poly (propylene imine) dendrimer first generation (Poly
(propyleneimine) Dendrimer, Generation1.0) (Formula (III
a)), DAB-Am-8, poly (propyleneimine) dendrimer, second generation (Poly (propyleneimine) Dendrimer, Gen.
eration2.0) (formula (IIIb)) (all manufactured by DSM). These compounds can also be synthesized using ethylenediamine and acrylonitrile as starting materials.

[0007] The terminal of the polypropyleneimine dendrimer, which is a polyfunctional amine compound, is modified with a liquid crystalline acrylate derivative having a mesogenic group. Such a liquid crystalline acrylate derivative is represented by the formula (I)
V) is used, for example, 4- (4'-cyanobiphenyloxycarbonyl) phenoxyethyl acrylate, 4- (4'-cyanobiphenyloxycarbonyl) phenoxypropyl acrylate, 4- (4'-cyanobiphenyl) (Oxycarbonyl) phenoxybutyl acrylate, 4- (4′-cyanobiphenyloxycarbonyl) phenoxypentyl acrylate, 4- (4′-cyanobiphenyloxycarbonyl) phenoxyhexyl acrylate, and the like. These acrylates can be used alone or in combination of two or more.

[0008] The liquid crystalline dendrimer of the present invention is obtained by reacting the polyfunctional amine compound with a liquid crystalline acrylate derivative in an organic solvent. The amount of the acrylate used is DAB-A based on 1 mol of the polyfunctional amine or poly (propylene imine) dendrimer.
In the case of m-8, 16 to 80 mol, preferably 16 to 20 mol
Mol, in the case of DAB-Am-4, 8 to 40 mol, preferably 8 to 10 mol, or 2 to 10 equivalents, preferably 2 to 2.5 equivalents to the amino group (of Am-8, Am-4 For any). As the reaction solvent, any of those conventionally known as these solvents may be used. Specifically, halogenated hydrocarbons such as tetrachloroethylene, 1,2-dichloroethane and chloroform; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; cyclic ether solvents such as tetrahydrofuran and dioxane;
Aromatic hydrocarbon solvents such as xylene; N-methyl-2
-Pyrrolidone, N, N-dimethylformamide, N, N-
An aprotic polar solvent such as dimethylacetamide can be used. These may be used alone, or 2
Mixtures of more than one species may be used.

[0009] The reaction temperature is -50 to 150 ° C, preferably 25 to 80 ° C. If the reaction temperature is lower than −50 ° C., the reaction rate is remarkably reduced, which is not preferable. Also, 150
If the reaction temperature exceeds ℃, the stability of the polyfunctional amine compound or the liquid crystalline acrylate derivative is not preferred.

The reaction time is 2 to 200 hours, preferably
18-90 hours. If the reaction time is shorter than this, the reaction does not proceed completely, which is not preferable. After completion of the reaction, the target liquid crystalline dendrimer can be obtained by concentrating and removing the solvent. Alternatively, purification may be performed by adding a poor solvent such as methanol, ethanol, isopropyl alcohol, hexane, and toluene, heating the mixture, and removing the supernatant.

[0011]

The present invention will be described more specifically with reference to examples and comparative examples. All syntheses were performed under a stream of nitrogen. The properties of the obtained liquid crystalline dendrimer were measured as follows.

[0012] ¹ H NMR  It was measured using JNM-LA300 (manufactured by JEOL Ltd.).
Was.IR  Measured using FT / IR-230 (manufactured by JASCO Corporation)
Was.Phase transition phenomenon  SSS-5000 DSC200 (Seiko Electronics Industry Co., Ltd.)
Temperature rise and fall under a nitrogen atmosphere at 10 ° C./min.
Measured at temperature rate.Molecular weight  Kratos Compact MALDI III mass spectrometer
(Manufactured by Shimadzu Corporation). In the examples
The acrylate used was disclosed in JP-A-9-133810
The production was carried out by the method described in 1.

Example 1 Synthesis of first generation propylene imine dendrimer (n = 2). In a 20 mL reaction vessel, (4- (4′-cyanobiphenyloxycarbonyl) phenoxyethyl) acrylate (0.88
mmol, 363.8 mg) and poly (propylene imine) dendrimer DAB-Am-4 (0.10 mmol, 31.6 mg), 2.0 ml of dichloromethane was added, and the mixture was stirred at 40 ° C. for 18 hours. After cooling to room temperature, this solution was dropped into toluene with vigorous stirring, and the resulting precipitate was collected to purify the target product. This was dried under reduced pressure to obtain 246 mg of a powdery white solid in a yield of 68%. M
The molecular weight by ALDI-TOF MS is the theoretical value m / z =
3623.8 (M ⁺ ), found m / z = 364
6.7 ((M + Na) ⁺ ). By IR, 173
A characteristic absorption of 0.8 cm ^-1 (CO) was observed.

The DSC of this liquid crystalline dendrimer was measured.
An endothermic peak was observed at ° C. In the course of the temperature drop, an exothermic peak was observed at 110 ° C.

Example 2 Synthesis of first-generation propyleneimine dendrimer (n = 6) Example 1 was repeated except that acrylic acid (4- (4'-cyanobiphenyloxycarbonyl) phenoxyhexyl) was used as the acrylic acid ester. Reaction and purification were carried out in the same manner as in Example 1 to obtain 212 mg of a powdery white solid in a yield of 52%. The molecular weight by MALDI-TPF MS is the theoretical value m / Z = 40
72.7 (M ^<+> ), found m / Z = 4095.
9 (M ⁺ Na ⁺ ). By IR, 1730.5
A characteristic absorption of cm ^-1 (CO) was observed.

Example 3 Synthesis of Second Generation Propyleneimine Dendrimer (n = 2) The reaction was carried out in the same manner as in Example 1 except that poly (propyleneimine) dendrimer DAB-Am-8 was used as the dendrimer. Purification was performed to obtain a powdery white solid in a yield of 51.
7 mg was obtained in a yield of 70%. The molecular weight measured by MALDI-TPF MS was m / Z = 748.0 (M ⁺ Na ⁺ ), whereas the theoretical value was m / Z = 7388.0 (M ⁺ ). IR
As a result, characteristic absorption of 1730.6 cm ^-1 (CO) was observed.

Example 4 Synthesis of second-generation propylene imine dendrimer (n = 6) (Imine) The reaction was carried out and purified in the same manner as in Example 1 except that the dendrimer DAB-Am-8 was used, to obtain 456 mg of a powdery white solid in a yield of 55%. The molecular weight measured by MALDI-TPF MS was m / Z = 8309.5 (M ⁺ Na ⁺ ), whereas the theoretical value was m / Z = 8285.7 (M ⁺ ). By IR, characteristic absorption of 1730.5 cm ^-1 (CO) was observed.

[0018]

The liquid crystalline dendrimer of the present invention is a thermotropic liquid crystal and has a small entanglement of the molecular chains of the dendrimer structure, so that the mesogen can be easily oriented. It is a nematic liquid crystalline polymer.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Hidesaku Nakano 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation (72) Inventor Sadahiro Nakanishi 1-2-1 Shimohozumi, Ibaraki-shi, Osaka F-term in Nitto Denko Corporation (reference) 4H006 AA01 AA02 AB46 QN30 4H027 BA01 BA11 CA04 CF04 4J043 PA04 PA13 PB09 QC02 RA08 SA02 SA05 SB01 TA35 TB01 UA142 UB011 UB241 XA14 XA19 XB27 ZA09 ZB23

Claims (4)

[Claims] 1. The following formula: (Where R is And n is an integer of 2 to 6. The liquid crystalline dendrimer represented by). 2. The following formula: And a polyfunctional amine compound represented by the following formula: (Wherein, n represents an integer of 2 to 6), wherein the liquid crystalline acrylate derivative is reacted in an organic solvent in the presence or absence of a catalyst. Item 10. A method for producing the liquid crystalline dendrimer according to Item 1. 3. The following formula: (Where R is And n is an integer of 2 to 6. The liquid crystalline dendrimer represented by). 4. The following formula: And a polyfunctional amine compound represented by the following formula: (Wherein, n represents an integer of 2 to 6), wherein the liquid crystalline acrylate derivative is reacted in an organic solvent in the presence or absence of a catalyst. 3. A method for producing a liquid crystal dendrimer according to 3.