JP2002302831A - Novel microfibrous structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the novel type of a structure capable of imparting a function similar to a carbon nanotube and a novel function by relatively simple chemical synthesis. SOLUTION: A condensed polymer is brought to a microfibrous structure having 0.5-500 nm diameter. The microfibrous structure comprises the condensed polymer consisting of at least one or more of polymers selected from polyimides, polyamides, polyesters, polycarbonates, polyarylates, and polyurethanes. The condensed polymer is preferably selected from polyimides.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel microfibrous structure.

[0002]

2. Description of the Related Art Carbon nanotubes (Nature, 354, 56 (1991)) as compounds with a highly controlled structure are expected to be applied as new functional materials.
For example, there are an electron emission type electron emission material and a hydrogen storage material for a fuel cell. However, the synthesis method is manufactured by a gas-phase method that consumes a large amount of energy, such as an arc discharge method or a pulse laser method, and many of the methods have low yields and require steps such as removal of impurities. There are problems such as. On the other hand, a structure in which calixarene is polymerized into a tube as a compound similar to a carbon nanotube has been proposed. (JP-A-11-246551) However, its structure is limited, and expected functions are limited.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a new type of structure capable of imparting a function similar to a carbon nanotube and a new function by relatively simple chemical synthesis.

[0004]

Means for Solving the Problems The present inventors have achieved the above-mentioned object by studying the control of the condensed polymer in the form of microfibrils, that is, the present invention is directed to a method comprising the condensed polymer. Having a diameter of 0.5
It is a microfibrous structure having a diameter of from 500 nm to 500 nm, and the condensation polymer is preferably at least one polymer selected from polyimide, polyamide, polyester, polycarbonate, polyarylate, and polyurethane.

More preferably, the condensation polymer is a polyimide.

Preferably, the microfibrous structure has a tube structure.

In the tube structure, metal atoms, metal ions,
It is preferable to include a metal compound.

It is preferred that the condensation polymer is helical.

It is preferable that the condensation polymer contains a functional group.

[0010] More preferably, the functional group is a carbazole group.

It is preferable that the microfibrous structure has conductivity.

It is preferable that the microfibrous structure shows hole mobility.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The condensation polymer in the present invention is a polymer obtained by polycondensation, such as polyimide, polyamide, polyester, polycarbonate, polyarylate, and polyurethane. Particularly, polyimide and polyamide are preferable as condensation polymers because of their heat resistance, and polyimide is particularly preferable.

The synthesis method is not particularly limited, but in the case of polyimide, which is a preferred example, there is a method of synthesizing a polyamic acid by polycondensation of an acid dianhydride and a diamine and closing the ring by heating or the like.

The acid dianhydride component as a polymerization component of the polyimide is para-terphenyl-3,4,3 ″, 4 ″.
-Tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride , 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 1,2,5,6-
Naphthalenetetracarboxylic dianhydride, 2,3,6,7
-Naphthalenetetracarboxylic dianhydride, 2,3,5
6-pyridinetetracarboxylic dianhydride, 1,4,5
8-naphthalenetetracarboxylic dianhydride, 3,4
9,10-perylenetetracarboxylic dianhydride, 4,
4'-sulfonyldiphthalic dianhydride, 3,3 ', 4
4'-tetraphenylsilanetetracarboxylic dianhydride, meta-terphenyl-3,3 ", 4,4" -tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride Anhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-
Tetramethyldisiloxane dianhydride, 1- (2,3-dicarboxyphenyl) -3- (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride and the like can be mentioned. Can be

The diamine component of the polyimide includes, for example, 4,4'-diaminodiphenyl ether,
4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, benzidine, metaphenylenediamine, 3,3'-dihydroxybenzidine, paraphenylenediamine, 1,5-naphthalenediamine,
2,6-naphthalenediamine, bis- (4-aminophenoxyphenyl) sulfone, bis- (4-aminophenoxyphenyl) sulfide, bis- (4-aminophenoxyphenyl) biphenyl, 1,4-bis- (4-amino Phenoxy) benzene, 1,3-bis- (4-aminophenoxy) benzene, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether-3
-Sulfonamide, 3,4'-diaminodiphenylether-4-sulfonamide, 3,4'-diaminodiphenylether-3'-sulfonamide, 3,3'-diaminodiphenylether-4-sulfonamide, 4,
4'-diaminodiphenylsulfone-3-sulfonamide, 3,4'-diaminodiphenylsulfone-4-sulfonamide, 3,4'-diaminodiphenylsulfone-
3'-sulfonamide, 3,3'-diaminodiphenylsulfon-4-sulfonamide, 4,4'-diaminodiphenylsulfide-3-sulfonamide, 3,4 '
-Diaminodiphenylsulfide-4-sulfonamide, 3,3'-diaminodiphenylsulfide-4-
Sulfonamide, 3,4'-diaminodiphenylsulfide-3'-sulfonamide, 1,4-diaminobenzene-2-sulfonamide, 4,4'-diaminodiphenylether-3-carbonamide, 3,4'-diaminodiphenylether -4-carbonamide, 3,4 '
-Diaminodiphenyl ether-3'-carbonamide, 3,3'-diaminodiphenylether-4-carbonamide, 4,4'-diaminodiphenylmethane-3
-Carbonamide, 3,4'-diaminodiphenylmethane-4-carbonamide, 3,4'-diaminodiphenylmethane-3'-carbonamide, 3,3'-diaminodiphenylmethane-4-carbonamide, 4,4'-diamino Diphenylsulfone-3-carbonamide, 3,
4'-diaminodiphenylsulfone-4-carbonamide, 3,4'-diaminodiphenylsulfone-3'-carbonamide, 3,3'-diaminodiphenylsulfone-4-carbonamide, 4,4'-diaminodiphenylsulfide- 3-carbonamide, 3,4'-diaminodiphenylsulfide-4-carbonamide, 3,
3'-diaminodiphenylsulfide-4-carbonamide, 3,4'-diaminodiphenylsulfide-
3'-sulfonamide, 1,4-diaminobenzene-2
-Carbonamide, 4,4'-bis (4-aminophenoxy) biphenyl, bis {4- (3-aminophenoxy) phenyl} sulfone and the like. The acid dianhydride component and the diamine component may be used in combination of two or more.

The length of the microfibrous structure in the present invention is preferably at least 5 times the diameter. If it is less than 5 times, the functions expected in the present invention may not be exhibited.

The diameter of the microfibrous structure of the present invention is 0.5
nm to 500 nm, preferably 1 to 200 nm.
If it is larger than 500 nm, the expected function is not exhibited, and if it is smaller than 0.5 nm, a structure cannot be formed. The diameter can be measured by, for example, a transmission electron microscope.

Any form may be used as long as it is fibrous, but a preferred example is a tube structure. The tube structure means that the center of the fibrous structure is hollow or a compound other than the condensation polymer is present. In the case of adopting a tube structure, it is preferable that the condensation polymer has a spiral shape. Further, it is preferable to include a metal atom, a metal ion, and a metal compound in the center of the tube structure.
In this case, it is preferable that metal atoms, metal ions, and metal compounds are continuously arranged in the length direction of the fibrous compound. By including metal atoms etc., conductivity is expressed,
In some cases, paramagnetism develops. When conductivity can be exhibited, it can be used as an electron emission type electron emission material. When the constancy can be expressed, the fibrous structure can be arranged at an arbitrary position in an arbitrary direction by an external magnetic field.

Here, the metal atoms are Al, Ti, V, C
r, Mn, Fe, Ni, Co, Cu, Zn, Zr, M
o, Ru, Rh, Pd, Ag, Cd, In, Sn, S
b, W, Re, Os, Ir, Pt and the like. Examples of such metal compounds include oxides, hydroxides, nitrates, sulfates, halides (chlorides, bromides, etc.).

In the present invention, the functional group means, for example, those exhibiting electron mobility, hole mobility, ion mobility, electro-optic effect, magnetism and the like. For example, a carbazole group exhibits hole mobility and exhibits a large hole mobility when incorporated into the microstructure of the present invention and arranged.

The structure according to the present invention can be used as an electron emission type electron emission material like a nanotube. It can be used as a hydrogen storage material, a hole transport material for organic EL, and the like.

[0023]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

The raw materials used are commercial products. The source of each raw material is shown. 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (manufactured by Wako Pure Chemical Industries), 3,3'-dihydroxybenzidine (manufactured by Wakayama Seika), ferric chloride (manufactured by Wako Pure Chemical Industries) ), 1-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) (Example 1) In a three-necked flask equipped with a reflux tube, 200 g of 1-methyl-2-pyrrolidone was added to 200 g of 3-methyl-2-pyrrolidone under a nitrogen stream.
1.08 g of 3'-dihydroxybenzidine is added and stirred under a nitrogen atmosphere. Here, 1.35 g of ferric chloride is added. The three-necked flask is cooled on ice and further stirred. To this, 1.47 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added and stirred for 3 hours. Thereafter, the three-necked flask is heated and stirred under reflux for 5 hours. After cooling to room temperature, the precipitated substance was
And vacuum drying for 24 hours. When this substance was observed with a transmission electron microscope, a fibrous material having a diameter of 1 to 100 nm was observed.

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Claims (10)

[Claims] 1. A microfibrous structure comprising a condensation polymer and having a diameter of 0.5 nm to 500 nm. 2. The condensation polymer is polyimide, polyamide,
2. The microfibrous structure according to claim 1, which is at least one or more polymers selected from polyester, polycarbonate, polyarylate, and polyurethane. 3. The method according to claim 1, wherein the condensation polymer is a polyimide.
The described microfibrous structure 4. The microfibrous structure according to claim 1, which has a tube structure. 5. The method according to claim 5, wherein the metal atom, metal ion,
The microfibrous structure according to claim 4, comprising a metal compound. 6. The condensed polymer is helical.
5. The microfibrous structure according to any one of 5. 7. The condensation polymer according to claim 1, which contains a functional group.
7. The microfibrous structure according to any one of 6. 8. The functional group is a carbazole group.
Microfibrous structure according to 9. The microfibrous structure according to claim 1, which exhibits conductivity. 10. The microfibrous structure according to claim 1, which exhibits hole mobility.