JPH0948849A - Interlock polymer comprising bifunctional 2-catenane derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer composed from a monomer having an interlock structure, not having a chemical bond between the repeating units, and useful as a raw material for functional materials such as polymer elastomers, etc. SOLUTION: An interlock polymer comprises a 2-catenane derivative of formula I (n is an integer of 0-2; X is an integer). The compound of formula I is obtained e.g. by reacting a 2-catenane derivative of formula II as a starting raw material with copper borofluoride, reacting the copper ion-introduced product with adipic dichloride and subsequently reacting the obtained compound with a cyanide ion to remove the copper ion. The bifunctional 2-catenane of formula II is obtained e.g. by cyclizing an amino-protected 10-aza-hexaethylene glycol with 2,4-bis-(4-hydroxyphenyl)-1,10-diazaphenanthroline by the method of Sovaju et al. and subsequently removing the protecting group from the product.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polymer having an interlock structure, and more particularly, to a polymer having an interlock structure, which has no chemical bond between its repeating units. The present invention relates to an interlocked polymer useful as a raw material for functional materials such as polymer elastomers.

[0002]

2. Description of the Related Art In recent years, much research has been conducted on polymer materials as polymer elastomers.

In order to form a polymer elastomer or the like, it is necessary for the polymer main chain to have high mobility, and it is known that a structure composed of repeating units having no chemical bond is particularly suitable. ing.

As a method of connecting molecules without such a direct chemical bond, an interlock structure in which two cyclic structures are connected in a chain is known.

However, no polymer having an interlock structure, that is, an interlocked polymer has been found so far.

[0006]

Under these circumstances, the present invention has been made with the object of providing an interlocked polymer useful as a polymer elastomer.

[0007]

DISCLOSURE OF THE INVENTION As a result of intensive studies to develop a novel interlocked polymer, the present inventors have found that a bifunctional 2-catenan derivative having an interlock structure and adipic acid dichloride. Finds that the object forms a polymer composed of an interlock structure,
Based on this finding, the present invention has been completed. That is, the present invention uses the formula

[0008]

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It is an interlocked polymer composed of a 2-catenan derivative represented by: The interlocked polymer represented by the formula (I) is a novel compound that has not been described in any literature, where n is an integer of 0 to 2 and X is an integer.

BEST MODE FOR CARRYING OUT THE INVENTION The interlocked polymer represented by the formula (I) is, for example, a compound represented by the formula:

[0010]

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A 2-catenan derivative represented by the formula (n has the same meaning as described above) is used as a starting material,
It can be manufactured through the steps of (A) introducing copper ions, (B) reacting with adipic acid dichloride, and (C) removing copper ions.

The above step (A) can be carried out by reacting the 2-catenan derivative with, for example, copper borofluoride. This reaction is preferably carried out in a solvent. The solvent at this time is not particularly limited, but an aprotic solvent such as methylene chloride or DMF is preferable.
This reaction is usually carried out by stirring at a temperature in the range of 0 to 50 ° C. for 5 to 36 hours under normal pressure. After completion of the reaction, the solvent is distilled off from the reaction mixture, followed by separation and purification using, for example, silica gel column chromatography.

[0013]

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The compound represented by the formula (wherein n has the same meaning as described above) is obtained as a black solid.

The step (B) is carried out by reacting the copper complex of the 2-catenan derivative obtained in the step (A) with, for example, adipic acid dichloride. This polycondensation reaction is preferably carried out in a solvent in the presence of a base catalyst. An aprotic solvent such as methylene chloride or hexane is used as the solvent at this time, and a solid catalyst such as potassium hydroxide or sodium hydroxide is also used as the basic catalyst, but liquid amines such as triethylamine, Pyridine and the like are preferred. This reaction is usually carried out by stirring at a temperature in the range of -10 to 50 ° C for 5 to 36 hours under normal pressure. After completion of the reaction, the basic catalyst was removed from the reaction mixture and the solvent was distilled off.
For example, separation using gel phase column chromatography,
If refined, the formula

[0016]

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A compound represented by the formula (n and X have the same meanings as described above, and X is usually 2 or more) is obtained as a black solid.

The above step (C) is carried out by reacting the compound obtained in the step (B) with, for example, cyanide ion. This reaction is preferably carried out in a solvent. At this time, a solvent having a high hydration power such as DMF or DMSO is used as the solvent, and potassium cyanide, sodium cyanide, tetrabutylammonium cyanate, etc. are used as the cyanide ion source. This reaction is
Usually, it is carried out by stirring under normal pressure at a temperature in the range of 0 to 50 ° C. for 5 to 36 hours. After completion of the reaction, the basic catalyst is removed from the reaction mixture, the solvent is distilled off, and the compound of the present invention represented by the above formula (I) is obtained by separating and purifying using, for example, gel phase column chromatography.
Obtained as a pale yellow solid.

[0019]

The interlocked polymer of the present invention is
It is a novel compound that has not been described in the literature and has repeating units linked by an interlock structure. Since it has no chemical bond between repeating units, it is extremely useful as a raw material for functional materials such as polymer elastomers.

[0020]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 Amino-protected 10-aza-hexaethylene glycol and 2,4-bis- (4-hydroxyphenyl)-
1,10-Diazaphenanthroline was cyclized by the method of Sauvage et al. And then protected to give the bifunctional 2-catenane. 20 mg of this 2-catenan was dissolved in 3 ml of DMF, 10 mg of copper borofluoride was added thereto, and the mixture was stirred at room temperature for 24 hours, then the solvent was distilled off, and the residue was dissolved in methylene chloride, and then dissolved in methylene chloride by silica gel column chromatography. By separating and purifying with methanol as a developing solvent, 21 mg of a product was obtained.

21 mg of 2-catenan introduced with copper ions
Was dissolved in 3 ml of methylene chloride, 10 mg of adipic acid dichloride and 2 ml of triethylamine were added thereto, and 24
After stirring at room temperature for an hour, the product was filtered off, washed with methylene chloride, dissolved in dimethylformamide (DMF), and then subjected to gel phase column chromatography to obtain D.
By separating and purifying using MF as a developing solvent, 15 mg of a polymer was obtained.

15 mg of the obtained polymer was added to 5 ml of DMF.
0.86 ml of an aqueous solution of sodium cyanide (1M) was added dropwise thereto at room temperature, and the mixture was stirred for 3 hours. The organic layer is extracted with methylene chloride, the organic layer is dried over magnesium sulfate, the solvent is distilled off, and the compound is represented by the formula (IV) by separating and purifying with DMF as a developing solvent by gel phase column chromatography. 4 mg of an interlocked polymer (n = 1 in the formula (IV)) was obtained. The molecular weight was measured by GPC to be 9.5 × 10 ⁵ . Calculated value (%) as elemental analysis value (C ₇₈ H ₈₄ N ₆ O ₁₄ ); C 70.46, H 6.37, N
6.32 Found (%); C 70.30, H 6.80, N
6.12

Claims (1)

[Claims] (1) Formula (1) An interlocked polymer comprising a 2-catenan derivative represented by the formula (n is an integer of 0 to 2 and X is an integer).