JP2003183386A - Polymer having fishing gut-knot structure and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer having a fishing gut-knot structure. <P>SOLUTION: The polymer having the fishing gut-knot structure is represented by formula (I) (wherein, A is a group which plays a role in connection; G is a bonding group; X is any anionic atom, provided that the above G has a structure smaller than the inner diameter of a dibenzo-24-crown-8-ether and having a size capable of passing through the crown ether ring; and n is an integer of ≥2), and its production method are provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer with Teguus structure and a method for producing the same.

[0002]

2. Description of the Related Art The main chain structure of a polymer depends on the type of monomer and the mode of polymerization. A variety of polymers are known, including molecules and polymers having a metal in the main chain. A polymer compound obtained by polymerizing a monomer is a structure obtained by a main chain structure in which a monomer molecule is bound by a covalent bond. In recent years, attention has been focused on catenane, which is a structure in which cyclic compounds are mechanically entangled with each other, and rotaxane, which is a structure in which a specific linear compound penetrates a cyclic portion of the cyclic compound. Since these compounds have been shown by Stoddart et al. In the United Kingdom to have the possibility of building molecular-scale machinery by utilizing their characteristic mechanical bonds (American Chemical Society, 1992, 114, No. 1) Compounds with various mechanical bonds have been synthesized, but there are still few examples of research and development toward practical use. In addition, it has been investigated to use a polymer as a method for utilizing these catenanes and rotaxanes, and it is expected that more attractive properties can be obtained by using polycatenans and polyrotaxanes. The present inventors have invented several structures as such novel substances (for example, 1. Japanese Patent Application No. 2000).
-71252 "Rotaxane spherical aggregates and a method for producing the same, and rotaxane spherical macromolecular polymers and a method for producing the same" Masumi Asakawa, Aiden Murphy, Toshimi Shimizu. 2.
Japanese Patent Application No. 11-176952 "Compounds containing a rotaxane structure in the main chain and intermediates thereof, and methods for producing the same" Masumi Asakawa, Aiden Murphy, David A. Ray,
Toshimi Shimizu. etc).

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a Taegus knot structure and a method for manufacturing the same.
This polymer with a Tegus knot structure can be used in the field of organic polymer materials as a low-temperature elastomer or a highly elastic rubber material.

[0004]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to develop a polymer having a Tegs-tie structure, and as a result,

[Chemical 4] (II) (In the formula, R represents a reactive substituent and X represents an arbitrary anion atom. Here, R represents dibenzo-24-.
The structure is smaller than the inner diameter of crown-8-ether, and the structure is such that it can pass through the crown ether ring. ) Is directly polymerized or polymerized by using an arbitrary linking group to give a novel general formula

[Chemical 5] (I) (In the formula, A is a group which plays a role of linking, G represents a bonding group, and X represents an arbitrary anion atom.
The G has a structure smaller than the inner diameter of dibenzo-24-crown-8-ether, and has a size capable of passing through the crown ether ring. n is 2
Represents the above integers. The present invention has been completed based on this finding by discovering that a Teguus knot structure represented by (4) can be obtained.

That is, according to the present invention, the following inventions are provided. (1) The following general formula (I)

[Chemical formula 6] (I) (In the formula, A is a group which plays a role of linking, G represents a bonding group, and X represents an arbitrary anion atom.
The G has a structure smaller than the inner diameter of dibenzo-24-crown-8-ether, and has a size capable of passing through the crown ether ring. n is 2
It is an integer above the above. ) Is represented by a Teguth structure polymer. (2) A Teguth knot structure polymer represented by the following general formula (I), characterized in that the Teguth knot structure polymer represented by the following general formula (II) is directly polymerized or polymerized using an arbitrary linking group. Production method.

[Chemical 7] (I) (In the formula, A is a group which plays a role of linking, G represents a bonding group, and X represents an arbitrary anion atom.
The G has a structure smaller than the inner diameter of dibenzo-24-crown-8-ether, and has a size capable of passing through the crown ether ring. n is 2
It is an integer above the above. )

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The Tegus-knot structure polymer of the present invention has a chemical structure represented by the following general formula (I).

[Chemical 8] (I) In the above formula, G represents a bonding group that plays a role of bonding the Teguth knot structure, and X represents any anion atom. However, G is dibenzo-24-crown-8.
-The structure is smaller than the inner diameter of the ether, and the structure is such that it can pass through the crown ether ring. G is a linking group that plays a role of binding the Teguus knot structure. It is a group formed by connecting the functional substituent R of the Teguth bond structure described later with an appropriate connecting group or by directly connecting the functional groups. By the action of the reactive functional group R, which is reactive, it is possible to synthesize the Tegus-bonded structure polymer in one step.
A reaction means such as condensation, polycondensation or addition reaction is adopted as the reaction means for connection. Specific examples of the substituent include an amide group, an ester group, an ether group, a carbonyl group, a sulfonamide group, and a thioether group. R needs to be a substituent having a lower acidity than secondary ammonium. A is a group which plays a role in linking when linked by a suitable linking group (G), and is an alkylene group, a dialkylene ether group, a phenylene group, a siladiyl group or the like. X represents any anion atom or anion molecule composed of a part of sodium perchlorate, ammonium hexafluorophosphate, trifluoroacetic acid, hydrochloric acid, sulfuric acid, sodium tetraphenylborate, and the like. The whole structure of this compound is such that a cyclic molecule (a ring-shaped portion formed by dibenzocrown ether) and a rod-shaped molecule (a portion formed by benzylamine and a substituent R) are secondary ammonium salts intruded into each other in the crown ether, It has a structure entwined with each other through a ring structure, and the structure entwined with each other through these ring structures is in a state of Tegusu knotting, which is one of the ways of tying a rope. This combination of compounds is mechanically linked without a covalent bond. Since such a complicated state is included in the bonding group, it is different from bonding only through ordinary condensation and polycondensation, and when a force such as pulling of the substance is applied, a specific elongation is caused. Etc. are expected, and can be expected to show properties derived from mechanical coupling. n
Is an integer of 2 or more.

Examples of the compound represented by the general formula (I) include compounds having the following structural formulas. Furthermore, the compound represented by formula (I) will be specifically described. In the formula, n is an integer of 2 or more.

[Chemical 9]

[Chemical 10]

[Chemical 11]

The method for producing the Teguth knot structure polymer represented by the following general formula (I) of the present invention is to directly polymerize the Teguth knot structure represented by the following general formula (II) or polymerize it using an arbitrary linking group. Manufactured by

[Chemical formula 12] (I) (In the formula, A is a group which plays a role of linking, G represents a bonding group, and X represents an arbitrary anion atom.
The G has a structure smaller than the inner diameter of dibenzo-24-crown-8-ether, and has a size capable of passing through the crown ether ring. n is 2
It is an integer above the above. )

[Chemical Formula 13] (II) (In the formula, R represents a reactive substituent and X represents an arbitrary anion atom. Here, R represents dibenzo-24-.
The structure is smaller than the inner diameter of crown-8-ether, and the structure is such that it can pass through the crown ether ring. ) By the action of the reactive substituent R, which is a reactive functional group, it is possible to synthesize a Teguth structure polymer in one step. A reaction means such as condensation, polycondensation or addition reaction is adopted as the reaction means for connection. Specific examples of the substituent include an amide group, an ester group, an ether group, a carbonyl group, a sulfonamide group, and a thioether group. R needs to be a substituent having a lower acidity than secondary ammonium.

The Taegus knot structure for manufacturing the above-mentioned Taegus knot structure polymer is manufactured as follows.
The Teguth knot structure represented by the following general formula (II) is protonated (by adding a protonic acid) to dimerize the Teguth knot structure represented by the following general formula (III) in a nonpolar solvent. Manufactured by

[Chemical formula 14] (II) (In the formula, R represents a reactive substituent and X represents an arbitrary anion atom. Here, R represents dibenzo-24-.
The structure is smaller than the inner diameter of crown-8-ether, and the structure is such that it can pass through the crown ether ring. )

[Chemical Formula 15] (III) (In the formula, R represents a reactive substituent.
Has a structure smaller than the inner diameter of dibenzo-24-crown-8-ether, and has a size that allows it to pass through the crown ether ring. ) This reaction is carried out in a non-polar solvent. Specifically, chloroform, methylene chloride, toluene, xylene and the like are used. The temperature is 10 ° C to 40 ° C. (After the reaction,
The desired product is obtained by evaporating the non-polar solvent. The obtained product is confirmed by mass spectrometry and NMR.

The Teguth knot structure obtained by the above reaction is polymerized by the following two methods. This is performed by (1) reacting the Teguth-tie structures with each other in a nonpolar solvent, or (2) reacting the Teguth-tie structures with a bifunctional reaction reagent in a nonpolar solvent. In the method (1), when reacting the Teguth knot structures with each other in a non-polar solvent, the reactive substituents R of the Teguth knot structures are reacted with each other, whereby the crown ether is converted into a secondary ammonium salt. Got into each other,
A structure in which a circular molecule and a rod-shaped molecule are intricately combined, and a Tegu's knot structure in the shape of a rope knot, which is mechanically connected, can be obtained. The method (2) is performed as follows. The following general formula (II)

[Chemical Formula 16] (II) (In the formula, R represents a reactive substituent.
Has a structure smaller than the inner diameter of dibenzo-24-crown-8-ether, and has a size that allows it to pass through the crown ether ring. ) In the non-polar solvent, the substituent R of the Teguth bond structure represented by the following general formula (IV) is represented by the bifunctional reaction reagent.

[Chemical Formula 17] (IV) (In the formula, P represents a reactive substituent.
Is a structure that is gently reacted with the above R in a nonpolar solvent to form a carbonyl group, an alkoxy group, an amide group, an acyl group, an alkyl group, and a ureylene group, a carboxyl group, an acyl halide group. , A formyl group, an isocyanato group, an amino group, a hydroxyl group, a halogen group, and a vinyl group. Further, in the formula, A represents a substituent, and has a structure such that the above R and R do not react in a nonpolar solvent. A is a group which plays a role in linking when a suitable linking group G and G are linked, and is a group selected from an alkylene group, a dialkylene ether group, a phenylene group, a siladiyl group and the like, and is not always necessary. ) Or a bifunctional reaction reagent (IV) is used to gently react the substituents R with each other in a nonpolar solvent to give a compound represented by the following general formula (I):

[Chemical Formula 18] (I) (In the formula, A is a group which plays a role of linking and is not always necessary. G represents a bonding group formed by reaction between the substituents P and R or a group formed by reaction between the substituents R, X
Represents any anion atom. However, G has a structure smaller than the inner diameter of dibenzo-24-crown-8-ether, and has a size that allows it to pass through the crown ether ring. n is an integer of 2 or more. ), Which has a structure in which secondary ammonium salts enter into each other in the crown ether and are entangled with each other through a ring structure, and the structure entangled with these ring structures is a rope knot. It is in the state of one Tegusu knot. By subjecting this structure to the above treatment, a mechanically linked polymer can be obtained.

EXAMPLES Next, the present invention will be described in more detail by way of examples. The invention is in no way limited by these examples.

Example 1 (Method for producing mechanically bound polymer) A monomer (structural formula) in which a crown ether derivative, which is a monomer for mechanically bound polymer production, self-assembles and dimerizes
V) 22.7 mg (0.016 mmol) and succinic acid chloride 2.53 mg chloroform (dehydrated) 0.16
What was dissolved in 3 ml was added at room temperature. After stirring at room temperature for 6 hours, it was dissolved in dichloromethane, washed with a saturated aqueous sodium hydrogen carbonate solution, the organic layer was dried over anhydrous magnesium sulfate, filtered to remove magnesium sulfate, and then the solvent was distilled off.

[Chemical 19] (V) As a result, a Taegus knot structure polymer represented by the following structural formula (VI) was obtained.

[Chemical Formula 20] (VI) Example 2 (Method for producing mechanically bound polymer) A monomer (structural formula) in which a crown ether derivative, which is a monomer for mechanically bound polymer production, self-assembles and dimerizes
V) 22.7 mg (0.016 mmol) of carbonyl chloride-introduced polystyrene (structural formula VII) 97.8 mg (terminal functional group 0.01 mmol) were dissolved in chloroform (dehydrated) 0.5 ml. The mixture was added at room temperature. After stirring at room temperature for 6 hours, it was dissolved in dichloromethane, washed with a saturated aqueous sodium hydrogen carbonate solution, the organic layer was dried over anhydrous magnesium sulfate, filtered to remove magnesium sulfate, and then the solvent was distilled off.

[Chemical 21] (V)

[Chemical Formula 22] (VII) As a result, a Taegus knot structure polymer represented by the following structural formula (VIII) was obtained.

[Chemical Formula 23] (VIII) Example 3 (Method for producing mechanically bound polymer) Monomer (structural formula) in which crown ether derivative, which is a monomer for mechanically bound polymer production, self-assembles and dimerizes
V) 28.3 mg (0.020 mmol), 1,12
Dodecanedioic acid 4.68 mg (0.020 mmol) in chloroform (dehydrated) -THF (dehydrated) 1: 1 solution 0.203
What was dissolved in ml was added at room temperature, the pressure was reduced, and the solvent was distilled off. Furthermore, 1-ethyl-3- (dimethylaminopropyl) -carbodiimide hydrochloride 3.90 mg (0.02
(0 mmol) dissolved in 0.203 ml of chloroform (dehydrated) was added, and the mixture was stirred at room temperature for 6 hours, dissolved in dichloromethane, washed with a saturated aqueous solution of sodium hydrogen carbonate, and the organic layer was dried over anhydrous magnesium sulfate. After removing magnesium sulfate by filtration, the solvent was distilled off.

[Chemical formula 24] (V) A Taegus knot structure polymer represented by the following structural formula (IX) was obtained.

[Chemical 25] (IX)

[0012]

EFFECTS OF THE INVENTION The novel polymer with Teguth knot structure obtained by the present invention is
It is a structure in which a secondary ammonium salt enters each other in crown ether, and the cyclic molecule and rod-shaped molecule have a structure similar to the Tegu's found in the Tegu's tie method of a rope. The polymer that is physically connected has a unique property because the property due to the structure of the monomer is reflected. By utilizing this characteristic, it can be effectively used in the field of organic polymer materials as a low temperature elastomer, a highly elastic rubber material, or the like.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J001 DA01 DC05 DC14 DC22 EB09                       EB72 EC43 EC83 GA13                 4J005 AA21 BA00                 4J029 AA01 AB01 AB04 AE18 BH01                       CH01 DA06                 4J034 CA15 CB03 CC05 CC08 CC12                       CC22 CC62 CD04 DA03 DC02                       DC06 HA07 HC03 QB15

Claims (2)

[Claims] 1. The following general formula (I): (In the formula, A is a group which plays a role of linking, G represents a bonding group, and X represents an arbitrary anion atom.
The G has a structure smaller than the inner diameter of dibenzo-24-crown-8-ether, and has a size capable of passing through the crown ether ring. n is 2
It is an integer above the above. ) Is represented by a Teguth structure polymer. 2. A Teguth knot structure represented by the following general formula (I), characterized in that the Teguth knot structure represented by the following general formula (II) is polymerized directly or by using an arbitrary linking group. Manufacturing method. [Chemical formula 2] (II) (In the formula, R represents a reactive substituent and X represents an arbitrary anion atom. Here, R represents dibenzo-24-.
The structure is smaller than the inner diameter of crown-8-ether, and the structure is such that it can pass through the crown ether ring. ) [Chemical Formula 3] (I) (In the formula, A is a group which plays a role of linking, G represents a bonding group, and X represents an arbitrary anion atom.
The G has a structure smaller than the inner diameter of dibenzo-24-crown-8-ether, and has a size capable of passing through the crown ether ring. n is 2
Represents the above integers. )