JP2000290365A - Polyketone and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polyketone which has a 1,3-diketone structure and can be used as an electrical or optical device material. SOLUTION: This polyketone comprises structural units represented by formula I and is produced by reacting X1-CO-R1-CO-X2 with a compound represented by formula II. In the formulas, R1 is an aliphatic, alicyclic or aromatic 1-50C hydrocarbon group optionally having a substituent optionally containing a heteroatom and/or a metal element; R2 and R3 are each H or a 1-12C aliphatic, alicyclic or aromatic hydrocarbon group optionally having a substituent optionally containing a heteroatom and/or a metal element; X1 and X2 are each halogen; M1 and M2 are each a divalent metal element; and Y1 and Y2 are each halogen. A polymer comprising one kind of structural units represented by formula I or a copolymer comprising two or more kinds of structural units represented by formula I is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyketone and a method for producing the same. More specifically, the present invention relates to a polyketone having a specific structure, particularly a polyketone having a 1,3 diketone structure, and a method for producing a polyketone, which comprises reacting a biscarboxylic acid halide with a specific halogen metal compound.

[0002]

BACKGROUND ART As polyketones, aromatic polyketones such as polyetheretherketone and polyetherketone, and aliphatic polyketones which are copolymers of olefins such as ethylene and propylene with carbon monoxide have been known. Was. These polyketones have excellent mechanical strength and heat resistance, and have been put to practical use as engineering plastics. However, the structures of these polyketones are limited to some extent, and for example, a polymer in which an aliphatic skeleton and an aromatic skeleton are mixed has not been obtained.

In addition to such polyketones, polycondensation-based aliphatic polymers such as polyesters and polyamides generally include groups formed by polycondensation (for example, ketone groups, ester groups and amide groups). The shorter the methylene number, the higher the rigidity and the higher the heat resistance.

[0004] However, polymers having one carbon atom between groups formed by polycondensation are not well known,
Nothing was known about polyketones. further,
The 1,3 diketone structure is known to cause keto-enol isomerization. If a polymer having this structure is present, there is a possibility that special functions such as electric characteristics and optical characteristics may be exhibited. A polymer having a 1,3 diketone structure in the main chain has not been known until now.

For this reason, there is a strong demand for the development of polyketones in which an aliphatic skeleton and an aromatic skeleton coexist, polyketones having 1 carbon atom between ketone groups, and polyketones having a 1,3 diketone structure in the main chain. Was rare.

Conventionally, methods for synthesizing polyketones include a method for synthesizing an aliphatic polyketone by reacting a vinyl monomer with carbon monoxide, a method for synthesizing an aromatic polyketone by a desalting polycondensation reaction, and a method for Friedel-Crafts. A method of synthesizing an aromatic polyketone by a known method has been known, but in each case, the molecular structure of the obtained polyketone is limited.

On the other hand, the present inventors have previously found that bis (iodinethio) methane is reacted with a carboxylic acid halide to synthesize a ketone (Angew. C).
hem. Int. Ed. Engl., 36, 24 (1997)).

In such a situation, the present inventors have conducted intensive studies and as a result, have found a method of synthesizing a polyketone having an arbitrary structure by applying such a ketone synthesis reaction to a polymer synthesis reaction. Thus, the present inventors have found that the above-mentioned polyketones can be obtained, and have completed the present invention.

[0009]

An object of the present invention is to provide a polyketone having a specific structure, particularly a polyketone having a 1,3-diketone structure, and a method for producing the same.

[0010]

SUMMARY OF THE INVENTION The polyketone of the present invention is characterized by having a structural unit (I) represented by the following formula:

[0011]

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(Wherein R ¹ is at least one kind of carbon atom selected from the group consisting of aliphatic, alicyclic and aromatic)
A group formed from ~ 50 hydrocarbon groups, which may have a substituent, the substituent may contain a hetero element and / or a metal element, and R ² and R ³ are Each independently, is a hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms selected from the group consisting of aliphatic, alicyclic and aromatic, and the hydrocarbon group may have a substituent, The substituent may contain a hetero element and / or a metal element).

[0013] The method for producing a polyketone of the present invention comprises:
In producing the above-mentioned polyketone, a compound represented by the following formula (II) is reacted with a compound represented by the following formula (III): X ¹ -CO-R ¹ -CO- X ² ... (II) (wherein, R ¹ is a group formed from at least one hydrocarbon group having 1 to 50 carbon atoms selected from the group consisting of aliphatic, alicyclic, and aromatic; , May have a substituent, and the substituent may contain a hetero element and / or a metal element, and X ¹ and X ² are each independently a halogen element.)

[0014]

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(Wherein R ² and R ³ are each independently a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom selected from the group consisting of aliphatic, alicyclic, and aromatic; The hydrocarbon group may have a substituent, the substituent may contain a hetero element and / or a metal element, and M ¹ and M ² are each independently a divalent metal element, Y ¹ and Y ² are each independently a halogen element).

[0016]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described specifically. Polyketone The polyketone of the present invention has a structural unit (I) represented by the following formula.

[0017]

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In the structural unit (I) represented by the above formula, R ¹ is formed from at least one hydrocarbon group having 1 to 50 carbon atoms selected from the group consisting of aliphatic, alicyclic and aromatic. And may have a substituent, and the substituent may contain a hetero element and / or a metal element.

Here, the substituent containing a hetero element is a substituent containing a hetero element such as halogen, oxygen, sulfur, nitrogen, etc., for example, a halogen such as fluorine, chlorine, bromine or iodine; Oxygen-containing groups such as acid groups, ester groups and ketone groups; sulfur or nitrogen-containing groups such as amino groups, amide groups and sulfonic acid groups; and heteroaromatic groups. Examples of the substituent containing a metal element include substituents containing a metal element such as a group containing a carboxylate metal base, a sulfonic acid metal base, and a metal complex.

Specifically, the group forming R ¹ includes:
Methylene group, methylmethylene group, ethylene group; trimethylene group, methylethylene group, ethylmethylene group. A C3 aliphatic hydrocarbon group such as a dimethylmethylene group, a C3 aliphatic hydrocarbon group, a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, an ethylethylene group; a pentamethylene An aliphatic hydrocarbon group having 5 carbon atoms such as a group, 1-methyltetramethylene group or 2,2-dimethyltrimethylene group; an aliphatic hydrocarbon group having 6 carbon atoms such as a hexamethylene group; An aliphatic hydrocarbon group of the formula 8; other linear or branched saturated or unsaturated aliphatic hydrocarbon groups having 2 to 50 carbon atoms; phenylmethylene group, diphenylmethylene group, 1-phenyl-1,2-ethylene group Aliphatic hydrocarbon groups having an aromatic substituent such as cyclopropylene group, 1,3-cyclobutylene group, 1,3-cyclopentyl group, 1,4-cyclohexyl And other saturated or unsaturated alicyclic hydrocarbon groups having 3 to 50 carbon atoms; an aliphatic hydrocarbon group having a substituent containing oxygen such as a hydroxymethylmethylene group or a 2-hydroxytrimethylene group; aminomethylmethylene An aliphatic hydrocarbon group having a substituent containing a hetero element such as a 2-amino-trimethylene group; 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group,
2,6-naphthylene group, 2,7-naphthylene group, 1,3
-Naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 2-methyl-1,3
-Phenylene group, 4-methyl-1,3-phenylene group,
5-methyl-1,3-phenylene group, 2-methyl-1,
4-phenylene group, 2,6-dimethyl-1,4-phenylene group, 2,5-dimethyl-1,4-phenylene group,
2,6-di-t-butyl-1,4-phenylene group, 5-
An aromatic hydrocarbon group such as a phenyl-1,3-phenylene group; an aromatic hydrocarbon group having an oxygen-containing substituent such as a 5-hydroxy-1,3-phenylene group; 5-amino-
Aromatic hydrocarbon group having a substituent containing a hetero element such as 1,3-phenylene group, 5-sulfonic acid-1,3-phenylene group; sodium 5-carboxylate-1,3-phenylene group, 5-sulfone Hydrocarbon group having a substituent containing a metal element such as sodium 1,3-phenylene group; heteroaromatic group such as 2,6-pyridinediyl group; and metal such as 1,1'-ferrosenylene group A complex group;

In the structural unit (I) represented by the above formula, R ¹ may be formed from only one kind of such groups, or may be formed from two or more kinds of such groups. Good. In the structural unit (I) represented by the above formula, R
¹ is, among such groups, a 1,4-phenylene group, a 1,3-phenylene group, a 2,6-naphthylene group, a methylene group, a methylmethylene group, an ethylene group, a trimethylene group, a methylethylene group, It is preferably a dimethylmethylene group, a tetramethylene group, a hexamethylene group, an octamethylene group, a 1,4-cyclohexyl group or a group having these groups.

In the structural unit (I) represented by the above formula, R ² and R ³ each independently represent a C 1 -C 1 group selected from the group consisting of aliphatic, alicyclic and aromatic.
2 hydrocarbon groups or hydrogen atoms, preferably
A hydrocarbon group or a hydrogen atom having 1 to 8 carbon atoms, and the hydrocarbon group may have a substituent, and the substituent may be a hetero element such as halogen, oxygen, sulfur, or nitrogen and / or a metal element; It may be contained.

Specifically, R ² and R ³ each independently represent a hydrogen atom; a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, an isobutyl group, a t-
Butyl group, other having 2 to 12 carbon atoms, preferably 2 carbon atoms
To 8 linear or branched saturated or unsaturated aliphatic hydrocarbon groups; cyclopropyl group, cyclobutyl group, cyclohexyl group, other having 3 to 12 carbon atoms, preferably 2 to 2 carbon atoms
8, a saturated or unsaturated alicyclic hydrocarbon group; an aliphatic hydrocarbon group having a substituent containing oxygen, such as a hydroxymethyl group, a 2-hydroxy 1-ethyl group, or a 3-hydroxy 1-propyl group; Methyl group, 2-amino-1-ethyl group,
Aliphatic hydrocarbon groups having a substituent containing a hetero element, such as 3-amino-1-propyl group, N, N-dimethylaminomethyl group; phenyl group, toluyl group, xylyl group, naphthyl group, biphenyl group, etc. Aromatic hydrocarbon group; aromatic hydrocarbon group having a substituent containing oxygen such as hydroxyphenyl group and phenyl carboxylate; aromatic having a substituent containing a hetero element such as aminophenyl group and phenyl sulfonate group Aromatic hydrocarbon groups having a substituent containing a metal element such as a sodium carboxylate-phenyl group and sodium phenyl sulfonate group; and a heteroaromatic group such as a pyridinyl group; .

Of these, R ² and R ³ are preferably each independently a hydrogen atom, a methyl group, an ethyl group or a phenyl group, and particularly preferably
Desirably, both ² and R ³ are hydrogen atoms, one of R ² and R ³ is a hydrogen atom and the other is a methyl group, or both R ² and R ³ are a methyl group.

The polyketone of the present invention has such R ¹ ,
It has a structural unit (I) represented by the above formula having R ² and R ³ . That is, the polyketone of the present invention may be a polymer composed of a single structural unit represented by the above formula (I), or a copolymer composed of two or more types of structural units represented by the above formula (I) Or a copolymer comprising the structural unit (I) represented by the above formula and another structural unit. The polyketone of the present invention is a polymer composed of a single structural unit represented by the above formula (I) or a copolymer composed of two or more structural units represented by the above formula (I). Is preferred.

Further, the polyketone of the present invention has the above formula (I)
In the case of a copolymer consisting of two or more types of structural units represented by, or a copolymer consisting of the structural unit (I) represented by the above formula and another structural unit, the polyketone is
A random copolymer having a structure in which each structural unit is randomly arranged may be a block copolymer having a structure in which a single polymer of each structural unit is arranged, but is a random copolymer. Is more preferred.

Particularly preferred examples of such a polyketone include those of the above formula wherein R ¹ has a 1,4-phenylene group and / or a 1,3-phenylene group, and R ² and R ³ are both hydrogen atoms. And a polyketone having a structural unit (I) represented by At this time, hydrogen of the 1,4-phenylene group and / or 1,3-phenylene group constituting R ¹ may be substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms. . Further, a polyketone having the structural unit (I) represented by the above formula wherein R ¹ is a methylene group and R ² and R ³ are both hydrogen atoms, and the like are also included.

The structural units constituting such polyketones include, for example, those shown below. Examples of the polyketone of the present invention include polyketones having the following structural units. Polyketones in which the following structural units independently form a polymer, and two or more of the following structural units are optional. Preferable examples include polyketones in which a random copolymer or a block copolymer is formed in a composition ratio.

[0029]

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In the present invention, among such structural units forming a polyketone, the above formulas a1 and a1 are particularly preferable.
The structural unit represented by 3, b1, b3, c1, d1, and d3 can be mentioned.

Further, such a polyketone may have a multi-branched structure as long as the desired properties are not impaired. The structure of the polyketone of the present invention can be confirmed by a known method. For example, the structure can be confirmed by measuring an infrared absorption spectrum.

When the infrared absorption spectrum is measured, for example, when carboxylic acid chloride is used as a substrate, the absorption of carbonyl is observed at around 1800 cm ^-1. When a measurement was made on a polyketone which formed a polymer in the above, an extremely strong absorption indicating a carbonyl of the ketone was observed at about 1690 cm ^-1 . Further, in the case of measuring a polyketone in which the structural unit represented by the formula a1 alone forms a polymer, ketone-enol isomerization occurs, so that broad strong absorption having a peak at about 1600 cm ⁻¹ of enol is obtained. A large sharp peak around 1720 cm ^{-1 of} ketone is observed.

Since the polyketone of the present invention exhibits a specific infrared absorption as described above, it can be easily confirmed by measuring an infrared absorption spectrum. In particular, in the case where the polyketone of the present invention is a polyketone in which the structural unit represented by the above-mentioned formula a1 alone forms a polymer, it is difficult to dissolve in a solvent, and thus the structure confirmation by this method is effective.

The polyketone of the present invention may optionally contain various compounding agents such as a crosslinking agent, a heat stabilizer, a weather stabilizer, a lubricant, a nucleating agent, a release agent, an inorganic filler, a pigment dispersant, a pigment or a dye. Can be used.

Such a polyketone can be appropriately molded and used. Molding can be performed by a conventionally known method, for example, melt molding such as injection molding, compression molding, calendar molding, extrusion molding, blow molding, or molding using a solvent such as cast molding may be performed. You may.

Since the polyketone of the present invention has the above-mentioned structure, it is particularly excellent in heat resistance. In addition, the polyketone of the present invention can be used for a wide range of applications from household products to industrial products in which conventional polymers have been used, such as food containers, electrical components, electronic components, automobile components, mechanical components, films, sheets, and fibers. In particular, polyketone having a 1,3-diketone structure that causes keto-enol isomerization can be used as an electrical or optical device material.

Process for Producing Polyketone The polyketone of the present invention can be produced by reacting a compound represented by the following formula (II) with a compound represented by the following formula (III). X ¹ -CO-R ¹ -CO-X ² (II)

[0038]

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In the above formula (II), R ¹ is an aliphatic,
A group formed from at least one kind of hydrocarbon group having 1 to 50 carbon atoms selected from the group consisting of alicyclic and aromatic, which may have a substituent, wherein the substituent is a hetero element and And / or may contain a metal element. R ¹ in the above formula (II) is the same as in the above formulas (I) and (I
It is the same as R ¹ in I).

In the above formula (II), X ¹ and X ² are each independently a halogen element. The halogen element constituting X ¹ and X ² is preferably selected from chlorine, bromine and iodine, and is particularly preferably chlorine. X ¹ and X ² may be the same or different halogen elements, but it is particularly preferable that both X ¹ and X ² are chlorine.

Examples of the compound represented by the above formula (II) include, for example, terephthalic acid chloride, isophthalic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, malonic acid chloride, methylmalonic acid chloride, fumaric acid chloride, Maleic chloride, glutaric chloride, 1-methylsuccinic chloride, dimethylmalonic chloride, adipic chloride, sebacic chloride, suberic chloride, 1,4-
And cyclohexanedicarboxylic acid chloride.

The compound represented by the above formula (II) may be used alone, or may be used by mixing several kinds. Further, the compound represented by the above formula (II) may contain a polyvalent carboxylic acid halide such as trimellitic acid trichloride and pyromellitic acid tetrachloride as long as the object of the present invention is not impaired.

In the above formula (III), R ² and R
³ is each independently a hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms selected from the group consisting of aliphatic, alicyclic and aromatic, and the hydrocarbon group has a substituent. And the substituent may contain a hetero element and / or a metal element. R ² in the above formula (III)
And R ^3, R ² in the above formula (I) and (II)
And R ³ .

In the above formula (III), M ¹ and M ² are each independently a divalent metal element. This M ¹
And M ² may be either a divalent typical metal element or a divalent transition metal element, but is preferably zinc or magnesium, and particularly preferably zinc. M ¹ and M ² may be the same divalent metal element or may be different, but it is particularly preferable that both M ¹ and M ² are zinc.

Further, in the above formula (III), Y ¹ and Y ² are each independently a halogen element. The halogen element constituting Y ¹ and Y ² is preferably selected from chlorine, bromine and iodine, and is particularly preferably iodine. Y ¹ and Y ² may be the same or different halogen elements, but it is particularly preferable that both Y ¹ and Y ² are iodine.

Examples of the compound represented by the above formula (III) include bis (iodozinthio) methane-1, 1-bis (iodozinthio) ethane, 2,2-bis (iodozinthio) propane and the like. .

The compound represented by the above formula (III) is described, for example, in A. Tetrahedron Lett, 24, 2043 (1
983), J. Org. Chem, 59, 2668 (1994), Angrw. Chem. Int.
Ed. Engl., 24, 36 (1997) and SYNLETT, p1369-1371.
(1998), and can be obtained, for example, by reacting zinc with a dihalogenated hydrocarbon such as diiodo hydrocarbon in a solvent such as THF.

The compound represented by the above formula (III) may be used alone, or may be used as a mixture of several kinds. Further, the compound represented by the formula (III) may include trimellitic acid trichloride, as long as the object of the present invention is not impaired.
It may contain a polyvalent carboxylic acid halide such as pyromellitic acid tetrachloride.

In the present invention, by reacting such compounds represented by the above formulas (II) and (III),
A polyketone as described above can be produced. The reaction of the compounds represented by the above formulas (II) and (III) can be carried out in a solution. For example, a compound represented by the above formula (III) such as bis (diiodinethio) methane can be reacted with tetrahydrofuran (hereinafter THF). A solution of the compound represented by the above formula (II) such as terephthalic acid dichloride in a solvent such as THF or THT is added dropwise to a solution dissolved in a solvent such as tetrahydrothiophene (hereinafter also referred to as THT). Obtained by stirring.

In such a reaction, the compound represented by the above formula (II) may be used as a solution, and the concentration of the solution is not particularly limited, but is usually 0.1 mol / L or more, preferably 0 mol / L or more. 0.2 mol / liter or more. Further, the compound represented by the above formula (III) may be used as a solution, and the concentration of the solution is not particularly limited, but is usually 0.1 mol / L or more, preferably 0.2 mol / L or more. It is desirable that

In such a reaction, 1 mol of the compound represented by the above formula (II) is added to 1 mol of the compound represented by the above formula (III).
It is desirable that the compound represented by the formula (I) is used usually in an amount of about 0.5 to 3 mol, preferably about 0.8 to 2.5 mol.

Further, the solvent used in the reaction is appropriately selected depending on the reaction substrate. Terephthalic acid dichloride is used as the compound represented by the above formula (II), and bis (diiodinethiol is used as the compound represented by the above formula (III). ) When methane is used, THT or the like is preferably used.

Such a reaction can be carried out without a catalyst or with a catalyst. As the catalyst used here,
Tris (2-furanyl) phosphine, tris [3,5-
Phosphorus compounds such as bis (trifluoromethyl) phenyl] phosphine; and metal complexes such as dibenzylideneacetone palladium.

The reaction is preferably carried out with stirring, the reaction temperature is usually 50 ° C. or lower, preferably 10 ° C. or lower, and the reaction time is usually 5 minutes to 5 minutes.
It is desirably 5 hours, preferably about 20 minutes to 3 hours. The above reaction can be confirmed by the formation of a solid in the solution, an increase in the solution viscosity, and the like.

After stirring for a predetermined time to react the compounds represented by the above formulas (II) and (III), these reaction products are treated with an acid. As the acid used for the acid treatment, an inorganic acid such as hydrochloric acid or sulfuric acid is preferably used, and hydrochloric acid is particularly preferable. Further, the temperature of the acid treatment is preferably 10 ° C. or less.

In this manner, the polyketone of the present invention can be synthesized. However, after such a reaction, it is preferable to purify by removing impurities, reaction residues and unreacted substances. The removal of impurities and the like can be performed by any method, for example, the following method.

An organic solvent such as ether is added to the mixture containing the reaction product obtained by the above-mentioned acid treatment, and the mixture is stirred and allowed to stand. The aqueous layer is removed, a base such as an aqueous sodium hydroxide solution is further added, and the mixture is stirred. Thereafter, the organic layer is removed from the obtained aqueous layer, organic layer, and solid layer. Subsequently, after adding an acid such as concentrated hydrochloric acid to make the mixture acidic, the aqueous layer is removed, the remaining organic layer and the solid layer are filtered, and the impurities and the like are removed by washing with water and alcohol. be able to. The temperature at which these purifications are carried out is arbitrary, but preferably at room temperature.

The polyketone thus obtained is particularly excellent in heat resistance, for example, food containers, electric parts, electronic parts, automobile parts, mechanical mechanism parts, films, sheets,
It can be effectively used as various materials such as fibers.
When the polyketone has a 1,3-diketone structure in particular, it can be used as an electrical or optical device material.

[0059]

The polyketone of the present invention is particularly excellent in heat resistance. According to the production method of the present invention, under mild conditions,
A polyketone having any structure can be efficiently produced.

[0060]

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

[0061]

Example 1 0.1 mol of diiodomethane was dissolved in tetrahydrofuran (THF), 0.3 mol of zinc (containing 5 mol% of lead) was added thereto, and the mixture was reacted at 25 ° C. for 1 hour. Bis (iodinethio) methane was obtained.

50 ml of tetrahydrothiophene (THT) was added to 25 ml of a THF solution (0.4 mol / L) of bis (iodinethio) methane obtained at room temperature. The mixture was concentrated under reduced pressure at room temperature, and the concentration was stopped when the total amount became about 40 ml. At this point, the THF had been almost distilled off. This was cooled in an ice bath, and 5 mL of a THT solution (1 mol / L) of terephthalic acid dichloride was added dropwise. The reaction solution turned clear yellow.

Subsequently, the ice bath was removed, and the mixture was stirred at room temperature. After about 10 minutes, the formation of a yellow solid starts,
After stirring for about 1 hour, the reaction mixture was mixed with 10 g of ice and 3M
It was taken up in a mixture with 30 ml of hydrochloric acid. After 50 mL of ether was added to the mixture, the mixture was introduced into a separating funnel, shaken, and allowed to stand. Then, the mixture was separated into an aqueous layer, an organic layer, and a solid layer. After removing the aqueous layer, 50 mL of a 5 M aqueous sodium hydroxide solution was added. Shake it again and let it rest,
An aqueous layer, an organic layer, and a solid layer were separated. After removing the organic layer, the mixture was acidified with concentrated hydrochloric acid, and the aqueous layer was removed. By filtering the remaining solid layer and organic layer with a glass filter,
A solid product was obtained. This solid was washed with water, further with methanol, and dried at room temperature under reduced pressure. The obtained solid product was yellow and the yield was 860 mg.

The obtained solid product was subjected to infrared absorption spectrum (I) using an infrared absorption spectrophotometer manufactured by JASCO Corporation.
R) was measured. The results are shown in FIG. As a result, the absorption of carbonyl of terephthalic acid dichloride as the reaction substrate almost disappeared, and a large broad absorption was observed around 1600 cm ^-1 and a large absorption was also observed around 1720 cm ^-1 . This absorption was considered to be due to the enol absorption of the former and the ketone absorption to the latter, confirming that a keto-enol type structure was formed.

The obtained solid product was measured by a differential scanning calorimeter (DSC) at a heating rate of 10 ° C., but no particular peak was observed up to 300 ° C. In addition, at the same time, the hot stage was set at 1 ° C / min.
Was observed under heating, but was not melted up to 300 ° C.

Further, the obtained substance was chloroform,
It was insoluble in all of ethanol, THF, benzene, and acetone. Also, no dissolution in hot o-chlorophenol was observed.

As described above, it was found that the obtained substance was infusible at a high temperature of 300 ° C. and insoluble in the above-mentioned solvent, but had a keto-enol structure in the molecule. From these results, the obtained solid product was obtained from the reaction substrate
It was presumed to be a polyketone comprising a structural unit represented by the following formula A1.

[0068]

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[0069]

Example 2 A THF solution of bis (iodinethio) methane obtained in the same manner as in Example 1 (0.4 mol / L)
To 25 ml was added 50 ml of THT at room temperature. The mixture was concentrated under reduced pressure at room temperature, and the concentration was stopped when the total amount became about 40 ml. At this point, the THF had been almost distilled off. This was cooled in an ice bath, and 5 ml of a THT solution (1 mol / l) of isophthalic acid dichloride was dropped, and the reaction solution became transparent yellow.

Subsequently, the ice bath was removed, and the mixture was stirred at room temperature. The formation of a yellow-white solid started after about 60 minutes, and after stirring for about 1 hour, the reaction mixture was poured into a mixture of 10 g of ice and 30 ml of 3M hydrochloric acid. After adding 50 ml of ether to the mixture, the mixture was introduced into a separating funnel, shaken, and allowed to stand to separate into an aqueous layer, an organic layer and a solid layer. After removing the aqueous layer, 50 ml of a 5 M aqueous sodium hydroxide solution was added. When shaken again and allowed to stand, the mixture was separated into an aqueous layer, an organic layer and a solid layer. After removing the organic layer, the mixture was acidified with concentrated hydrochloric acid, and the aqueous layer was removed. A solid product was obtained by filtering the remaining solid layer and organic layer with a glass filter. Wash this solid with water,
It was further washed with methanol and dried under reduced pressure at room temperature. The obtained solid product was yellow-white, and the yield was 360 mg.

The infrared absorption spectrum of the obtained solid product was measured in the same manner as in Example 1. The results are shown in FIG. As a result, as in Example 1, 1600c
Large broad absorption is seen around m ^-1 and 172
Large absorption was also observed around 0 cm ^-1 .

Further, with respect to the obtained solid product,
A differential scanning calorimeter (DSC) measurement was performed in the same manner as in Example 1. As a result, it had a glass transition point at 145 ° C. and an endothermic peak near 270 ° C. Furthermore, melting was observed around this temperature by observation using a hot stage.

Further, the obtained solid product was insoluble in any of chloroform, ethanol, THF, benzene and acetone, but dissolved in hot o-chlorophenol. The solution was cooled to 25 ° C., and the intrinsic viscosity [η] was measured to be 0.1 (dl / g).

From these results, it was estimated that the obtained solid product was a polyketone composed of the structural unit represented by the following formula B1 from the reaction substrate.

[0075]

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[Brief description of the drawings]

FIG. 1 shows the solid product I obtained in Example 1.
The R measurement results are shown.

FIG. 2 shows the solid product I obtained in Example 2.
The R measurement results are shown.

Claims (11)

[Claims] 1. A polyketone having a structural unit (I) represented by the following formula: (Wherein, R ¹ is a group formed from at least one hydrocarbon group having 1 to 50 carbon atoms selected from the group consisting of aliphatic, alicyclic, and aromatic, and has a substituent. And the substituent may contain a hetero element and / or a metal element. R ² and R ³ each independently represent a carbon selected from the group consisting of aliphatic, alicyclic and aromatic A hydrocarbon group or a hydrogen atom of Formulas 1 to 12, which may have a substituent, and the substituent may contain a hetero element and / or a metal element). 2. The polyketone according to claim 1, comprising only the structural unit (I) represented by the above formula. 3. The polyketone according to claim 1, comprising a structural unit (I) represented by the above formula and another structural unit. 4. In the structural unit (I) represented by the above formula, R ¹ is 1,4-phenylene group, 1,3-phenylene group, 2,6-naphthylene group, methylene group, methylmethylene group, ethylene And at least one hydrocarbon group selected from the group consisting of a group, a trimethylene group, a methylethylene group, a dimethylmethylene group, a tetramethylene group, a hexamethylene group, an octamethylene group, and a 1,4-cyclohexyl group. The polyketone according to any one of claims 1 to 3. 5. In the structural unit (I) represented by the above formula, R ² and R ³ are each independently at least one kind of carbon selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group and a phenyl group. The polyketone according to any one of claims 1 to 4, which has a hydrogen group. 6. In the structural unit (I) represented by the above formula, R ¹ is a 1,4-phenylene group and / or 1,3
- having a phenylene group, polyketone according to any one of claims 1 to 3 R ² and R ³ are both hydrogen atoms. 7. The polyketone according to claim 1, wherein in the structural unit (I) represented by the above formula, R ¹ is a methylene group, and R ² and R ³ are both hydrogen atoms. 8. A method for producing the polyketone according to claim 1, wherein a compound represented by the following formula (II) is reacted with a compound represented by the following formula (III): X ¹ —CO—R ¹ —CO—X ² (II) (wherein, R ¹ is at least one kind of carbon having 1 to 1 carbon atoms selected from the group consisting of aliphatic, alicyclic and aromatic). a group formed from a hydrocarbon group of 50 may have a substituent, substituents may contain a hetero element and / or metal elements, X ¹ and X ² are each (Independently a halogen element.) (Wherein, R ² and R ³ each independently represent a C 1 -C 1 group selected from the group consisting of aliphatic, alicyclic, and aromatic)
A hydrocarbon group or a hydrogen atom, wherein the hydrocarbon group may have a substituent, and the substituent may contain a hetero element and / or a metal element; M ¹ and M ² Are each independently a divalent metal element, and Y ¹ and Y ² are each independently a halogen element. 9. The method for producing a polyketone according to claim 8, wherein in the formula (II), X ¹ and X ² are chlorine. 10. In the above formula (III), M ¹ and M
^The method for producing a polyketone according to claim 8 or 9, wherein ² is zinc. 11. In the above formula (III), Y ¹ and Y
^The method for producing a polyketone according to any one of claims 8 to 10, wherein ² is iodine.