JP4234623B2 - Aromatic polyketone and aromatic polyketone precursor having 1,1'-binaphthyl-6,6'-ylene skeleton, and method for producing them - Google Patents

Description

  The present invention relates to an aromatic polyketone having an 1,1'-binaphthyl-6,6'-ylene skeleton, an aromatic polyketone precursor, and a method for producing them.

  Conventionally, a polymer having a 2,2′-disubstituted-1,1′-binaphthylene skeleton has extended molecular chains mainly at the 2,2′-position and 4,4′-position close to the axial asymmetric center. It was limited to things. Non-Patent Document 1 discloses a method for synthesizing an aromatic polycarbonate having a chiral 1,1′-binaphthyl-2,2′-ylene skeleton in the main chain, and the resulting aromatic polycarbonate is disclosed. -Bonate is said to have a helical structure. On the other hand, Non-Patent Document 2 discloses chiral poly (2,2) -dihydroxy-2,2′-dimethoxy-1,1′-binaphthyl and 2,3-dihydroxynaphthalene by asymmetric oxidative coupling polymerization. 3-dihydro-1,4-binaphthalene) is described. In Non-Patent Document 1, the molecular chain is extended at the 2,2'-position, and in Non-Patent Document 2, the molecular chain is extended at the 4,4'-position.

  On the other hand, as a polymer extended in the molecular chain at the 6,6′-position, which is a position away from the axial asymmetric center, chiral 6,6′-dibromo-2,2′-bis (methoxymethyl) Non-patent document 3 reports the synthesis of optically active poly (1,1′-bi-2-naphthol) derivatives by aromatic coupling polymerization of -1,1′-binaphthyl in the presence of nickel chloride and zinc. Yes.

Further, in a carbon monoxide atmosphere, chiral 6,6′-dibromo-2,2′-dimethoxy-1,1′-binaphthyl-6,6′-dibromo-2,2′-diethoxy-1,1′- It is reported in Non-Patent Documents 4 and 5 that a fully aromatic polyamide can be produced by reacting binaphthyl and an aromatic diamine in the presence of a palladium catalyst.
Journal of the American Chemical Society, Vol. 120, No. 18, 4530 Macromolecules, Vol. 35, No. 7, 2437 and Vol. 36, No. 8, 2604 Journal of Organic Chemistry, Vol. 61, No. 16, p. 5200 Polymer Journal, Vol. 30, No. 2, p. 161 Polymer 43:17 4829

  However, an aromatic ketone having a molecular chain extended at the 6,6′-position of the 2,2′-disubstituted-1,1′-binaphthylene skeleton and a method for producing the same are not known.

  Therefore, an object of the present invention is to provide an aromatic polyketone having a molecular chain extended at the 6,6′-position of a 2,2′-disubstituted-1,1′-binaphthylene skeleton and a method for producing the same. Another object of the present invention is to provide a precursor of the above aromatic polyketone and a method for producing the same.

  “Aromatic polyketone having a molecular chain extended at the 6,6′-position of a 2,2′-disubstituted-1,1′-binaphthylene skeleton” provided by the present invention, that is, “1,1′-binaphthyl-6,6 ′” The “aromatic polyketone having an ylene skeleton” is an aromatic polyketone represented by the following general formulas (1), (2) and (3). Hereinafter, the aromatic polyketones represented by the general formulas (1), (2) and (3) are abbreviated as “aromatic polyketone 1”, “aromatic polyketone 2” and “aromatic polyketone 3”, respectively. There is.

［式中、Ｒ^１及びＲ^２はそれぞれ独立にアルコキシ基、アルキル基又はアロイルフェノキシ基を示し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＲ^２５はそれぞれ独立に、水素原子又はアルキル基を示し、Ｒ^３１及びＲ^４１はそれぞれ独立に水素原子、アルキル基又はアリール基を示す。但し、Ｒ^３１又はＲ^４１を有するベンゼン環に結合した単結合の置換位置は、カルボニル基に対して３位又は４位である。また、複数存在するＲ^３１及びＲ^４１のそれぞれは同一でも異なっていてもよい。］ Aromatic polyketone 1:
Poly [(1,1′-binaphthyl-6,6′-ylene) arylene dicarbonyl] comprising a repeating unit represented by the following general formula (1).

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or an alkyl group, and R ³¹ and R ⁴¹ each independently represent a hydrogen atom, an alkyl group or an aryl group. However, the substitution position of the single bond bonded to the benzene ring having R ³¹ or R ⁴¹ is the 3rd or 4th position with respect to the carbonyl group. A plurality of R ³¹ and R ⁴¹ may be the same or different. ]

［式中、Ｒ^１及びＲ^２はそれぞれ独立にアルコキシ基、アルキル基又はアロイルフェノキシ基を示し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^３２及びＲ^４２はそれぞれ独立に、水素原子又はアルキル基を示す。但し、複数存在するＲ^３２及びＲ^４２のそれぞれは同一でも異なっていてもよい。なお、Ｚ^１は、以下のいずれかの２価基であり、

２価基中のＺ^１１は−ＣＨ_２−、−ＣＨ（ＣＨ_３）_２−又は−Ｏ−を示し、ｎは０、１又は２を示す。］ Aromatic polyketone 2:
Poly [(1,1′-binaphthyl-6,6′-ylene) carbonyl (1,4-phenylene) (arylene dioxy) (1,4-) having a repeating unit represented by the following general formula (2) Phenylene) carbonyl].

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³² and R ⁴² each independently represent a hydrogen atom or an alkyl group. However, each of a plurality of R ³² and R ⁴² may be the same or different. Z ¹ is any of the following divalent groups:

Z ¹¹ in the divalent group represents —CH ₂ —, —CH (CH ₃ ) ₂ — or —O—, and n represents 0, 1 or 2. ]

［式中、Ｒ^１及びＲ^２はそれぞれ独立にアルコキシ基、アルキル基又はアロイルフェノキシ基を示し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＲ^２５はそれぞれ独立に、水素原子又はアルキル基を示す。なお、Ｚ^２は以下のいずれかの２価基であり、

２価基中のＺ^２１は−ＣＨ_２−、−ＣＨ（ＣＨ_３）_２−又は−Ｏ−を示す。］ Aromatic polyketone 3:
Poly [(1,1′-binaphthyl-6,6′-ylene) (arylene carbonyl)] represented by the following general formula (3).

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or an alkyl group. Z ² is any of the following divalent groups:

Z ²¹ in the divalent group represents —CH ₂ —, —CH (CH ₃ ) ₂ — or —O—. ]

［式中、Ｒ^１及びＲ^２はそれぞれ独立にアルコキシ基、アルキル基又はアロイルフェノキシ基を示し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＲ^２５はそれぞれ独立に、水素原子又はアルキル基を示し、Ｒ^３１及びＲ^４１はそれぞれ独立に水素原子、アルキル基又はアリール基を示し、Ｘ^１はフッ素原子、塩素原子、臭素原子、ヨウ素原子、メチル基、メトキシ基又はトリフルオロメチル基を示す。但し、Ｒ^３１又はＲ^４１を有するベンゼン環に結合したＸ^１の置換位置は、カルボニル基に対して３位又は４位である。また、複数存在するＲ^３１及びＲ^４１のそれぞれは同一でも異なっていてもよい。］ The precursor of the aromatic polyketone 1 and 2 is 6,6′-bis (arylcarbonyl) binaphthyl (hereinafter sometimes abbreviated as “binaphthyl 4”) represented by the following general formula (4). Applicable.

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or an alkyl group, R ³¹ and R ⁴¹ each independently represent a hydrogen atom, an alkyl group or an aryl group, and X ¹ represents a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, a methyl group, a methoxy group or a trifluoromethyl group is shown. However, the substitution position of X ¹ bonded to the benzene ring having R ³¹ or R ⁴¹ is the 3rd or 4th position with respect to the carbonyl group. A plurality of R ³¹ and R ⁴¹ may be the same or different. ]

［式中、Ｒ^１及びＲ^２はそれぞれ独立にアルコキシ基、アルキル基又はアロイルフェノキシ基を示し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＲ^２５はそれぞれ独立に、水素原子又はアルキル基を示し、Ｒ^３１及びＲ^４１はそれぞれ独立に水素原子、アルキル基又はアリール基を示し、Ｘ^１０は塩素原子、臭素原子又はヨウ素原子を示す。但し、Ｒ^３１又はＲ^４１を有するベンゼン環に結合したＸ^１０の置換位置は、カルボニル基に対して３位又は４位である。また、複数存在するＲ^３１及びＲ^４１のそれぞれは同一でも異なっていてもよい。］ As a manufacturing method of the aromatic polyketone 1, a manufacturing method in which 6,6′-bis (arylcarbonyl) binaphthyl represented by the following general formula (4a) is coupled with a coupling agent is preferable.

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or an alkyl group, R ³¹ and R ⁴¹ each independently represent a hydrogen atom, an alkyl group or an aryl group, and X ¹⁰ represents a chlorine atom, a bromine atom or an iodine atom. Show. However, the substitution position of X ¹⁰ bonded to the benzene ring having R ³¹ or R ⁴¹ is the 3rd or 4th position with respect to the carbonyl group. A plurality of R ³¹ and R ⁴¹ may be the same or different. ]

［式中、Ｒ^１及びＲ^２はそれぞれ独立にアルコキシ基、アルキル基又はアロイルフェノキシ基を示し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^３２及びＲ^４２はそれぞれ独立に、水素原子又はアルキル基を示す。但し、複数存在するＲ^３２及びＲ^４２のそれぞれは同一でも異なっていてもよい。なお、Ｚ^１は、以下のいずれかの２価基であり、

２価基中のＺ^１１は−ＣＨ_２−、−ＣＨ（ＣＨ_３）_２−又は−Ｏ−を示し、ｎは０、１又は２を示す。］ As a manufacturing method of the aromatic polyketone 2, a manufacturing method in which a 6,6′-bis (arylcarbonyl) binaphthyl represented by the following general formula (4b) and a compound represented by the following general formula (5) are reacted. Is preferred.

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³² and R ⁴² each independently represent a hydrogen atom or an alkyl group. However, each of a plurality of R ³² and R ⁴² may be the same or different. Z ¹ is any of the following divalent groups:

Z ¹¹ in the divalent group represents —CH ₂ —, —CH (CH ₃ ) ₂ — or —O—, and n represents 0, 1 or 2. ]

［式中、Ｒ^１及びＲ^２はそれぞれ独立にアルコキシ基、アルキル基又はアロイルフェノキシ基を示し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＲ^２５はそれぞれ独立に、水素原子又はアルキル基を示し、Ｘ^２はＯＨ基又は塩素原子を示す。なお、Ｚ^２は以下のいずれかの２価基であり、

２価基中のＺ^２１は−ＣＨ_２−、−ＣＨ（ＣＨ_３）_２−又は−Ｏ−を示す。］ As a manufacturing method of the aromatic polyketone 3, a manufacturing method in which a compound represented by the following general formula (6) and a compound represented by the following general formula (7) are reacted is preferable.

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or an alkyl group, and X ² represents an OH group or a chlorine atom. Z ² is any of the following divalent groups:

Z ²¹ in the divalent group represents —CH ₂ —, —CH (CH ₃ ) ₂ — or —O—. ]

［式中、Ｒ^１及びＲ^２はそれぞれ独立にアルコキシ基、アルキル基又はアロイルフェノキシ基を示し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＲ^２５はそれぞれ独立に、水素原子又はアルキル基を示し、Ｒ^３１及びＲ^４１はそれぞれ独立に水素原子、アルキル基又はアリール基を示し、Ｘ^１はフッ素原子、塩素原子、臭素原子、ヨウ素原子、メチル基、メトキシ基又はトリフルオロメチル基を示す。但し、Ｒ^３１又はＲ^４１を有するベンゼン環に結合したＸ^１の置換位置は、カルボニル基に対して３位又は４位である。また、複数存在するＲ^３１及びＲ^４１のそれぞれは同一でも異なっていてもよい。］ In addition, 6,6′-bis (arylcarbonyl) binaphthyl represented by the above general formula (4), which is effective as a precursor of the aromatic polyketone 1 and 2, is a compound represented by the following general formula (6): The compound represented by the following general formulas (8a) and (8b) can be obtained by a production method of reacting in the presence of a diphosphorus pentoxide-methanesulfonic acid mixture.

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or an alkyl group, R ³¹ and R ⁴¹ each independently represent a hydrogen atom, an alkyl group or an aryl group, and X ¹ represents a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, a methyl group, a methoxy group or a trifluoromethyl group is shown. However, the substitution position of X ¹ bonded to the benzene ring having R ³¹ or R ⁴¹ is the 3rd or 4th position with respect to the carbonyl group. A plurality of R ³¹ and R ⁴¹ may be the same or different. ]

と表すときは、フェニル基が４つのＲ基と１つのＸ基で置換していることを意味する。この場合において、複数存在するＲのそれぞれは同一でも異なっていてもよく、上記と同様の骨格には同様の解釈が適用される。 In the present invention,

Means that the phenyl group is substituted with four R groups and one X group. In this case, each of a plurality of R may be the same or different, and the same interpretation is applied to the same skeleton as described above.

  An aromatic polyketone having a molecular chain extended at the 6,6'-position of a 2,2'-disubstituted-1,1'-binaphthylene skeleton and a method for producing the same are provided. Moreover, the precursor of the said aromatic polyketone and its manufacturing method are provided. In addition, the aromatic polyketone of the present invention is an optically active wholly aromatic polyketone and is expected to have a helical structure. Furthermore, the main chain is composed of an aromatic ring and a ketone carbonyl group, and is excellent in heat resistance and chemical resistance. Therefore, it can be used even under severe conditions that cannot be applied to conventional helical polymers obtained by addition polymerization such as methacrylic acid esters.

  Hereinafter, preferred embodiments of the aromatic polyketones 1 to 3 and the binaphthyl 4 of the present invention and the production methods thereof will be described.

(Aromatic polyketone 1 and its production method)
In the general formula (1), R ¹ and R ² are an alkoxy group, an alkyl group, or an aroylphenoxy group. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably a methoxy group. The alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group. As the aroylphenoxy group, 4-benzoylphenoxy group and 4-toluylphenoxy group are preferable, and 4-benzoylphenoxy group is more preferable.

From the viewpoint of creating a heat-resistant material with high symmetry, R ¹ and R ² are preferably the same group, and are preferably methoxy groups that are electron donating groups in that binaphthyl 4 can be efficiently obtained. It is.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are a hydrogen atom or an alkyl group. The alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group.

In order to obtain binaphthyl 4 with good yield by improving the electron density at the 6,6′-position, the positions of the alkyl groups are preferably R ¹² and R ²² . Further, from the viewpoint of ease of molecular synthesis, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are all preferably hydrogen atoms.

R ³¹ and R ⁴¹ are each independently a hydrogen atom, an alkyl group or an aryl group. The alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group. As the aryl group, 4-benzoylphenyl group and 4-nitrophenyl group are preferable, and 4-benzoylphenyl group is more preferable.

To maintain the polymerization reactivity, the substitution position of the alkyl group or aryl group, X in the ortho-position of the carbonyl group and the para-position of the group X ¹ (general formula is a starting compound of an aromatic polyketone 1 (4) ¹ Means a group). Moreover, both R ³¹ and R ⁴¹ are preferably hydrogen atoms in terms of ease of molecular synthesis.

In the aromatic polyketone 1, the substitution position of the single bond bonded to the benzene ring having R ³¹ or R ⁴¹ is the 3rd or 4th position with respect to the carbonyl group. That is, a single bond between the repeating units, relative to the carbonyl group attached to the benzene ring having R ³¹ or R ^41, are formed between the 3-position -3 position between or 4 position -4.

  In addition, the aromatic polyketone 1 may include a repeating unit other than the repeating unit represented by the general formula (1), but may be only the repeating unit represented by the general formula (1). preferable. In this case, the number of repeating units represented by the general formula (1) is typically 10 to 20.

The aromatic polyketone 1 can be produced by coupling the compound represented by the general formula (4a) with a coupling agent. Here, it is preferable to use a combination of nickel bromide (NiBr ₂ , which functions as a catalyst) and zinc (Zn, which functions as a reducing agent) as the coupling agent. Further, it is preferable to use triphenylphosphine and 2,2′-bipyridine in combination to increase the coupling efficiency.

  The coupling reaction is preferably performed at 60 to 120 ° C. and more preferably at 100 ° C. in a polar solvent such as N, N-dimethylacetamide under an inert gas atmosphere such as nitrogen. After the coupling reaction, the aromatic polyketone 1 can be obtained as a solid by dropping it into an acidic alcohol (methanol / hydrochloric acid or the like).

(Aromatic polyketone 2 and method for producing the same)
In the general formula (2), R ¹ and R ² are an alkoxy group, an alkyl group, or an aroylphenoxy group. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are hydrogen atoms or alkyl groups, and R ³² and R ⁴² are each independently A hydrogen atom or an alkyl group. The types of these groups, the substitution positions and suitable conditions, and the effects exerted are the same as those in the aromatic polyketone 1 (provided that R ³² and R ⁴² correspond to the cases of R ³¹ and R ⁴¹ ). .)

In the aromatic polyketone 2, the substitution position of the —O— bond bonded to the benzene ring having R ³² or R ⁴² is the 4-position with respect to the carbonyl group. That is, the —O—Z ¹ —O— bond between the repeating units is formed between the 4-position and the 4-position with respect to the carbonyl group bonded to the benzene ring having R ³² or R ⁴² .

  In addition, the aromatic polyketone 2 may include a repeating unit other than the repeating unit represented by the general formula (2), but may be only the repeating unit represented by the general formula (2). preferable. In this case, the number of repeating units represented by the general formula (2) is typically 5 to 15.

The aromatic polyketone 2 can be obtained by reacting the compound represented by the general formula (4b) with the compound represented by the general formula (5) (aromatic nucleophilic substitution polymerization). In carrying out this reaction, a weak base such as potassium carbonate (K ₂ CO ₃ ) may be allowed to coexist with the compound represented by the general formula (5). As the compound represented by the general formula (5), bis (4-hydroxyphenyl) methane, bisphenol A, bis (4-hydroxyphenyl) ether, 9,9-bis (hydroxyphenyl) fluorene and the like are used. .

  The aromatic nucleophilic substitution polymerization is preferably performed at 150 to 220 ° C. in a polar solvent such as N-methylpyrrolidone or diphenylsulfone under an inert gas atmosphere such as nitrogen. After the aromatic nucleophilic substitution polymerization, the aromatic polyketone 2 can be obtained by removing the solvent.

(Aromatic polyketone 3 and method for producing the same)
In the general formula (3), R ¹ and R ² are an alkoxy group, an alkyl group, or an aroylphenoxy group. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are a hydrogen atom or an alkyl group. The types of these groups, the substitution positions and suitable conditions, and the effects exerted are the same as those in the aromatic polyketone 1.

  The aromatic polyketone 3 may include a repeating unit other than the repeating unit represented by the general formula (3), but is preferably composed of only the repeating unit represented by the general formula (3). In this case, the number of repeating units represented by the general formula (3) is typically 5 to 20.

The aromatic polyketone 3 can be obtained by reacting the compound represented by the general formula (6) and the compound represented by the general formula (7) (electrophilic aromatic acylation-type substitution polymerization). In carrying out this reaction, when a compound of the general formula (7) in which X ² is a chlorine atom is used, the reaction is preferably carried out in the presence of trifluoromethanesulfonic acid or aluminum chloride, and X ² is an OH group. When the compound of the general formula (7) is used, the reaction is preferably carried out in the presence of a diphosphorus pentoxide-methanesulfonic acid mixture. Examples of the compound of the general formula (7) in which X ² is a chlorine atom include terephthaloyl dichloride, isophthaloyl dichloride, methylene bisbenzoic acid dichloride, dimethylmethylene bisbenzoic acid dichloride, and 2,6-naphthalenedicarboxylic acid dichloride. Examples of the compound of the general formula (7) in which ² is an OH group include 4,4′-oxybisbenzoic acid.

  The electrophilic aromatic acylation-type substitution polymerization is preferably performed at 20 to 60 ° C. in an inert gas atmosphere such as nitrogen. In addition, when using trifluoromethanesulfonic acid, 50 degreeC is especially preferable when using aluminum chloride. After electrophilic aromatic acylation-type substitution polymerization, the aromatic polyketone 3 can be obtained by filtration, washing with hot water and drying under reduced pressure.

(Binaphtil 4 and production method thereof)
In the general formula (4), R ¹ and R ² are an alkoxy group, an alkyl group, or an aroylphenoxy group. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are a hydrogen atom or an alkyl group, and R ³¹ and R ⁴¹ are each independently A hydrogen atom, an alkyl group or an aryl group; The types of these groups, the substitution positions and suitable conditions, and the effects exerted are the same as those in the aromatic polyketone 1.

X ¹ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group or a trifluoromethyl group, but when X ¹ is a chlorine atom, a bromine atom or an iodine atom, the precursor of the aromatic polyketone 1 When X ¹ is a fluorine atom, it can be used as a precursor of aromatic polyketone 2. In binaphthyl 4, the substitution position of X ¹ bonded to the benzene ring having R ³¹ or R ⁴¹ is the 3rd or 4th position with respect to the carbonyl group.

  Binaphthyl 4 reacts the compound represented by the general formula (6) with the compounds represented by the general formulas (8a) and (8b) in the presence of a diphosphorus pentoxide-methanesulfonic acid mixture ( Condensation reaction). The diphosphorus pentoxide-methanesulfonic acid mixture is used as a condensing agent and a solvent for the product binaphthyl 4, the compound represented by the general formula (6), and the compounds represented by the general formulas (8a) and (8b). Function. Therefore, it is preferable to use 10 mL (15 g) or more of the diphosphorus pentoxide-methanesulfonic acid mixture with respect to 1 mmol of the compounds represented by the general formulas (8a) and (8b).

By using the compounds represented by the general formulas (8a) and (8b), binaphthyl 4 can be obtained as a mixture. However, when obtaining single-component binaphthyl 4, the target compound may be separated from the mixture. However, when the corresponding R ³¹ and R ⁴¹ are the same group, the target compound binaphthyl 4 can be easily obtained while avoiding the problem of separation from the mixture.

  The condensation reaction is preferably performed at 20 to 60 ° C. After the condensation reaction, binaphthyl 4 can be obtained by separating the liquid into basic.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

[Production of binaphthyl 4]
Example 1
2,2′-Dimethoxy-1,1′-binaphthyl and 4-fluorobenzoic acid were dissolved in a 1:10 (mass ratio) mixture of diphosphorus pentoxide and methanesulfonic acid, and mixed at 60 ° C. for 24 hours. Thereafter, the reaction was stopped by dropping the reaction solution into water. A 10M aqueous sodium hydroxide solution was added to make the liquid basic, followed by extraction with chloroform by a liquid separation operation. Anhydrous magnesium sulfate was added as a desiccant, this was filtered off, and then the solvent was distilled off under reduced pressure to obtain a crude product. This was purified by silica gel column chromatography to obtain a product. When this product was analyzed by ¹ H-NMR, the δ values were as follows, and the product was 6,6′-bis (4-fluorobenzoyl) -2,2′-dimethoxy-1,1 ′. -Turned out to be binaphthyl. The yield was 100 mol%. The reaction formula is shown below.
¹ H-NMR (300 MHz, CDCl ₃ ): 3.83 (6H, s), 7.17 (2H, d, J = 8.7 Hz), 7.19 (4H, dd, J = 8.7, 6.3 Hz), 7.54 (2H, d, J = 8.7Hz), 7.69 (2H, dd, J = 8.7, 1.8Hz), 7.90 (4H, dd, J = 8.7, 5.4Hz), 8.09 (2H, d, J = 8.7Hz), 8.30 (2H, dd, J = 1.8Hz) ppm

(Example 2)
The same operation as in Example 1 was performed except that 4-fluorobenzoic acid was changed to 3-chlorobenzoic acid. When the obtained product was analyzed by ¹ H-NMR, the δ values were as follows, and the product was 6,6′-bis (3-chlorobenzoyl) -2,2′-dimethoxy-1, It was found to be 1'-binaphthyl. The yield was 92 mol%.
¹ H-NMR (300 MHz, CDCl ₃ ): 3.83 (6H, s), 7.19 (2H, d, J = 8.4 Hz), 7.45 (2H, t, J = 8.4 Hz), 7.55 (2H, d, J = 8.4Hz), 7.57 (2H, d, J = 8.7Hz), 7.70 (2H, dd, J = 8.7, 1.5Hz), 7.72 (2H, d, J = 8.7Hz), 7.83 (2H, t, J = 1.5Hz), 8.11 (2H, d, J = 8.7Hz), 8.31 (2H, d, J = 1.5Hz) ppm

(Example 3)
The same operation as in Example 1 was performed except that 4-fluorobenzoic acid was changed to 4-chlorobenzoic acid. When the obtained product was analyzed by ¹ H-NMR, the δ values were as follows, and the product was 6,6′-bis (4-chlorobenzoyl) -2,2′-dimethoxy-1, It was found to be 1'-binaphthyl. The yield was 90 mol%.
¹ H-NMR (300 MHz, CDCl ₃ ): 3.83 (6H, s), 7.18 (2H, d, J = 8.4 Hz), 7.48 (4H, d, J = 8.7 Hz), 7.54 (2H, d, J = 8.4Hz), 7.69 (2H, dd, J = 1.8, 8.4 Hz), 7.81 (4H, d, J = 8.7Hz), 8.09 (2H, d, J = 8.4Hz), 8.29 (2H, d, J = 1.8Hz) ppm

(Example 4)
The same operation as in Example 1 was performed except that 4-fluorobenzoic acid was changed to 3-bromobenzoic acid. As a result, 6,6′-bis (3-bromobenzoyl) -2,2′-dimethoxy-1,1′-binaphthyl was obtained. The yield was 90 mol%.

(Example 5)
The same operation as in Example 1 was performed except that 4-fluorobenzoic acid was changed to 4-bromobenzoic acid. When the obtained product was analyzed by ¹ H-NMR, the δ values were as follows, and the product was 6,6′-bis (4-bromobenzoyl) -2,2′-dimethoxy-1, It was found to be 1'-binaphthyl. The yield was 92 mol%.
¹ H-NMR (300 MHz, CDCl ₃ ): 3.83 (6H, s), 7.18 (2H, d, J = 8.4 Hz), 7.54 (2H, d, J = 8.4 Hz), 7.65 (4H, d, J = 8.7Hz), 7.69 (2H, dd, J = 8.4, 1.8Hz), 7.73 (4H, d, J = 8.7Hz), 8.09 (2H, d, J = 8.4Hz), 8.29 (2H, d, J = 1.8Hz) ppm

(Example 6)
The same operation as in Example 1 was performed except that 4-fluorobenzoic acid was changed to 3-iodobenzoic acid. As a result, 6,6′-bis (3-iodobenzoyl) -2,2′-dimethoxy-1,1′-binaphthyl was obtained.

(Example 7)
The same operation as in Example 1 was performed except that 4-fluorobenzoic acid was changed to 4-iodobenzoic acid. When the obtained product was analyzed by ¹ H-NMR, the δ values were as follows, and the product was 6,6′-bis (4-iodobenzoyl) -2,2′-dimethoxy-1, It was found to be 1'-binaphthyl. The yield was 92 mol%.
¹ H-NMR (300 MHz, CDCl ₃ ): 3.83 (6H, s), 7.18 (2H, d, J = 8.7 Hz), 7.54 (2H, d, J = 8.7 Hz), 7.57 (4H, d, J = 8.4Hz), 7.69 (2H, dd, J = 8.4, 1.5Hz), 7.87 (4H, d, J = 8.4Hz), 8.08 (2H, d, J = 8.4Hz), 8.28 (2H, d, J = 1.5Hz) ppm

(Example 8)
The same operation as in Example 1 was performed except that 4-fluorobenzoic acid was changed to 4-toluic acid. When the obtained product was analyzed by ¹ H-NMR, the δ values were as follows, and the product was 6,6′-bis (4-methylbenzoyl) -2,2′-dimethoxy-1, It was found to be 1'-binaphthyl. The yield was 100 mol%.
¹ H-NMR (300 MHz, CDCl ₃ ): 2.46 (6H, s), 3.82 (6H, s), 7.18 (2H, d, J = 8.7 Hz), 7.30 (4H, d, J = 8.4 Hz), 7.53 (2H, d, J = 8.7Hz), 7.70 (2H, dd, J = 8.4, 1.5Hz), 7.78 (4H, d, J = 8.4Hz), 8.08 (2H, d, J = 8.4Hz), 8.31 (2H, d, J = 1.5Hz) ppm

Example 9
The same operation as in Example 1 was performed except that 4-fluorobenzoic acid was changed to 3-toluic acid. When the obtained product was analyzed by ¹ H-NMR, the δ values were as follows, and the product was 6,6′-bis (3-methylbenzoyl) -2,2′-dimethoxy-1, It was found to be 1'-binaphthyl. The yield was 100 mol%.
¹ H-NMR (300 MHz, CDCl ₃ ): 2.44 (6H, s), 3.83 (6H, s), 7.21 (2H, d, J = 9.0 Hz), 7.35-7.43 (4H, m), 7.54 (2H, d, J = 9.0Hz), 7.64 (2H, d, J = 7.2Hz), 7.69 (2H, s), 7.74 (2H, d, J = 9.0Hz), 8.09 (2H, d, J = 9.0Hz) 8.34 (2H, s) ppm

(Example 10)
The same operation as in Example 1 was performed except that 4-fluorobenzoic acid was changed to 4-methoxybenzoic acid. When the obtained product was analyzed by ¹ H-NMR, the δ values were as follows, and the product was 6,6′-bis (4-methoxybenzoyl) -2,2′-dimethoxy-1, It was found to be 1'-binaphthyl. The yield was 92 mol%.
¹ H-NMR (300 MHz, CDCl ₃ ): 3.82 (6H, s), 3.89 (6H, s), 6.98 (4H, d, J = 9.0 Hz), 7.19 (2H, d, J = 8.7 Hz), 7.52 (2H, d, J = 9.0Hz), 7.67 (2H, dd, J = 1.5, 9.0Hz), 7.89 (4H, d, J = 8.7Hz), 8.08 (2H, d, J = 8.7Hz), 8.30 (2H, d, J = 1.5Hz) ppm

[Production of aromatic polyketone 1]
(Example 11)
To a solution of 6,6′-bis (4-chlorobenzoyl) -2,2′-dimethoxy-1,1′-binaphthyl (0.2 mmol) in N, N-dimethylacetamide (2 mL) was added nickel bromide (0. 1 mmol), zinc (0.6 mmol), triphenylphosphine (0.2 mmol), and 2,2′-bipyridine (0.1 mmol) were added under a nitrogen atmosphere and mixed at 100 ° C. for 2 hours. After cooling to room temperature, an ocherous solid was obtained by dropwise addition to a mixed solution of methanol and hydrochloric acid (1: 6 by volume). This was washed with methanol and dried under reduced pressure overnight. When the obtained product was analyzed by ¹ H-NMR, the δ values were as follows, and the product was poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′- Irene) carbonyl (4,4′-biphenylene) carbonyl]. The yield was 95 mol%. The reaction formula is shown below.
¹ H-NMR (300 MHz, CDCl ₃ ): 3.83 (6H, pseudo s), 7.20 (2H, pseudo d, J = 9.0 Hz), 7.55 (2H, pseudo d, J = 9.0 Hz), 7.76-7.81 (6H , M), 7.98 (4H, pseudo d, J = 9.0Hz), 8.11 (2H, pseudo d, J = 9.0Hz), 8.38 (2H, pseudo s)

Example 12
6,6′-bis (4-chlorobenzoyl) -2,2′-dimethoxy-1,1′-binaphthyl is converted to 6,6′-bis (3-chlorobenzoyl) -2,2′-dimethoxy-1,1 The same operation as in Example 11 was performed except that it was changed to '-binaphthyl. When the obtained product was analyzed by ¹ H-NMR, the δ values were as follows, and the product was poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′- Irene) carbonyl (3,3′-biphenylene) carbonyl].
¹ H-NMR (500 MHz, CDCl ₃ ): 3.78 (6H, pseudo s), 7.20 (2H, pseudo d, J = 9.0 Hz), 7.47 (4H, pseudo d, J = 11.0 Hz), 7.57 (2H, pseudo d, J = 9.0Hz), 7.75 (2H, pseudo d, J = 9.0Hz), 7.83 (4H, pseudo t, J = 11.0Hz), 8.04 (2H, pseudo d, J = 9.0Hz), 8.11 (2H , pseudo s), 8.35 (2H, pseudo s)

(Example 13)
6,6′-bis (4-chlorobenzoyl) -2,2′-dimethoxy-1,1′-binaphthyl is converted to 6,6′-bis (4-bromobenzoyl) -2,2′-dimethoxy-1,1 The same operation as in Example 11 was performed except that it was changed to '-binaphthyl. As a result, poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′-ylene) carbonyl (4,4′-biphenylene) carbonyl] was obtained. The yield was 92 mol%.

(Example 14)
6,6′-bis (4-chlorobenzoyl) -2,2′-dimethoxy-1,1′-binaphthyl is converted to 6,6′-bis (3-bromobenzoyl) -2,2′-dimethoxy-1,1 The same operation as in Example 11 was performed except that it was changed to '-binaphthyl. As a result, poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′-ylene) carbonyl (3,3′-biphenylene) carbonyl] was obtained. The yield was 92 mol%.

(Example 15)
6,6′-bis (4-chlorobenzoyl) -2,2′-dimethoxy-1,1′-binaphthyl is converted to 6,6′-bis (4-iodobenzoyl) -2,2′-dimethoxy-1,1 The same operation as in Example 11 was performed except that it was changed to '-binaphthyl. As a result, poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′-ylene) carbonyl (4,4′-biphenylene) carbonyl] was obtained. The yield was 81 mol%.

[Production of aromatic polyketone 2]
(Example 16)
Potassium carbonate (0.6 mmol), 6,6′-bis (4-fluorobenzoyl) -2,2′-dimethoxy-1,1′-binaphthyl (0.2 mmol), bis (4-hydroxyphenyl) methane (0 .2 mmol)) in N-methylpyrrolidone (2 mL) (diphenylsulfone may be used in place of N-methylpyrrolidone) was mixed at 180 ° C. for 2 hours under a nitrogen atmosphere. After cooling to room temperature, the solvent was removed by washing 3 times with acetone and 3 times with boiling water. Then, poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′-ylene) carbonyl (1,4-phenylene) oxy (1,4-phenylene) is dried by heating under reduced pressure. Methylene (1,4-phenylene) oxy (1,4-phenylene) carbonyl] was obtained. The yield was 90 mol%. The reaction formula is shown below.

(Example 17)
The same operation as in Example 16 was performed except that bisphenol A was used instead of bis (4-hydroxyphenyl) methane. Thus, poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′-ylene) carbonyl (1,4-phenylene) oxy (1,4-phenylene) isopropylidene (1,4- Phenylene) oxy (1,4-phenylene) carbonyl] was obtained.

(Example 18)
The operation was performed in the same manner as in Example 16 except that bis (4-hydroxyphenyl) ether was used instead of bis (4-hydroxyphenyl) methane. Thus, poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′-ylene) carbonyl (1,4-phenylene) oxy (1,4-phenylene) oxy (1,4-phenylene ) Oxy (1,4-phenylene) carbonyl].

Example 19
The same operation as in Example 16 was performed except that 9,9-bis (hydroxyphenyl) fluorene was used instead of bis (4-hydroxyphenyl) methane. This gives poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′-ylene) carbonyl (1,4-phenylene) (9,9-fluorenylylene-4,4′-diphenoxy) ( 1,4-phenylene) oxy (1,4-phenylene) carbonyl] was obtained.

[Production of aromatic polyketone 3]
(Example 20)
2,2′-Dimethoxy-1,1′-binaphthyl (0.2 mmol) and terephthaloyl dichloride (0.2 mmol) were dissolved in trifluoromethanesulfonic acid (6 mmol) and mixed at 50 ° C. for 24 hours. And the reaction solution was dripped at water. This was collected by filtration and washed three times with hot water. The obtained solid was dried by heating under reduced pressure overnight to obtain a product. When this product was analyzed by ¹ H-NMR, the δ values were as follows, and the product was poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′-ylene). Was found to be terephthaloyl]. The yield was 94 mol%. The reaction formula is shown below. Here, trifluoromethanesulfonic acid was used as a reagent, but aluminum chloride may be used instead. However, in that case, 1,2-dichloroethane must be added as a solvent.
¹ H-NMR (300 Hz, DMSO-d ₆ ): 3.86 (6H, s), 7.15-7.31 (2H, m), 7.42-7.58 (2H, m), 7.64-7.87 (2H, m), 7.88-8.10 (4H, m), 8.12−8.27 (2H, m), 8.46 (2H, s)

(Example 21)
The same operation as in Example 20 was performed except that terephthaloyl dichloride was changed to isophthaloyl dichloride. When the obtained product was analyzed by ¹ H-NMR, the δ values were as follows, and the product was poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′- Irene) isophthaloyl]. The yield was 90%.
¹ H-NMR (300 Hz, CDCl ₃ ): 3.78 (6H, s), 7.01–7.21 (2H, m), 7.37–7.54 (2H, m), 7.55–7.66 (1H, m), 7.67–7.86 (2H , M), 7.87-8.17 (4H, m), 8.28 (2H, s), 8.31 (1H, s)

(Example 22)
The same operation as in Example 20 was performed except that terephthaloyl dichloride was changed to methylenebisbenzoic acid dichloride. As a result, poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′-ylene) carbonyl (1,4-phenylene) methylene (1,4-phenylene) carbonyl] was obtained.

(Example 23)
The same operation as in Example 20 was carried out except that terephthaloyl dichloride was changed to dimethylmethylenebisbenzoic acid dichloride. As a result, poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′-ylene) carbonyl (1,4-phenylene) isopropylidene (1,4-phenylene) carbonyl] was obtained.

(Example 24)
The same operation as in Example 20 was performed except that terephthaloyl dichloride was changed to 2,6-naphthalenedicarboxylic acid dichloride. As a result, poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′-ylene) carbonyl (2,6-naphthylene) carbonyl] was obtained.

(Example 25)
2,2′-dimethoxy-1,1′-binaphthyl (0.2 mmol) and 4,4′-oxybisbenzoic acid (0.2 mmol) were mixed in a diphosphorus pentoxide-methanesulfonic acid mixture (2 mL) at a mass ratio of 1:10. ) And stirred at 60 ° C. for 24 hours. The reaction solution was diluted 2-fold with methanesulfonic acid and then added dropwise to water. This was collected by filtration and washed three times with hot water and an aqueous sodium carbonate solution. The obtained solid was dried by heating under reduced pressure overnight to obtain a product. When this product was analyzed by ¹ H-NMR, the δ values were as follows, and the product was poly [(2,2′-dimethoxy-1,1′-binaphthyl-6,6′-ylene). Carbonyl (1,4-phenylene) oxy (1,4-phenylene) carbonyl]. The yield was 97 mol%.
¹ H-NMR (300 Hz, CDCl ₃ ): 3.82 (6H, pseudo s), 7.15 (4H, pseudo d, J = 7.8 Hz), 7.21 (2H, pseudo d, J = 8.7 Hz), 7.53 (2H, pseudo d, J = 8.4Hz), 7.70 (2H, pseudo d, J = 8.7Hz), 7.92 (4H, pseudo d, J = 7.5Hz), 8.33 (2H, s)

  The aromatic polyketone of the present invention is an optically active wholly aromatic polyketone and is expected to have a helical structure. Furthermore, the main chain is composed of an aromatic ring and a ketone carbonyl group, and is excellent in heat resistance and chemical resistance. Therefore, it can be used even under severe conditions that cannot be applied to conventional helical polymers obtained by addition polymerization such as methacrylic acid esters. Specifically, it can be applied to a polymer catalyst, a polymer reaction field, an optically active substance separation membrane, an optically active column chromatography filler, a heat-resistant optical / electronic material, etc. under strong acid and strong base conditions.

Claims (27)

Poly [(1,1′-binaphthyl-6,6′-ylene) arylene dicarbonyl] comprising a repeating unit represented by the following general formula (1).

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or an alkyl group, and R ³¹ and R ⁴¹ each independently represent a hydrogen atom, an alkyl group or an aryl group. However, the substitution position of the single bond bonded to the benzene ring having R ³¹ or R ⁴¹ is the 3rd or 4th position with respect to the carbonyl group. A plurality of R ³¹ and R ⁴¹ may be the same or different. ] The poly [(1,1'-binaphthyl-6,6'-ylene) arylene dicarbonyl] according to claim ^1, wherein R ¹ and R ² are both methoxy groups. The R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³¹ and R ⁴¹ are all hydrogen atoms. Poly [(1,1′-binaphthyl-6,6′-ylene) arylenedicarbonyl]. Poly [(1,1′-binaphthyl-6,6′-ylene) carbonyl (1,4-phenylene) (arylene dioxy) (1,4-) having a repeating unit represented by the following general formula (2) Phenylene) carbonyl].

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³² and R ⁴² each independently represent a hydrogen atom or an alkyl group. However, each of a plurality of R ³² and R ⁴² may be the same or different. Z ¹ is any of the following divalent groups:

Z ¹¹ in the divalent group represents —CH ₂ —, —CH (CH ₃ ) ₂ — or —O—, and n represents 0, 1 or 2. ] The poly [(1,1′-binaphthyl-6,6′-ylene) carbonyl (1,4-phenylene) (arylene dioxy) (1) according to claim 4, wherein both R ¹ and R ² are methoxy groups. , 4-phenylene) carbonyl]. The R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³² and R ⁴² are all hydrogen atoms. Poly [(1,1′-binaphthyl-6,6′-ylene) carbonyl (1,4-phenylene) (aryleneoxy) (1,4-phenylene) carbonyl]. Poly [(1,1′-binaphthyl-6,6′-ylene) (arylene carbonyl)] represented by the following general formula (3).

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or an alkyl group. Z ² is any of the following divalent groups:

Z ²¹ in the divalent group represents —CH ₂ —, —CH (CH ₃ ) ₂ — or —O—. ] The poly [(1,1′-binaphthyl-6,6′-ylene) (arylene dicarbonyl)] according to claim 7, wherein R ¹ and R ² are both methoxy groups. The poly [(1,1) according to claim 7 or 8, wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are all hydrogen atoms. '-Binaphthyl-6,6'-ylene) (arylene dicarbonyl)]. 6,6′-bis (arylcarbonyl) binaphthyl represented by the following general formula (4).

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or an alkyl group, R ³¹ and R ⁴¹ each independently represent a hydrogen atom, an alkyl group or an aryl group, and X ¹ represents a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, a methyl group, a methoxy group or a trifluoromethyl group is shown. However, the substitution position of X ¹ bonded to the benzene ring having R ³¹ or R ⁴¹ is the 3rd or 4th position with respect to the carbonyl group. A plurality of R ³¹ and R ⁴¹ may be the same or different. ] The 6,6′-bis (arylcarbonyl) binaphthyl according to claim 10, wherein R ¹ and R ² are both methoxy groups. The R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³¹ and R ⁴¹ are all hydrogen atoms. 6,6′-bis (arylcarbonyl) binaphthyl. A poly [(1,1′-binaphthyl) represented by the following general formula (1) is coupled with a coupling agent to 6,6′-bis (arylcarbonyl) binaphthyl represented by the following general formula (4a). -6,6'-Irene) arylenedicarbonyl].

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or an alkyl group, R ³¹ and R ⁴¹ each independently represent a hydrogen atom, an alkyl group or an aryl group, and X ¹⁰ represents a chlorine atom, a bromine atom or an iodine atom. Show. However, the substitution position of X ¹⁰ or the single bond bonded to the benzene ring having R ³¹ or R ⁴¹ is the 3rd or 4th position with respect to the carbonyl group. A plurality of R ³¹ and R ⁴¹ may be the same or different. ] The production method according to claim 13, wherein R ¹ and R ² are both methoxy groups. The R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³¹ and R ⁴¹ are all hydrogen atoms. Production method. A poly (6) -bis (arylcarbonyl) binaphthyl represented by the following general formula (4b) is reacted with a compound represented by the following general formula (5). Production method of [(1,1′-binaphthyl-6,6′-ylene) carbonyl (1,4-phenylene) (arylenedioxy) (1,4-phenylene) carbonyl].

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³² and R ⁴² each independently represent a hydrogen atom or an alkyl group. However, each of a plurality of R ³² and R ⁴² may be the same or different. Z ¹ is any of the following divalent groups:

Z ¹¹ in the divalent group represents —CH ₂ —, —CH (CH ₃ ) ₂ — or —O—, and n represents 0, 1 or 2. ] The production method according to claim 16, wherein R ¹ and R ² are both methoxy groups. The R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³² and R ⁴² are all hydrogen atoms. Production method. A poly [(1,1′-binaphthyl-6) represented by the following general formula (3) is reacted with a compound represented by the following general formula (6) and a compound represented by the following general formula (7). , 6′-Irene) (arylene carbonyl)].

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or an alkyl group, and X ² represents an OH group or a chlorine atom. Z ² is any of the following divalent groups:

Z ²¹ in the divalent group represents —CH ₂ —, —CH (CH ₃ ) ₂ — or —O—. ] The production method according to claim 19, wherein R ¹ and R ² are both methoxy groups. ^21. The production method according to claim 19 or 20, wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are all hydrogen atoms. X ² is a chlorine atom, and in the presence of trifluoromethanesulfonic acid or aluminum chloride, the compound represented by the general formula (6) is reacted with the compound represented by the general formula (7). Item 22. The production method according to any one of Items 19 to 21. X ² is an OH group, and the compound represented by the general formula (6) is reacted with the compound represented by the general formula (7) in the presence of a diphosphorus pentoxide-methanesulfonic acid mixture. The manufacturing method as described in any one of Claims 19-21. A compound represented by the following general formula (6) and a compound represented by the following general formulas (8a) and (8b) are reacted in the presence of a diphosphorus pentoxide-methanesulfonic acid mixture. A method for producing 6,6′-bis (arylcarbonyl) binaphthyl represented by (4).

[Wherein, R ¹ and R ² each independently represent an alkoxy group, an alkyl group or an aroylphenoxy group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or an alkyl group, R ³¹ and R ⁴¹ each independently represent a hydrogen atom, an alkyl group or an aryl group, and X ¹ represents a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, a methyl group, a methoxy group or a trifluoromethyl group is shown. However, the substitution position of X ¹ bonded to the benzene ring having R ³¹ or R ⁴¹ is the 3rd or 4th position with respect to the carbonyl group. A plurality of R ³¹ and R ⁴¹ may be the same or different. ] The production method according to claim 24, wherein R ¹ and R ² are both methoxy groups. The production method according to claim 24 or 25, wherein R ³¹ and R ⁴¹ are the same group. Both ^{R 11, R 12, R 13} , R 14, R 15, R 21, R 22, R 23, R 24, R 25, R 31 and ^{R 41} is a hydrogen atom, any of claim 24 to 26 The manufacturing method according to claim 1.