JPH10176055A - Production of 1-naphthol polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer excellent in heat resistance and low in gel content by polymerizing 1-naphthol in the presence of an oxidizing agent and a specific catalyst low in the odor in an organic solvent. SOLUTION: This method for producing 1-naphthol polymer comprises polymerizing 1-naphthol in the presence of an oxidizing agent (preferably oxygen or a peroxide) and a transition metal complex catalyst containing the 4-11 group transition metal atoms in the larger number than 1/6 of the conformation number of a ligand per >= tri-dentate ligand containing N, P, O or S as coordination atoms [preferably, a complex catalyst of the formula (M is a residue containing the 4-11 group transition metal atom; R<1> , R<6> are each H, a hydrocarbon, O<-> , amino, etc.; R<2> , R<5> are each independently H, a hydrocarbon, carbonyl, cyano, etc.; R<3> , R<4> are each independently H, a hydrocarbon, etc.; R<7> is a bifunctional hydrocarbon, etc.), etc.]. Thereby, the method can inhibit a coupling reaction at the 2-position of the 1-naphthol and enables to produce the polymer low in gel contact.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a 1-naphthol polymer.

[0002]

2. Description of the Related Art Oxidative polymerization using a transition metal complex catalyst of 2,6-dimethylphenol (for example, see JP-B-63-663).
No. 091, JP-A-59-131627, and many others. ) (Poly (2,6-dimethyl-1,4-phenylene ether))
(Hereinafter sometimes abbreviated as PPE) is known to be a useful resin. However, since PPE is susceptible to oxidative degradation of a methyl group substituted on an aromatic ring, PPE
There is a drawback that it is difficult to perform melt molding alone, and it is generally positioned as a general-purpose engineering plastic as a polymer alloy with polystyrene.

On the other hand, the oxidized polymer of 1-naphthol proposed in Soviet Patent No. 219202 has no substituted methyl group which is susceptible to oxidative deterioration, and can be expected as a high heat-resistant polymer. As a catalyst used in the oxidative polymerization method of 1-naphthol in an organic solvent, Soviet Patent 2
19202, Polymer, Vol. 15, 392 (1974) and Polymer
er, Vol. 18, 1081 (1977), describes a catalyst comprising a copper salt and a nitrogen-containing compound such as pyridine. However, since these catalysts use a nitrogen-containing compound such as pyridine, their odor has been a problem.

Further, Japanese Unexamined Patent Publication (Kokai) No. 5-178982 discloses an unsubstituted 1-naphthol or a 1-naphthol having a substituent at the 2-position.
-A method is described in which naphthol is subjected to oxygen oxidative polymerization using a catalyst comprising a copper salt and pyridine or triethylamine in an organic solvent, but specifically disclosed is a method having a substituent at the 2-position. It concerns only the polymerization of naphthol. According to the knowledge obtained by the present inventors, the generation of a gel component tends to increase during the oxidative polymerization of 1-naphthol.
Although the details of this cause are unknown, if only the oxygen atom of 1-naphthol and the carbon atom at the 4-position are coupled, a linear polymer is obtained, and the carbon atom at the 2-position of 1-naphthol also undergoes a coupling reaction. It is presumed that gelation occurs when it is involved.

[0005] JP-A-53-65834 discloses copper,
Oxidative coupling of 1-naphthol in an aqueous solvent is described using a catalyst comprising manganese, cobalt or iron and an amine containing alkanolamine, etc., but in oxidative coupling in an aqueous solution, dinaphthoquinone is mainly formed. And only a trace amount of the polymer was obtained.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for economically producing a 1-naphthol oxidized polymer having a low gel content and excellent heat resistance using a catalyst having a low odor. It is in.

[0007]

Under these circumstances, the present inventors have conducted intensive studies to achieve the above object, and as a result, completed the present invention. That is, the present invention relates to a method for determining the number of transition metal atoms belonging to Group 4 to Group 11 per one of tridentate or higher ligands in which the coordinating atom is a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom. The present invention relates to a method for producing a 1-naphthol polymer in which 1-naphthol is polymerized in an organic solvent in the presence of an oxidizing agent using a transition metal complex catalyst having more than 1/6 codons.

[0008]

Next, the present invention will be described in detail. (1) Transition metal complex catalyst The transition metal complex catalyst used in the present invention is a transition metal complex catalyst having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom. It is a transition metal complex catalyst in which the number of group transition metal atoms is more than 1/6 of the number of conformations of the ligand.

The transition metal in the transition metal complex catalyst of the present invention is a transition metal belonging to Groups 4 to 11 of the Periodic Table of the Elements (IUPAC revised edition of inorganic chemical nomenclature 1989). Preferred are transition metals of the first transition element series, more preferred are manganese, iron, cobalt and copper, particularly preferred are manganese. The valence of the transition metal can be appropriately selected from those normally existing in the natural world, and for example, in the case of manganese, divalent or trivalent can be used.

The tridentate or more ligand in the transition metal complex catalyst of the present invention is a tridentate or more ligand whose coordinating atom is a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom. In the present invention, a ligand refers to a molecule or an ion bonded to a certain atom by a coordination bond, as described in the Dictionary of Chemistry (First Edition, Tokyo Kagaku Dojin, 1989). The atoms directly involved in the bond are called coordinating atoms. A tridentate or higher ligand is a ligand having 3 or more coordinating atoms.

Although the details are unknown, the transition metal complex catalyst of the present invention can suppress the 2-position coupling reaction of 1-naphthol by using such a tridentate or higher ligand. It is thought that a suitable environment around the transition metal atom is obtained, and a polymer having a low gel content can be synthesized.

The tridentate or higher ligand used in the present invention may itself be a neutral molecule or an ion. The preferably used tridentate or higher ligand is a neutral molecule or an anion having a valence of 1 or more and less than the number of conformations.

Specific examples of the tridentate ligand include 1,2,3
-Trihydroxypropane, 2-amino-1,3-propanediol, 1,3-diamino-2-propanol,
1,3,5-trihydroxypentane, 3-amino-
1,5-pentanediol, 2,4,6-heptanetrione, 1-phenyl-1,3,5-hexanetrione,
Diethylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, di- (2-mercaptoethyl) thioether, bis (1-diphenylphosphinoethyl) ether, 3,3-diformyl-4-methylphenol, 3-formyl- Salicylic acid, diethylene triamine, 1,7-dimethyldiethylene triamine, 1,7
-Diethyldiethylenetriamine, 1,7-dipropyldiethylenetriamine, 1,7-diphenyldiethylenetriamine, 1,1,4,7,7-pentamethyldiethylenetriamine, N- (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl ) Phenylenediamine, N- (2-hydroxyethyl) -1,3-propanediamine, N- (3-hydroxypropyl) ethylenediamine, N- (3-hydroxypropyl)-
N ', N'-diethylethylenediamine, diethanolamine, di-2-propanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-
Propyldiethanolamine, N-phenyldiethanolamine, di-2-hydroxyethylthioether,
3-glycylamino-1-propanol, methyliminodiacetic acid, di- (2-pyridylmethyl) amine, di- (2
-Pyridylethyl) amine, di- (2-imidazolylmethyl) amine, di- (2-oxazolylmethyl) amine, di- (2-thiazolylmethyl) amine, N- (2-
Pyridylmethylidene) -N- (2-pyridylmethyl) amine, N- (2-furylmethylidene) -N- (2-pyridylmethyl) amine, N- (2-thiophenylmethylidene) -N- (2-pyridyl Methyl) amine, 2,2 ':
6 ′, 2 ″ -terpyridine, 3- (2-pyridylmethylimino) -2-butanone, 3- (2-pyridylmethylimino) -2-butanone oxime, 3- (2-pyridylethylimino) -2- Butanone oxime, 3- (2-aminoethylimino) -2-butanone oxime, 3- (2
-Hydroxyethylimino) -2-butanone, 4- (2
-Pyridylmethylimino) -2-pentanone, N-salicylidene- (2-pyridylmethyl) amine, N-salicylidene- (2-pyridylethyl) amine, N-salicylidene-N ', N'-dimethylethylenediamine, N-salicylidene -N ', N'-diethylethylenediamine,
N-salicylidene-N ', N'-dipropylethylenediamine, N-salicylidene-N', N'-diphenylethylenediamine, 4- (2-hydroxyethylimino)
-2-pentanone, 4- (2-hydroxypropylimino) -2-pentanone, 4- (3-hydroxypropylimino) -2-pentanone, 4- (2-hydroxycyclohexylimino) -2-pentanone, 4- ( 2-hydroxyphenylimino) -2-pentanone, 5- (2-
(Hydroxyethylimino) -3-heptanone, 1,1,
1,5,5,5-hexafluoro-4- (2-hydroxyethylimino) -2-pentanone, 1,1,1-trifluoro-4- (2-hydroxyethylimino) -2-
Pentanone, 4- (2-droxyethylimino) -3-
Methyl-2-pentanone, 4- (2-hydroxyethylimino) -3-ethyl-2-pentanone, 4- (2-hydroxyethylimino) -3-propyl-2-pentanone, 4- (2-hydroxyethylimino ) -3-Phenyl-2-pentanone, 4- (2-droxyethylimino) -3-methoxy-2-pentanone, 4- (2-hydroxyethylimino) -3-methoxycarbonyl-2-
Pentanone, 4- (2-hydroxyethylimino) -3
-Cyano-2-pentanone, 4- (2-hydroxyethylimino) -3-nitro-2-pentanone, 4- (2-
(Hydroxyethylimino) -3-chloro-2-pentanone, 3- (2-hydroxyethylimino) -1,3-diphenyl-1-propanone, 4- (2-hydroxyethylimino) -2-butanone, 5- ( 2-hydroxyethylimino) -3-pentanone, 6- (2-hydroxyethylimino) -4-hexanone, 5- (2-hydroxyethylimino) -2-methyl-3-pentanone, 5-
(2-hydroxyethylimino) -2,2-dimethyl-
3-pentanone, 3- (2-hydroxyethylimino)
-1-phenyl-1-propanone, N-salicylidene-
2-hydroxyethylamine, N-salicylidene-3-
Hydroxypropylamine, N-salicylidene-2-hydroxyaniline, N- (5-methylsalicylidene)-
2-hydroxyaniline, N- (5-methoxysalicylidene) -2-hydroxyaniline, N- (5-nitrosalicylidene) -2-hydroxyaniline, N- (3,5
-Dimethylsalicylidene) -2-hydroxyaniline,
N- (3,5-di-t-butylsalicylidene) -2-hydroxyaniline, N-salicylidene-2-hydroxy-5-methylaniline, N-salicylidene-2-hydroxy-5-nitroaniline, 3- (2-hydroxyethylimino) propionic acid, 3- (2-hydroxyethylimino) butyric acid, methyl 3- (2-hydroxyethylimino) propionate, ethyl 3- (2-hydroxyethylimino) propionate, 3- ( 2-hydroxyethylimino) propionic acid amide, N- (2-hydroxyethyl) malonic acid monoethyl ester monoamide, N-salicylideneglycine, N-salicylidenealanine, N-
Salicylidene valine, N-salicylideneleucine, tris (2-pyridyl) methane, trispirazolyl borate, 1,4,7-triazacyclononane and the like, or
Examples thereof include anions obtained by removing one or more protons from them.

A specific example of a tetradentate ligand is tris (2
-Pyridylmethyl) amine, tris (2-imidazolylmethyl) amine, tris (1-methyl2-imidazolylmethyl) amine, tris (2-benzimidazolylmethyl) amine, tris (2-benzoxazolylmethyl) amine
Amine, tris (2-benzthiazolylmethyl) amine, tris (1-pyrazolylmethyl) amine, tris (3,5-dimethyl-1-pyrazolylmethyl) amine,
Tris (3,5-dipropyl-1-pyrazolylmethyl)
Amine, tris (3,5-diphenyl-1-pyrazolylmethyl) amine, nitrilotriacetic acid, nitrilotriethanol, nitrilotri-1-propanol, tris (2-
Pyridyl-2-ethyl) amine, tris (1-pyrazolyl-2-ethyl) amine, N- (2-mercaptoethyl) -N, N-diethanolamine, N- (diphenylphosphinoethyl) -N, N-diethanolamine, Triethylene glycol, tripropylene glycol, triethylene tetramine, N, N ""-dimethyltriethylenetetramine, N, N, N "", N ""-tetramethyltriethylenetetramine, N, N'-bis (2
-Hydroxyethyl) ethylenediamine, N, N'-bis (3-hydroxypropyl) ethylenediamine, N,
N'-ethylenediamine diacetate, N, N'-bis (2-
Pyridylmethyl) ethylenediamine, N, N'-bis (2-imidazolylmethyl) ethylenediamine,
N'-bis (2-benzimidazolylmethyl) ethylenediamine, N, N'-bis (2-mercaptoethyl) ethylenediamine, N, N'-bis (diphenylphosphinoethyl) ethylenediamine, N, N'-disalicylideneethylenediamine , N, N'-bis (1-methyl-3
-Oxobutylidene) ethylenediamine, N-2-hydroxyethyl-N'-salicylideneethylenediamine,
N-2-hydroxyethyl-N′-salicylidene-1,
3-propylenediamine, N-3-hydroxypropyl-N′-salicylidene-1,3-propylenediamine,
N-3-hydroxypropyl-N'-salicylideneethylenediamine, N-2-dimethylaminoethyl-N'-
Salicylideneethylenediamine, N-2-pyridylmethyl-N'-salicylideneethylenediamine, N, N'-
Bis (2-amino-3-benzylidene) ethylenediamine, 1- (diacetylmonooximino) -3- (diacetylmonooximatimino) propane, 12-crown-4,1,4,8,11-tetraazacyclotetradecane 1,4,8,11-tetraazacyclotetradecane-5,7-dione, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, 1,4,7, 10-tetrathiacyclododecane,
2,3,9,10-tetramethyl-1,4,8,11-
Tetraazacyclotetradeca-1,3,8,10-tetraene, 5,7,12,14-tetramethyl-1,4,
8,11-tetraazacyclotetradeca-4,6,1
Examples thereof include 1,13-tetraene, porphyrin, and thalocyanine, and anions obtained by removing one or more protons therefrom.

Specific examples of the pentadentate ligand include tetraethylene glycol, tetrapropylene glycol, tetraethylenepentamine, N, N ′ ″-dimethyltetraethylenepentamine, N, N, N ′ ″, N '''-Tetramethyltetraethylenepentamine, N, N''-bis (2
-Hydroxyethyl) diethylenetriamine, N,
N "-bis (3-hydroxypropyl) diethylenetriamine, N, N" -diethylenetriamine, diacetate, N, N "-bis (2-pyridylmethyl) diethylenetriamine, N, N" -bis (2-imidazolyl Methyl) diethylenetriamine, N, N ″ -bis (2-
Benzimidazolylmethyl) diethylenetriamine,
N, N "-bis (2-mercaptoethyl) diethylenetriamine, N, N" -bis (diphenylphosphinoethyl) diethylenetriamine, N, N "-disalicylidenediethylenetriamine, N- (3-oxopentylidene) -N "-salicylidenediethylenetriamine, N, N" -bis (3-oxobutylidene) diethylenetriamine, N, N "-bis (3-oxobutylidene) -dipropylenetriamine, N, N" -bis (3 -Oxobutylidene) -N'-methyldipropylenetriamine, N, N "-bis (1-methyl-3-oxobutylidene) -N'-methyldipropylenetriamine, N, N" -bis (3-oxopentylidene )-
N'-methyldipropylenetriamine, N, N "-bis (3-oxohexylidene) -N'-methyldipropylenetriamine, N, N" -bis (4-methyl-3-
(Oxopentylidene) -N′-methyldipropylenetriamine, N, N ″ -bis (4,4-dimethyl-3-oxopentylidene) -N′-methyldipropylenetriamine, N, N ″ -bis ( 4-phenyl-3-oxobutylidene) -N′-methyldipropylenetriamine,
N, N "-bis (4-trifluoromethyl-3-oxobutylidene) -N'-methyldipropylenetriamine, N, N" -bis (2-cyano-3-oxobutylidene) -N'-methyldipropylenetriamine , N,
N "-bis (2-cyano-3-oxobutylidene)-
N'-methyldipropylenetriamine, N, N "-bis (2-nitro-3-oxobutylidene) -N'-methyldipropylenetriamine, N, N" -bis (2-carboxylethylidene) -N'- Methyldipropylenetriamine, N, N "-bis [2- (methoxycarbonyl) ethylidene] -N'-methyldipropylenetriamine, N, N" -bis [2- (dimethylaminocarbonyl) ethylidene] -N ' -Methyldipropylenetriamine, N, N '-(3-aza-5,5-pentylenelene)
-Bis (salicylic acid amide), N, N '-(3-aza-
1,5-pentylenelen) -bis (monomethylmonomalonate), N, N ″ -bis (1-methyl-3-oxobutylidene) diethylenetriamine, N-2-hydroxyethyl-N ″ -salicylidenediethylenetriamine, N-3-hydroxypropyl-N "-salicylidenediethylenetriamine, N-3-hydroxypropyl-N'-salicylideneethylenediamine, N-2-dimethylaminoethyl-N" -salicylidenediethylenetriamine, N- 2-pyridylmethyl-N ″ -salicylidenediethylenetriamine, N, N ″ -bis (2-
Amino-3-benzylidene) diethylenetriamine,
1,5-bis (salicylideneamino) -3-pentanol, 2,6-bis [N- (2-hydroxyethyl) iminomethyl] -4-methylphenol, 2,6-bis [N
-(3-hydroxypropyl) iminomethyl] -4-methylphenol, 2,6-bis [N- (2-hydroxyphenyl) iminomethyl] -4-methylphenol,
2,6-bis [N- (2-pyridylmethyl) iminomethyl] -4-methylphenol, 2,6-bis [N- (2
-Pyridylethyl) iminomethyl] -4-methylphenol, 2,6-bis [N- (2-dimethylaminoethyl) iminomethyl] -4-methylphenol, 2,6-
Bis [N- (2-pyridylmethyl) aminomethyl] -4
-Methylphenol, 2,6-bis [N- (2-pyridylethyl) aminomethyl] phenol, 15-crown-5,1,4,7,10,13-pentathiacyclopentadecane, or a proton therefrom And one or more anions thereof.

Specific examples of the hexadentate ligand include N, N,
N ′, N′-ethylenediaminetetraacetic acid, N, N, N ′,
N'-1,3-propylenediaminetetraacetic acid, N, N,
N ′, N′-1,2-phenylenediaminetetraacetic acid, N,
N, N ', N'-tetrakis (2-aminoethyl) ethylenediamine, N, N, N', N'-tetrakis (2-
Hydroxyethyl) ethylenediamine, N, N, N ',
N'-tetrakis (3-aminopropyl) ethylenediamine, N, N, N ', N'-tetrakis (3-hydroxypropyl) ethylenediamine, N, N, N', N'-tetrakis (2-dimethylaminoethyl) ethylenediamine N, N, N ', N'-tetrakis (2-mercaptoethyl) ethylenediamine, N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine,
N, N ′, N′-tetrakis (2-pyridylethyl) ethylenediamine, N, N, N ′, N′-tetrakis (2
-Imidazolylmethyl) ethylenediamine, N, N,
N ′, N′-tetrakis (2-benzimidazolylmethyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-oxazolylmethyl) ethylenediamine,
N, N ', N'-tetrakis (2-thiazolylmethyl)
Ethylenediamine, 1,2-bis [bis (2-hydroxyethyl) phosphino] ethane, 1,2-bis [6′-
Di (pyridin-2 "-yl) methylpyridin-2'-yl] ethane, pentaethylene glycol, pentaethylenehexaamine, 18-crown-6,1,4,7,1
0,13,16-hexamethyl-1,4,7,10,1
3,16-hexaazacyclooctadecane, 1,4
7,10,13,16-hexathiacyclooctadecane, N, N ″ ′-(diphenylphosphino) -tetraethylenetriamine, N, N′-bis [2- (2-hydroxyethylamino) ethyl] malonic acid Amides, N, N '
-Bis [2- (2-hydroxyethylamino) ethyl]
Oxalamide, 2,3-bis [2- (2-hydroxyethylamino) ethylimino] butane, 2,4-bis [2- (2-hydroxyethylamino) ethylimino]
Pentane, N, N'-bis [2- (2-aminoethylamino) ethyl] malonamide, N, N'-bis (5-
Amino-3-hydroxypentyl) malonic acid amide;
1,3-bis (3-formyl-5-methylsalicylideneamino) propane, 11,13-dimethyl-3,7,1
5,19-tetraazatricyclo [19.3.1.1]
9,13] hexacosa-2,7,9,11,13 (2
6), 14,19,21 (25), 22,24-decaene-25,26-diol, N, N'-ethylenebis (3-carboxysalicylideneamine), 5,5'-
Examples thereof include (1,2-ethanediyldinitrilo) bis (1-phenyl-1,3-hexanedione) and the like, and anions obtained by removing one or more protons therefrom.

Specific examples of the heptadentate ligand include 2,6-bis [bis (2-pyridylmethyl) aminomethyl] -4-
Methylphenol, 2,6-bis [bis (2-pyridylethyl) aminomethyl] -4-methylphenol,
6-bis [bis (2-dimethylaminoethyl) aminomethyl] -4-methylphenol, 2,6-bis [bis (2-imidazolylmethyl) aminomethyl] -4-methylphenol, 2,6-bis [bis (2-benzimidazolylmethyl) aminomethyl] -4-methylphenol, 2,6-bis [bis (2-oxazolylmethyl) aminomethyl] -4-methylphenol, 2,6-bis [bis (2- Thiazolylmethyl) aminomethyl] -4-
Methylphenol, 1,3-bis [bis (2-pyridylmethyl) amino] -2-propanol, hexaethylene glycol, N, N ″ ″-bis (2-hydroxyethyl) -tetraethylenepentamine, N ''''
-Bis (3-hydroxypropyl) -tetraethylenepentamine, N, N ""-bis (salicylidene) -tetraethylenepentamine, 2,6-bis [2- (2-
Hydroxyethylamino) ethyliminomethyl] -4-
Methylphenol, 2,6-bis [2- (2-hydroxyethylamino) ethylaminomethyl] -4-methylphenol, 2,6-bis [2- (2-aminoethylamino) ethyliminomethyl] -4- Methylphenol,
Examples thereof include 2,6-bis [2- (2-pyridylmethylamino) ethyliminomethyl] -4-methylphenol and the like, and anions obtained by removing one or more protons therefrom.

Specific examples of the octadentate ligand include heptaethylene glycol, N, N ″ ″ ′-bis (2-hydroxyethyl) -tetraethylenehexaamine,
N ″ ″ ″-bis (3-hydroxypropyl) -tetraethylenehexamine, N, N ″ ″ ″-bis (salicylidene) -tetraethylenehexamine, N, N ′
-Bis [2- {2- (2-hydroxyethylamino) ethylamino} ethylamino] malonamide, N, N'-
Bis [2- {2- (3-hydroxypropylamino) ethylamino} ethylamino] malonamide, N, N'-
Bis [2- {2- (2-aminoethylamino) ethylamino} ethylamino] malonamide, N, N′-bis [2- {2- (2-pyridylmethylamino) ethylamino} ethylamino] malonamide, Alternatively, an anion or the like obtained by removing one or more protons from them can be mentioned.

As a specific example of a ligand of 9 or more positions (m is an integer of 8 or more), a neutral molecule such as HO— (CH ₂ CH ₂ O) _m —H, Anions obtained by removing more than that can be cited.

In the ligand of the present invention, the number of conformations is 3
To 8, more preferably 3 to 6, and even more preferably 4.

In the ligand of the present invention, the coordinating atom is preferably a nitrogen atom or an oxygen atom.

In the transition metal complex catalyst of the present invention, the number of the transition metal atoms per one of the ligands must be more than 1/6 of the number of the ligands. The number of transition metal atoms is 2 or more in the case of a ligand, and 3 or more in the case of a 12-dentate ligand. Preferably, the number of the transition metal atoms per one ligand is 1 / (the number of the ligands).
More than 6 and less than the number of conformations of the ligand, more preferably more than 1/6 of the number of conformations of the ligand, and 1/3 of the number of conformations of the ligand It is as follows. When the number of transition metal atoms per one ligand is 1/6 or less of the number of conformations of the ligand, a reaction active site assumed on the transition metal atom is determined by the ligand. It is not preferable because it may be blocked and lose catalytic activity.

In the transition metal complex catalyst of the present invention, the structure other than the ligand and the transition metal atom is not particularly limited as long as the catalytic activity is not deactivated. In some cases, the transition metal complex catalyst of the present invention requires a counter ion to maintain electrical neutrality. As the counter anion, a conjugated base of Bronsted acid is usually used, and specific examples include fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, carbonate ion, perchlorate ion, Tetrafluoroborate ion, hexafluorophosphate ion, methanesulfonic acid ion, trifluoromethanesulfonic acid ion,
Examples include toluenesulfonic acid ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate ion, hydroxide ion, oxide ion, methoxide ion, ethoxide ion and the like. As the counter cation, a cation such as an alkali metal or an alkaline earth metal can be appropriately used. In the transition metal complex of the present invention, a solvent or the like may be coordinated during the raw material of the complex, the synthesis process and / or the oxidative polymerization process.

The transition metal complex catalyst of the present invention is preferably a complex represented by the following general formula (I). (Wherein, M represents a residue containing a Group 4-11 transition metal atom. R ¹ and R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, O ⁻ , a hydrocarbonoxy group, Represents a substituted hydrocarbonoxy group, an amino group or a substituted amino group,
R ² and R ⁵ each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, a hydrocarbon oxycarbonyl group, a substituted hydrocarbon oxycarbonyl group, a cyano group, or a nitro group. Or a halogen atom, and R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group or O ⁻ . R ⁷ represents a bifunctional hydrocarbon group or a substituted hydrocarbon group. R ¹ and R ² and / or R ⁵ and R ⁶ may form a ring. )

In the above general formula (I), M is the fourth to the first.
It is a residue containing a Group 1 transition metal atom, such as a Group 4-11 transition metal atom or a transition metal atom to which a group such as ＯO 2 is bonded.

The hydrocarbon group in the general formula (I) is preferably an alkyl group having 1 to 20 carbon atoms, an aralkyl group and an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group and an iso group. -Propyl group, n-butyl group, iso-butyl group, t-butyl group, pentyl group,
Cyclopentyl, hexyl, cyclohexyl, octyl, decyl, benzyl, phenyl, naphthyl and the like.

The substituted hydrocarbon group in the general formula (I) is a hydrocarbon group substituted with a halogen atom, an alkoxy group, an amino group, a substituted amino group, a nitro group, or the like.

[0028] O in the above general Formulas (I) ^- shows that removing one proton from the hydroxy group.

The hydrocarbon oxy group in the above formula (I) is preferably an alkoxy group having 1 to 20 carbon atoms and an aryloxy group, and specifically, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a hexyloxy group. Group, octyloxy group, phenoxy group, naphthoxy group and the like.

The substituted hydrocarbon oxy group in the general formula (I) is a hydrocarbon oxy group substituted with a halogen atom, an alkoxy group, an amino group and the like.
Examples include a trifluoromethoxy group, a 2-t-butyloxyethoxy group, and a 3-diphenylaminopropoxy group.

The substituted amino group in the general formula (I) is preferably a substituted amino group having 1 to 20 carbon atoms.
Specifically, methylamino group, ethylamino group, propylamino group, butylamino group, phenylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, methylethylamino group, methylpropylamino group , A methylbutylamino group, a diphenylamino group, a dinaphthylamino group, and the like.

The hydrocarbon oxycarbonyl group in the general formula (I) is preferably a hydrocarbon oxycarbonyl group having 1 to 20 carbon atoms, specifically, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, Examples include a t-butyloxycarbonyl group and a phenoxycarbonyl group.

The substituted hydrocarbon oxycarbonyl group in the above general formula (I) is a hydrocarbon oxycarbonyl group substituted by a halogen atom, an alkoxy group, an amino group and the like, and specific examples include a trifluoromethoxycarbonyl group, 2-t-butyloxyethoxycarbonyl group, 3-
And a diphenylaminopropoxycarbonyl group.

The halogen atom in the general formula (I) is preferably a chlorine atom, a bromine atom and an iodine atom, and more preferably a chlorine atom and a bromine atom.

In the above general formula (I), R ⁷ is a bifunctional hydrocarbon group or a substituted hydrocarbon group, and specific examples include a 1,2-ethylene group, a 1,2-propylene group,
Alkylene groups such as 1,3-propylene group and 1,4-butylene group; arylalkylene groups such as 1,2-diphenyl-1,2-ethylene group; 1,2-cyclopentylene group;
Cycloalkylene group such as 1,2-cyclohexylene group;
1,2-phenylene group, 1,2-naphthylene group, 2,3
Arylene groups such as -naphthylene group; substituted alkylene groups such as 1,2-tetrafluoroethylene group; and the like, preferably 1,2-ethylene group, 1,3-propylene group, and 1,2-diphenyl. -1,2-ethylene group,
A 1,2-cyclohexylene group and a 1,2-phenylene group.

Specific examples of the tetradentate ligand in the transition metal complex represented by the general formula (I) include N, N'-disalicylideneethylenediamine, N- (3-oxopentylidene) -N'- Salicylideneethylenediamine, N,
N'-bis (3-oxobutylidene) ethylenediamine, N, N'-bis (3-oxobutylidene) -1,3
-Propanediamine, N, N'-bis (3-oxobutylidene) -1,2-phenylenediamine, N, N'-bis (1-methyl-3-oxobutylidene) ethylenediamine, N, N'-bis (3-oxo (Pentylidene) ethylenediamine, N, N'-bis (3-oxohexylidene) ethylenediamine, N, N'-bis (4-methyl-
3-oxopentylidene) ethylenediamine, N, N '
-Bis (4,4-dimethyl-3-oxopentylidene)
Ethylenediamine, N, N'-bis (4-phenyl-3
-Oxobutylidene) ethylenediamine, N, N'-bis (4-trifluoromethyl-3-oxobutylidene)
Ethylenediamine, N, N'-bis (2-cyano-3-oxobutylidene) ethylenediamine, N, N'-bis (2-cyano-3-oxobutylidene) ethylenediamine, N, N'-bis (2-nitro-3-oxobutylidene) Ethylenediamine, N, N'-bis (2-carboxylethylidene) ethylenediamine, N, N'-bis [2- (methoxycarbonyl) ethylidene] ethylenediamine, N, N'-bis [2- (dimethylaminocarbonyl) ethylidene] ethylenediamine , N, N'-
(1,2-ethylene) -bis (salicylic acid amide),
N, N ′-(1,2-ethylene) -bis (malonic acid monomethylmonoamide) and the like, or an anion obtained by removing one or more protons therefrom can be mentioned.

The transition metal complex catalyst of the present invention is more preferably a complex represented by the following general formula (II). (Wherein, M represents a residue containing a Group 4-11 transition metal atom. R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group or a substituted hydrocarbon group, and R ⁷ represents a bifunctional R ^{8 to} R ¹⁵ each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, a substituted amino group,
Represents a nitro group or a halogen atom. )

In the above formula (II), M, a hydrocarbon group, a substituted hydrocarbon group, a bifunctional hydrocarbon group or a substituted hydrocarbon group, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, a substituted amino group, a halogen The atom is represented by the above general formula (I)
And the same as described above.

In the above general formula (II), R ³ , R ⁴ , R
^7, more preferably as R ⁸ to R ^15, a hydrogen atom or a hydrocarbon group R ^3, R ⁴ are each independently, R ⁷
Is an alkylene group, an arylalkylene group, a cycloalkylene group, or an arylene group, and R ^{8 to} R ¹⁵ are each independently a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbonoxy group, a substituted amino group, or a nitro group. , Chlorine atom,
It is a bromine atom. Particularly preferably, R ^3, R ⁴ are each independently a hydrogen atom, a methyl group, a phenyl group, R ⁷
Is 1,2-ethylene group, 1,3-propylene group, 1,2
-Diphenyl-1,2-ethylene group, 1,2-cyclohexylene group, 1,2-phenylene group, and R ^{8 to} R ¹⁵
Are each independently a hydrogen atom, a methyl group, an ethyl group, n-
Propyl group, iso-propyl group, n-butyl group, t-
Butyl, benzyl, trifluoromethyl, methoxy, dimethylamino, nitro, chlorine and bromine.

The method for synthesizing the transition metal complex of the present invention is, for example, as follows.
It can be obtained by a general method as described in J. Inorg. Nucl. Chem., 1974, Vol. 36, pp. 531. As the transition metal complex, a complex synthesized in advance can be used, but the complex may be formed in a reaction system.

In the present invention, the catalysts can be used alone or as a mixture. In the present invention, the catalyst can be used in any amount,
-0.01-50 mol% is preferable, and 0.02-10 mol% is more preferable as a molar amount equivalent to a transition metal atom with respect to naphthol.

(2) Reaction Solvent As the reaction solvent of the present invention, an organic solvent is used. When water is used as the solvent, CC-coupled dinaphthoquinone becomes the main product, which is not preferable. Preferred organic solvents include aromatic hydrocarbons such as benzene, toluene and xylene; linear and cyclic aliphatic hydrocarbons such as heptane and cyclohexane; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene and dichloromethane; acetonitrile, benzonitrile Nitriles such as methanol, ethanol, n-propyl alcohol, iso-
Alcohols such as propyl alcohol; ethers such as dioxane, tetrahydrofuran and ethylene glycol dimethyl ether; N, N-dimethylformamide, N
Amides such as methylpyrrolidone; nitro compounds such as nitromethane and nitrobenzene. These are used alone or as a mixture. More preferred organic solvents are mixed solvents of aromatic hydrocarbons and alcohols.

The reaction solvent has a concentration of 1-naphthol of preferably 0.5 to 50% by weight, more preferably 1 to 30% by weight.
It is used in such a ratio as to be% by weight.

(3) Oxidative polymerization In the present invention, any oxidizing agent may be used.
Preferably, oxygen or peroxide can be used. Oxygen may be a mixture with an inert gas or air. Examples of peroxides include hydrogen peroxide, t
-Butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, peracetic acid, perbenzoic acid, and the like. Oxygen is more preferably used as the oxidizing agent.

In the present invention, the use amount of the oxidizing agent is not particularly limited. When oxygen is used, it is generally used in an excess of 1 equivalent or more relative to 1-naphthol. When peroxide is used, it is usually used in an amount of at least 3 equivalents to 1-naphthol, but it is preferable to use at least 2 equivalents.

When the transition metal complex catalyst has, as a counter ion, a conjugate base of an acid stronger than naphthol, a base that does not inactivate the transition metal complex catalyst is used.
It is preferable to use a counter ion and an equivalent or more at the time of polymerization. Examples of such bases include hydroxides, oxides and alkoxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, calcium oxide, sodium methoxide and sodium ethoxide. Usually commonly used are alkali metal hydroxides and alkoxides, particularly preferably alkali metal hydroxides. These bases are preferably supplied to the reaction system as they are or in a state of being dissolved in a polar solvent such as alcohol.

The reaction temperature for carrying out the present invention is not particularly limited as long as the reaction medium is kept in a liquid state. Even when the pressure is equal to or higher than the boiling point at normal pressure, it is possible to maintain the liquid state by pressurization. A preferred temperature range is -20C to 100C, more preferably 0C to 60C.

[0048]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited by these examples.

Infrared absorption spectrum analysis of polymer: measured using a 1600 infrared spectrophotometer (KBr method) manufactured by PerkinElmer.

Gel content of polymer [%]: The polymer was dissolved in chloroform at room temperature, and the insoluble portion was collected by filtration and dried under reduced pressure at 100 ° C. for 5 hours. The percentage of the weight of the chloroform-insoluble portion obtained relative to the charged weight of the polymer was defined as the gel content [%].

Weight average molecular weight (Mw), number average molecular weight (Mn) of the polymer: gel permeation chromatography (pump: 600E system manufactured by Waters, detector: UV / VIS-484 manufactured by Waters, detection wavelength: 254 nm) , Column: Ultrastyra manufactured by Waters
gel Linear = 1 + 1000A = 1 + 100A = 1
(Developing solvent: chloroform), and the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured as standard polystyrene equivalent values.

The complex used in this example was the following complex (Mn
(tBu, Me-salchen). ),

The following complexes (abbreviated as Mn (tBu, Me-saldpen)) and

The following complex (abbreviated as Mn (salen)) is shown. The synthesis of these complexes is described in J. Inorg. Nucl. Chem., 1974, Vol.
6, pp. 531.

Example 1 In a 100 ml two-necked round bottom flask equipped with a magnetic stirrer,
An oxygen gas inlet tube was attached. Mn (tBu, Me-salche
n) 0.32 mmol, sodium hydroxide 1.28 mmol
1 was dissolved in 18.5 g of methanol.
A solution obtained by dissolving 50 mmol of naphthol in 31.5 g of xylene was added. Place the flask in a water bath at 40 ° C
While stirring, while blowing oxygen gas,
The reaction was performed for 5 hours. After completion of the reaction, the mixture was acidified with concentrated hydrochloric acid and added to 500 ml of methanol with stirring. The precipitated polymer was collected by filtration, washed three times with 50 ml of methanol, and washed with 10 ml of methanol.
It dried under reduced pressure at 0 degreeC for 5 hours. The results are shown in Table 1, and the infrared absorption spectrum is shown in FIG.

Examples 2-3 A polymer was obtained in the same manner as in Example 1 except that the catalyst was changed as shown in Table 1. Table 1 shows the results.

[0057]

[Table 1]

[0058]

As described above, 1-naphthol is oxidized in an organic solvent using the transition metal complex catalyst comprising a tridentate or higher ligand of the present invention and a transition metal atom belonging to groups 4 to 11 of the present invention. By the polymerization method, a 1-naphthol polymer having extremely low gel content and excellent heat resistance can be synthesized in high yield.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of the polymer of Example 1.

Claims (8)

[Claims] 1. The method according to claim 1, wherein the coordination atom is a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom.
The number of transition metal atoms of the group 1 to group 11 is 1 / the number of conformations of the ligand.
Polymerizing 1-naphthol in the presence of an oxidizing agent in an organic solvent using more than six transition metal complex catalysts
A method for producing a naphthol polymer. 2. The 1-transition metal complex according to claim 1, wherein the transition metal complex is a transition metal complex of the first transition metal series.
A method for producing a naphthol polymer. 3. The method for producing a 1-naphthol polymer according to claim 1, wherein the ligand is a nitrogen atom or an oxygen atom. 4. The method for producing a 1-naphthol polymer according to claim 1, wherein said ligand has a conformation number of 3 to 8. 5. The method according to claim 1, wherein the number of transition metal atoms per ligand is more than 1/6 of the number of conformations of the ligand and is equal to or less than the number of conformers. 5. The method for producing a 1-naphthol polymer according to any one of items 1 to 4. 6. The transition metal complex catalyst according to the following general formula (I)
3. 1- according to claim 1 or 2, characterized by:
A method for producing a naphthol polymer. (Wherein, M represents a residue containing a Group 4-11 transition metal atom. R ¹ and R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, O ⁻ , a hydrocarbonoxy group, Represents a substituted hydrocarbonoxy group, an amino group or a substituted amino group,
R ² and R ⁵ each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, a hydrocarbon oxycarbonyl group, a substituted hydrocarbon oxycarbonyl group, a cyano group, or a nitro group. Or a halogen atom, and R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group or O ⁻ . R ⁷ represents a bifunctional hydrocarbon group or a substituted hydrocarbon group. R ¹ and R ² and / or R ⁵ and R ⁶ may form a ring. ) 7. The transition metal complex catalyst according to the following general formula (II)
3. 1- according to claim 1 or 2, characterized by:
A method for producing a naphthol polymer. (Wherein, M represents a residue containing a Group 4-11 transition metal atom. R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group or a substituted hydrocarbon group, and R ⁷ represents a bifunctional R ^{8 to} R ¹⁵ each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, a substituted amino group,
Represents a nitro group or a halogen atom. ) 8. The method according to claim 1, wherein the oxidizing agent is oxygen or peroxide.
A method for producing a naphthol polymer.