JP2002080587A - Method of producing oxyphenol oxidative condensate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing an oxidative polycondensate of an oxyphenol having increased heat stability by increasing the reactivity in the oxidative polycondensation reaction of the oxyphenol. SOLUTION: An oxyphenol represented by formula (I) (wherein R1-R5 are mutually independent and each H atom, a hydrocarbon group, a substituted hydrocarbon group, amino group, a hydrocarbonoxy group, a substituted hydrocarbonoxy group, amino group, a substituted amino group, mercapto group, a substituted mercapto group or a halogen atom; R1 and R2, R2 and R3, R3 and R4 and/or R4 and R5 may form a ring, but any one among R1 through R5 is an aliphatic hydrocarbonoxy group or a substituted aliphatic hydrocarbonoxy group and any one among R1, R3 and R5 is H atom) is subjected to the oxidative polycondensation reaction in the presence of a copper complex catalyst comprising a tridentate ligand compound bearing a nitrogen atom as a ligand atom and a copper atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an oxyphenol oxidized condensate.

[0002]

2. Description of the Prior Art Oxidative condensation of phenols
18692) is a formalin-free, room temperature reaction,
Since by-products can be produced by an environmentally friendly oxidative condensation method of using only water, they have recently attracted particular attention. (Chemistry and Industry, Vol. 53, No. 4, 501-505 (2000)). The present inventors, in the oxidative polymerization of a number of phenols,
A method using a tridentate ligand / copper complex catalyst is proposed.
JP-A-10-45899 discloses an oxidative polymerization of phenol, JP-A-10-45904 discloses an oxidative polymerization of 4-phenoxyphenol, and JP-A-10-168180 discloses an oxidative polymerization of 2-phenylphenol.
No. 559 reports the oxidative polymerization of alkylphenols. It is described that the use of the present copper complex catalyst shows activity in a low-temperature reaction, gives a polymer having few ortho branches or CC bonds, and improves the thermal stability of the obtained polymer. However, the properties of these reactions and their products change when the phenols are different, and cannot be easily inferred. For example, the effect of using a tridentate ligand / copper complex catalyst is determined by phenols and reaction conditions. For example,
Regarding 2-phenylphenol, if it is polymerized in a specific reaction solvent and at a specific reaction temperature, copper / tridentate ligand catalyst (Example 1 of JP-A-10-168180) can be used to produce copper / phenylphenol. Bidentate ligand catalyst (JP-A-10-16817)
Even when Example 2) of JP-A No. 9 is used, a temperature of 100 ° C.
The weight loss up to 400 ° C. was substantially similar. Regarding the oxidative polymerization of 2,5-dimethylphenol, in Japanese Patent No. 3035559, the copper / bidentate ligand catalyst (Example 2) was replaced by the copper / bidentate ligand catalyst (Comparative Example 1). ), The reaction rate was lower.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a production method capable of obtaining a condensate having enhanced thermal activity and improved thermal stability in oxidative condensation of an oxyphenol compound.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above problems and found that the above problems can be solved by the following invention. (1) The oxyphenol compound represented by the general formula (I) is oxidatively condensed in the presence of a copper complex catalyst comprising a tridentate ligand compound in which a coordinating atom is a nitrogen atom and a copper atom. A method for producing an oxyphenol oxidized condensate.

[0005]

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(Wherein R ^{1 to} R ⁵ independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbonoxy group, a substituted hydrocarbonoxy group, an amino group, a substituted amino group,
Mercapto group, a substituted mercapto group or a halogen atom, but ^{R 1} and ^R 2, ^{R 2} and ^R 3, ^{R 3} and ^{R 4} and / or ^{R 4} and ^{R 5} may form a ring, ^{R 1} any one of to R ⁵ is an aliphatic hydrocarbon group or a substituted aliphatic hydrocarbon group, one of R ^1, R ³ or R ⁵ is a hydrogen atom. (2) The method for producing an oxyphenol oxidative condensate according to (1), wherein the copper complex catalyst is represented by the general formula (II).

[0007]

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(Where R⁶Is a hydrocarbon group, substituted hydrocarbon
Represents a group or a hydrogen atom; ⁶Are the same but different
It may be. R⁷Is a divalent hydrocarbon group or substituted carbon
Represents a hydride group, and all R⁷Are the same but different
Is also good. X is a counter anion, and n is the number of X
And is appropriately determined by the valences of copper and X. )

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The process for producing an oxyphenol oxidized condensate according to the present invention comprises the steps of: converting an oxyphenol compound represented by the above general formula (I) into a tridentate ligand compound whose coordinating atom is a nitrogen atom; This is a method characterized by carrying out oxidative condensation in the presence of an atomic copper complex catalyst. The hydrocarbon group for R ^{1 to} R ⁵ in the general formula (I) is preferably an alkyl group having 1 to 30 carbon atoms (more preferably 1 to 20 carbon atoms), or a carbon group having 3 to 30 carbon atoms. (More preferably having 3 to 20 carbon atoms), an aralkyl group having 7 to 30 carbon atoms (more preferably having 7 to 20 carbon atoms) or 6 to 30 carbon atoms.
(More preferably having 6 to 20 carbon atoms) aryl group, specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, t- Butyl group, pentyl group, cyclopentyl group,
Hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, pentadecyl group, octadecyl group, benzyl group, 2-phenylethyl group, 1-phenylethyl group, phenyl group, 4-methylphenyl group, 1-naphthyl group, And a 2-naphthyl group.

The substituted hydrocarbon group for R ^{1 to} R ⁵ in the general formula (I) is preferably a halogen atom, a hydroxyl group,
C1-C30 substituted with an alkoxy group, amino group, substituted amino group or the like (more preferably C1-C3)
An alkyl group having 20 to 30 carbon atoms, more preferably a cycloalkyl group having 3 to 30 carbon atoms (more preferably, having 3 to 20 carbon atoms), and a cycloalkyl group having 7 to 30 carbon atoms, and more preferably having 7 to 20 carbon atoms.
An aralkyl group or an aryl group having 6 to 30 carbon atoms (more preferably, 6 to 20 carbon atoms), and specific examples thereof include a trifluoromethyl group, a 2-t-butyloxyethyl group, And a dimethylaminopropyl group. The aliphatic hydrocarbon oxy group for R ^{1 to} R ⁵ in the general formula (I) is preferably a group having 1 carbon atom.
An alkoxy group having from 100 to 100 carbon atoms, a cycloalkoxy group having from 3 to 100 carbon atoms, an alkenyloxy group having from 2 to 100 carbon atoms or an alkynyloxy group having from 2 to 100 carbon atoms, specifically, a methoxy group and an ethoxy group , N-propoxy group, iso-propoxy group, n-butoxy group,
iso-butoxy group, t-butoxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, cyclohexyloxy group, octyloxy group, nonyloxy group, dodecyloxy group, pentadecyloxy group, octadecyloxy group, docosyloxy group, triacetate Contyloxy group, hexacontyloxy group, allyloxy group, 3
-Propenyloxy group and the like.

The substituted aliphatic hydrocarbonoxy group represented by R ^{1 to} R ⁵ in the general formula (I) is preferably a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a substituted amino group, or the like. 1 to 100 alkoxy group, cycloalkoxy group having 3 to 100 carbon atoms, 2 carbon atoms
-100 alkenyloxy groups or 2-1 carbon atoms
00 is an alkynyloxy group, and specific examples thereof include a trifluoromethoxy group, a 2-t-butyloxyethoxy group, and a 3-dimethylaminopropoxy group.
The substituted amino group in R ^{1 to} R ⁵ in the general formula (I) is an amino group substituted with one or two hydrocarbon groups, and preferably has 1 to 30 carbon atoms (more preferably, 1 to 30 carbon atoms). An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms (more preferably, 3 to 20 carbon atoms), and a cycloalkyl group having 7 to 30 carbon atoms (more preferably, 7 to 30 carbon atoms) 20) aralkyl groups or 6 to 30 carbon atoms (more preferably 6 to 20 carbon atoms)
An amino group substituted with an aryl group, specifically, a methylamino group, a dimethylamino group, a diethylamino group,
-n-propylamino group, di-iso-propylamino group, di-n-butylamino group, di-iso-butylamino group, di-t-butylamino group, pentylamino group, cyclopentylamino group, hexylamino group , Cyclohexylamino, octylamino, nonylamino, benzylamino, 2-phenylethylamino, 1-phenylethylamino, phenylamino, 4-methylphenylamino, 4-ethylphenylamino and the like. Can be

The substituted mercapto group in R ^{1 to} R ⁵ in the general formula (I) is a mercapto group substituted with a hydrocarbon group, and preferably has 1 to 30 carbon atoms (more preferably, carbon atom). An alkyl mercapto group having 1 to 20 carbon atoms, a cycloalkyl mercapto group having 3 to 30 carbon atoms (more preferably 3 to 20 carbon atoms), and a C 7 to C 30 carbon atom (more preferably 7 to 20 carbon atoms) 20) an aralkyl mercapto group or an aryl mercapto group having 6 to 30 carbon atoms (more preferably, 6 to 20 carbon atoms), specifically, a methyl mercapto group, an ethyl mercapto group, an n-propyl mercapto group, iso-propyl mercapto group, n-butyl mercapto group, iso-
Butyl mercapto group, t-butyl mercapto group, pentyl mercapto group, cyclopentyl mercapto group, hexyl mercapto group, cyclohexyl mercapto group, octyl mercapto group, nonyl mercapto group, benzyl mercapto group, 2-phenylethyl mercapto group, 1-phenylethyl mercapto group Group, phenylmercapto group, 4-methylphenylmercapto group, 4-ethylphenylmercapto group and the like.

In the general formula (I), R¹~ R⁴C in
Rogen atoms are fluorine, chlorine, bromine,
Uranium atom, fluorine atom, chlorine atom, bromine
Atoms are more preferred, and fluorine and chlorine atoms are even more preferred.
Good. R of the above general formula (I)¹~ R⁵Of which R¹When
R², R²And R³, R³And R⁴And / or R⁴And R⁵But
When forming a ring, a 5- to 7-membered ring is preferable.¹And R
², R²And R³, R³And R⁴And / or R⁴And R⁵But-
(CH₂)₃-Group,-(CH₂)₄-Group or -CH = C
H-CH = CH- to form a ring
Is more preferred. R of the above general formula (I)¹~ R⁵Horse
At least one group is an aliphatic hydrocarbonoxy group or
Is a substituted aliphatic hydrocarbonoxy group. The oxy-based charcoal
The number of elementary atoms is preferably 1 to 100, more preferably
It is preferably 1 to 50, and more preferably 1 to 30.
And particularly preferably 1 to 22. Placement of the oxy group
The number of permutations is 1 to 4, preferably 1 to 3, or 1 or
2 is more preferable and 1 is particularly preferable. Placement of the oxy group
When the permutation is 1, the substitution position is R¹~ R³Any of
Where R²Is particularly preferred. The oxy group
Is preferably an aliphatic hydrocarbonoxy group,
And a cycloalkyl group is more preferred.
Groups are more preferred, and linear alkyl groups are particularly preferred.
No. R of the above general formula (I)¹~ R⁵In, aliphatic coal
Other than hydrogen oxy group or substituted aliphatic hydrocarbon oxy group
Is preferably a hydrogen atom, a carbon atom number of 1 to 9
A hydrocarbon group or a substituted hydrocarbon group having 1 to 9 carbon atoms
Or a halogen atom, more preferably a hydrogen atom
Or a hydrocarbon group having 1 to 6 carbon atoms, more preferably
Preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
And particularly preferably a hydrogen atom.

In the present invention, the oxyphenol compound represented by the general formula (I) may be obtained by oxidative condensation of the oxyphenol compound alone or as a mixture.
Or a phenol compound represented by the formula (IV) and / or a bisphenol compound represented by the following general formula (V), followed by oxidative condensation.

[0015]

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Wherein R ⁸ is independently of each other a hydrogen atom,
A hydrocarbon group having 1 to 9 carbon atoms, a substituted hydrocarbon group having 1 to 9 carbon atoms, a hydrocarbon oxy group having 1 to 9 carbon atoms,
A substituted hydrocarbon oxy group having 1 to 9 carbon atoms, an amino group,
A substituted amino group having 1 to 9 carbon atoms, a mercapto group, a substituted mercapto group having 1 to 9 carbon atoms or a halogen atom, and two adjacent R ⁸ may form a ring.
R ⁹ represents an oxygen atom, a sulfur atom, a divalent hydrocarbon group or a divalent substituted hydrocarbon group, and m is 1 or 0. ) A hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, a substituted amino group, a mercapto group, a mercapto group, or a halogen atom hydrocarbon group for R ⁸ in the general formulas (III) to (V). Are the same as those of R ¹ in the above general formula (I), except that the number of carbon atoms is limited to 1 to 9. The general formula (III) to
Of ^{R 8} of (V), when the two ^{R 5} adjacent to form a ring, 5-7 membered ring is preferred, two adjacent ^{R 8}
There - (CH _{2) 3} - group, - (CH _{2) 4} - group or -CH
More preferably, they form a ring as a ＝ CH—CH ＝ CH— group. R ^{8 in the} above general formulas (III) to (V) is preferably a hydrogen atom or a carbon atom having 1 to 9 carbon atoms.
A hydrocarbon group, a substituted hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, more preferably a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, still more preferably a hydrogen atom or a carbon atom. An alkyl group having 1 to 4 atoms, particularly preferably a hydrogen atom or a methyl group.

The divalent hydrocarbon group represented by R ⁹ in the above formula (V) includes an alkylene group having 1 to 9 carbon atoms,
An aralkylene group having 7 to 9 carbon atoms or an arylene group having 6 to 9 carbon atoms is preferable. Specific examples include a methylene group, a 1,1-ethylene group, a 1,2-ethylene group,
1,1-propylene group, 1,3-propylene group, 2,2
-Propylene group, 1,1-butylene group, 2,2-butylene group, 3-methyl-2,2-butylene group, 3,3-dimethyl-2,2-butylene group, 1,1-pentylene group, 3 ,
3-pentylene group, 1,1-hexylene group, 1,1-heptylene group, 1,1-octylene group, 1,1-nonylene group, 1,1-cyclopentylene group, 1,1-cyclohexylene group Phenylmethylene group, 1-phenyl-1,1
-An ethylene group, a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group.

The divalent substituted hydrocarbon group for R ⁹ in the above formula (V) includes a halogen atom, an alkoxy group,
An alkylene group having 1 to 9 carbon atoms, an aralkylene group having 7 to 9 carbon atoms, or an arylene group having 6 to 9 carbon atoms, which is substituted with a disubstituted amino group or the like, is preferred. -2,2-propylene group, pentafluorophenylmethylene group, 4-methoxyphenylmethylene group, 4-dimethylaminophenylmethylene group and the like. As R ^{9 in the} above general formula (V), an oxygen atom or a divalent hydrocarbon group is preferable, and an alkylene group having 1 to 9 carbon atoms or a C 7 to 9 carbon atom is preferable.
Are more preferable, and an alkylene group having 1 to 6 carbon atoms is more preferable.

A catechol monoether compound represented by the above formula (I), a phenol compound represented by the above formula (III), a phenol compound represented by the above formula (IV) and / or a phenol compound represented by the above formula (IV) When a mixture of the bisphenol compounds represented by (V) is used, the mixing ratio is appropriately determined within a range that does not impair the physical properties of the desired condensate. It is at least 30 mol%, more preferably at least 50 mol%, further preferably at least 80 mol% (these phenols may be hereinafter referred to as phenolic starting materials).

The catalyst used in the present invention is a copper complex catalyst comprising a tridentate ligand whose coordinating atom is a nitrogen atom and a copper atom. The tridentate ligand in the copper complex catalyst is a tridentate ligand whose coordinating atom is a nitrogen atom. The 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 Chemical Dojin, 1989). The atoms directly involved in the bond are called coordinating atoms. A tridentate ligand is a ligand having three coordinating atoms.

The tridentate ligand used in the copper complex catalyst is not particularly limited, except that the coordinating atom is a nitrogen atom. Specific examples of such tridentate ligands include diethylenetriamine, bis (2-pyridylmethyl) amine, bis (2-pyridylethyl) amine, bis (2-imidazolylmethyl) amine, bis (2-oxazolylmethyl) ) Amine, bis (2-thiazolylmethyl) amine, N- (2
-Pyridylmethylidene) -N- (2-pyridylmethyl)
Amine, 2,2 ': 6', 2 "-terpyridine, 3-
(2-pyridylmethylimino) -2-butanone oxime, tris (2-pyridyl) methane, tris (2-imidazolyl) methane, tris (1-pyrazolyl) methane,
Tris (1-pyrazolyl) phosphate, tris (1-
Pyrazolyl) borate, 1,4,7-triazacyclononane, and the like, and derivatives thereof. The valence of the copper atom in this copper complex catalyst is from 0 to 3
The valence is preferably monovalent or divalent. In this copper complex catalyst, the ratio between the tridentate ligand and the copper atom is not particularly limited, but as the complex to be substantially formed, one or more copper atoms per one tridentate ligand are preferable. . More preferably 1
３3, more preferably 1.

In the copper complex catalyst, the structure other than the ligand and the copper atom is not particularly limited as long as the catalytic activity is not deactivated. Further, a solvent or the like may be coordinated to the copper complex catalyst during the complex raw material, the synthesis process and / or the oxidative condensation process. In some cases, the copper complex catalyst 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, nitrate, carbonate, perchlorate, tetrafluoroborate, hexafluorophosphate, methanesulfonate, trifluoromethanesulfonate, toluenesulfonate, acetate, trifluoroacetate, propion Acid ions, benzoate ions, hydroxide ions, oxide ions, methoxide ions, ethoxide ions and the like can be mentioned. As the counter anion, preferably chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, acetate ion, hydroxide ion or methoxide ion, more preferably chloride ion, bromide ion, sulfate ion or It is a nitrate ion. As the counter cation, a cation such as an alkali metal or an alkaline earth metal can be appropriately used. The copper complex catalyst is more preferably a copper complex represented by the above general formula (II).

The hydrocarbon group represented by R ⁶ in the general formula (II) includes an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a C 7 to 20 carbon atom.
Aralkyl group or aryl group having 6 to 20 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-
Butyl, t-butyl, 1-pentyl, 3-pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, 3,5 -Dimethylcyclohexyl group, benzyl group, 2-phenylethyl group, 1-phenylethyl group, phenyl group, 1-naphthyl group, 2-naphthyl group and the like.

The substituted hydrocarbon group represented by R ⁶ in the general formula (II) is the above-mentioned preferred hydrocarbon group substituted by a halogen atom, an alkoxy group, a disubstituted amino group and the like. Examples include a phenylmethyl group, a methoxyethyl group, a diphenylaminopropyl group and the like. As R ^{6 in the} general formula (II), a hydrocarbon group is preferable, an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms is more preferable, and an alkyl group having 2 to 12 carbon atoms is preferable. Is more preferred. As the divalent hydrocarbon group for R ⁷ in the general formula (II), an alkylene group having 1 to 20 carbon atoms or a C ⁶ to C 6
20 arylene groups are preferred, and specific examples include a methylene group, a 1,2-ethylene group, a 1,2-propylene group,
1,3-propylene group, 2,4-butylene group, 2,4-
Dimethyl-2,4-butylene group, 1,2-diphenyl-
1,2-ethylene, 1,2-cyclopentylene group, 1,
Examples thereof include a 2-cyclohexylene group and a 1,2-phenylene group. The divalent substituted hydrocarbon group for R ⁷ in the general formula (II) is a halogen atom, an alkoxy group,
The preferred divalent hydrocarbon group substituted with a disubstituted amino group or the like, and specific examples thereof include tetrafluoro-
Examples thereof include a 1,2-ethylene group, a 4,5-dimethoxy-1,2-phenylene group, and a 4-dimethylamino-1,2-phenylene group. R ^{7 in the} above general formula (II) is preferably a divalent hydrocarbon group, and has 1 to 1 carbon atoms.
20 alkylene groups are more preferred, and having 2 to 6 carbon atoms.
Are more preferred, and a 1,2-ethylene group is particularly preferred.

In the above general formula (II), the valence of copper is usually 1 or 2, X is a counter anion,
n is the number of X and is determined by the valence of copper. In the general formula (II), the structure other than the above is not particularly limited as long as the catalyst ability is not deactivated. Further, a solvent or the like may be coordinated in the raw material of the complex, in the synthesis process and / or the oxidative coupling reaction process.

The copper complex can be synthesized, for example, by a method in which a tridentate ligand compound and a copper compound are mixed in an appropriate solvent. As the copper compound, a Bronsted acid salt of copper or the like is appropriately used. As the tridentate ligand compound, commercially available products can be used as appropriate, but J. Chem. So
c. Dalton Trans., 83-90 (1993). and J. Am. Chem. So
c., 8865-8866, 117 (1995) and the like. As the copper complex, a complex synthesized in advance can be used, but the complex may be formed in a reaction system. The catalyst can be used in any amount, but is generally used in an amount of 0.0 as copper relative to the phenolic starting material.
It is preferably from 0.01 to 50 mol%, more preferably from 0.01 to 10 mol%.

When the copper valence of the copper complex is divalent and a conjugate base of an acid stronger than phenol is used as a counter ion, a base which does not inactivate the copper complex catalyst is added to the counter ion. It is preferable that 1/4 equivalent or more of the above is coexisted at the time of condensation. Examples of such bases include:
Sodium hydroxide, potassium hydroxide, calcium oxide,
Hydroxides, oxides, alkoxides of alkali metals or alkaline earth metals such as sodium methoxide and sodium ethoxide; methylamine, ethylamine,
Amines such as propylamine, butylamine, dibutylamine and triethylamine; and pyridines such as pyridine, 2-methylpyridine, 2,6-dimethylpyridine and 2,6-diphenylpyridine. Alkoxides, amines or pyridines as counter ions
It is more preferable to make / 4 equivalents or more coexist, and it is more preferable to make pyridines coexist in 以上 equivalent or more.

The oxidizing agent in the oxidative condensation reaction of the present invention includes:
Oxygen or peroxide is preferred. Oxygen may be a mixture with an inert gas or air. Examples of the peroxide include hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide,
Cumene hydroperoxide, dicumyl peroxide, peracetic acid, perbenzoic acid and the like can be shown. More preferred oxidizing agents are oxygen or hydrogen peroxide. The amount of the oxidizing agent is not limited, but when oxygen is used, it is usually used in a large excess of 0.5 equivalent or more based on phenol, and when peroxide is used, usually 0.5 to Use 3 equivalents. As the oxidizing agent, oxygen is preferable. The oxidative condensation can be carried out in the absence of a reaction solvent, but it is generally preferable to use a solvent. The solvent is not particularly limited as long as it is inert to the phenolic starting material and liquid at the reaction temperature. Preferred examples of the solvent 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 , Nitriles such as benzonitrile; methanol, ethanol, n-
Alcohols such as propyl alcohol and iso-propyl alcohol; ethers such as dioxane, tetrahydrofuran and ethylene glycol dimethyl ether;
Amides such as N-dimethylformamide and N-methylpyrrolidone; nitro compounds such as nitromethane and nitrobenzene; and water. Aromatic hydrocarbons, chain and cyclic aliphatic hydrocarbons, halogenated hydrocarbons, nitriles, ethers or nitro compounds are more preferred, and aromatic hydrocarbons or halogenated hydrocarbons are more preferred. These are used alone or as a mixture.

When the solvent is used, it is used in such a ratio that the concentration of the phenolic starting material is preferably 0.5 to 50% by weight, more preferably 1 to 30% by weight.
The reaction temperature of the oxidative condensation is not particularly limited as long as the reaction medium is kept in a liquid state. If no solvent is used, a temperature above the melting point of the phenolic starting material is required. A preferred temperature range is 0 ° C to 200 ° C, more preferably 0 ° C to
The temperature is 150C, more preferably 0C to 100C. When this reaction is carried out from the viewpoint of energy saving, a preferable reaction temperature is 10 ° C to 60 ° C. The reaction time varies depending on conditions such as the amount of catalyst and reaction temperature,
It is usually 1 hour or more, preferably 3 to 300 hours. The condensate obtained by the production method of the present invention has a structure having a repeating unit represented by the following basic structural formula (VI) and / or the following basic structural formula (VII).

[0030]

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[0031]

EXAMPLES 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. (I) Raw material synthesis and analysis Raw material synthesis: n-octadecyloxy group-substituted phenolic starting materials are described in J. Am. Chem. Soc., 120, 12274 (199).
Synthesized with reference to 8).

The conversion of the phenolic starting material (Con
v.): 15 mg of a reaction mixture containing diphenyl ether as an internal standard was sampled, acidified by adding a small amount of concentrated hydrochloric acid, and 2 g of methanol was added to obtain a measurement sample. This sample was subjected to high performance liquid chromatography (SC8020 system manufactured by Tosoh Corporation, detector: PD-8020 manufactured by Tosoh Corporation, detection wavelength: 278 nm, column: Y
Analysis was performed using ODS-AM manufactured by MC, developing solvent: methanol / water or tetrahydrofuran / methanol / water), and diphenyl ether was quantified as an internal standard substance.

Number average molecular weight (Mn) and weight average molecular weight (Mw) of the condensate were analyzed by gel permeation chromatography, and the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured in terms of standard polystyrene. 3-
For methoxyphenol condensate, pump: SC8020 system manufactured by Tosoh Corporation, detector: RI- manufactured by Tosoh Corporation
8020, column: TSKGELα-M 2 manufactured by Tosoh Corporation
This was measured at 60 ° C. using a developing solvent: N, N-dimethylformamide containing 0.4 wt% LiCl. For other condensates, see Polymer Laboratories PL-GP
Polymer Laboratories Plge with C210 system
l 3 columns of 10um MIXED-B, 1,2-dichlorobenzene (2,6-di-t-butyl-4-methylphenol 0.01% w /
v) was used as a developing solvent, and the measurement was performed at 140 ° C.

10% loss on heating (Td5) of condensate: T
In G analysis (TG-DTA2000S, manufactured by MAC SCIENCE), the temperature was raised from room temperature to 500 ° C. at a rate of 10 ° C./min in an argon atmosphere, and the temperature at which the weight was reduced by 5% was measured.

(Ii) Oxidative condensation Example 1 A 2 L rubber balloon filled with oxygen was attached to a 25 ml two-necked round bottom flask equipped with a magnetic stirrer, and the inside of the flask was replaced with oxygen. To this, Cu (Cl) ₂ (1,4,7-triisopropyl-1,4,7-triazacyclononane) (J. Am.
Chem. Soc., 120, 8529, (1998). Abbreviated as Cu (tacn). ) 0.03 mmol was added, and 0.6 mmol of 3-n-octadecyloxyphenol and 0.3 mmol of 2,6-diphenylpyridine as a base dissolved in 1.2 g of toluene were added. This was kept warm at 40 ° C. and stirred vigorously. After 72 hours, concentrated hydrochloric acid was added to make the mixture acidic, 25 ml of methanol was added, and the precipitated condensate was collected by filtration. After washing three times with 10 ml of methanol and drying under reduced pressure, a condensate was obtained. Table 1 shows the analysis results of the condensate. From the infrared absorption spectrum, the condensate mainly has an oxyphenylene structure because the O—H stretching vibration peak at about 3500 cm ⁻¹ of the condensate is considerably reduced as compared with that of the monomer. You can see that.

Example 2 A 2 L rubber balloon filled with oxygen was attached to a 25 ml two-necked round bottom flask equipped with a magnetic stirrer, and the inside of the flask was replaced with oxygen. 0.03 mmol of Cu (tacn) was added thereto, and 0.6 mmol of 2-n-octadecyloxyphenol was added.
And 0.3 mmol of 2,6-diphenylpyridine as a base
Was dissolved in 1.2 g of toluene. This is 4
It was kept warm at 0 ° C. and stirred vigorously. After 240 hours, a post-treatment was carried out in the same manner as in Example 1 to obtain a condensate. Table 1 shows the analysis results of the condensate. From the infrared absorption spectrum, this condensate mainly had an oxyphenylene unit.

Example 3 A 2 L rubber balloon filled with oxygen was attached to a 25 ml two-necked round bottom flask equipped with a magnetic stirrer, and the inside of the flask was replaced with oxygen. 0.03 mmol of Cu (tacn) was added thereto, and 0.6 mmol of 4-n-octadecyloxyphenol was added.
And 3 g of pyridine as a base and 1.2 g of toluene
Was added. This was kept warm at 40 ° C. and stirred vigorously. After 133 hours, a post-treatment was carried out in the same manner as in Example 1 to obtain a condensate. Table 1 shows the analysis results of the condensate. From the infrared absorption spectrum, this condensate mainly had an oxyphenylene unit.

Example 4 A 2 L rubber balloon filled with oxygen was attached to a 25 ml two-necked round bottom flask equipped with a magnetic stirrer, and the inside of the flask was replaced with oxygen. 0.06 mmol of Cu (tacn) was added thereto, and 1.2 mmol of 3-methoxyphenol and 0.6 mmol of 2,6-diphenylpyridine as a base dissolved in 2.4 g of toluene were added. This was kept warm at 40 ° C. and stirred vigorously. After 100 hours, a post-treatment was carried out in the same manner as in Example 1 to obtain a condensate. Table 1 shows the analysis results of the condensate. From the infrared absorption spectrum, this condensate had at least an oxyphenylene unit.

Comparative Example 1 The catalyst was Cu ₂ (Cl) ₂ (OH) ₂ (N, N, N ′, N′-tetramethylethylenediamine) ₂ (manufactured by Tokyo Chemical Industry Co., Ltd .; abbreviated as Cu (tmed)).
A condensate was obtained in the same manner as in Example 1 except that the amount was changed to 03 mmol (0.06 mmol in terms of Cu). Table 1 shows the analysis results of the condensate. From the infrared absorption spectrum, this condensate had at least an oxyphenylene unit.

[0040]

[Table 1]

The results of Examples 1 to 3 show that according to the present invention, an oxyphenol oxidized condensate having high thermal stability can be obtained in a good yield under mild reaction conditions. From Example 4 and Comparative Example 1, Cu (tcn) catalyst was used.
d) It can be seen that the reaction rate is higher, the condensate yield is higher, the molecular weight of the condensate is higher, and the thermal stability of the condensate is significantly improved as compared with the case where a catalyst is used.

[0042]

According to the method of the present invention for producing an oxyphenol oxidative condensate using a copper complex catalyst comprising a tridentate ligand compound in which the coordinating atom is a nitrogen atom and a copper atom, the object of the present invention is to achieve high heat stability. An excellent effect is obtained in that an oxyphenol oxidized condensate having a molecular weight of 4 formalin can be efficiently obtained under mild conditions.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kiyoshi Fujisawa 4-201-706, Azuma, Tsukuba-shi, Ibaraki Prefecture (72) Inventor Shiro Kobayashi 1-1-1, Higashi, Tsukuba-shi, Ibaraki Prefecture F-term in the National Institute of Advanced Industrial Science and Technology (Reference) 4J005 AA23 BB04 4J032 CA16 CB03 CB12 CD02 CE03

Claims (2)

[Claims] An oxyphenol compound represented by the general formula (I) is oxidatively condensed in the presence of a copper complex catalyst comprising a tridentate ligand compound in which a coordinating atom is a nitrogen atom and a copper atom. For producing an oxyphenol oxidized condensate. Embedded image (Wherein, R ^{1 to} R ⁵ independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbonoxy group, a substituted hydrocarbonoxy group, an amino group, a substituted amino group, a mercapto group,
A substituted mercapto group or a halogen atom, R ¹ and R
² , R ² and R ³ , R ³ and R ⁴ and / or R ⁴ and R ⁵ may form a ring, but one of R ^{1 to} R ⁵ is an aliphatic hydrocarbonoxy group or It is a substituted aliphatic hydrocarbonoxy group, and any one of R ¹ , R ^3, or R ⁵ is a hydrogen atom. ) 2. The copper complex catalyst represented by the general formula (II)
2. The oxyphenolic acid according to claim 1, wherein
A method for producing a chemical condensate. Embedded image(Where R⁶Is a hydrocarbon group, substituted hydrocarbon group or hydrogen
Represents an atom, all R ⁶May be the same or different
No. R⁷Represents a divalent hydrocarbon group or a substituted hydrocarbon group.
And all R⁷May be the same or different. X is
A counter anion, wherein n is the number of X,
And the valence of X. )