JP2001302788A - Method for manufacturing crystalline poly(2,5- disubstituted-1,4-phenyleneoxide) - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel method for manufacturing a crystalline poly(2,5- disubstitued-1,4-phenylenoxide) and a copper complex catalyst therefor. SOLUTION: A 2,5-disubstituted phenol represented by formula (I) (wherein two R1S are each same or different, and are each an unsubstited or substituted hydrocarbon group) is oxidation-polymerized in the presence of a copper complex catalyst comprising (A) a copper ion, (B) a bidentate ligand in which the ligand atom is a nitrogen atom and (C) hydroxide ion or a hydrocarbon oxide ion wherein the molar ratio of (B)/(A) is 0.01-100 and the molar ratio of (C)/(A) is 0.01-100. The polymerization is carried out until the conversion of the phenol reaches 50-97% to obtain a crystalline poly(2,5-disubstituted-1,4-phenyleneoxide).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to crystalline poly (2,5)
-Disubstituted-1,4-phenylene oxide) and a copper complex catalyst used for the production.

[0002]

2. Description of the Related Art Poly (2,6-disubstituted-1,4-phenylene oxide) is synthesized by oxidative polymerization of 2,6-disubstituted phenol and is widely known to exhibit high heat resistance. For example, J. Am. Chem. Soc. 81, 6335-633.
6 (1959) contains poly (2,6-dimethyl-1,4-phenylene oxide) in Macromolecules, 2, 107-108 (19
69) reports poly (2,6-diphenyl-1,4-phenylene oxide). The use of phenols having substituents at the 2- and 6-positions is described in J. Polym. Sci.
: Part A: Polymer Chemistry, 36, 505-517 (1998)
To block the coupling at the two ortho positions, as described in

On the other hand, when there is no substituent at one ortho position,
As the oxidative polymerization of 5-disubstituted phenol, Ecletica Q
uim., 18, 93-100 (1993) using a copper / tetramethylethylenediamine catalyst, Polymer, 20 (8), 995-1002.
(1979) Method using copper / dimethylpyridine catalyst, Ch
em. Prum., 22 (9), 451-454 (1972) using a copper / monoalkylamine catalyst, Polimery, 14 (11), 535-53.
8 (1969) discloses a method using a copper / dialkylamine catalyst, a method using a manganese / alkoxide catalyst in Japanese Patent Publication No. 47-619, a method using a basic copper / pyridine catalyst in Japanese Patent Publication No. 50-28999, Kosho 48-
No. 20239 reports a method using a manganese / salicylaldehyde imine catalyst.

However, the polymers obtained by the methods using these catalysts do not crystallize once melted. In general, if the polymer crystallizes after melting,
It is known that the heat resistance of a melt molded body is maintained up to the crystal melting point, and that the solvent resistance is improved. Therefore, the conventional polymer does not crystallize after being melted, so that there is a problem that the original heat resistance and solvent resistance cannot be sufficiently exhibited. The cause is presumed to be that the conventional method cannot sufficiently suppress side reactions such as the ortho-position coupling reaction and the oxygen addition reaction, and that the polymer contains many structures other than the 1,4-phenylene oxide structure. Is done. By using a copper complex catalyst comprising a tridentate ligand in which the coordinating atom is nitrogen and a copper atom, the present inventors can convert crystalline poly (2,5-disubstituted phenol) from 2,5-disubstituted phenol. -1,4-phenylene oxide) (Japanese Patent Application No. 2000-25621). This polymer exhibits a high crystalline melting point even after melting and cooling, and is expected as a crystalline polymer having high heat resistance and solvent resistance.

[0005]

An object of the present invention is to provide a novel method for producing crystalline poly (2,5-disubstituted-1,4-phenylene oxide). A further object of the present invention is to provide a copper complex catalyst suitable for use in the method for producing the crystalline poly (2,5-disubstituted-1,4-phenylene oxide).

[0006]

That is, the present invention provides the following. (1) When oxidatively polymerizing a 2,5-disubstituted phenol represented by the following general formula (I), (A) copper ion, (B)
A bidentate ligand whose coordinating atom is a nitrogen atom, and (C) a hydroxide ion or a hydrocarbon oxide ion, wherein the molar ratio (B) / (A) of (A) and (B) is 0.01 And the conversion of the 2,5-disubstituted phenol is 50 in the presence of a copper complex catalyst wherein the molar ratio (C) / (A) of (A) and (C) is 0.01 to 100. ~
A method for producing crystalline poly (2,5-disubstituted-1,4-phenylene oxide), wherein polymerization is performed until the amount reaches 97%.

[0007]

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(Wherein R ¹ represents a hydrocarbon group or a substituted hydrocarbon group, and two R ^{1 s} may be the same or different from each other.) (2) The bidentate ligand is represented by the following general formula: (2) The method for producing crystalline poly (2,5-disubstituted-1,4-phenylene oxide) according to (1), which is represented by (2).

[0009]

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(Wherein R ² represents hydrogen or a hydrocarbon group, and all R ^{2 s} may be the same or different from each other;
Two R ² may form a ring adjacent. R ³ represents a divalent hydrocarbon group. (3) The crystalline poly (2,5-disubstituted-1,4-phenylene oxide) according to (1) or (2), wherein the copper complex catalyst is represented by the following general formula (III): ) Manufacturing method.

[0011]

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(Wherein R ² and R ³ represent the above-mentioned general formula (I)
It has the same meaning as those of I). R ⁴ represents a hydrogen atom or a hydrocarbon group. X represents a counter ion,
n is the number of X, and is appropriately determined so that the copper complex in the formula maintains electrical neutrality. (4) The conversion of the 2,5-disubstituted phenol is 60 to 9
Polymerization is performed until the amount reaches 0% (1)
To the crystalline poly (2,5) according to any one of the items (3) to (3).
-Disubstituted-1,4-phenylene oxide). (5) (A) a copper ion, (B) a bidentate ligand in which a coordination atom is a nitrogen atom, and (C) a hydroxide ion or a hydrocarbon oxide ion, and a mole of (A) and (B) The ratio (B) / (A) is 0.01 to 100, and the molar ratio (C) / (A) of (A) and (C) is 0.01
Crystalline poly (2,5-disubstituted-1,4-
Copper complex catalyst for the production of phenylene oxide).

[0013]

As the hydrocarbon group for R ¹ in the general formula representing the 2,5-disubstituted phenol of the embodiment of the present invention (I), preferably carbon atoms 1 to 30 (more preferably a carbon An alkyl group having 1 to 20 atoms, having 7 to 30 carbon atoms (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), specifically, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an 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,
Examples thereof include a 4-methylphenyl group, a 1-naphthyl group, and a 2-naphthyl group.

The substituted hydrocarbon group for R ¹ in the general formula (I) is preferably a halogen atom, an alkoxy group,
An alkyl group having 1 to 30 carbon atoms (more preferably 1 to 20 carbon atoms) substituted with a disubstituted amino group or the like;
7 to 30 carbon atoms (more preferably 7 to 7 carbon atoms)
20) aralkyl groups and aryl groups having 6 to 30 carbon atoms (more preferably 6 to 20 carbon atoms), and specific examples thereof include trifluoromethyl group, 2-t-butyloxyethyl group and 3 -Diphenylaminopropyl group and the like. The two R ^{1 in} the general formula (I) are preferably a hydrocarbon group having 1 to 30 carbon atoms, more preferably a hydrocarbon group having 1 to 20 carbon atoms, and this hydrocarbon group Is more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 6 carbon atoms. A methyl group is particularly preferred. In the present invention, the 2,5-disubstituted phenol represented by the general formula (I) may be oxidized and polymerized alone or in combination, and the phenol represented by the following general formula (IV) and / or Oxidative polymerization may be performed by mixing with bisphenol represented by the general formula (V).

[0015]

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(Wherein R ⁵ and R ⁶ represent a hydrogen atom, a hydrocarbon group or a substituted hydrocarbon group, and two R ⁵ and R ^{6
May be the} same or different, and two R ⁵ and / or two R ⁶ may form a ring. R ⁷ is a hydrogen atom, a phenoxy group, a hydrocarbon group or a substituted hydrocarbon group. )

[0017]

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(Where R⁵And R⁶Is the above general formula (IV)
Has the same meaning as those of ⁵And R⁶Are the same
But may be different, two substituted on the same benzene ring.
Two R ⁵And / or two R⁶May form a ring
No. R⁸Represents an oxygen atom, a sulfur atom, a divalent hydrocarbon group or
Represents a divalent substituted hydrocarbon group, and m is 1 or 0
You. )

In the general formula (IV), R⁵And R⁶In
As the hydrocarbon group, two R⁵And two R⁶The ring
When not formed, it preferably has 1 to 30 carbon atoms.
An alkyl group (more preferably having 1 to 20 carbon atoms),
A compound having 7 to 30 carbon atoms (more preferably 7 to 20 carbon atoms)
Aralkyl group or 6 to 30 carbon atoms (more preferably
Is a 6-20) aryl group. Specifically methyl
Group, ethyl group, n-propyl group, iso-propyl group,
n-butyl group, iso-butyl group, t-butyl group, pen
Tyl group, cyclopentyl group, hexyl group, cyclohexyl
Octyl, decyl, dodecyl, pentadecyl
Group, octadecyl group, benzyl group, 2-phenylethyl
Group, 1-phenylethyl group, phenyl group, 4-methyl
Phenyl group, 1-naphthyl group, 2-naphthyl group, etc.
Can be Two R⁴And / or two R⁵Form a ring
In which case a 5- to 7-membered ring is preferred and two R⁴And / or
Two R⁵Is-(CH₂)₃-Group,-(CH₂)₄-Group
Or form a ring as a -CH = CH-CH = CH- group
More preferably, it is. Of the above general formula (IV)
R⁵And R⁶Has two R groups⁵Passing
Two R⁶When does not form a ring, preferably halo
Substituted with a gen atom, an alkoxy group, a disubstituted amino group, etc.
Having 1 to 30 carbon atoms (more preferably 1 to 20 carbon atoms)
An alkyl group having 7 to 30 carbon atoms (more preferably 7
-20) aralkyl groups or 6-30 carbon atoms;
(More preferably 6-20) aryl groups,
Examples include a trifluoromethyl group, 2-t-butyl
Xyethyl group, 3-diphenylaminopropyl group and the like.
I can do it. Two R⁵And two R⁶Place where forms a ring
In this case, a 5- to 7-membered ring having the above substituent is preferable,
Two R⁵And two R⁶Has the substituent described above,
H₂-O-CH₂-Group,-(CH ₂)₃-,-(C
H₂)₄-Group or -CH = CH-CH = CH- group
More preferably, they form a ring.

R ⁵ and R ^{6 in} the formula (IV) are preferably a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Group. Particularly preferably, R ⁵ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
R ⁶ is a hydrogen atom or a methyl group. The above general formula (I
Specific examples and preferred groups of the hydrocarbon group or substituted hydrocarbon group for R ⁷ in V) are the same as those for R ¹ in the above general formula (I). The above general formula (IV)
R ⁷ is preferably a hydrogen atom, a phenoxy group or a group having 1 to 30 carbon atoms (more preferably 1 to 30 carbon atoms).
20) hydrocarbon groups, particularly preferably a hydrogen atom,
It is a phenoxy group or a hydrocarbon group having 1 to 6 carbon atoms, and specific examples include a hydrogen atom and a phenoxy group.

Specific examples and preferred groups of R ⁵ and R ⁶ in the general formula (V) are the same as those in the general formula (IV). Examples of the divalent hydrocarbon group for R ⁸ in the general formula (V) include an alkylene group having 1 to 30 carbon atoms (more preferably, 1 to 20 carbon atoms) and a C ^{7 to} 30 (more preferably, Preferably 7 to 2 carbon atoms
0) aralkylene group or an arylene group having 6 to 30 carbon atoms (more preferably, 6 to 20 carbon atoms), and specific examples thereof include a methylene group, a 1,1-ethylene group, and 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-dodecylene group, 1,1-pentadecylene group, 1,1-octadecylene group, 1,1-cyclopentylene group, 1,1-cyclohexylene group, phenylmethylene Group, diphenylmethylene group, 1-phenyl-1,1-ethylene group, 9,9-fluorene group, α, α′-1,4-diisopropylphenylene group, 1,2-phenylene group, 1,3-phenylene group , 1,4-phenylene group.

Examples of the divalent substituted hydrocarbon group for R ⁸ in the general formula (V) include a halogen atom, an alkoxy group,
An alkylene group having 1 to 30 carbon atoms (more preferably 1 to 20 carbon atoms) substituted with a disubstituted amino group or the like, or an alkylene group having 7 to 30 carbon atoms (more preferably 7 to 20 carbon atoms) ) Aralkylene groups or 6 to 30 carbon atoms
(More preferably having 6 to 20 carbon atoms) are preferred. Specific examples thereof include hexafluoro-2,
Examples thereof include a 2-propylene group, a pentafluorophenylmethylene group, a 4-methoxyphenylmethylene group, and a 4-dimethylaminophenylmethylene group. As R ^{8 in the} general formula (V), an oxygen atom or a divalent hydrocarbon group is preferable, an alkylene group having 1 to 20 carbon atoms or an aralkylene group having 7 to 20 carbon atoms is more preferable, and 1-6 alkylene groups are more preferred.

The 2,5-disubstituted phenol represented by the general formula (I) is mixed with the phenol represented by the general formula (IV) and / or the bisphenol represented by the general formula (V). When used, the mixing ratio is appropriately determined within a range that does not impair the physical properties of the target polymer.
-Disubstituted phenol is based on all phenol monomers,
It is preferably at least 80 mol%, more preferably 90 mol%.
Mol% or more, more preferably 95 mol% or more (these phenols may be hereinafter referred to as phenolic starting materials).

The catalyst of the present invention comprises (A) copper ion, (B)
A bidentate ligand whose coordinating atom is a nitrogen atom, and (C) a hydroxide ion or a hydrocarbon oxide ion, wherein the molar ratio (B) / (A) of (A) and (B) is 0.01 And a copper complex catalyst wherein the molar ratio (C) / (A) of (A) and (C) is 0.01 to 100. The three components (A), (B) and (C) are indispensable. If any one of them is missing, it is not preferable because polymerization activity is lost or a crystalline polymer cannot be obtained. When (B) / (A) is more than 100, it is not economically preferable. When (B) / (A) is less than 0.01, the polymerization activity of the catalyst is undesirably reduced. (B) / (A) is preferably from 0.1 to 50, more preferably from 0.2 to 1
0, more preferably 0.5 to 5, and 1 is particularly preferred. If (C) / (A) exceeds 100,
It is not economically preferable, and if it is less than 0.01, it is not preferable because a crystalline polymer cannot be obtained. (C) /
(A) is preferably 0.1 to 10, more preferably 0.2 to 5, further preferably 0.5 to 2, and 1 is particularly preferred.

The (A) copper ion in the copper complex catalyst has a valence of 1 to 3, preferably 1 or 2, and more preferably divalent. Regarding (B) a bidentate ligand in which the coordinating atom is a nitrogen atom in the copper complex catalyst, the term “ligand” refers to an atom as described in the Chemical Dictionary (1st edition, Tokyo Chemical Dojin, 1989). Refers to a molecule or ion that is bound to a coordination bond. The atoms directly involved in the bond are called coordinating atoms. A bidentate ligand is a ligand having two coordinating atoms. As such bidentate ligands, ethylenediamine, 1,
Diamine compounds such as 3-propanediamine, 1,2-cyclohexanediamine, and 1,2-phenylenediamine;
Bipyridyl compounds such as 2,2'-bipyridyl; 2,3-
Dioxime compounds such as butanedioxime and 2,4-pentanedioxime; 2,3-bis (N-methylimino)-
Butane, 2,3-bis (N-phenylimino) -butane, 1,3-bis (N-methylimino) -butane, 2,
Examples thereof include diimino compounds such as 4-bis (N-methylimino) -pentane. Preferred bidentate ligands are bidentate ligands represented by the above general formula (II).

The hydrocarbon group represented by R ² in the general formula (II) may be an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or 6 to 20 carbon atoms.
Are preferred, specifically, a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a t-butyl group, a 1-pentyl group, and a 3-pentyl group , Cyclopentyl group, hexyl group,
Cyclohexyl group, octyl group, decyl group, 4-methylcyclohexyl group, 4-t-butylcyclohexyl group,
3,5-dimethylcyclohexyl group, benzyl group, 2-
Examples include a phenylethyl group, a 1-phenylethyl group, a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
As R ^{2 in the} general formula (II), a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms is preferable, and a hydrogen atom or An alkyl group having 1 to 12 carbon atoms is more preferable, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is further preferable, and a hydrogen atom or a methyl group is particularly preferable. As the divalent hydrocarbon group for R ³ in the general formula (II), an alkylene group having 1 to 20 carbon atoms, an aralkylene group having 7 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms is preferable. As specific examples, methylene group, 1,2-ethylene group, 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, 1,2-cyclohexylene group, 1,2-phenylene group, etc. Can be mentioned. As R ^{3 in the} above general formula (II), an alkylene group having 1 to 12 carbon atoms, an aralkylene group having 7 to 12 carbon atoms or 6 to 12 carbon atoms.
Are preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, and 1,2-ethylene group and 1,3
-Propylene groups are particularly preferred.

As the (C) hydroxide ion or hydrocarbon oxide ion in the copper complex catalyst, one represented by the general formula (VI) R ⁴ —O (R ⁴ represents a hydrogen atom or a hydrocarbon group) is used. preferable.

The hydrocarbon group for R ⁴ in the general formula (VI) is preferably an alkyl group having 1 to 20 carbon atoms or a phenyl group, specifically, a methyl group, an ethyl group,
n-propyl group, iso-propyl group, n-butyl group,
iso-butyl group, t-butyl group, 1-pentyl group, 3
-Pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, 3,5
-Dimethylcyclohexyl group, phenyl group and the like. As R ^{4 in the} general formula (VI), a hydrogen atom or an alkyl group having 1 to 12 carbon atoms or a phenyl group is preferable, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable, and a hydrogen atom or a carbon atom is preferable. An alkyl group having 1 to 4 atoms is more preferable, and a hydrogen atom or a methyl group is particularly preferable.

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. For example, a base without the ability to coordinate to a copper atom, such as 2,6-diphenylpyridine, may be added. In addition, a solvent or the like may be coordinated to the copper complex catalyst during the complex raw material, synthesis process and / or oxidative polymerization 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 ion,
Nitrate, carbonate, perchlorate, tetrafluoroborate, hexafluorophosphate, methanesulfonate, trifluoromethanesulfonate, toluenesulfonate, acetate, trifluoroacetate, propionate, Benzoate ion and the like can be mentioned. The counter anion is preferably a chloride ion, a bromide ion, an iodide ion, a sulfate ion, a nitrate ion or an acetate ion, and more preferably a chloride ion, a bromide ion, a sulfate ion or a nitrate ion. As the counter cation, a cation such as an alkali metal or an alkaline earth metal can be appropriately used. More preferably, the copper complex catalyst is a copper complex represented by the general formula (III).

R ² and R ³ in the above formula (III)
Specific examples and preferred groups of are the same as those in the above general formula (II), and R ⁴ in the above general formula (III)
Specific examples and preferred groups of are the same as those in the above general formula (VI). In the above general formula (III), X
Is a counter anion, n is the number of X,
Determined by the valence of copper. The copper complex catalyst may have the structure of the above general formula (III) in advance or in the reaction system. As the copper complex, a complex synthesized in advance can be used, but the complex may be formed in a reaction system. When a complex is formed in the reaction system, (A) a copper salt (preferably copper chloride or bromide), (B) a bidentate ligand and (C) an alkali metal (preferably sodium or potassium) A mixture of a hydroxide or a hydrocarbon oxide compound in a reaction solvent can be used as it is as a catalyst. The catalyst can be used in any amount, but generally, the amount of copper is preferably 0.001 to 50 mol%, more preferably 0.01 to 10 mol%, based on the phenolic starting material.

The oxidizing agent in the oxidative polymerization reaction for producing the polymer of the present invention is not particularly limited, but oxygen or peroxide is preferable. More preferably, it is oxygen, which may be a mixture with an inert gas, or air. The amount of oxygen to be used is usually at least an equivalent or a large excess with respect to the phenolic starting material. Oxidative polymerization 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,
Alcohols such as ethanol, n-propyl alcohol and isopropyl alcohol; ethers such as dioxane, tetrahydrofuran and ethylene glycol dimethyl ether; amides such as N, N-dimethylformamide and N-methylpyrrolidone; nitro such as nitromethane and nitrobenzene Compounds; water and the like. Aromatic hydrocarbons, chain and cyclic aliphatic hydrocarbons, halogenated hydrocarbons, nitriles, ethers or nitro compounds are more preferred, aromatic hydrocarbons or halogenated hydrocarbons are more preferred, and aromatics are preferred. Hydrocarbons are particularly 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 polymerization 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 feature of the oxidative polymerization of the present invention is that the polymerization is carried out until the conversion of the 2,5-disubstituted phenol reaches 50 to 97%. The conversion at the end of the oxidative polymerization is 97
% Is not preferable because the crystallinity of the obtained polymer is lost, and if it is lower than 50%, the polymer yield is not sufficient, which is not preferable. The conversion at the end of the oxidative polymerization is preferably from 60 to 90%, more preferably from 70 to 90%, further preferably from 75 to 90%, and particularly preferably from 75 to 85%.
%.

The polymer obtained by the present invention is a poly (2,5-) having a repeating unit represented by the following general formula (VII).
Di-substituted-1,4-phenylene oxide), and the structure other than the repeating unit represented by the following general formula (VII) is not particularly limited, and may be a random or block copolymer. The content of the repeating unit represented by the following general formula (VII) is appropriately determined within a range that does not impair the physical properties of the target polymer, and is preferably 80 unit% or more based on the total number of repeating units. It is preferably at least 90 unit%, more preferably at least 95 unit%.

[0034]

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(In the formula, R ¹ has the same meaning as that of the general formula (I).) The polymer obtained in the present invention shows crystallinity. The crystallinity as referred to in the present invention means that when cooling after melting, shows an exothermic peak of crystallization of 5 J / g or more at 150 ° C. or more, and / or when the melt is cooled and then heated again, It indicates an endothermic peak of heat of crystal fusion of 5 J / g or more at 150 ° C. or more.

[0036]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(I) Analysis Conversion of monomer (Conv.): 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 (pump: SC802 manufactured by Tosoh Corporation).
0 system, detector: Tosoh PD-8020, detection wavelength: 278 nm, column: YMC ODS-AM,
Developing solvent: methanol / water = 68: 32, changed to 100/0 after 38 minutes, then 5
(Maintained until 0 min) and quantified using diphenyl ether as an internal standard.

Number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer: The polymer was 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.
Polymer Laboratories PL-GPC210 System
o-Dichlorobenzene (abbreviated as oDCB) was used as a developing solvent (2,6-di-t-butyl-4-methylphenol 0.01%) with three columns of Plgel 10um MIXED-B manufactured by olymer Laboratories.
w / v content) at 140 ° C. Crystallization temperature (Tc), heat of crystallization (Hc) and melting temperature (Tm), heat of fusion (Hm) of polymer after melting: Differential scanning calorimetry (MAC SCIE)
NCE DSC3200S) was performed under an argon atmosphere. First, when the temperature is raised from room temperature to 350 ° C. at 10 ° C./min and kept for 5 minutes, and then cooled from 350 ° C. to room temperature at 10 ° C./min, when the exothermic peak of 5 J / g or more at 150 ° C. or more is shown, The peak top temperature was defined as the crystallization temperature (Tc), and the peak area was defined as the heat of crystallization (Hc). Then, once again
When the temperature is raised from room temperature to 350 ° C or more at 0 ° C / min, 1
When an endothermic peak of 5 J / g or more was shown at 50 ° C. or more, the peak top temperature was taken as the melting temperature (Tm), and the peak area was taken as the heat of fusion (Hm). When no crystallization or melting peak was observed, it was regarded as ND.

(Ii) Oxidative polymerization Example 1 In a 25 ml two-necked round bottom flask equipped with a magnetic stirrer,
A 2 L rubber balloon filled with oxygen was attached, and the inside of the flask was replaced with oxygen. In addition, Cu ₂ (tmed) ₂ (OH)
₂ Cl ₂ (Tokyo Kasei Co., Ltd., where tmed is N, N, N ', N'-
Represents tetramethylethylenediamine. ) 0.006
mmol and 2,5-dimethylphenol 1.2 mmol
l and 0.06 mmol of 2,6-diphenylpyridine dissolved in 2.4 g of toluene were added. This was kept warm at 40 ° C. and stirred vigorously. After 1.6 hours (the conversion of 2,5-dimethylphenol was 79%), a few drops of concentrated hydrochloric acid were added to make the mixture acidic, 25 ml of methanol was added, and the precipitated polymer was collected by filtration. After washing three times with 10 ml of methanol and drying under reduced pressure at 60 ° C. for 6 hours, a polymer was obtained. Table 1 shows the analysis results of the polymer. The IR spectrum of the obtained polymer was the same as that of the poly (2,5-dimethyl-1,4-phenylene oxide) reported in the 76th Annual Meeting of the Chemical Society of Japan, II-1305, 3H102 (1999). )
It is confirmed that the IR spectrum is similar to that of the above.

Comparative Example 1 A polymer was obtained in the same manner as in Example 1 except that the reaction time was changed to 6 hours (the conversion of 2,5-dimethylphenol was 98%). Table 1 shows the analysis results of the polymer.

Comparative Example 2 In a 25 ml two-necked round bottom flask equipped with a magnetic stirrer,
A 2 L rubber balloon filled with oxygen was attached, and the inside of the flask was replaced with oxygen. To this, 0.06 mmol of cuprous chloride (abbreviated as CuCl) was added, and N, N, N'N'-tetramethylethylenediamine (abbreviated as tmed) 2.
52 mmol, 2,6-diphenylpyridine 0.6 mmo
A solution prepared by dissolving 1.2 mmol of 1,2,5-dimethylphenol in 2.4 g of toluene was added. This was kept warm at 40 ° C. and stirred vigorously. After 6 hours (the conversion of 2,5-dimethylphenol was 60%), post-treatment was carried out in the same manner as in Example 1 to obtain a polymer as a methanol-insoluble portion. Table 1 shows the analysis results of the polymer.

From Example 1 and Comparative Example 1, when the conversion of 2,5-dimethylphenol at the end of the polymerization reaction exceeded 97%, Tc and Tm of the obtained polymer were not observed and crystallinity was lost. It is understood that it is done. Further, as shown in Comparative Example 2,
With the Cu / tmed catalyst (absence of hydroxide ion or alkoxide ion) described in Ecletica Quim., 18, 93-100 (1993), Tc and Tm of the obtained polymer were not observed and crystallinity was exhibited. It turns out that it does not.

[0043]

[Table 1]

[0044]

According to the present invention, (A) copper ion,
(B) a bidentate ligand whose coordinating atom is a nitrogen atom; and (C) a crystalline poly (2,5-disubstituted-1) with an inexpensive copper complex catalyst comprising a hydroxide ion or a hydrocarbon oxide ion. , 4-phenylene oxide) can be produced, and a great economic effect can be expected.

 ──────────────────────────────────────────────────続 き Continuing on 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 Materials Technology Institute (Reference) 4J005 AA26 BB04

Claims (5)

[Claims] 1. An oxidative polymerization of a 2,5-disubstituted phenol represented by the following general formula (I), wherein (A) a copper ion and (B) a bidentate coordination in which a coordination atom is a nitrogen atom. And (C) a hydroxide ion or a hydrocarbon oxide ion, and the molar ratio of (A) to (B) (B)
/ (A) is 0.01 to 100, and the molar ratio of (A) to (C) (C) / (A) is 0.01 to 100 in the presence of a copper complex catalyst. A process for producing crystalline poly (2,5-disubstituted-1,4-phenylene oxide), wherein polymerization is carried out until the conversion of disubstituted phenol reaches 50 to 97%. Embedded image (In the formula, R ¹ represents a hydrocarbon group or a substituted hydrocarbon group, and two R ^{1 s} may be the same or different from each other.) 2. The crystalline poly (2,5-disubstituted-1,4-phenylene oxide) according to claim 1, wherein the bidentate ligand is represented by the following general formula (II). Production method. Embedded image (Wherein R ² represents hydrogen or a hydrocarbon group;
² may be the same or different, and two adjacent R ² may form a ring. R ³ represents a divalent hydrocarbon group. ) 3. The crystalline poly (2,5-disubstituted-1,4-phenylene oxide) according to claim 1 or 2, wherein the copper complex catalyst is represented by the following general formula (III). Production method. Embedded image (In the formula, R ² and R ³ have the same meanings as those in the above general formula (II). R ⁴ represents a hydrogen atom or a hydrocarbon group. X represents a counter ion, and n represents the number of X. Is appropriately determined so that the copper complex in the formula maintains electrical neutrality.) 4. The process according to claim 1, wherein the polymerization is carried out until the conversion of the 2,5-disubstituted phenol reaches 60 to 90%. 2,5-disubstituted-1,4-phenylene oxide). 5. It comprises (A) a copper ion, (B) a bidentate ligand whose coordination atom is a nitrogen atom, and (C) a hydroxide ion or a hydrocarbon oxide ion,
The molar ratio (B) / (A) of (A) and (B) is 0.01 to 1
00, and the molar ratio (C) / (A) of (A) to (C) is from 0.01 to 100.
(1,4-phenylene oxide) Copper complex catalyst for production.