JP2001040088A - Amorphous 2,5-di-substituted phenol oxidation polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer having a high transparency and a low molding shrinkage percentage and useful for the production of uniform film moldings and injection moldings by carrying out oxidative polymerization of a specific 2,5-di-substituted phenol compound and a specified phenol compound in a specific amount. SOLUTION: This amorphous 2,5-di-substituted phenol oxidation polymer is obtained by using (A) a 2,5-di-substituted phenol compound of formula I [R1 is a 1-8C (substituted)hydrocarbon] and (B) a phenol compound of formula II [R2 is H or a (substituted)hydrocarbon; R3 is H or phenoxy] as a starting raw material, regulating the amount of the component A to 0.1-99.9 mol% and carrying out oxidative polymerization. The content of the component A is preferably 10-95 mol%. The reaction is preferably carried out by using a copper complex catalyst composed of a tridentate ligand which is nitrogen atom and copper atom in the presence of oxygen and the reactional temperature is preferably 0-200 deg.C. The polymer preferably contains substantially no gel component and the number-average molecular weight thereof is preferably 500-1,000,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an oxidized polymer of a 2,5-disubstituted phenol.

[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) reports poly (2,6-dimethylphenylene oxide), and Macromolecules, 2, 107-108 (1969) reports poly (2,6-diphenylphenylene 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.

By using a copper complex catalyst comprising a tridentate ligand in which the coordinating atom is nitrogen and a copper atom, the present inventors have made it possible to convert 2,5-dimethylphenol having no substituent at one ortho position. , Crystalline poly (2,5-dimethyl-1,4
-Phenylene oxide) (Proceedings of the 76th Annual Meeting of the Chemical Society of Japan, II-130
5, Lecture number 3H102 (1999)). This polymer exhibits a high crystalline melting point even after melting and cooling, and is expected to be developed for various uses as a crystalline polymer having high heat resistance and solvent resistance.

[0004]

It is an object of the present invention to provide an amorphous 2,5-disubstituted phenolic polymer.

[0005]

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) Starting from a 2,5-disubstituted phenol compound represented by the general formula (I) and a phenol compound represented by the general formula (II), the ratio of the 2,5-disubstituted phenol is 0.1 to An amorphous 2,5-disubstituted phenol oxidized copolymer obtained by oxidative polymerization with 99.9 mol%.

[0006]

Embedded image

Wherein R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms or a substituted hydrocarbon group having 1 to 8 carbon atoms;
Two R ¹ may be the same or different. R ² represents a hydrogen atom, a hydrocarbon group or a substituted hydrocarbon group, two R ² may be the same or different, and two R ² may form a ring. R ³ is a hydrogen atom or a phenoxy group. (2) Amorphous 2,5-disubstituted phenol oxidation as described in (1), which is obtained by oxidative polymerization with the proportion of 2,5-disubstituted phenol being 10 to 95 mol%. Copolymer. (3) 2,5-diethylphenol, 2,5-dibutylphenol, and 2,5-diethylphenol represented by the general formula (I) -a
An amorphous 2,5-disubstituted phenol oxidized polymer obtained by oxidative polymerization using at least one phenol compound selected from the group consisting of disubstituted phenols as a starting material.

[0008]

Embedded image

(In the formula, R ¹¹ and R ¹² represent different acyclic alkyl groups having 1 to 8 carbon atoms.) (4) It is characterized by substantially not containing a gel component (1) The 2,5-disubstituted phenol oxidized polymer according to the item (2) or (3). (5) The 2,5-disubstituted phenol oxidized polymer according to any one of (1) to (4), wherein the number average molecular weight is from 500 to 1,000,000.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION A first aspect of the present invention is to use a 2,5-disubstituted phenol compound represented by the above formula (I) and a phenol compound represented by the above formula (II) as starting materials, A copolymer obtained by oxidative polymerization with the ratio of the 2,5-disubstituted phenol being 0.1 to 99.9 mol%. The hydrocarbon group having 1 to 8 carbon atoms in R ¹ of the general formula (I) is preferably an alkyl group having 1 to 8 carbon atoms (including a cycloalkyl group), and an aralkyl having 7 to 8 carbon atoms. And aryl groups having 6 to 8 carbon atoms, specifically, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, pentyl Group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, benzyl group, 2-phenylethyl group,
Examples thereof include a 1-phenylethyl group, a phenyl group, a 4-methylphenyl group, and a 4-ethylphenyl group. The substituted hydrocarbon group having 1 to 8 carbon atoms in R ¹ of the general formula (I) is preferably an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, an alkoxy group, a disubstituted amino group, or the like. (Including a cycloalkyl group), an aralkyl group having 7 to 8 carbon atoms or an aryl group having 6 to 8 carbon atoms, and specific examples thereof include a trifluoromethyl group and a 2-t-
Examples include a butyloxyethyl group and a 3-dimethylaminopropyl group.

The two R ^{1 in} the general formula (I) are preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a carbon atom. More preferably, it is an alkyl group of Formulas 1 to 4. When two R ² do not form a ring, the hydrocarbon group for R ² in the general formula (II) preferably has 1 to 30 carbon atoms (more preferably 1 to 20 carbon atoms).
An alkyl group (including a cycloalkyl group) having 7 to 30 carbon atoms (more preferably having 7 to 20 carbon atoms)
It is an aralkyl group or an aryl group having 6 to 30 carbon atoms (more preferably, 6 to 20 carbon atoms). 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, Examples include a decyl group, a pentadecyl group, an octadecyl group, a benzyl group, a 2-phenylethyl group, a 1-phenylethyl group, a phenyl group, a 4-methylphenyl group, a 1-naphthyl group, and a 2-naphthyl group. When two ^{R 2} may form a ring, 5-7 membered ring is preferred, the two ^{R 2} is - (CH _{2) 3} - group, - (CH ₂₎
It is preferable to form a ring as a ₄ -group or a —CHＣＨCH—CH ＝ CH— group.

When R ² does not form a ring, the substituted hydrocarbon group represented by R ² in the general formula (II) is preferably substituted with a halogen atom, an alkoxy group, a disubstituted amino group or the like. An alkyl group having 1 to 30 (more preferably 1 to 20 carbon atoms), an aralkyl group having 7 to 30 carbon atoms (more preferably 7 to 20 carbon atoms) or 6 to 30 carbon atoms (more It is preferably an aryl group having 6 to 20 carbon atoms, and specific examples include a trifluoromethyl group, a 2-t-butyloxyethyl group,
And a 3-diphenylaminopropyl group. When two R ² may form a ring, preferably two R ² is a 5- to 7-membered ring having the substituents, two R ²
There have the substituent - _{(CH 2) 3} - group, - (CH
_{2) 4} - is preferably one which forms a ring as a group or -CH = CH-CH = CH- group. General formula (II)
R ² is preferably a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and is preferably a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms.
An alkyl group or an aralkyl group of 0 is more preferable,
A hydrogen atom or an alkyl group having 1 to 20 carbon atoms is particularly preferred.

In the production of the copolymer of the present invention,
The proportion of the 2,5-disubstituted phenol compound in the total phenol compound as a starting material is from 0.1 to 99.9 mol%, preferably from 10 to 95 mol%, more preferably from 25 to 90 mol%. %.

The copolymer of the present invention has a poly (phenylene oxide) structure having a repeating unit represented by the following general formula (IV) and the following general formula (V). The proportion of the two repeating units basically corresponds to the proportion of each starting material as a constituent. Therefore,
The repeating unit represented by the general formula (IV) generally accounts for 0.1 to 99.9 unit%, preferably 10 to 95 unit%, more preferably 25 to 95 unit%, based on all repeating units.
90 unit%.

[0015]

Embedded image

(Wherein, R ¹ and R ² have the same meanings as described above.)

A second aspect of the present invention is selected from the group consisting of 2,5-diethylphenol, 2,5-dibutylphenol and 2,5-disubstituted phenol represented by the above general formula (I) -a. At least one of the phenolic compounds
An amorphous 2,5-disubstituted phenol oxidized polymer obtained by oxidative polymerization using a seed as a starting material. 2,5-
As dibutylphenol, 2,5-di-t-butylphenol, 2,5-di-iso-butylphenol,
Examples thereof include 2,5-di-n-butylphenol and 2,5-dicyclobutylphenol.
Butylphenol is preferred. Specific examples of the acyclic alkyl group having 1 to 8 carbon atoms for R ¹¹ and R ¹² in the general formula (I) -a include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n- Butyl group, iso-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group and the like. The above general formula (I)
R ¹¹ and R ¹² of -a each have 1 to 1 carbon atoms different from each other.
6 non-cyclic alkyl groups are preferable, non-cyclic alkyl groups having 1 to 4 carbon atoms different from each other are more preferable, and non-cyclic alkyl groups having 1 to 3 carbon atoms different from each other are further preferable. The oxidized polymer of the present invention may be a homopolymer of 2,5-diethylphenol, 2,5-dibutylphenol or a 2,5-disubstituted phenol represented by the general formula (I) -a, or A copolymer obtained by mixing and oxidative polymerization may be used.

The polymer according to the second aspect of the present invention has a repeating unit represented by the following general formula (VI).
The content of the repeating unit represented by the following general formula (VI) is not particularly limited, but is 50 unit% with respect to all repeating units.
Or more, preferably 70 unit% or more, and 90% or more.
The unit% is more preferable.

[0019]

Embedded image

(Wherein R ¹¹ and R ¹² are represented by the general formula (I) -a
Or R ¹¹ and R ¹² are each an ethyl group or a butyl group. )

Any of the polymers of the present invention does not show an exothermic peak (crystallization peak) of 5 J / g or more at 150 ° C. or more when cooled after melting, and when heated again after cooling. It is an amorphous polymer that does not show an endothermic peak (crystal dissolution peak) of 5 J / g or more at 150 ° C. or more. The presence or absence of a crystallization peak and a crystal melting peak in the polymer is measured as follows. That is, the differential scanning calorimetry is performed in an argon atmosphere, and the temperature at which the polymer is completely melted from room temperature at 10 ° C./min (complete melting temperature).
Up to 10 ° C / min after 5 minutes at full melting temperature
When the sample is cooled from the complete melting temperature to room temperature, the presence or absence of an exothermic peak (crystallization peak) of 5 J / g or more at 150 ° C. or more is examined. Next, when the temperature is raised again from room temperature to a complete melting temperature at 10 ° C./min, an endothermic peak (crystal melting peak) of 5 J / g or more at 150 ° C. or more is examined.

The polymer of the present invention is preferably substantially free of a gel component. The absence of gel content means that, for example, 1 mg of polymer is added to 1 ml of 1,2-dichlorobenzene.
It can be confirmed by dissolving at 50 ° C. The phrase "substantially free of a gel component" means that the gel component contained in the polymer is preferably 5% by weight or less, more preferably 2% by weight or less, and most preferably the gel component is contained. Means not being done. Although the molecular weight of the polymer of the present invention is not particularly limited, the number average molecular weight is 500 to 1,000,000.
Is preferable, 1,000 to 100,000 is more preferable, and 2,000 to 50,000 is still more preferable.

Hereinafter, a preferred method for producing the polymer of the present invention will be described in detail.

The oxidative polymerization of the phenolic starting material is preferably carried out in the presence of oxygen using a copper complex catalyst comprising a tridentate ligand which 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. This ligand is defined in the Chemical Dictionary (1st edition, Tokyo Chemical Dojin, 1989)
Refers to a molecule or ion that is linked to an atom by a coordinate bond. The atoms directly involved in the bond are called coordinating atoms. A tridentate ligand is a ligand having three coordinating atoms. On the other hand, a catalyst comprising a bidentate or monodentate ligand in which the coordinating atom is a nitrogen atom and a copper atom is not preferable because the resulting polymer contains a gel component.

The tridentate ligand used in the 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, or the like, or Derivatives thereof can be mentioned.

The valence of the copper atom in this copper complex catalyst is 0.
It is trivalent, but 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. . The number is more preferably 1 to 3, and even 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. In the copper complex catalyst of the present invention, a solvent or the like may be coordinated in the raw material of the complex, the synthesis process and / or the oxidative polymerization process.

In some cases, the copper complex catalyst requires a counter ion for maintaining 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, hexafluorophosphate, methanesulfonate, trifluoromethanesulfonate, toluenesulfonate, acetate, trifluoroacetate, propionate, benzoate, hydroxide, oxide ion,
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 used for producing the polymer of the present invention is more preferably a copper complex represented by the following general formula (III).

[0031]

Embedded image

(Where R⁴Represents a hydrogen atom, a hydrocarbon group or
Represents a substituted hydrocarbon group, and all R ⁴Are the same but different
It may be. R⁵Is a difunctional hydrocarbon group or
Represents a substituted hydrocarbon group, wherein all R⁵Are the same but different
May be. X is a counter anion, and n is
The number is appropriately determined by the valences of copper and X. )

The hydrocarbon group represented by R ⁴ in the general formula (III) 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.

The substituted hydrocarbon group for R ⁴ in the general formula (III) is the above-mentioned preferred hydrocarbon group substituted with a halogen atom, an alkoxy group, a disubstituted amino group and the like.
Specific examples include a pentafluorophenylmethyl group, a methoxyethyl group, a diphenylaminopropyl group, and the like.

As R ^{4 in the} general formula (III), a hydrocarbon group is preferable, an alkyl group having 1 to 20 carbon atoms or an aralkyl group is more preferable, and an alkyl group having 2 to 12 carbon atoms is more preferable.

The bifunctional hydrocarbon group represented by R ⁵ in the general formula (III) may be an alkylene group having 1 to 20 carbon atoms (including a cycloalkylene group) or 6 carbon atoms.
To 20 arylene groups are preferable, and specific examples thereof include a methylene group, an ethylene group, a 1,2-propylene group, and a 1,3
-Propylene group, 2,4-butylene group, 2,4-dimethyl-2,4-butylene group, 1,2-diphenyl-1,2
-Ethylene, 1,2-cyclopentylene, 1,2-cyclohexylene, 1,2-phenylene and the like.

The bifunctional substituted hydrocarbon group represented by R ⁵ in the general formula (III) is preferably the aforementioned difunctional substituted hydrocarbon group substituted with a halogen atom, an alkoxy group, a disubstituted amino group, or the like. And specific examples include a tetrafluoro-1,2-ethylene group, 4,5-dimethoxy-1,
Examples thereof include a 2-phenylene group and a 4-dimethylamino-1,2-phenylene group.

R ^{5 in the} above formula (III) is preferably a bifunctional hydrocarbon group, more preferably an alkylene group having 1 to 20 carbon atoms, and further preferably an alkylene group having 2 to 6 carbon atoms. And 1,2-ethylene groups are particularly preferred.

In the above general formula (III), the valence of copper is 1
Or 2, X is a counter anion, and n is the number of Xs, determined by the valence of copper.

In the general formula (III), the structure other than the above is not particularly limited as long as the catalyst ability is not deactivated. In the transition metal complex catalyst of the present invention, a solvent or the like may be coordinated in the raw material of the complex, the synthesis process and / or the oxidative coupling reaction process.

The copper complex can be synthesized by, for example, a method of mixing a tridentate ligand compound and a copper compound in an appropriate solvent. As the transition metal compound, a Bronsted acid salt of a transition metal or the like is appropriately used. As the tridentate ligand compound, commercially available products can be used as appropriate.
Chem. Soc. Dalton Trans., 83-90 (1993).
em. Soc., 8865-8866, 117 (1995) and the like can also be synthesized. As the copper complex, a complex synthesized in advance can be used, but the complex may be formed in a reaction system.

In the present invention, these catalysts can be used alone or as a mixture. The catalyst can be used in any amount, but generally, the amount of the transition metal compound is preferably 0.001 to 50 mol%, more preferably 0.01 to 10 mol%, based on the phenolic starting material.

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. And at least 1/4 equivalent are preferably co-present during the polymerization. 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 a counter ion and 1
It is more preferable to make / 4 equivalent or more coexist, and it is even more preferable to make substituted pyridines coexist in 以上 equivalent or more.

In the oxidative polymerization for producing the polymer of the present invention, oxygen is used as an oxidizing agent, and 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.

The 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. Examples of preferred solvents include benzene,
Aromatic hydrocarbons such as toluene and xylene; linear and cyclic aliphatic hydrocarbons such as heptane and cyclohexane; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene and dichloromethane; nitriles such as acetonitrile and benzonitrile; methanol and ethanol Alcohols such as dioxane, n-propyl alcohol and iso-propyl alcohol; ethers such as dioxane, tetrahydrofuran and ethylene glycol dimethyl ether; amides such as N, 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,
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 polymerization is not particularly limited as long as the reaction medium is kept in a liquid state. When a solvent is not used, the temperature is preferably higher than the melting point of the phenolic starting material.
A preferred temperature range is 0 ° C to 200 ° C, more preferably 0 ° C to 150 ° C, and even more preferably 0 ° C to 1 ° C.
00 ° C.

The oxidized 2,5-disubstituted phenolic polymer of the present invention can be used alone or as a composition with another polymer and / or modifier. As the polymer component of the composition, specifically, polyolefins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, polyacrylonitrile and copolymers thereof; polyoxymethylene, polyphenylene oxide, Polyethers such as poly (2,6-dimethyl-1,4-phenylene oxide) and copolymers thereof; polyethylene terephthalate, polybutylene terephthalate, poly (ethylene-
Polyesters such as 2,6-dinaphthalate), poly (4-oxybenzoate), poly (2-oxy-6-naphthalate) and copolymers thereof; polyamides such as nylon 6, nylon 66; polycarbonate; polyphenylene Sulfide; polysulfone; polyethersulfone; polyetheretherketone; polyimide; polyetherimide; phenolic resin, urea resin,
Thermosetting polymers such as melamine resins and epoxy resins can be mentioned. As the modifier component of the composition, specifically, 2,6-di-t-butylphenol derivative,
Stabilizers such as 2,6,6-tetramethylpiperidine; flame retardants such as polyhalides and phosphate esters; surfactants; and flow modifiers.

[0049]

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) 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.

Polymer Solubility: 1 mg of the polymer is 1 m of 1,2-dichlorobenzene (abbreviated as oDCB).
In addition to the above, the presence or absence of an insoluble portion (referred to as a gel component) when heated to 150 ° C. was observed.

Number average molecular weight (Mn) and weight average molecular weight (Mw) of polymer: Analysis was performed by gel permeation chromatography, and weight average molecular weight (Mw) and number average molecular weight (Mn) were measured as standard polystyrene equivalent values.
Polymer Laboratories PL-GPC210 System
The procedure was carried out at 140 ° C. using three columns of PLgel 10um MIXED-B manufactured by olymer Laboratories, and oDCB (containing 2,6-di-t-butyl-4-methylphenol 0.01% w / v) as a developing solvent.

Crystallization temperature (Tc) after melting of the polymer,
Heat of crystallization (Hc), melting temperature (Tm), heat of fusion (Hm): Differential scanning calorimetry (MAC SCIENCE DSC3200)
S) was performed under an argon atmosphere. First, 10 ° C / min
The temperature is raised from room temperature to 350 ° C., and after keeping the temperature for 5 minutes, 10 ° C.
/ Min at 150 ° C when cooled from 350 ° C to room temperature
When an exothermic peak of 5 J / g or more is shown above, the peak top temperature is defined as the crystallization temperature (Tc), and the peak area is defined as the heat of crystallization (Hc). Next, again at 10 ° C / mi
When the temperature rises from room temperature to 350 ° C. with n, if the endothermic peak shows 5 J / g or more at 150 ° C. or more, the peak top temperature is defined as the melting temperature (Tm), and the peak area is defined as the heat of fusion (Hm). . If no crystallization or melting peak is observed, N.I. D. And

IR analysis of polymer: infrared spectrophotometer PARAGON1000 (KBr method) manufactured by PerkinElmer
It measured using.

(Ii) Oxidative polymerization Example 1 A 2 L rubber balloon filled with oxygen was attached to a 25 ml two-neck 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)
(See J. Am. Chem. Soc., 120, 8529-8530, (1998).
Abbreviated as u (tacn). ) 0.06 mmol, 0.3 mmol of 2,5-dimethylphenol and 0.9 mmol of 2-methylphenol as copolymerized phenol, and as a base
0.6 mmol of 2,6-diphenylpyridine in toluene
The solution dissolved in 4 g was added. Keep this at 40 ° C,
Stir vigorously. After 24 hours, a few drops of concentrated hydrochloric acid were added to make the mixture acidic, then 25 ml of methanol was added, and the precipitated polymer was collected by filtration. Wash three times with 10 ml of methanol at 60 ° C
After drying under reduced pressure for 6 hours, a polymer was obtained. Table 1 shows the analysis results of the polymer.

Examples 2 to 5 Except that the total amount of starting materials used was 1.2 mmol and the molar ratio of copolymerized phenol and 2,5-dimethylphenol to copolymerized phenol was changed as shown in Table 1, A polymer was obtained in the same manner as in Example 1. Table 1 shows the analysis results of the polymer.

From the IR analysis of the polymers of Examples 1 to 4, all of these polymers were found to have 890 cm ^-1 characteristic of a 2,5-dimethylphenol polymer and characteristic characteristic of a 2-methylphenol polymer. A peak at 750 cm ^-1 was observed. Example 2
The IR chart of the polymer is shown in FIG. From IR analysis of the polymer of Example 5, a characteristic 890 cm ^-1 2,5-dimethylphenol polymer, peaks characteristic 720 cm ^-1 2-octadecyl phenol polymer was detected.

Reference Example 1 1.2 mm only of 2,5-dimethylphenol as a monomer
A polymer was obtained in the same manner as in Example 1 except that ol was used. Table 1 shows the results.

[0059]

[Table 1]

Example 6 2,5-diethylphenol (Chem. Comm.
584 (1974).) Except that only 1.2 mmol was used to obtain a polymer. Table 2 shows the analysis results of the polymer. The obtained polymer was subjected to NMR analysis (LA600, manufactured by JEOL) at 25 ° C. in chloroform-d. 1H
-NMR (600MHz) shows 1.18ppm (6H, t), 2.63ppm (4H,
q), a peak at 6.69 ppm (2H, s) was observed, and 13C-NMR (150
MHz), 14.6ppm, 23.1ppm, 118.6ppm, 133.1ppm, 1
A peak at 50.5 ppm was observed. From these, it was found that the polymer obtained in this example had only a 2,5-diethyl-1,4-phenylene oxide structure.

Example 7 The monomer was 2,5-di-t-butylphenol (J. Am. Chem.
Soc., 73, 4983, (1951)) except that the reaction time was changed to 72 hours to obtain a polymer.
Table 2 shows the results. Incidentally, the obtained polymer was oDCB-d4
At 25 ° C., NMR analysis (LA600 manufactured by JEOL) was performed. 1H-NMR
(600MHz), ~ 1.5ppm (18H) and ~ 6.9ppm (2H)
Since the peak group was observed in each case, the polymer obtained in this example was mainly composed of 2,5-di-t-butyl-
Although it has a 1,4-phenylene oxide structure, it was found that other structures were also included.

Example 8 A polymer was obtained in the same manner as in Example 6, except that the monomer was changed to 2-iso-propyl-5-methylphenol. Table 2 shows the results. The obtained polymer was chloroform-d
At 25 ° C., NMR analysis (LA600 manufactured by JEOL) was performed. 1H-NMR
(600MHz), 1.21ppm (6H, d), 2.16ppm (3H, s),
3.32ppm (1H, m), 6.56ppm (1H, s), 6.78ppm (1H, s)
Was observed. 13.1pp from 13C-NMR (150MHz)
m, 22.9ppm, 27.1ppm, 116.9ppm, 118.9ppm, 127.2pp
m, peaks at 137.1 ppm, 150.3 ppm, 150.4 ppm and some unknown peaks were observed. From these, the polymer obtained in this example was almost 2-iso-propyl-5-methyl-
It was found that it had a 1,4-phenylene oxide structure.

[0063]

[Table 2]

[0064]

The oxidized 2,5-disubstituted phenolic polymer of the present invention has excellent properties such as high transparency and small molding shrinkage since it is amorphous. Further, according to these polymers containing substantially no gel component, their industrial significance is large, for example, a uniform film molded product or injection molded product can be produced.

[Brief description of the drawings]

FIG. 1 is an IR chart of a polymer obtained in Example 2 of the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kiyoshi Fujisawa 4-201-706, Azuma, Tsukuba, Ibaraki Prefecture (72) Inventor Yoshihiko Morooka 3-1-9 Chihaya, Toshima-ku, Tokyo (72) Inventor Shiro Kobayashi Ibaraki Prefecture 1-1-1, Higashi, Tsukuba-shi F-term (in reference) 4M005 AA26 BA00 BB01

Claims (5)

[Claims] 1. A 2,5-disubstituted phenol compound represented by the general formula (I) and a phenol compound represented by the general formula (II) are used as starting materials, and the ratio of the 2,5-disubstituted phenol is 0.1%. An amorphous 2,5-disubstituted phenol oxidized copolymer obtained by oxidative polymerization with 1 to 99.9 mol%. Embedded image (Wherein, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms or a substituted hydrocarbon group having 1 to 8 carbon atoms, and two R ¹ may be the same or different. R ² is a hydrogen atom represents a hydrocarbon group or substituted hydrocarbon group, two R ² may be the same or different, may .R ³ be two R ² is to form a ring is a hydrogen atom or a phenoxy group. ) 2. The ratio of 2,5-disubstituted phenol is 10
The amorphous 2,5-disubstituted phenol oxidized copolymer according to claim 1, wherein the oxidized polymer is obtained by oxidative polymerization in an amount of up to 95 mol%. (3) 2,5-diethylphenol, 2,5-
Starting from at least one phenolic compound selected from the group consisting of dibutylphenol and 2,5-disubstituted phenol represented by formula (I) -a as a starting material, amorphous 2,5- Disubstituted phenol oxidized polymer. Embedded image (Wherein R ¹¹ and R ¹² are different from each other in the number of carbon atoms 1 to 8)
Represents a non-cyclic alkyl group. ) 4. The oxidized 2,5-disubstituted phenol polymer according to claim 1, wherein the polymer is substantially free of a gel component. 5. A compound having a number average molecular weight of 500 to 1,000,000.
5. The method according to claim 1, wherein the value is 00.
Item 2. The oxidized 2,5-disubstituted phenolic polymer according to item 1.