JP3431561B2 - Amorphous 2,5-disubstituted phenol oxidized polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an oxidative polymer of 2,5-disubstituted phenol.

[0002]

It is widely known that poly (2,6-disubstituted-1,4-phenylene oxide) is synthesized by oxidative polymerization of 2,6-disubstituted phenol and exhibits 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). Phenols having substituents at the 2- and 6-positions are used in J. Polym. Sci .: Part A: Polymer
This is to block the coupling at the two ortho positions, as described in Chemistry, 36, 505-517 (1998).

By using a copper complex catalyst composed of a tridentate ligand having a nitrogen as a coordinating atom and a copper atom, the inventors of the present invention have realized that from a 2,5-dimethylphenol having no substituent at one ortho position. , Crystalline poly (2,5-dimethyl-1,4
-Successful synthesis of phenylene oxide (Proceedings of 76th Annual Meeting of the Chemical Society of Japan II-130)
5, lecture number 3H102 (1999)). The present polymer develops a high crystalline melting point even after melting and cooling, and is expected to be used for various applications as a crystalline polymer having high heat resistance and solvent resistance.

[0004]

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

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies in view of the above problems, the present inventors have found that the following problems can be solved by the following inventions. (1) The 2,5-disubstituted phenol compound represented by the general formula (I) and the phenol compound represented by the general formula (II) are used as starting materials, and the proportion of the 2,5-disubstituted phenol is 0.1 to 0.1%. Amorphous 2,5-disubstituted phenol oxidation copolymer obtained by oxidative polymerization as 99.9 mol%.

[0006]

[Chemical 3]

(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms or a substituted hydrocarbon group having 1 to 8 carbon atoms,
The 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 according to item (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-represented by the general formula (I) -a
An amorphous 2,5-di-substituted phenol oxidative polymer obtained by oxidative polymerization using at least one phenol compound selected from the group consisting of di-substituted phenols as a starting material.

[0008]

[Chemical 4]

(In the formula, R ¹¹ and R ¹² are different from each other and represent a non-cyclic alkyl group having 1 to 8 carbon atoms.) (4) It is characterized by containing substantially no gel component (1), The 2,5-di-substituted phenol oxidation polymer according to the item (2) or (3). (5) The 2,5-di-substituted phenol oxidation polymer according to any one of items (1) to (4), which has a number average molecular weight of 500 to 1,000,000.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In a first aspect of the present invention, a 2,5-disubstituted phenol compound represented by the above general formula (I) and a phenol compound represented by the above general formula (II) are used as starting materials. It is a copolymer obtained by oxidative polymerization with the proportion of the 2,5-disubstituted phenol being 0.1 to 99.9 mol%. As the hydrocarbon group having 1 to 8 carbon atoms in R ¹ of the general formula (I), preferably, an alkyl group having 1 to 8 carbon atoms (including a cycloalkyl group), and aralkyl having 7 to 8 carbon atoms. Group or an aryl group having 6 to 8 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, 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 above 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 2-t-.
Examples thereof include a butyloxyethyl group and a 3-dimethylaminopropyl group.

The two R ¹ 's in the above general formula (I) are preferably hydrocarbon groups having 1 to 8 carbon atoms, more preferably alkyl groups having 1 to 6 carbon atoms, and more preferably carbon atoms. More preferably, it is an alkyl group of the number 1 to 4. As the hydrocarbon group for R ² in the general formula (II), when two R ² do not form a ring, it preferably has 1 to 30 carbon atoms (more preferably 1 to 20 carbon atoms).
A) alkyl group (including 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 thereof 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 form a ring, a 5- to 7-membered ring is preferable, and two R ² are — (CH ₂ ) ₃ -group, — (CH ₂ ).
It is preferable to form a ring as a ₄ -group or a -CH = CH-CH = CH- group.

The substituted hydrocarbon group represented by R ² in the general formula (II) is preferably the number of carbon atoms substituted with a halogen atom, an alkoxy group, a disubstituted amino group or the like when the two R ² do not form a ring. 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 an alkyl group having 6 to 30 carbon atoms (more Preferred is an aryl group having 6 to 20 carbon atoms, and specific examples include a trifluoromethyl group, a 2-t-butyloxyethyl group,
Examples thereof include 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 ) It is preferable that it forms a ring as a ₄ -group or a -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 a hydrogen atom or 1 to 2 carbon atoms.
More preferably an alkyl group or aralkyl group of 0,
A hydrogen atom or an alkyl group having 1 to 20 carbon atoms is particularly preferable.

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

The above-mentioned copolymer of the present invention has a poly (phenylene oxide) structure having repeating units represented by the following general formulas (IV) and (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) is usually 0.1 to 99.9 unit%, preferably 10 to 95 unit%, and more preferably 25 to 9% with respect to all repeating units.
90 units%.

[0015]

[Chemical 5]

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

The 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
It is an amorphous 2,5-di-substituted phenol oxidation polymer obtained by oxidative polymerization using seeds as a starting material. 2,5-
As dibutylphenol, 2,5-di-t-butylphenol, 2,5-di-iso-butylphenol,
2,5-di-n-butylphenol, 2,5-dicyclobutylphenol and the like can be mentioned, but 2,5-di-t-
Butylphenol is preferred. Specific examples of the acyclic alkyl group having 1 to 8 carbon atoms in R ¹¹ and R ¹² of the general formula (I) -a include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n- Examples thereof include a butyl group, an iso-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group and an n-octyl group. The above general formula (I)
-A in which R ¹¹ and R ¹² have different carbon atoms from 1 to
A non-cyclic alkyl group having 6 carbon atoms is preferable, a non-cyclic alkyl group having 1 to 4 carbon atoms different from each other is more preferable, and a non-cyclic alkyl group having 1 to 3 carbon atoms different from each other is further preferable. The oxidation 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 homopolymer of these. It may be a copolymer obtained by mixing and performing oxidative polymerization.

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% by weight based on all repeating units.
Or more, more preferably 70 unit% or more, and 90
The unit% or more is more preferable.

[0019]

[Chemical 6]

(Wherein R ¹¹ and R ¹² are represented by the general formula (I) -a
Or has the same meaning as in, or both R ¹¹ and R ¹² are ethyl groups or butyl groups. )

None of the polymers of the present invention shows an exothermic peak (crystallization peak) of 5 J / g or more at 150 ° C. or more when melted and cooled, and when heated again after cooling, It is an amorphous polymer showing no endothermic peak (crystal dissolution peak) of 5 J / g or more at 150 ° C or higher. 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 was carried out in an argon atmosphere, and the temperature at which the polymer was completely melted from room temperature at 10 ° C./min (complete melting temperature)
Up to 10 minutes at 10 ℃ / min.
When cooled from the complete melting temperature to room temperature with, 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 again raised from room temperature to the complete melting temperature at 10 ° C./min, the presence or absence of 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 gel-free. The absence of gel content means that 1 mg of polymer is equivalent to 1 ml of 1,2-dichlorobenzene.
It can be confirmed by melting at 50 ° C. “Substantially free of gel content” means that the gel content contained in the polymer is preferably 5% by weight or less, more preferably 2% by weight or less, and most preferably the gel content is contained. It means not being done. The molecular weight of the polymer of the present invention is not particularly limited, but the number average molecular weight is 500 to 1,000,000.
Is preferred, 1,000 to 100,000 is more preferred, and 2,000 to 50,000 is even more preferred.

The preferred method for producing the polymer of the present invention is described in detail below.

The above-mentioned oxidative polymerization of the phenolic starting material is preferably carried out in the presence of oxygen using a copper complex catalyst composed of 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 coordination atom is a nitrogen atom. This ligand is a chemistry dictionary (1st edition, Tokyo Kagaku Dojin, 1989).
As described in, a molecule or ion bonded to an atom by a coordinate bond. The atom that is directly involved in the bond is called the coordinating atom. The tridentate ligand is a ligand having three coordination atoms. On the other hand, a catalyst composed of a bidentate or monodentate ligand whose 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 coordination atom is a nitrogen atom. Specific examples of such a tridentate ligand 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. Examples thereof include derivatives thereof.

The valence of the copper atom in this copper complex catalyst is 0.
Is trivalent, but monovalent or divalent is preferable. In this copper complex catalyst, the ratio of the tridentate ligand to the copper atom is not particularly limited, but the complex to be substantially formed is preferably one or more copper atoms per one tridentate ligand. . The number is more preferably 1 to 3, and even more preferably 1.

In this copper complex catalyst, the structure other than the ligand and the copper atom is not particularly limited as long as it does not deactivate the catalytic ability. The copper complex catalyst of the present invention may be coordinated with a solvent or the like in the starting material of the complex, the synthesis process and / or the oxidative polymerization process.

The copper complex catalyst may require counter ions capable of maintaining electrical neutrality. As the counter anion, a conjugate base of Bronsted acid is usually used, and specific examples thereof include fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, carbonate ion, perchlorate ion, Tetrafluoroborate ion, hexafluorophosphate ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate ion, hydroxide ion, oxide ion,
Examples include methoxide ion and ethoxide ion. The counter anion is preferably chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, acetate ion, hydroxide ion or methoxide ion, and more preferably chloride ion, bromide ion, sulfate ion or It is 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]

[Chemical 7]

(Where R is^FourIs a hydrogen atom, a hydrocarbon group or
Represents a substituted hydrocarbon group, all R ^FourAre the same but different
You may R⁵Is a bifunctional hydrocarbon group or
Represents a substituted hydrocarbon group, all R⁵Are the same or different
You may stay. X is a counter anion and n is X
It is the number and is appropriately determined by the valences of copper and X. )

The hydrocarbon group for R ⁴ in the above general formula (III) is an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or 6 to 20 carbon atoms.
Is preferred, and specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, t-butyl group, 1-pentyl group, 3-pentyl group. , A cyclopentyl group, a hexyl group,
Cyclohexyl group, octyl group, decyl group, 4-methylcyclohexyl group, 4-t-butylcyclohexyl group,
3,5-dimethylcyclohexyl group, benzyl group, 2-
Examples thereof 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 above general formula (III) is the above-mentioned preferred hydrocarbon group substituted with a halogen atom, an alkoxy group, a disubstituted amino group or the like,
Specific examples include a pentafluorophenylmethyl group, a methoxyethyl group, a diphenylaminopropyl group and the like.

As R ^{4 in the} above 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 further preferable.

The bifunctional hydrocarbon group for R ⁵ in the above general formula (III) is an alkylene group having 1 to 20 carbon atoms (including cycloalkylene group) or 6 carbon atoms.
To 20 arylene groups are preferred, and specific examples include methylene group, 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
Examples thereof include ethylene, 1,2-cyclopentylene group, 1,2-cyclohexylene group, and 1,2-phenylene group.

The difunctional substituted hydrocarbon group for R ⁵ in the above general formula (III) is the above-mentioned preferred bifunctional 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 2-phenylene group and 4-dimethylamino-1,2-phenylene group.

As R ^{5 in the} above general formula (III), a bifunctional hydrocarbon group is preferable, an alkylene group having 1 to 20 carbon atoms is more preferable, and an alkylene group having 2 to 6 carbon atoms is further preferable. , 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, n is the number of X, and is determined by the valence of copper.

In the above general formula (III), the structures other than those described above are not particularly limited as long as the catalytic activity is not deactivated. The transition metal complex catalyst of the present invention may be coordinated with a solvent or the like in the starting material of the complex, the synthesis process and / or the oxidative coupling reaction process.

The copper complex can be synthesized, for example, by a method of mixing the tridentate ligand compound and the copper compound in a suitable 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 appropriately used, but J.
Chem. Soc. Dalton Trans., 83-90 (1993). And J. Am. Ch.
It is also possible to synthesize by referring to em. Soc., 8865-8866, 117 (1995) and the like. As the copper complex, a complex synthesized in advance can be used, but a complex may be formed in the reaction system.

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

When the copper valence of the copper complex is divalent and has a conjugate base of an acid stronger than phenol as a counter ion, a base that does not inactivate the copper complex catalyst is used as the counter ion. It is preferable to coexist with 1/4 equivalent or more during the polymerization. Examples of such bases include:
Sodium hydroxide, potassium hydroxide, calcium oxide,
Alkali metal or alkaline earth metal hydroxides, oxides, alkoxides such as sodium methoxide and sodium ethoxide; methylamine, ethylamine,
Examples include amines such as propylamine, butylamine, dibutylamine, and triethylamine; pyridines such as pyridine, 2-methylpyridine, 2,6-dimethylpyridine, and 2,6-diphenylpyridine. Alkoxides, amines or pyridines as counterions and 1
/ 4 equivalents or more are more preferably present, and substituted pyridines are more preferably 1/2 equivalent or more.

Oxygen is used as an oxidizing agent in the oxidative polymerization for producing the polymer of the present invention, and it may be a mixture with an inert gas or air. The amount of oxygen used is usually equivalent to or larger than the phenolic starting material and used in large excess.

The oxidative polymerization can be carried out in the absence of a reaction solvent, but it is generally desirable 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. To give an example of a preferred solvent, benzene,
Aromatic hydrocarbons such as toluene and xylene; chain 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 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 Kind; water and the like can be mentioned. Aromatic hydrocarbon-based, chain and cyclic aliphatic hydrocarbons, halogenated hydrocarbons, nitriles, ethers or nitro compounds are more preferable,
Aromatic hydrocarbon-based or halogenated hydrocarbons are more preferable. These are used alone or as a mixture.

When the solvent is used, 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 in a liquid state. When no solvent is used, a temperature above the melting point of the phenolic starting material is desirable.
The preferred temperature range is 0 ° C to 200 ° C, more preferably 0 ° C to 150 ° C, and further preferably 0 ° C to 1 ° C.
It is 00 ° C.

The 2,5-disubstituted phenol oxidation polymer of the present invention can be used alone or as a composition with other polymers and / or modifiers. Specific examples of the polymer component of the composition include polyolefins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethylmethacrylate, polyvinyl acetate, polyacrylonitrile and copolymers thereof; polyoxymethylene, polyphenylene oxide, Polyethers such as poly (2,6-dimethyl-1,4-phenylene oxide) and their copolymers; 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; phenol resin, urea resin,
Thermosetting polymers such as melamine resins and epoxy resins can be mentioned. As the modifier component of the composition, specifically, a 2,6-di-t-butylphenol derivative, 2,
Examples thereof include stabilizers such as 2,6,6-tetramethylpiperidines; flame retardants such as polyhalides and phosphoric acid esters; surfactants; and flow modifiers.

[0049]

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

(I) Conversion rate of analyzed monomer (Conv.): 15 mg of a reaction mixture containing diphenyl ether as an internal standard substance was sampled and acidified by adding a small amount of concentrated hydrochloric acid to 2 g of methanol.
Was added to obtain a measurement sample. This sample was subjected to high performance liquid chromatography (pump: Tosoh SC802
0 system, detector: PD-8020 manufactured by Tosoh Corporation, detection wavelength: 278 nm, column: ODS-AM manufactured by YMC.
Developing solvent: Methanol / water = Change from 68:32 to 100/0 38 minutes later, then 5
Analysis was carried out), and diphenyl ether was quantified as an internal standard substance.

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

Number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer were analyzed by gel permeation chromatography, and the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured as standard polystyrene conversion values.
With the Polymer Laboratories PL-GPC210 system, P
Three PLgel 10um MIXED-B manufactured by olymer Laboratories were used as columns, and oDCB (containing 2,6-di-t-butyl-4-methylphenol 0.01% w / v) was used as a developing solvent at 140 ° C.

Crystallization temperature (Tc) of the polymer after melting,
Heat of crystallization (Hc), melting temperature (Tm), heat of melting (Hm): Differential scanning calorimetry (DSC3200, MAC SCIENCE)
S) was performed under an argon atmosphere. First, 10 ℃ / min
After heating from room temperature to 350 ° C for 5 minutes, 10 ° C
150 ℃ when cooled from 350 ℃ to room temperature at 1 / min
When the exothermic peak of 5 J / g or more is shown above, the peak top temperature was taken as the crystallization temperature (Tc), and the peak area was taken as the heat of crystallization (Hc). Then again 10 ℃ / mi
When an endothermic peak of 5 J / g or more is shown at 150 ° C or higher when the temperature is raised from room temperature to 350 ° C with n, the peak top temperature is the melting temperature (Tm), and the peak area is the heat of fusion (Hm). . If no crystallization or melting peak is seen, then N. D. And

IR analysis of polymer: Infrared spectrophotometer PARAGON 1000 (KBr method) manufactured by Perkin Elmer
Was measured using.

(Ii) Oxidative Polymerization Example 1 A 25 ml two-neck round bottom flask equipped with a magnetic stirrer was equipped with a 2 L rubber balloon filled with oxygen, and the inside of the flask was replaced with oxygen. In addition to this, Cu (Cl ₂ ) (1,4,7-triisopropyl-1,4,7-triazacyclononane)
(See J. Am. Chem. Soc., 120, 8529-8530, (1998)., C
Abbreviated as u (tacn). ) 0.06 mmol is added, and 2,5-dimethylphenol 0.3 mmol, 2-methylphenol 0.9 mmol as a copolymerized phenol, and a base
0.6 mmol of 2,6-diphenylpyridine in toluene 2.
What was melt | dissolved in 4 g was added. Keep it at 40 ℃,
Stir vigorously. After 24 hours, 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. Wash 3 times with 10 ml of methanol, 60 ℃
After being dried under reduced pressure for 6 hours, a polymer was obtained. The analysis results of this polymer are shown in Table 1.

Examples 2 to 5 Examples were carried out except that the total amount of the starting materials charged was 1.2 mmol and the molar ratio of the copolymerized phenol and 2,5-dimethylphenol and the copolymerized phenol charged was changed as shown in Table 1. A polymer was obtained in the same manner as in Example 1. The analysis results of this polymer are shown in Table 1.

From the IR analysis of the polymers of Examples 1 to 4, all of these polymers were found to have a characteristic of 2,5-dimethylphenol polymer of 890 cm ^-1 and a characteristic of 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 Only 2,5-dimethylphenol as a monomer is 1.2 mm
A polymer was obtained in the same manner as in Example 1 except that ol was used. The results are shown in Table 1.

[0059]

[Table 1]

Example 6 2,5-Diethylphenol (Chem. Comm.
A polymer was obtained in the same manner as in Example 1 except that 1.2 mmol was used only for 584 (1974). Table 2 shows the analysis results of this polymer. The obtained polymer was subjected to NMR analysis (LA600 manufactured by JEOL) in chloroform-d at 25 ° C. 1H
-From NMR (600MHz), 1.18ppm (6H, t), 2.63ppm (4H, t)
q), 6.69 ppm (2H, s) peak is observed, and 13 C-NMR (150
MHz), 14.6ppm, 23.1ppm, 118.6ppm, 133.1ppm, 1
A peak of 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 changed to 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.
The results are shown in Table 2. The obtained polymer was used as oDCB-d4
In the middle, NMR analysis (LA600 manufactured by JEOL) was performed at 25 ° C. 1H-NMR
From (600MHz), ~ 1.5ppm (18H) and ~ 6.9ppm (2H)
Since a peak group was observed in each of the samples, the polymer obtained in this example was mainly 2,5-di-t-butyl-
It was found that it has a 1,4-phenylene oxide structure, but also contains other structures.

Example 8 A polymer was obtained in the same manner as in Example 6 except that 2-iso-propyl-5-methylphenol was used as the monomer. The results are shown in Table 2. The obtained polymer was changed to chloroform-d
In the middle, NMR analysis (LA600 manufactured by JEOL) was performed at 25 ° C. 1H-NMR
From (600MHz), 1.21ppm (6H, d), 2.16ppm (3H, s),
3.32ppm (1H, m), 6.56ppm (1H, s), 6.78ppm (1H, s)
The peak of was seen. From 13C-NMR (150MHz), 16.1pp
m, 22.9ppm, 27.1ppm, 116.9ppm, 118.9ppm, 127.2pp
m, 137.1 ppm, 150.3 ppm, 150.4 ppm peaks and some unknown peaks were observed. From these, the polymer obtained in this Example was almost 2-iso-propyl-5-methyl-
It was found to have a 1,4-phenylene oxide structure.

[0063]

[Table 2]

[0064]

EFFECTS OF THE INVENTION Since the 2,5-di-substituted phenol oxide polymer of the present invention is amorphous, it has excellent properties such as high transparency and low molding shrinkage. In addition, these polymers, which do not substantially contain a gel component, have a great industrial significance such that a uniform film molded product or injection molded product can be produced.

[Brief description of drawings]

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

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihiko Morooka 3-1-9 Chihaya, Toshima-ku, Tokyo (72) Inventor Shiro Kobayashi 1-1, Higashi, Tsukuba-shi, Ibaraki Institute of Industrial Science and Technology (56) ) Reference JP-A-2000-226449 (JP, A) JP-A-2000-336166 (JP, A) JP-A-56-104935 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 65/44 CA (STN)

Claims (5)

(57) [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. Amorphous 2,5-disubstituted phenol oxidation copolymer obtained by oxidative polymerization as 1-99.9 mol%. [Chemical 1] (In the formula, 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 a substituted hydrocarbon group, two R ² may be the same or different, and two R ² may form a ring, and R ³ is a hydrogen atom or a phenoxy group. ) 2. The proportion of 2,5-disubstituted phenol is 10
The amorphous 2,5-di-substituted phenol oxidation copolymer according to claim 1, which is obtained by oxidative polymerization in an amount of ˜95 mol%. 3. 2,5-Diethylphenol, 2,5-
Amorphous 2,5-obtained by oxidative polymerization using at least one phenol compound selected from the group consisting of dibutylphenol and 2,5-disubstituted phenol represented by the general formula (I) -a as a starting material. Di-substituted phenol oxidation polymer. [Chemical 2] (In the formula, R ¹¹ and R ¹² are different from each other and have 1 to 8 carbon atoms.
Represents a non-cyclic alkyl group. ) 4. The 2,5-di-substituted phenol oxidation polymer according to claim 1, 2 or 3, which is substantially free of a gel component. 5. A number average molecular weight of 500 to 1,000,0.
It is 00, Any one of Claims 1-4 characterized by the above-mentioned.
The 2,5-di-substituted phenol oxidation polymer according to the item.