TW201945353A - Cyclic poly(arylene ether ketone) and production method therefor - Google Patents

Abstract

The present invention addresses the problem of providing a cyclic poly(arylene ether ketone) capable of being obtained in high yield. The cyclic poly(arylene ether ketone) of the present invention is represented by chemical formula (I), wherein X is an ether or ketone group, Ar1, Ar2, and Ar3 each represent an optionally substituted arylene group, and n is a positive integer. In chemical formula (I), at least some of the Ar1 and Ar3 moieties are arylene groups bonded at meta positions.

Description

Cyclic polyarylene ether ketone and manufacturing method thereof

The present invention relates to a cyclic polyarylene ether ketone and a method for producing the same.

Polyarylene ether ketone has been used in various applications in industrial fields having excellent mechanical properties, heat resistance, and chemical resistance. In addition, when a polymer is impregnated with a base material such as particles or fibers to form a composite material, it can have both the moldability of a resin and various characteristics of the base material, and can be widely used in various applications. Among them, a fiber-reinforced composite material made of poly (arylene ether ketone) and reinforcing fibers such as glass fiber or carbon fiber is used as a material for airplanes or automobiles, and is expected to expand in the future.

However, super engineering plastics such as polyarylene ether ketone have a very high melting point, making it difficult to impregnate the fiber material uniformly. As an effective impregnation method for these polymers, a relatively low molecular weight cyclic oligomer is heated and melted in the presence of fibers to impregnate the reinforcing fibers, and the cyclic oligomer is converted into a high degree of polymerization by ring-opening polymerization. A method for obtaining a fiber-reinforced composite material by using a polymer (for example, Patent Document 1). However, the cyclic oligomer disclosed in Patent Document 1 must suppress the intermolecular reaction under high dilution conditions during synthesis, and has a problem of low yield. Inevitably, the yield of the cyclic oligomer that becomes the precursor of the matrix resin becomes a bottleneck in terms of cost and technology in obtaining the fiber-reinforced composite material.

[Questions to be Solved by the Invention]

The object of the present invention is to impart a cyclic polyarylene ether ketone that can be obtained in a high yield.

[Means to solve the problem]

The cyclic poly (arylene ether ketone) of the present invention is a cyclic poly (arylene ether ketone) represented by the following chemical formula (I), which is at least a part of Ar ¹ and Ar ³ in chemical formula (I). Cyclic poly (arylene ether ketone) based on an arylene group bonded in meta position.

(However, X is an ether group or a keto group, and Ar ¹ , Ar ² , and Ar ³ each represent an arylene group which may have a substituent, and n is a positive integer).

The cyclic poly (arylene ether ketone) of the present invention is preferably a cyclic poly (arylene ether ketone) having Ar ^{2 of} a meta-phenylene unit and a para-phenylene unit of the chemical formula (I), Ar ¹ The molar ratio (m ₁ / p ₁ ) between the phenylene unit (m ₁ ) and the p-phenylene unit (p ₁ ) is preferably 0.05 or more and 1 or less.

Further, Ar ³ having a chemical formula (I) of cyclic poly (arylene ether ketone) having two constituent units of m-phenylene unit and p-phenylene unit is also preferred, and phenylene unit (m) between Ar ³ ₃ ) The molar ratio (m ₃ / p ₃ ) to the p-phenylene unit (p ₃ ) is preferably 0.05 or more and 1 or less. In the present invention, the cyclic polyarylidene preferably has a cyclic dimer component having a repeating unit n of 2 of 30% by mass or less.

The cyclic polyarylidene ether ketone of the present invention can be obtained by the following production method: a cyclic polyarylate which reacts a dihalogenated aromatic ketone, a m-dihydroxy aromatic compound, and a p-dihydroxy aromatic compound. A method for producing ether ketone; or a method for producing cyclic polyarylidene ether ketone by reacting m-dihalofluorenyl aromatic compound, p-dihalofluorenyl aromatic compound and diaryl ether.

The present invention includes a molding material obtained by impregnating the cyclic poly (arylene ether ketone) of the present invention with a fiber-reinforced substrate, and impregnating the cyclic poly (arylene ether ketone) of the present invention with a fiber-reinforced substrate. Method for producing ring-shaped polymer-reinforced fiber-reinforced composite material of poly (arylene ether ketone).

[Inventive effect]

The cyclic polyarylidene ether ketone of the present invention can be obtained in a high yield because it has an arylate group bonded in the meta position in the main chain structure. The cyclic polyarylidene ether ketone of the present invention is excellent in impregnation with reinforcing fibers, and thus can be obtained by a fiber-reinforced composite having excellent physical properties.

According to the method for producing a cyclic poly (arylene ether ketone) of the present invention, a cyclic poly (arylene ether ketone) can be produced in a high yield.

The present invention is explained in detail below.

The cyclic poly (arylene ether ketone) of the present invention is a poly (arylene ether ketone) having a cyclic structure represented by the following chemical formula (I), which is at least a part of Ar ¹ and Ar ^{3 in} the chemical formula (I). Aryl is a cyclic poly (arylene ether ether ketone) of an arylene group bonded in meta position. In the present invention, the arylidene group of at least one of Ar ¹ and Ar ³ in the chemical formula (I) may be an arylate group bonded by meta position. Both Ar ¹ and Ar ³ may have an arylene group bonded in meta position.

(However, X is an ether group or a keto group, and Ar ¹ , Ar ² , and Ar ³ each represent an arylene group which may have a substituent, and n is a positive integer).
The repeating unit represented by n in Chemical Formula (I) is a positive integer, preferably 2 or more and 20 or less, more preferably 2 or more and 15 or less, and even more preferably 2 or more and 10 or less. When n is in this range, it is easy to synthesize, and it becomes a cyclic polyarylene ether ketone which is easy to impregnate fibers and the like. When n is too small, the synthesis tends to be difficult to change. When n is too large, the melting point of the cyclic polyarylene ether ketone becomes high, and the impregnation efficiency of fibers and the like tends to decrease.

In the present invention, the cyclic dimer component having a repeating unit n of 2 is preferably 30% by mass or less based on the total amount of the cyclic polyarylene ether ketone represented by the chemical formula (I). The cyclic dimer component having a repeating unit n of 2 is more preferably 20% or less, and still more preferably 10% or less. When the dimer component is in this range, the fluidity at the time of heating and melting of the cyclic polyarylene ether ketone can be improved. When the cyclic dimer component contains 0.01% or more, the impact resistance of the high molecular weight poly (arylene ether ketone) obtained by ring-opening polymerization of the cyclic poly (arylene ether ketone) is improved.

X in Chemical Formula (I) is an ether group or a ketone group. In formula (I), X is an ether-based cyclic polyarylidene ether ketone. Also known as cyclic polyarylidene ether ether ketone (PEEK), dihalogenated aromatic ketone compounds and dihydroxy aromatic compounds can be used. Obtained by copolymerization and the like. Cyclic poly (arylene ether ketone) in which X is a keto group in chemical formula (I) is also known as cyclic poly (arylene ether ketone ketone) (PEKK). Obtained by copolymerization and the like.

Ar ¹ , Ar ² , and Ar ³ in the chemical formula (I) are respectively an arylene group which may have a substituent, and it is preferable that Ar ² is an arylene group (para-phenylene structure) bonded in a para position. The present invention is a cyclic polyarylidene ether ketone in which at least a part of Ar ¹ and Ar ³ in chemical formula (I) is an arylene group (meta-phenylene structure) bonded in meta position. When a m-phenylene structure is present in the main chain, a cyclic structure is easily formed because the poly (arylene ether) chain is bent. Therefore, a cyclic polyarylene ether ketone can be obtained in a high yield. In addition, the cyclic polyarylene ether ketone having such a curved structure is excellent in impregnation with reinforcing fibers. Therefore, when the cyclic polyarylene ether ketone of the present invention is used as a precursor of a matrix resin, a material can be obtained by a fiber-reinforced composite having excellent physical properties.

In the present invention, Ar ¹ or Ar ³ in chemical formula (I) may not necessarily be meta-bonded, as long as a part of Ar ¹ or Ar ³ in the repeating unit in chemical formula (I) is meta-bonded arylene Just fine. In the present invention, Ar ¹ and Ar ³ which are not meta-bonded are preferably para-bonded arylene (p-phenylene structure).

The cyclic poly (arylene ether ketone) of the present invention is preferably a cyclic poly (arylene ether ketone) in which Ar ^{1 of} formula (I) has two constituent units of a m-phenylene unit and a p-phenylene unit. Ar ¹ with inter-phenylene units and when the two kinds of the constituent units of the phenylene units, Ar-phenylene units ₍₁ m) between ¹ and the molar ratio of the phenylene units (P ₁₎ of the (m ₁ / p ₁ ) is preferably 0.05 or more and 1 or less. When the molar ratio (m ₁ / p ₁ ) is within this range, a cyclic poly (arylene ether ketone) can be obtained in a good yield. When these cyclic poly (arylene ether ketone) s are subjected to ring-opening polymerization, a high molecular weight poly (arylene ether ketone) having excellent heat resistance and mechanical properties can be obtained. When the molar ratio (m ₁ / p ₁ ) is too large, there are many bending structures, and the heat resistance and mechanical properties of the high molecular weight poly (arylene ether ketone) obtained by ring-opening polymerization of cyclic poly (arylene ether ketone) tend to decrease. . On the other hand, when the molar ratio (m ₁ / p ₁ ) is too small, the molecular chain tends to become rigid and the yield of the obtained cyclic polyarylene ether ketone tends to decrease.

The cyclic polyarylene ether ketone in which Ar ¹ contains a m-phenylene unit can be obtained by copolymerizing a dihalogenated aromatic ketone compound and a dihydroxy aromatic compound containing a meta-isomer. The Mohr ratio (m ₁ / p ₁ ) can be adjusted by the ratio of the isomers between the monomers used in the copolymerization.

In addition, the cyclic polyarylene ether ketone of the present invention is also preferably a cyclic polyarylene ether ketone having Ar ^{2 of} a meta-phenylene unit and a para-phenylene unit in the chemical formula (I). . Ar ³ has the inter-phenylene units and when the two kinds of the constituent units of the phenylene units, Ar-phenylene unit (m ₃₎ molar ratio of between ³ and phenylene units (P ₃₎ of the (m ₃ / p ₃ ) is preferably 0.05 or more and 1 or less. When the molar ratio (m ₃ / p ₃ ) is within this range, a cyclic poly (arylene ether ketone) can be obtained in a good yield. When these cyclic poly (arylene ether ketone) s are subjected to ring-opening polymerization, a high molecular weight poly (arylene ether ketone) having excellent heat resistance and mechanical properties can be obtained. When the molar ratio (m ₃ / p ₃ ) is too large, there are many bending structures, and there is a tendency that the heat resistance and mechanical properties of high molecular weight poly (arylene ether ketone) obtained by ring-opening polymerization of cyclic poly (arylene ether ketone) tend to decrease. . On the other hand, if the molar ratio (m ₃ / p ₃ ) is too small, the molecular chain tends to become rigid, and the yield of the obtained cyclic polyarylene ether ketone tends to decrease.

Ar ³ A cyclic polyarylene ether ketone containing a m-phenylene unit can be obtained by dihalogenated aromatic ketone compounds containing di-halo isomers and dihydroxy groups contained in at least one aryl group. It is obtained by copolymerization of an aromatic compound, or copolymerization of a dihalogenated fluorenyl aromatic compound containing a meta-isomer and a diaryl ether, and the like. The Moire ratio (m ₃ / p ₃ ) can be adjusted by the ratio of the isomers between the monomers used in the copolymerization.

As described above, the cyclic poly (arylene ether ketone) of the present invention has a meta-phenylene structure in the main chain, so the poly-arylene ether chain is easily bent to form a cyclic structure, which can be obtained in high yield. Since the cyclic poly (arylene ether ketone) having such a curved structure is excellent in impregnation with reinforcing fibers, the cyclic poly (arylene ether ketone) of the present invention can have excellent physical properties when used as a matrix resin precursor. Fiber reinforced composites.

<Production method of cyclic polyarylene ether ketone>
The cyclic poly (arylene ether ketone) of the present invention can be obtained by synthesizing a cyclic poly (arylene ether ketone) using a monomer containing a meta isomer. The cyclic polyarylidene ether ketone may be combined with a dihalogenated aromatic ketone compound and a dihydroxy aromatic compound, or a dihalogenated fluorenyl aromatic compound and a diaryl ether for copolymerization reaction, or a halogenated fluorenyl hydroxy aromatic Obtained by polymerization. The polymerization method is not particularly limited, and conventionally known polymerization methods such as solution polymerization, melt polymerization, suspension polymerization, and interfacial polymerization can be used. The cyclic poly (arylene ether ketone) can be obtained by subjecting a linear poly (arylene ether) to a heating reaction.

Examples of the method for obtaining the cyclic polyarylene ether ketone include the following methods (a) to (g).
(a) A production method of heating and reacting a mixture containing at least a dihalogenated aromatic ketone compound, a dihydroxy aromatic compound, a base, and an organic polar solvent.
(b) A production method of heating and reacting a mixture containing at least a dihalofluorenyl aromatic compound, a diaryl ether, a base, and an organic polar solvent.
(c) A manufacturing method of heating and reacting a mixture containing at least a linear polyarylene ether, a dihalogenated aromatic ketone compound, a dihydroxy aromatic compound, a base, and an organic polar solvent.
(d) A method of heating and reacting a mixture containing at least a linear polyarylene ether ketone, a dihalofluorenyl aromatic compound, a diaryl ether, a base, and an organic polar solvent.
(e) A production method of heating and reacting a mixture of an organic polar solvent containing at least one or more of a linear polyarylene ether ketone, at least an inorganic alkali metal salt or an organic alkali metal salt.
(f) A production method of heating and reacting a mixture containing at least a dihalogenated aromatic ketone compound, a dihydroxy aromatic ketone compound, a base, and an organic polar solvent.
(g) A production method of heating and reacting a mixture containing at least a hydroxy halogenated aromatic ketone compound, a dihydroxy aromatic compound, a base, and an organic polar solvent.

When a dihalogenated aromatic ketone compound and a dihydroxy aromatic compound are combined to produce the cyclic polyarylidene ether ketone of the present invention, a meta-dihydroxy aromatic compound is used as the dihydroxy aromatic compound to obtain the cyclic polyarylidene of the present invention. Arylene ether ketone (cyclic polyarylene ether ether ketone).

In the present invention, as the dihydroxy aromatic compound, it is preferred to use a meta-dihydroxy aromatic compound and a para-dihydroxy aromatic compound together. In this case, the mole of the meta-dihydroxy aromatic compound / p-dihydroxy aromatic compound is preferably 0.05 or more and 1 or less. By setting the molar ratio of the meta-dihydroxy aromatic compound / p-dihydroxy aromatic compound to be in this range, a cyclic polyarylidene ether ketone can be obtained in a good yield. In addition, when these cyclic poly (arylene ether ketone) s are subjected to ring-opening polymerization, a high molecular weight poly (arylene ether ketone) having excellent heat resistance and mechanical properties can be obtained. When the molar ratio of the meta-dihydroxy aromatic compound / p-dihydroxy aromatic compound is too small, the molecular chain becomes rigid and the yield of the obtained cyclic polyarylene ether ketone tends to decrease. On the other hand, when the molar ratio is too large, the bent structure occupies more than half of the molecular chain, and the heat resistance and mechanical properties of the high molecular weight poly (arylene ether ketone) obtained by the ring-opening polymerization described later tend to decrease.

Examples of the dihalogenated aromatic ketone compound include difluorobenzophenone, dichlorobenzophenone, dibromobenzophenone and derivatives thereof. Among them, from the viewpoint of reactivity, difluorobenzophenone is preferred. These dihalogenated aromatic ketone compounds may be used alone, and it is not a problem to use them as a mixture of two or more kinds.

Examples of m-dihydroxy aromatic compounds include resorcinol (m-dihydroxybenzene), 2,4-toluenediol, 3,5-toluenediol, p-xylene-2,6-diphenol, M-xylene-4,6-diphenol and the like. Among them, resorcinol is preferably used.

Examples of para-dihydroxy aromatic compounds include hydroquinone (p-dihydroxybenzene), 2,5-toluenediol, p-xylene-2,5-diphenol, and the like. Among them, hydroquinone is preferably used.

The amount of the dihydroxy aromatic compound used in combination of m-dihydroxy aromatic compound and para-dihydroxy aromatic compound is preferably in the range of 0.8 to 1.2 mol relative to the dihalogenated aromatic ketone compound, more preferably It is preferably in the range of 0.9 to 1.1 moles, more preferably in the range of 0.95 to 1.05 moles, and particularly preferably in the range of 0.98 to 1.03 moles. By setting the amount of the dihydroxy aromatic compound in the above-mentioned preferable range, the decomposition reaction of the cyclic polyarylidene ether ketone generated can be suppressed, and the separation from the cyclic polyarylate ether ketone can also be suppressed. The formation of difficult linear polyarylene ether ketone is preferred.

When a dihalogenated fluorenyl aromatic compound and a diaryl ether are combined to produce the cyclic polyarylidene ether ketone of the present invention, a m-dihalogenated fluorenyl aromatic compound is used as the dihalogenated fluorenyl aromatic compound, and the present invention can be obtained. Cyclic poly (arylene ether ketone).

In the present invention, as the dihalogenated fluorenyl aromatic compound, a m-dihalogenated fluorenyl aromatic compound and a p-dihalogenated fluorenyl aromatic compound are preferably used in combination. In this case, the mole of the meta-dihalofluorenyl aromatic compound / p-dihalofluorenyl aromatic compound is preferably 0.05 or more and 1 or less. By setting the molar ratio within this range, cyclic polyarylene ether ketone can be obtained in a good yield. In addition, when these cyclic poly (arylene ether ketone) s are subjected to ring-opening polymerization, a high molecular weight poly (arylene ether ketone) having excellent heat resistance and mechanical properties can be obtained. When the molar ratio is too small, the molecular chain becomes rigid and the yield of the obtained cyclic polyarylene ether ketone tends to be easily reduced. On the other hand, when the molar ratio is too large, the bent structure occupies more than half of the molecular chain, and thus the heat resistance and mechanical properties of the aromatic poly (arylene ether ketone) obtained by the ring-opening polymerization described later tend to decrease.

Examples of the m-dihalofluorenyl aromatic compound include, for example, m-xylylene chloride and derivatives thereof.

Examples of the p-dihalofluorenyl aromatic compound include, for example, p-xylylene chloride and derivatives thereof.

Examples of the diaryl ether include diphenyl ether and derivatives thereof.

Examples of the alkali used in the production of the cyclic polyarylidene ether ketone include alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, and alkaline earths such as calcium carbonate, strontium carbonate, and barium carbonate. Carbonates of metals, Lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate and other alkali metal bicarbonates, calcium bicarbonate, strontium bicarbonate, barium bicarbonate and other alkaline earth metal carbonates Hydrogen salts, or hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide, strontium hydroxide, and barium hydroxide Among them, from the viewpoint of easy and reactivity, carbonates such as sodium carbonate and potassium carbonate, and sodium bicarbonates such as sodium bicarbonate and potassium bicarbonate are preferred, and sodium carbonate and potassium carbonate are more preferred. Better use of potassium carbonate. These can be used alone, and it is not a problem to mix two or more. These bases are preferably used in the form of an anhydrous substance, but they can also be used as a hydrate or an aqueous mixture. The term "aqueous mixture" used herein refers to an aqueous solution, a mixture of an aqueous solution and a solid component, or a mixture of water and a solid component.

As the organic polar solvent used in the production method of the cyclic poly (arylene ether ketone), if it is a bad side reaction that does not substantially cause reaction hindrance or decomposition of the cyclic poly (arylene ether ketone) produced, It is not particularly limited. Specific examples of such organic polar solvents include toluene, N-methyl-1-pyrrolidone (NMP), N-methylcaprolactam, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), hexamethylsulfonamide, tetramethylurea, etc. Dimethylene fluorene (DMSO), dimethyl fluorene, diphenyl fluorene, cyclopentadiene and other fluorene / fluorene-based solvents, benzonitrile and other nitrile solvents, diphenyl ethers and other diaryl ethers, Ketones such as benzophenone and acetophenone and mixtures thereof.

It is desirable that the amount of the organic polar solvent in the mixture when producing the cyclic polyarylidene ether ketone is preferably 1.20 liters or more, more preferably 1.30 liters or more, and 1.50 liters relative to the 1.0 benzene ring component in the mixture. Liters or more, particularly preferably 2.0 liters or more. In addition, the upper limit of the amount of the organic polar solvent in the mixture is not particularly limited, but it is preferably 100 liters or less, more preferably 50 liters or less, and more preferably 20 liters or less relative to 1.0 mol of the benzene ring component in the mixture. It is preferably less than 10 liters.

The amount of the alkali used in the method for producing a cyclic poly (arylene ether ketone) is preferably equal to or greater than the equivalent of the stoichiometric ratio to the monomer. The reaction temperature varies depending on the types and amounts of raw materials, bases, organic polar solvents, etc. used, so it cannot be determined uniformly, but usually ranges from 120 to 350 ° C. The reaction time cannot be specified because it depends on the type and amount of the raw materials used or the reaction temperature, but it is preferably 0.1 hours or more, more preferably 0.5 hours or more, and even more preferably 1 hour or more. On the other hand, there is no particular upper limit to the reaction time, and the reaction can proceed sufficiently within 40 hours, preferably within 10 hours, and more preferably within 6 hours. In addition, the environment at the time of manufacture is desirably performed in a non-oxidizing environment, preferably in an inert environment such as nitrogen, helium, and argon, and is preferably performed in a nitrogen environment based on economy and ease of handling.

In the present invention, the amount of the cyclic dimer component formed by the repeating unit n of 2 in the cyclic polyarylidene ether ketone obtained as described above is also preferably controlled. Specifically, the amount of the cyclic dimer component is preferably 30% by mass or less, and more preferably 0.01 to 20% by mass. When the amount of the cyclic dimer component is within this range, the fluidity of the cyclic poly (arylene ether ketone) during heating and melting can be improved.

As a method for controlling the amount of the cyclic dimer component, a solid-liquid separation method using a solvent can be used. Specifically, the crude cyclic polyarylidene ether ketone was dissolved in an ether-based solvent, and then the undissolved matter that was not dissolved in the ether-based solvent was removed by filtration. The ether-based solvent has a low solubility in the cyclic dimer component and a high solubility in the cyclic component with a repeating unit n of 3 or more. Therefore, the cyclic polymer can be separated by using a ether-based solvent for solid-liquid separation treatment. The cyclic dimer component contained in the arylidene ether ketone composition is adjusted to a desired amount.

As the ether-based solvent, tetrahydrofuran, diethyl ether, triethyl ether, diisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, 1,4-dioxane, and 2-methyl ether can be used. Oxy-2-methylpropane, particularly preferably tetrahydrofuran.

＜ Manufacturing method of polyarylene ether ketone ＞
The cyclic poly (arylene ether ketone) of the present invention can be converted into a high-molecular-weight poly (arylene ether ketone) by ring-opening polymerization.

The heating temperature during the ring-opening polymerization reaction may be appropriately selected according to the composition or molecular weight of the cyclic polyarylene ether ketone and the environment during heating. From the viewpoint of performing the reaction in a shorter time, it is preferably 200 ° C or higher, and more preferably 240 ° C or higher. On the other hand, from the viewpoint of suppressing side reactions such as decomposition reactions, the heating temperature is preferably 450 ° C or lower, and more preferably 400 ° C or lower. The heating time is appropriately selected in accordance with various characteristics of the cyclic polyarylene ether ketone and the heating temperature. From the viewpoint of sufficient conversion of the cyclic polyarylene ether ketone, the heating time is preferably 0.01 hours or more, and more preferably 0.05 hours or more. On the other hand, from the viewpoint of suppressing side reactions such as decomposition reactions, it is preferably 100 hours or less, more preferably 20 hours or less, still more preferably 10 hours or less, still more preferably 6 hours or less, and even more preferably Less than 3 hours.

In the ring-opening polymerization of cyclic poly (arylene ether ketone), a polymerization catalyst may be used as required. The polymerization catalyst is a catalyst for accelerating the ring-opening polymerization reaction of a cyclic polyarylidene ether ketone. The compound having this effect is not particularly limited, and an alkali such as an inorganic alkali metal salt or an organic alkali metal salt can be used. Examples of the metal salt include alkali metal halides such as sodium fluoride, potassium fluoride, cesium fluoride, and lithium chloride, and examples of the organic alkali metal salt include sodium methoxide, potassium methoxide, and ethoxylate. Alkali metal alkoxides such as sodium, potassium ethoxide, sodium third butoxide, potassium third butoxide, etc. or sodium phenoxide, potassium phenoxide, sodium 4-phenoxyphenoxide, potassium 4-phenoxyphenoxide Alkali metal phenoxides such as lithium acetate, sodium acetate, potassium acetate and the like. These catalysts can be used alone or in combination of two or more. By performing the ring-opening polymerization of the cyclic poly (arylene ether ketone) in the presence of these preferred catalysts, the reaction time can be reduced.

The amount of the polymerization catalyst used varies depending on the molecular weight of the target high molecular weight poly (arylene ether ketone) and the type of catalyst, but it is usually the chemical formula (I) of the main constituent unit of the cyclic poly (arylene ether ketone). The repeating unit is 1 mol, and is 0.001 to 20 mol%, more preferably 0.005 to 15 mol%, and still more preferably 0.01 to 10 mol%. By adding the amount of the catalyst in the preferable range, there is a tendency that the ring-opening polymerization of the cyclic poly (arylene ether ketone) is performed in a short time.

The method for adding the polymerization catalyst is not particularly limited, but examples thereof include a method of heating the polyarylene ether ketone into a molten liquid, mixing the polymerization catalyst in the molten solution, or bringing the polyarylene ether ketone into contact with the polymerization catalyst. A method of heating a mixture of vehicles to form a molten liquid.

The molding material of the present invention is a molding material based on the poly (arylene ether ketone) as a matrix obtained by impregnating the above-mentioned cyclic poly (arylene ether ketone) in any substrate and ring-opening polymerization of the cyclic poly (arylene ether ketone). . The base material is not limited as long as it does not hinder the ring-opening polymerization reaction of the cyclic polyarylene ether ketone. Examples are particles, continuous fibers, long fibers, short fibers, non-woven fabrics, films, and the like.

The fiber-reinforced composite material can be obtained by impregnating the fiber-reinforced base material with the cyclic polyarylene ether ketone of the present invention and performing ring-opening polymerization. When the fiber-reinforced composite material is produced by using the cyclic poly (arylene ether ketone) of the present invention, the cyclic poly (arylene ether ketone) can be impregnated with the fiber-reinforced substrate to perform ring-opening polymerization at the same time, or the cyclic poly (arylene) aryl group can be used Ether ketone impregnates the forming material of the fiber-reinforced substrate as an intermediate.

When the fiber-reinforced composite material is produced using the cyclic poly (arylene ether ketone) of the present invention, the cyclic poly (arylene ether ketone) may be used alone or as a resin composition containing the aforementioned polymerization catalyst. The resin composition may contain resins other than linear polyarylene ether ketone or polyarylene ether ketone, and may also contain inorganic fillers, flame retardants, and conductivity imparting to the extent that the purpose is not impaired. Agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration suppressants, antibacterial agents, insect repellents, deodorants, anti-colorants, heat stabilizers, release agents, antistatic agents, plasticizers, lubricants, colorants Additives, pigments, dyes, foaming agents, foam inhibitors, coupling agents and other additives.

The molding material of the present invention is a molding material obtained by impregnating the above-mentioned cyclic polyarylene ether ketone into a fiber-reinforced substrate.

The reinforcing fiber material is not particularly limited, and examples thereof include carbon fiber, glass fiber, polyamide fiber, silicon carbide fiber, polyester fiber, ceramic fiber, alumina fiber, boron fiber, metal fiber, mineral fiber, rock fiber, and Slag fiber and so on.

Among these reinforcing fibers, carbon fibers, glass fibers, and polyamide fibers are preferred. From the viewpoint of obtaining a fiber-reinforced composite material having a specific strength, a high specific elasticity, a light weight and a high strength, carbon fibers are more preferred. From the viewpoint of excellent tensile strength, polyacrylonitrile (PAN) -based carbon fibers are particularly preferred.

When the PAN-based carbon fiber is used as the reinforcing fiber, the tensile elastic modulus is preferably 100 to 600 GPa, more preferably 200 to 500 GPa, and particularly preferably 230 to 450 GPa. The tensile strength is preferably 2000 MPa to 10,000 MPa, and more preferably 3000 to 8000 MPa. The carbon fiber diameter is preferably 4 to 20 μm, and more preferably 5 to 10 μm. By using these carbon fibers, the mechanical properties of the fiber-reinforced composite material obtained can be improved.

The reinforcing fibers are preferably used in a sheet form. Examples of the reinforcing fiber sheet include, for example, a sheet in which a plurality of reinforcing fibers are aligned in one direction, or a bidirectional fabric such as plain woven or woven fabric, a multiaxial fabric, a non-woven fabric, a matt, knitted, braided, Reinforced fiber made from paper. Among these, when a reinforcing fiber is used as a continuous fiber and formed into a thin sheet, a unidirectionally aligned sheet, a bidirectional fabric, or a multiaxial fabric base material is preferable because a fiber-reinforced composite material having more excellent mechanical properties can be obtained. The thickness of the sheet-like reinforcing fiber substrate is preferably 0.01 to 3 mm, and more preferably 0.1 to 1.5 mm.

The content of the cyclic polyarylene ether ketone in the entire molding material is preferably 15 to 60% by mass based on the total mass of the molding material. The resin content is preferably from 20 to 55 mass%, more preferably from 25 to 50 mass%.

The method of impregnating the cyclic polyarylene ether ketone into the reinforcing fiber substrate is not particularly limited, and any method conventionally known can be adopted. Specifically, a hot-melt method or a solvent method can be preferably used.

The hot-melt method is to apply a resin composition containing a cyclic polyarylidene ether ketone to a thin film to form a resin composition film on a release paper, and laminate the resin composition film on a reinforcing fiber substrate. A method of impregnating a resin composition into a reinforcing fiber substrate layer by heating under pressure.

The method for forming the resin composition into a resin composition film is not particularly limited, and any conventionally known method may be used. Specifically, the die is extruded, and a resin composition is cast and cast on a support such as a release paper or a film using an applicator, a reverse roll coater, a notch wheel coater, etc. to obtain a resin composition.物 Film. The temperature of the resin when manufacturing the film is appropriately determined according to the composition or viscosity of the resin composition. The resin composition may be impregnated into the reinforcing fiber base material layer once or in a plurality of times.

The solvent method is a method in which a resin composition is formed into a varnish using an appropriate solvent, and the varnish is impregnated into a reinforcing fiber base material layer. Among these conventional methods, it can be manufactured better by a hot-melt method without using a solvent.

After impregnating the fiber-reinforced substrate with the cyclic polyarylene ether ketone of the present invention, ring-opening polymerization is performed to convert the cyclic polyarylene ether ketone into a high-molecular-weight polyarylene ether ketone to obtain a fiber-reinforced composite. material.

The heating temperature during the ring-opening polymerization reaction may be appropriately selected corresponding to the composition or molecular weight of the cyclic polyarylidene ether ketone and the environment during heating. From the viewpoint of reacting in a shorter time, it is preferably 200 ° C or higher, more preferably 250 ° C or higher, and even more preferably 280 ° C or higher. On the other hand, from the viewpoint of suppressing side reactions such as decomposition reactions, the heating temperature is preferably 450 ° C or lower, and more preferably 400 ° C or lower. The heating time can be appropriately selected according to various characteristics of the cyclic polyarylene ether ketone, heating conditions, and the like. From the viewpoint of sufficient conversion of the cyclic polyarylene ether ketone, the heating time is preferably 0.01 hours or more, and more preferably 0.05 hours or more. On the other hand, from the viewpoint of suppressing side reactions such as decomposition reactions, the heating time is preferably 100 hours or less, more preferably 20 hours or less, still more preferably 10 hours or less, still more preferably 6 hours or less, and still more preferably 3 hours. the following.

The method for forming the fiber-reinforced composite material of the present invention is not particularly limited, and examples thereof include production of injection molding, resin injection molding, reaction injection molding, autoclave molding, pressure molding, filament winding molding, and press molding. A molding method with excellent properties, which can be used in combination.

The fiber-reinforced composite material of the present invention thus obtained can be suitably used for coatings for automobiles, airplanes, electrical and electronic equipment, medical supplies, sports and leisure products, and the like.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

[test methods]
＜ Glass transition point and melting point ＞
A differential scanning calorimeter (DSC Q2000, manufactured by TA Instruments) was used as a measuring device, and the glass transition temperature was measured from the deviation from the reference line, and the melting point was measured from the melting peak. The measurement was performed at a temperature range from 30 ° C to 400 ° C under a nitrogen inflow (20 ml / min) and a temperature increase rate of 20 ° C / min.

＜ Starting flow temperature ＞
As a measuring device, a melting point meter (Melting Point B-545 manufactured by BUCHI Corporation) was used. The measurement was performed at a temperature rising rate of 5 ° C / min in a temperature range from room temperature to 350 ° C. The temperature at which the molten cyclic compound started to flow was visually confirmed.

<Cyclic Dimer>
The spectrum obtained by the liquid chromatography measurement was used to calculate from the peak area ratio corresponding to the cyclic dimer. The measurement device used a liquid chromatograph (L-2000 series manufactured by Hitachi High-Technology Co., Ltd.), the detector used L-2400 (made by Hitachi High-Technology Co., Ltd.), and the detection wavelength was set to 270 nm. Mightysil RP-18GP150-4.6 (manufactured by Kanto Chemical Co., Ltd.) was used for the column, and tetrahydrofuran · 0.1% trifluoroacetic acid aqueous solution was used for the mobile phase at a measurement temperature of 40 ° C.

<Example 1>
4,4'-difluorobenzophenone was used as the dihalogenated aromatic ketone, resorcinol was used as the meta-dihydroxy aromatic compound, and hydroquinone was used as the p-dihydroxy aromatic compound to separate the meta- The synthesis of the cyclic poly (arylene ether ether ketone) was performed in such a manner that the molar ratio (m ₁ / p ₁ ) of the phenylene unit (m ₁ ) and the p-phenylene unit (p ₁ ) was set to 0.1.

That is, 2.4 g of 4,4'-difluorobenzophenone, 0.11 g of resorcinol, 0.99 g of hydroquinone, and 2.28 g of anhydrous potassium carbonate were dissolved in 150 mL of DMF and 10 mL of toluene at 140 ° C. Heated and stirred for 1 hour, and heated and stirred at 145 ° C for 4 hours. The molar ratio of resorcinol to hydroquinone is 0.11.

After completion of the reaction, it was washed in 300 mL of 1% acetic acid water at 70 ° C. for 30 minutes, and then washed with pure water to obtain a cake. The obtained crude product was washed with a Soxhlet extractor using chloroform to obtain a cyclic compound (C-1). The yield of the obtained cyclic compound was 7.8%, which was the higher.

<Example 2>
A cyclic compound (C-2) was obtained in the same manner as in Example 1 except that the amount of each agent was set to 10 times. The yield of the obtained cyclic compound was 7.8%, which was the higher. Table 1 shows the ratio of the cyclic dimer component and the onset temperature.

0.5 g of the obtained cyclic compound (C-2) was mixed with 0.013 g of cesium fluoride, and heated at 300 ° C. for 60 minutes under a nitrogen atmosphere to obtain a polymerization reaction product (P-2). The glass transition temperature measured by DSC measurement was 162 ° C, and the melting point was 339 ° C.

The obtained polymerization reaction product (P-2) was pulverized and weighed 15 mg, and stirred in 10 g of tetrahydrofuran for 10 minutes to extract an unreacted cyclic oligomer component. After performing liquid chromatography measurement, no unreacted cyclic oligomer component was confirmed.

<Example 3>
1.65 g of the cyclic compound (C-2) obtained in Example 2 was dissolved in 50 g of tetrahydrofuran at room temperature with stirring for 10 minutes. Undissolved matter was removed from the obtained solution by filtration. From the filtered solution, tetrahydrofuran of the solvent was removed using a rotary evaporator to obtain 1.27 g of a purified cyclic compound (C-3). Table 1 shows the ratio of the cyclic dimer component and the onset temperature. Example 3, in which the amount of the cyclic dimer component was 30% by mass or less, started to flow at 260 ° C, and is a cyclic compound having excellent fluidity when impregnated into a fiber bundle.

Next, 0.5 g of the obtained purified cyclic compound (C-3) and 0.013 g of cesium fluoride were mixed, and heated at 300 ° C. for 60 minutes under a nitrogen atmosphere to obtain a polymerization reaction product (P-3). The glass transition temperature measured by DSC measurement was 148 ° C and the melting point was 333 ° C, maintaining excellent heat resistance.

The obtained polymerization reaction product (P-3) was pulverized and weighed 15 mg, and stirred in 10 g of tetrahydrofuran for 10 minutes to extract an unreacted cyclic oligomer component. After performing liquid chromatography measurement, no unreacted cyclic oligomer component was confirmed.

<Example 4>
Synthesis of cyclic poly (arylene ether ether ketone) was performed so that m ₁ / p _{1 was} 0.25. Except that 0.22 g of resorcinol and 0.88 g of hydroquinone were used so that the molar ratio of resorcinol to hydroquinone was 0.25, the same operation as in Example 1 was performed to obtain a cyclic compound (C- 4). The yield of the obtained cyclic compound was high at 11.6%.

<Example 5>
Synthesis of cyclic poly (arylene ether ether ketone) was performed such that m ₁ / p _{1 was} 0.4. Except that 0.33 g of resorcinol and 0.77 g of hydroquinone were used so that the molar ratio of resorcinol to hydroquinone was 0.43, a cyclic compound (C- 5). The yield of the obtained cyclic compound was very high at 19.5%.

<Example 6>
A cyclic compound (C-6) was obtained in the same manner as in Example 5 except that the amount of each agent was set to 10 times. The yield of the obtained cyclic compound was 19.5%, which was very high. Table 1 shows the ratio of the cyclic dimer component and the onset temperature.

<Example 7>
1.65 g of the cyclic compound (C-6) obtained in Example 6 was dissolved in 50 g of tetrahydrofuran and stirred at room temperature for 10 minutes. Undissolved matter was removed from the obtained solution by filtration, and tetrahydrofuran was removed using a rotary evaporator to obtain 1.5 g of a purified cyclic compound (C-7). Table 1 shows the ratio of the cyclic dimer component and the onset temperature. Example 7 in which the amount of the cyclic dimer component was 30% by mass or less, started to flow at 240 ° C., and was a cyclic compound having excellent fluidity when impregnated with a fiber bundle. The glass transition temperature measured by DSC measurement was 142 ° C, maintaining excellent heat resistance. In addition, no melting point was observed, and it was amorphous.

Next, 0.5 g of the obtained purified cyclic compound (C-7) and 0.013 g of cesium fluoride were mixed and heated at 300 ° C. for 60 minutes in a nitrogen atmosphere to obtain a polymerization reaction product (P-7).

The obtained polymerization reaction product (P-7) was pulverized and weighed 15 mg, and stirred in 10 g of tetrahydrofuran for 10 minutes to extract an unreacted cyclic oligomer component. After performing liquid chromatography measurement, no unreacted cyclic oligomer component was confirmed.

〈Comparative example 1〉
The synthesis of a cyclic polyarylidene ether ether ketone was performed without using m-dihydroxy aromatic compound so that m ₁ / p ₁ became 0. That is, a cyclic compound (C-8) was obtained in the same manner as in Example 1 except that 1.10 g of hydroquinone was used instead of resorcinol. The yield of the cyclic compound obtained in Comparative Example 1 without using the meta isomer was 6.5%, which was low.

〈Comparative example 2〉
A cyclic compound (C-9) was obtained in the same manner as in Comparative Example 1 except that the used amount of each agent was set to 10 times. The yield of the obtained cyclic compound is 6.5%, which is lower. Table 1 shows the ratio of the cyclic dimer component and the onset temperature. The cyclic compound of Comparative Example 2 had no flow at a temperature up to 350 ° C.

0.5 g of the obtained cyclic compound (C-9) was mixed with 0.013 g of cesium fluoride, and heated at 300 ° C. for 60 minutes under a nitrogen atmosphere to obtain a polymerization reaction product (P-9). The glass transition temperature measured by DSC measurement was 163 ° C, and the melting point was 351 ° C.

The obtained polymerization reaction product (P-9) was pulverized and weighed 15 mg, and stirred in 10 g of tetrahydrofuran for 10 minutes to extract an unreacted cyclic oligomer component. After performing liquid chromatography measurement, no unreacted cyclic oligomer component was confirmed.

[Prior technical literature]
[Patent Literature]

Patent Document 1: International Publication No. 2011/081080

Claims (8)

A cyclic poly (arylene ether ketone), which is characterized by a cyclic poly (arylene ether ketone) represented by the following chemical formula (I), and is at least part of an arylene group of Ar ¹ and Ar ^{3 in} the chemical formula (I). A cyclic polyarylidene ether ketone which is an arylate bonded in meta position, (However, X is an ether group or a keto group, and Ar ¹ , Ar ² , and Ar ³ each represent an arylene group which may have a substituent, and n is a positive integer). For example, the cyclic polyarylidene ether ketone of claim 1, wherein Ar ¹ has two constituent units of a m-phenylene unit and a p-phenylene unit, and a phenylene unit (m ₁ ) and a p-phenylene unit between Ar ¹ The molar ratio (m ₁ / p ₁ ) of the phenyl unit (p ₁ ) is 0.05 or more and 1 or less. For example, the cyclic polyarylidene ether ketone of claim 1 or 2, in which Ar ³ has two constituent units of a m-phenylene unit and a p-phenylene unit, and the phenylene unit (m ₃ ) between Ar ³ and molar ratio of the phenylene units (p ₃₎ of the (m ₃ / p ₃₎ 1 or less is 0.05 or more. The cyclic polyarylene ether ketone according to any one of claims 1 to 3, wherein the cyclic dimer component having a repeating unit n of 2 is 30% by mass or less. A method for producing a cyclic polyarylidene ether ketone, which is characterized by reacting a dihalogenated aromatic ketone, a meta-dihydroxy aromatic compound, and a p-dihydroxy aromatic compound. A method for producing cyclic polyarylidene ether ketone, which is characterized by reacting m-dihalogenated fluorenyl aromatic compound, p-dihalogenated fluorenyl aromatic compound and diaryl ether. A molding material obtained by impregnating a cyclic polyarylene ether ketone according to any one of claims 1 to 4 with a fiber-reinforced substrate. A method for manufacturing a fiber-reinforced composite material, which comprises impregnating the cyclic poly (arylene ether ketone) according to any one of claims 1 to 4 in a fiber-reinforced substrate, and opening the cyclic poly (arylene ether ketone) ring. polymerization.