JPH05339362A - Production of aromatic copolymer - Google Patents

Abstract

PURPOSE:To produce an arom. copolyether excellent in mechanical strengths, heat resistance, solvent resistance. etc., at a high yield in a short time by reacting a specific dihalogenoarom. ketone compd., a specific dihalogenobenzonitrile, and a specific dihydric phenol in the presence of two specific compds. in a solvent. CONSTITUTION:A dihalogenoarom. ketone compd. of formula I (wherein X is halogen; and n is 1 or 2), a dihalogenobenzonitrile of formula II, and a dihydric phenol of formula II (wherein Ar is an arom. residue) are reacted in the presence of an alkali metal carbonate (e.g. K2CO3) and KF in a solvent (e.g. diphenyl sulfone) to give an arom. copolyether having repeating units of formulas IV and V.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an aromatic polyether copolymer, more specifically, a high molecular weight aromatic polyether excellent in mechanical strength, heat resistance and solvent resistance. The present invention relates to a method capable of producing a system copolymer in a short time and in a high yield.

[0002]

2. Description of the Related Art In recent years, various engineering resins having excellent mechanical strength and heat resistance have been developed, and some of them have already been put into practical use. However, the performance of all of these resins has not been fully satisfied in all aspects. In addition, the fields of application expected for engineering resins include automobile fields, aviation fields, electrical / electronic fields, precision machinery fields,
In a very wide range of fields such as OA equipment and optical communication equipment,
In addition, there is a wide variety, and with the expansion of applications and the sophistication of functions, the required performance is becoming more and more severe. Therefore, conventional engineering resins cannot sufficiently meet such demands, and development of new resins satisfying such demanded performances is desired.

Further, various studies have been made on the production method of these engineering resins, but various points to be improved still remain.

By the way, as a typical engineering resin, an aromatic polyether resin having excellent heat resistance is known. The aromatic polyether-based resin includes aromatic polyether ketone, aromatic polycyano ether, and further aromatic poly (ether ketone / cyano ether) -based copolymer. Among these,
Aromatic poly (ether ketone / cyanoether) -based copolymers, which are classified as aromatic polyether-based copolymers, have excellent basic properties as an engineering resin such as mechanical strength, heat resistance, and solvent resistance. In particular, it has been attracting attention as a resin having excellent properties such as a high glass transition temperature, and this copolymer has, for example, a dihalogeno aromatic ketone compound, a dihalogenobenzonitrile, and a dihydric phenol which are alkali metal carbonates. It is known that it can be suitably produced by reacting (copolymerizing) in a solvent such as a neutral polar solvent in the presence of a salt and / or an alkali metal hydrogencarbonate (Japanese Patent Laid-Open No. 2-255833). (See Japanese Patent Laid-Open No. 3-162416).

However, in the method for producing an aromatic polyether copolymer described in these publications, when the reaction is carried out without adding a reaction accelerator when polymerizing as described above, the yield of the polymer is reduced. The rate tends to be insufficient, and in order to obtain a polymer having a sufficiently high molecular weight, a reaction at a high temperature for a long time is required. Therefore, if such a reaction at a high temperature for a long time is performed, the produced polymer is decomposed. It has been found to have drawbacks such as being prone to occur.

Incidentally, Japanese Patent Laid-Open No. 17852/1989 discloses that
As a method for producing an aromatic polyether ketone, a technique is disclosed in which potassium fluoride is added as a reaction accelerator to a reaction system to suitably perform a polymerization reaction.

In this publication, however, the polymer to be produced is an aromatic polyetherketone homopolymer, and the polymer is the above-mentioned aromatic poly (etherketone / cyanoether) copolymer. Compared to,
Generally, it has low crystallinity and poor heat resistance.

The present invention has been made in view of the above circumstances. An object of the present invention is to solve the above-mentioned conventional problems by polymerizing with a specific reaction accelerator when producing an aromatic polyether copolymer, and to obtain a higher yield than the conventional one. Therefore, it is possible to obtain a polymer having excellent properties such as high heat resistance of a polymer sufficiently easily under a more mild reaction condition in a shorter reaction time, and it is remarkably practically advantageous. An object of the present invention is to provide a method for producing an advantageous aromatic polyether copolymer.

[0009]

DISCLOSURE OF THE INVENTION The present inventors have found that a dihalogeno aromatic ketone compound, a dihalogenobenzonitrile and a dihydric phenol are neutralized in the presence of an alkali metal carbonate and / or an alkali metal hydrogen carbonate. Regarding the method of obtaining an aromatic polyether-based copolymer by reacting (copolymerizing) in a solvent such as a polar solvent, there is no problem such as manufacturing defects as seen in the conventional method, and We have conducted intensive studies with the goal of establishing a technique for producing a polymer having a sufficiently high molecular weight in a high yield by a reaction at a lower temperature for a shorter time. As a result, by carrying out the reaction in the presence of a specific reaction accelerator, that is, potassium fluoride, the target can be easily achieved, and a desired polymer excellent in various properties such as mechanical strength and heat resistance. To
It has been found that a high yield can be produced in a short time.

The present inventors have completed the present invention mainly based on these findings. That is, the invention according to claim 1 has the following general formula (Formula 1);

[0011]

[Chemical 1]

{However, X in the formula (Formula 1) represents a halogen atom, and n is 1 or 2. } The dihalogeno aromatic ketone compound (Chemical formula 1) represented by the following general formula (Chemical formula 2);

[0013]

[Chemical 2]

{However, X in the formula (Formula 2) represents a halogen atom. } And the following general formula (Formula 3);

[0015]

[Chemical 3]

{However, Ar in the formula (Formula 3) represents an aromatic residue. } A divalent phenol represented by the formula (Chemical Formula 3) is reacted in a solvent in the presence of an alkali metal carbonate and / or an alkali metal hydrogencarbonate and potassium fluoride to produce an aromatic compound. A method for producing a polyether copolymer, wherein the invention according to claim 2 is characterized in that the aromatic polyether copolymer is at least the following general formula (Formula 4);

[0017]

[Chemical 4]

{However, n in the formula (Formula 4) is 1 or 2
And Ar represents an aromatic residue. } And the following general formula (Formula 5);

[0019]

[Chemical 5]

{However, Ar in the formula (Formula 5) represents an aromatic residue. } It is a manufacturing method of the aromatic polyether type copolymer according to claim 1 containing a repeating unit represented by the formula (Chemical Formula 5), and the invention according to claim 3 is the aromatic polyether. The molar ratio of the repeating unit (Chemical Formula 4) to the total of the repeating unit (Chemical Formula 4) and the repeating unit (Chemical Formula 5) in the system copolymer is 0.50 to 0.90, and the repeating unit (Chemical Formula 4) is The molar ratio of Chemical formula 5) is 0.50
The method for producing an aromatic polyether copolymer according to claim 2, wherein the amount is 0.10.

In the method of the present invention, in the dihalogeno aromatic ketone compound (Formula 1) represented by the general formula (Formula 1) used as a raw material monomer for copolymerization, X represents a halogen atom. , Fluorine atom, chlorine atom, bromine atom and iodine atom. The two X's in the dihalogeno aromatic ketone compound (Formula 1) may be the same halogen atom or different halogen atoms. This dihalogeno aromatic ketone compound (Chemical formula 1)
From the viewpoint of reactivity, it is usually preferred that the halogen atom X is a fluorine atom or a chlorine atom.
Particularly, a dichloroaromatic ketone compound having a chlorine atom is preferably used. Further, from the substitution position of the halogen atom in the dihalogeno aromatic ketone compound (Chemical formula 1),
Usually, 4,4'-dihalogenobenzophenone or bis (4-halobenzoyl) type compounds are preferred.

In the above general formula (Formula 1), n represents 1 or 2, but in general, from the viewpoint of easy availability of raw materials, n
Preferred are dihalogenobenzophenones where 1 is 1.
Specific examples of the dihalogeno aromatic ketone compound (Formula 1) include, for example, 4,4′-dichlorobenzophenone, 4,4′-difluorobenzophenone, 4-chloro-4′-fluorobenzophenone and 3,4′-dichloro. Dihalogenobenzophenones such as benzophenone, 1,
4-bis (4-chlorobenzoyl) benzene, 1,4-
1,4 such as bis (4-fluorobenzoyl) benzene
-Bis (4-halobenzoyl) s and the like can be mentioned. Among these, 4,4'-dichlorobenzophenone and 1,4-bis (4-chlorobenzoyl) benzene are particularly preferable, and 4,4'-dichlorobenzophenone is particularly preferable.

These dihalogeno aromatic ketone compounds (Chemical Formula 1) may be used alone or in combination of two or more.

In the method of the present invention, in the dihalogenobenzonitrile (Chemical formula 2) represented by the above general formula (Chemical formula 2) used as a raw material monomer for copolymerization, X represents a halogen atom, and the dihalogenobenzonitrile (Chemical formula 2) Two X's in 2) may be the same halogen atom or different halogen atoms. This dihalogenobenzonitrile (Chemical formula 2)
In terms of reactivity and the like, those in which the halogen atom is usually a fluorine atom or a chlorine atom are preferably used, and dichlorobenzonitrile, which is a chlorine atom, is particularly preferably used. Further, the substitution position of the halogen atom in dihalogenobenzonitrile (Chemical Formula 2) is usually preferably the 2,6-position and the 2,4-position.

Specific examples of the dihalogenobenzonitrile (Chemical Formula 2) include, for example, 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile and 2,4-
Examples thereof include dichlorobenzonitrile and 2,4-difluorobenzonitrile. Among these,
2,6-dichlorobenzonitrile, 2,4-dichlorobenzonitrile and the like are preferable, and 2,6-dichlorobenzonitrile is particularly preferable.

These dihalogenobenzonitriles (Formula 2) may be used alone or in combination of two or more.

In the method of the present invention, as the dihydric phenol (Chemical Formula 3) represented by the general formula (Chemical Formula 3) used as a raw material monomer for copolymerization, conventional aromatic polyethers and aromatic polycarbonates are used. A dihydric phenol or the like that can be used as a monomer in the production of the above can be used, and specific examples of the dihydric phenol include, for example, the following general formula (formula 6)

[0028]

[Chemical 6]

{Wherein R ¹ has ¹ to 8 carbon atoms
Is an alkyl group, a cycloalkyl group having 5 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 6 carbon atoms
An aryloxy group or a cyano group that is ~ 10,
p represents an integer of 0 to 4, preferably 0 to 2 and particularly preferably 0. }, Or the following general formula (Formula 7) or general formula (Formula 8)

[0030]

[Chemical 7]

[0031]

[Chemical 8]

{However, in the formula (Formula 7), R ² and R ³
Have the same meaning as R ¹ above, and R ² and R ³ may be the same or different from each other. k
And j each represent an integer of 0 to 4, preferably an integer of 0 to 2, and particularly preferably 0, and may be the same as or different from each other. Further, in the formula (Formula 8), R ⁴ and R ⁵ have the same meanings as R ¹ described above, and R ⁴ and R ⁵ may be the same or different from each other. S
Represents an integer of 0 to 4, preferably an integer of 0 to 2, particularly preferably 0, and t represents an integer of 0 to 2, particularly preferably 0.
Indicates. } Or a dihydroxynaphthalene represented by the following general formula (Formula 9)

[0033]

[Chemical 9]

(However, in the formula, R ⁶ and R ⁷ have the same meaning as R ¹ and may be the same as or different from each other. U and V each represent an integer of 0 to 2, particularly preferably 0, and U and V may be the same or different from each other. Y is a single bond,-
O -, - S -, - CO -, - SO 2 -, the following formula -
(CR ⁸ R ⁹ ) _q- << wherein R ⁸ and R ⁹
Are respectively a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 to 8 carbon atoms.
And the aryl groups may be the same or different. q represents an integer of 1 to 8, preferably 1 to 4, and particularly preferably 1. >> A divalent group represented by or the following general formula (Formula 10)

[0035]

[Chemical 10]

However, in the formula, r represents an integer of 5 to 8. >>} bisphenols represented by can be preferably used.

The above R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶
Specific examples of R ⁷ and R ⁷ include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, methylcyclopentyl group, cyclopentylmethyl group, cyclohexylmethyl group, Examples thereof include a phenyl group, a benzyl group, a tolyl group, a methoxy group, an ethoxy group, a propoxy group, a phenoxy group and a cyano group, and among them, a methyl group is particularly preferable.

When Y in the general formula (Formula 5) is a divalent group represented by the general formula — (CR ⁸ R ⁹ ) _q —, specific examples of R ⁸ and R ^{9 in} the above formula are shown. Can include, for example, hydrogen atom, methyl group, ethyl group, propyl group, phenyl group, tolyl group, benzyl group, cyclohexyl group and the like.

The formula _{^{- (CR 8 R 9) q}} - preferred as the divalent group represented by, for example, -CH ₂ -,
> CH (CH ₃ ),> C (CH ₃ ) ₂ ,> CH (C ₆ H
₅ ),> C (CH ₃ ) (C ₆ H ₅ ), and the like. Among them,> C (CH ₃ ) ₂ is particularly preferable.

Specific examples of the dihydric phenols represented by the above general formulas (Formula 6) to (Formula 9) are, for example,
1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxynaphthalene, 1,5-
Dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl (4,4'-bisphenol), 3,4'-dihydroxybiphenyl, 3, 3-dihydroxybiphenyl,
4,4'-dihydroxydiphenyl ether, 4,4 '
-Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis ( 4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) ethane,
1,2-bis (4-hydroxyphenyl) ethane, 1,4
-Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylmethane,
Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -2-phenylethane,
Examples thereof include 1,1-bis (4-hydroxyphenyl) cyclohexane and the like, or those having a substituent such as R ¹ and R ² mentioned above.

Among these, those not having a substituent such as R ¹ and R ² are preferable from the viewpoint of easy availability of raw materials, and 1,4-dihydroxybenzenes and 2,6-dihydroxynaphthenes. , 1,4-dihydroxynaphthalene, 4,4′-bisphenol and the like are preferable from the viewpoint of physical properties of the obtained polymer, and among them, 1,4-dihydroxynaphthalene is particularly preferable.
Hydroxybenzene (hydroquinone), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 4,4′-dihydroxybiphenyl and the like are preferable.

These dihydric phenols may be used alone or in combination of two or more. In the method of the present invention, the above reaction (copolymerization) is carried out using an alkali metal carbonate and / or an alkali metal hydrogen carbonate as a reaction raw material component.

Examples of the alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate.
Among these, sodium carbonate and potassium carbonate are preferable.

Examples of the alkali metal hydrogencarbonate include lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, rubidium hydrogencarbonate and cesium hydrogencarbonate. Among these, sodium hydrogen carbonate and potassium hydrogen carbonate are preferable.

In the method of the present invention, sodium carbonate and potassium carbonate can be particularly preferably used among the above various alkali metal carbonates and / or alkali metal hydrogen carbonates.

These alkali metal carbonates and / or alkali metal hydrogen carbonates may be used alone or in combination of two or more.

In the method of the present invention, the above reaction (polymerization)
The solvent used in this case is not particularly limited, and a wide variety of solvents or solvent systems used or proposed in the known polymerization reaction of this type of polymer can be used. Usually, a neutral polar solvent or a mixed solvent containing it as a main component (for example, a mixed solvent with an aromatic solvent such as toluene) is preferably used.

Examples of the neutral polar solvent include N 2
-Methyl-2-pyrrolidone (NMP), 2,6-dimethylimidazoline (DMI), dimethylacetamide (D
MAc), dimethylformamide (DMF), diphenyl sulfone (DPS), N-methylcaprolactam (N
MC), benzophenone, fluorene, dibenzothiophenyl sulfone and the like, but are not limited thereto.

In the method of the present invention, at least the dihalogeno aromatic ketone compound (Chemical formula 1), the dihalogenobenzonitrile (Chemical formula 2) and the dihydric phenol are added to the alkali metal carbonate and / or the alkali metal hydrogen carbonate. Copolymerization is carried out by reacting in the solvent in the presence of a salt,
It is important to carry out the reaction in the presence of at least potassium fluoride as described above. That is, the object of the present invention can be achieved for the first time by carrying out the reaction in the presence of at least the potassium fluoride.

By carrying out the reaction (copolymerization) in the presence of potassium fluoride in this manner, the reaction can be remarkably promoted, and compared with the case where potassium fluoride is not added as in the conventional method. The polymer can be made sufficiently high in molecular weight by a reaction at a lower temperature for a short time, and the yield of the polymer can be remarkably improved.

As the potassium fluoride, pure ones, industrial ones, commercially available products and the like can be used as they are. This potassium fluoride can be added to and mixed with the reaction raw material system or the reaction progress system in various forms such as powder form, slurry form, solution form such as aqueous solution, etc., but in any case, it is uniform during the reaction. It is desirable to use so as to be mixed with. The potassium fluoride to be used may contain other components such as impurities within the range not impairing the object of the present invention.

Here, the ratio of potassium fluoride used in the above reaction (hereinafter, this may be represented by (KF)) is the molar ratio of the dihydric phenols (Chemical Formula 3) to be subjected to the reaction (Chemical Formula 3). KF / Chemical 3), usually (1/100)
~ (200/100), preferably (10/100) ~
It is appropriate to select in the range of (100/100).
Here, the usage ratio {molar ratio (KF / chemical formula 3)} is 1 /
If it is less than 100, the addition ratio of potassium fluoride is too small, and the effect of obtaining a sufficiently high molecular weight polymer in a high yield by a reaction at a lower temperature for a shorter time may not be obtained, or it may be sufficiently exhibited. In some cases, the object of the present invention may not be sufficiently achieved. On the other hand, this usage ratio {molar ratio (KF / Chemical formula 3)} is 200 /
Even if it is larger than 100, the above effect cannot be further improved commensurate with the increase in the usage rate, so that the excess potassium fluoride content is wasted.
On the contrary, separation and purification of the polymer may be disadvantageous.

The ratio of the dihalogeno aromatic ketone compound (Chemical formula 1) used in the reaction is a molar ratio (Chemical formula 1 / Chemical formula 2) to the dihalogenobenzonitrile (Chemical formula 2) used in the reaction, and is usually ( 0.5 / 0.5) to (0.
9 / 0.1), preferably (0.6 / 0.4) ~
It is preferable to select the range of (0.8 / 0.2).
This usage ratio {molar ratio (chemical formula 1 / chemical formula 2)} is 0.5 /
If it is less than 0.5, it may be difficult to control the reaction for making the copolymer composition of the obtained polymer suitable, and there may be problems such as deterioration of properties such as crystallinity of the produced polymer. If it exceeds /0.1, it becomes difficult to control the reaction to obtain a polymer having a suitable copolymerization composition, which may cause problems such as deterioration in toughness, strength, electrical properties and the like of the produced polymer. ..

In the method of the present invention, the ratio of the dihydric phenol (Chemical Formula 3) used is preferably the total amount of the dihalogeno aromatic ketone compound (Chemical Formula 1) and the dihalogenobenzonitrile (Chemical Formula 2) used. On the other hand, the molar ratio
In (Chemical formula 1 + Chemical formula 2)}, it is usually preferable to select in the range of 0.90 to 1.00, and particularly preferable to select in the range of 0.95 to 0.99.

The ratio of the alkali metal carbonate and / or the alkali metal hydrogen carbonate used in the reaction is the ratio of the alkali metal carbonate and the alkali metal hydrogen carbonate to the amount of the dihydric phenol (Formula 3) used. The ratio of the total amount used is an equivalent ratio, and it is usually preferable to select it in the range of 1.01 to 2.5, and it is particularly preferable to select it in the range of 1.03 to 1.5. Here, for dihydric phenols, 1 mol is calculated as 2 equivalents, while for alkali metal carbonates and alkali metal hydrogen carbonates, the usual calculation is performed. For example, in the case of alkali metal carbonates, 1 mol is calculated. 2 equivalents, and in the case of alkali metal hydrogencarbonate, 1 mole is calculated as 1 equivalent.

The preferred ratio of the solvent used cannot be uniformly determined because it depends on other conditions such as the type of solvent used, but when a neutral polar solvent is used, the total molar amount of the reaction raw materials used is 200 ml of the amount of {(Chemical formula 1) + (Chemical formula 2) + (Chemical formula 3)} of the neutral polar solvent used
The ratio is usually 0.05 mol / 200 ml ~
It is preferable to select the ratio in the range of 1.0 mol / 200 ml.

In carrying out the above-mentioned reaction, the order of mixing the components and the mixing system for constituting the reaction system can be arbitrarily and arbitrarily selected from those conventionally used.
Each component such as a reaction raw material may be added to the solvent at the same time or sequentially. Of course, the potassium fluoride may be added before the start of the reaction, during the reaction, or a combination thereof. The solvent may also be added stepwise such that a part of the solvent is appropriately added (added) during the reaction. At that time, a method of adding solvents of different types and compositions is also suitably used.

The above reaction can be suitably carried out usually at a temperature in the range of 150 to 380 ° C, preferably 200 to 350 ° C. Here, if the reaction temperature is lower than 150 ° C., the reaction is unlikely to occur. On the other hand, if the reaction temperature is higher than 380 ° C., the produced polymer or the like is easily decomposed. The reaction time for allowing the reaction to proceed sufficiently cannot be uniformly set because it varies depending on other conditions such as reaction temperature and temperature mode, but is usually about 0.1 to 10 hours,
Preferably, a sufficiently high molecular weight polymer can be obtained with a reaction time of about 0.5 to 6 hours.

The reaction may be carried out at the same temperature all the time, but the reaction temperature may be changed continuously or stepwise in an appropriate mode according to the reaction progress (degree of polymerization). A changing method is preferably adopted. For example, the reaction is performed at a relatively low temperature of, for example, about 150 to 250 ° C. to produce a polymer having a relatively low molecular weight such as an oligomer, and then the reaction temperature is increased to, for example, about 300 to 340 ° C. A method of producing a polymer having a desired high molecular weight is preferably adopted.

In the method of the present invention, since potassium fluoride is used in the reaction system, a sufficiently high molecular weight polymer can be used in a reaction for a relatively short time at a reaction temperature in a relatively low temperature range as described above. It can be obtained in a very high yield. Further, since the reaction can be suitably carried out in such a sufficiently low temperature range, various advantages such as prevention of decomposition and modification of the produced polymer occur.

If necessary, other components other than the above-mentioned various components, such as a branching agent and other monomer components, are appropriately added to or coexistent with the reaction system as long as the object of the present invention is not impaired. You may let me.

As described above, the desired polymer comprising the repeating unit (Formula 4) represented by the general formula (Formula 4) and the repeating unit (Formula 5) represented by the general formula (Formula 5) Aromatic polyether-based copolymer) can be easily synthesized.

Thus, aromatic polyether copolymers having various desired structures and copolymerization compositions can be obtained. The repeating units (Formula 4) and (Formula 5)
The content ratio of the compound is (0.
5 / 0.5) to (0.9 / 0.1), especially
A polymer in the range of (0.6 / 0.4) to (0.8 / 0.2) is preferable. Aromatic polyether-based copolymers in the range of such copolymerization composition are more excellent in heat resistance such as high glass transition temperature and melting point, and particularly excellent in strength, heat resistance, and electrical characteristics. This is because it has excellent characteristics and performance.

As described above, a desired polymer (aromatic polyether copolymer having various structures and copolymer compositions) having a sufficiently high molecular weight and excellent properties was prepared under mild conditions for a short time. It can be obtained in high yield by the reaction.

In fact, according to the method of the present invention, the polymer produced is measured at 400 ° C. under a load of 5, according to JIS K7210.
Melt index (MI) measured under the condition of 000 g
Is usually 0.1 to 500 g / 10 minutes, preferably 0.2
~ 200 g / 10 minutes. The polymer having this MI in the above range is particularly excellent in mechanical strength, heat resistance, solvent resistance and the like, and has very good moldability. Can be easily obtained.

Further, according to the method of the present invention, the polymer produced is an aromatic polyether copolymer comprising repeating units (Chemical Formula 4) and (Chemical Formula 5) as described above. Generally, a polymer having good crystallinity and a high crystal melting point T _m and a high glass transition temperature T _g can be easily obtained, as compared with the homopolymer (aromatic polyether ketone, etc.) described above. Above all, by setting the copolymerization composition of the polymer, that is, the content ratio of the repeating units (Chemical Formula 4) and (Chemical Formula 5) within the above-mentioned preferable range, the glass transition temperature T _g is particularly high, and the heat resistance is further excellent. It can be a polymer and indeed has, for example, a T _g of 1.
70 to 200 ° C. and a crystal melting point T _m of 300 to 45
It is possible to easily obtain an even more excellent polymer having extremely high heat resistance such as 0 ° C.

Furthermore, according to the method of the present invention, a sufficiently high molecular weight polymer having the above-mentioned excellent properties can be easily produced by a reaction at a relatively low temperature for a short time, and the produced polymer can be obtained. In some cases, the desired polymer can be obtained with an extremely high yield of 100% or a yield close to 100%.

The excellent effect of the present invention as described in detail above is that the dihalogeno aromatic ketone compound (Chemical formula 1)
And dihalogenobenzonitrile (Chemical Formula 2) and divalent phenols (Chemical Formula 3) are used as raw materials, and they are copolymerized in the presence of at least potassium fluoride as a specific reaction accelerator. It has been achieved.

The polymer synthesized as described above can be obtained as a polymer having a desired degree of purification by separating, recovering and purifying from the reaction product mixture according to a conventional method. For example, the polymer is separated and recovered by removing the solvent and the like, and is washed with an appropriate washing liquid such as methanol or hot water, or if necessary, the alkaline component such as hydrochloric acid is removed in this washing step. A method of suitably performing post-treatment such as desalting with an agent or the like, and further appropriately drying is preferably used. At that time, a method of appropriately crushing the polymer to enhance the cleaning effect can also be suitably adopted.

As described above in detail, according to the method of the present invention, the glass transition temperature and the crystal melting point are high, and the thermal decomposition initiation temperature is also extremely high, which is extremely excellent in heat resistance, mechanical strength and resistance. It is also excellent in solvent properties and the like, and it is possible to efficiently produce various aromatic polyether-based copolymers that are polymers having excellent practical performance such as good moldability. For example, it can be suitably and advantageously used as a material in a wide range of fields including the fields of electric and electronic devices, the field of aviation, the field of machines, and the like.

[0071]

The present invention will be described in more detail below with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.

Example 1 30 equipped with an argon gas introduction tube, a stirrer, a C-shaped tube, a thermocouple, and a band heater
In a 0 ml separable flask, 21.726 g (0.086 mol) of 4,4'-dichlorobenzophenone, 2,6
-Dichlorobenzonitrile 6.378 g (0.037 mol), 4,4'-biphenol 22.345 g (0.1
20 mol), 17.418 g of anhydrous potassium carbonate (0.1
26 mol), 160 g of diphenyl sulfone (733 mol), 0.697 g of potassium fluoride (0.012 mol)
Was charged and heated to 150 ° C. with a mantle heater until the raw materials other than anhydrous potassium carbonate were dissolved. After confirming the dissolution, the temperature inside the reactor was adjusted to 2 ° C / m while stirring.
The temperature was raised to 250 ° C. at a rate of in and kept for 90 minutes to generate an oligomer. Next, the temperature inside the reactor was raised to 340 ° C. at a rate of 2 ° C./min, and the reaction was allowed to continue for 20 minutes to substantially complete the reaction.

After the reaction was completed, the contents of the reactor were put into a vat to be solidified and roughly crushed with a spoon. Thereafter, the mixture was further finely pulverized with a Waring blender, washed successively with hot methanol 6 times, once with an oxalic acid aqueous solution and 3 times with hot water, and then dried at 130 ° C. overnight to obtain a target polymer powder. ..

The thus-obtained polymer was confirmed by NMR and IR analysis to be an aromatic polyether copolymer having the structural unit and copolymerization composition shown below.

[0075]

[Chemical 11]

The following data were obtained by measuring the characteristics of this aromatic polyether copolymer. That is, using a nozzle with a diameter of 2 mm and a length of 8 mm, the load of 4, 8
The MI obtained by measurement under the conditions of 50 g and 400 ° C. was 2.57 g / 10 min, the glass transition temperature Tg was 185.4 ° C., the crystal melting point Tm was 365.6 ° C., and the crystallization temperature was Tcc was 242.3 ° C. and thermal decomposition start temperature (5% weight loss, in air) Td was 564 ° C. The polymer yield was 98%.

(Example 2) Polymerization was carried out in the same manner as in Example 1 except that the amount of potassium fluoride was changed to 3.486 g (0.060 mol) in Example 1, and the obtained polymer was used. The post-treatment was carried out to obtain a powder polymer.

The obtained powder polymer was confirmed to be an aromatic polyether copolymer in the same manner as in Example 1. Further, when the characteristics of this aromatic polyether copolymer were measured in the same manner as in Example 1, the MI was 1.72 g / 10 min, the glass transition temperature Tg was 185.6 ° C., and the crystal melting point Tm was Was 363.2 ° C, the crystallization temperature Tcc was 245.2 ° C, and the thermal decomposition initiation temperature (5% weight loss, in air) Td was 564 ° C. The polymer yield was 98%.

Example 3 In Example 1, the amount of potassium fluoride was changed to 3.486 g (0.060 mol) and the potassium fluoride was introduced at a temperature in the reactor of 250 ° C. Example 1 except for the above
Polymerization was carried out in the same manner as above, and the obtained polymer was subjected to the same post-treatment to obtain a powder polymer.

The obtained powder polymer was confirmed to be an aromatic polyether copolymer in the same manner as in Example 1. Further, when the characteristics of this aromatic polyether copolymer were measured in the same manner as in Example 1, the MI was 1.29 g / 10 min, the glass transition temperature Tg was 186.5 ° C., and the crystal melting point Tm was Was 356.3 ° C., the crystallization temperature Tcc was 268.6 ° C., and the thermal decomposition onset temperature (5% weight loss, in air) Td was 565 ° C. The polymer yield was 97%.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that potassium fluoride was not used in Example 1 and the reaction time at 340 ° C. was changed to 30 minutes. The polymer was subjected to the same post-treatment to obtain a powder polymer.

The powder polymer thus obtained was analyzed in the same manner as in Example 1 to confirm that it was an aromatic polyether copolymer. Further, when the characteristics of this aromatic polyether copolymer were measured in the same manner as in Example 1, the MI was 6.40 g / 10 min, the glass transition temperature Tg was 182.6 ° C., and the crystal melting point Tm was Is 35
5 ° C., crystallization temperature Tcc is 240.2 ° C.,
Thermal decomposition start temperature (5% weight loss, in air) Td is 562 ° C
Met. The polymer yield was 94%.

Comparative Example 2 Polymerization was conducted in the same manner as in Example 1 except that potassium fluoride was not used in Example 1 and the reaction time at 340 ° C. was changed to 50 minutes. The polymer was subjected to the same post-treatment to obtain a powder polymer.

The powder polymer obtained was analyzed in the same manner as in Example 1 to confirm that it was an aromatic polyether copolymer. Further, when the characteristics of this aromatic polyether copolymer were measured in the same manner as in Example 1, the MI was 12.25 g / 10 min, the glass transition temperature Tg was 181.0 ° C., and the crystal melting point Tm was Is 3
60.5 ° C., crystallization temperature Tcc is 238.5 ° C., thermal decomposition initiation temperature (5% weight loss, in air) Td is 5
It was 60 ° C. The polymer yield was 93%.

<Discussion> From the results of Examples 1 to 3 and Comparative Examples 1 and 2 described above, according to the method of the present invention, since potassium fluoride is used, the reaction is carried out at a high temperature for a short time. However, it is clear that the yield of the polymer is improved to nearly 100%, and that the Tg, Tcc, and Tm of the obtained aromatic polyether copolymer are high and the heat resistance is also greatly improved. is there.

[0086]

As described above, in the method of the present invention, the dihalogeno aromatic ketone compound (Chemical formula 1), the dihalogenobenzonitrile (Chemical formula 2) and the dihydric phenol (Chemical formula 3) are used as the main raw material monomers. When the reaction (copolymerization) is carried out, since a specific method of carrying out the reaction in the presence of at least a specific reaction accelerator of potassium fluoride is used, compared with the conventional method which does not use potassium fluoride, Polymer yield can be significantly improved,
Moreover, it is possible to easily obtain an aromatic polyether copolymer having a sufficiently high molecular weight and excellent properties by a reaction at a lower temperature for a short time. Further, in the method of the present invention, the obtained polymer is an aromatic polyether copolymer comprising the repeating units (Formula 4) and (Formula 5) by the copolymerization reaction, and these copolymers are Repeating units such as conventional aromatic polyether ketone homopolymers (Chemical Formula 4)
A homopolymer consisting of or a repeating unit (Chemical Formula 5)
Compared with a homopolymer made of, for example, the glass transition temperature is high and the heat resistance is excellent. Therefore, it can be advantageously used in a wider range of fields of application and is also excellent in application.

That is, according to the present invention, various aromatic compounds which have a sufficient high molecular weight and are excellent in practical properties such as mechanical strength, heat resistance, solvent resistance and moldability, and particularly excellent in heat resistance. In practical use, a polyether-based copolymer {aromatic poly (ether ketone / cyanoether) -based copolymer} can be easily obtained in a short reaction time under sufficiently mild conditions and at a high yield. It is possible to provide a remarkably excellent method for producing an aromatic polyether copolymer.

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[Procedure amendment]

[Submission date] July 19, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

In the method of the present invention, in the dihalogeno aromatic ketone compound (Formula 1) represented by the general formula (Formula 1) used as a raw material monomer for copolymerization, X represents a halogen atom. , Fluorine atom and
A chlorine atom may be mentioned. The two X's in the dihalogeno aromatic ketone compound (Formula 1) may be the same halogen atom or different halogen atoms. From the viewpoint of reactivity, etc., the dihalogeno aromatic ketone compound (Chemical Formula 1) is usually preferably used when the halogen atom X is a fluorine atom or a chlorine atom, and in particular, a dichloroaromatic ketone which is a chlorine atom. Compounds are preferably used. Also, in view of the substitution position of the halogen atom in the dihalogeno aromatic ketone compound (Formula 1), a 4,4′-dihalogenobenzophenone or bis (4-halobenzoyl) type compound is usually preferable.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0033

[Correction method] Change

[Correction content]

[0033]

[Chemical 9]

[Procedure 3]

[Document name to be amended] Statement

[Item name to be corrected] 0040

[Correction method] Change

[Correction content]

Specific examples of the dihydric phenols represented by the above general formulas (Formula 6) to (Formula 9) are, for example,
1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxynaphthalene, 1,5-
Dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl (4,4'-biphenoxy Lumpur), 3,4'-dihydroxybiphenyl, 3,3-dihydroxybiphenyl, 4,
4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 2,2-bis (4-hydroxy Phenyl) propane, 2,2-bis (4-hydroxyphenyl) butane,
1,1-bis (4-hydroxyphenyl) ethane, 1,
2-bis (4-hydroxyphenyl) ethane, 1,4-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylmethane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -2-phenylethane,
Examples thereof include 1,1-bis (4-hydroxyphenyl) cyclohexane and the like, or those having a substituent such as R ¹ and R ² mentioned above.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

Among these, those not having a substituent such as R ¹ and R ² are preferable from the viewpoint of easy availability of raw materials, and 1,4-dihydroxybenzenes and 2,6-dihydroxynaphthenes. , 1,4-dihydroxy naphthalenes, preferably from the viewpoint of physical properties of the polymer such as 4,4'-biphenol is obtained, among others, 1,4-di
Hydroxybenzene (hydroquinone), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 4,4′-dihydroxybiphenyl and the like are preferable.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

Examples of the neutral polar solvent include N 2
-Methyl-2-pyrrolidone (NMP), 2,6- dimethyl
Examples thereof include, but are not limited to, rumidazolidone (DMI), dimethylacetamide (DMAc), dimethylformamide (DMF), diphenylsulfone (DPS), N-methylcaprolactam (NMC), and benzophenone .

Claims (3)

[Claims] 1. The following general formula (Formula 1); {However, X in the formula (Formula 1) represents a halogen atom, and n
Is 1 or 2. } The dihalogeno aromatic ketone compound (Chemical formula 1) represented by the following formula and the following general formula (Chemical formula 2); {However, X in the formula (Formula 2) represents a halogen atom. }
A dihalogenobenzonitrile (Chemical Formula 2) and the following general formula (Chemical Formula 3); {However, Ar in the formula (Formula 3) represents an aromatic residue. }
And a dihydric phenol represented by the formula (3) are reacted in a solvent in the presence of an alkali metal carbonate and / or an alkali metal hydrogen carbonate and potassium fluoride. Process for producing ether-based copolymer. 2. The aromatic polyether-based copolymer,
At least the following general formula (Formula 4); {However, n in the formula (Formula 4) represents 1 or 2, and Ar
Represents an aromatic residue. } And the following general formula (Formula 5); {However, Ar in the formula (Formula 5) represents an aromatic residue. }
The method for producing an aromatic polyether-based copolymer according to claim 1, which comprises a repeating unit represented by the formula (Chemical Formula 5). 3. The repeating unit (Chemical Formula 4) and the repeating unit (Chemical Formula 5) in the aromatic polyether copolymer.
And the repeating unit (Chemical formula 4) has a molar ratio of 0.50 to 0.90, and the repeating unit (Chemical formula 5) is
The method for producing an aromatic polyether copolymer according to claim 2, wherein the molar ratio of is 0.50 to 0.10.