WO2022230932A1

WO2022230932A1 - Aromatic polyether copolymer, method for producing aromatic polyether copolymer, and method for adjusting thermophysical properties of aromatic polyether copolymer

Info

Publication number: WO2022230932A1
Application number: PCT/JP2022/019058
Authority: WO
Inventors: 颯志並木
Original assignee: 出光興産株式会社
Priority date: 2021-04-27
Filing date: 2022-04-27
Publication date: 2022-11-03

Abstract

An aromatic polyether copolymer which comprises a repeating unit represented by formula (1) and a repeating unit represented by formula (2).

Description

Aromatic polyether copolymer, method for producing aromatic polyether copolymer, and method for adjusting thermophysical properties of aromatic polyether copolymer

TECHNICAL FIELD The present invention relates to an aromatic polyether copolymer, a method for producing an aromatic polyether copolymer, and a method for adjusting thermophysical properties of an aromatic polyether copolymer.
Specifically, the present invention relates to an aromatic polyether copolymer excellent in workability, a method for producing an aromatic polyether copolymer, and a method for adjusting thermophysical properties of an aromatic polyether copolymer.

Polyetheretherketone (abbreviated as "PEEK"), which is a type of crystalline aromatic polyether, is known (Patent Document 1).
PEEK has excellent heat resistance and mechanical strength, and is used as a metal substitute material due to these characteristics. In recent years, its applications have expanded to include automobiles, aircraft, and the medical field.

JP-A-59-93724

When processing (for example, molding) PEEK, processing under high temperature conditions is required due to its excellent heat resistance. However, it is difficult to flexibly impart thermophysical properties suitable for various processing conditions to PEEK, and its workability is limited.

In the conventional technology including Patent Document 1, there is room for further improvement in terms of such workability.

One of the objects of the present invention is to provide an aromatic polyether copolymer excellent in workability, a method for producing the aromatic polyether copolymer, and a method for adjusting the thermophysical properties of the aromatic polyether copolymer. be.

As a result of intensive studies, the present inventors found that a specific aromatic polyether copolymer can flexibly impart thermophysical properties suitable for various processing conditions and has excellent processability. completed the invention.
According to the present invention, the following aromatic polyether copolymer and the like can be provided.
1. An aromatic polyether copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).

2. 2. The aromatic polyether copolymer according to 1, wherein the integral ratio X represented by the following formula (I _X ) exceeds 0% in the ¹ H-NMR spectrum.
X [%] = {(C/2)/(A/8+B/4)} x 100 ( _IX )
(In formula (I _X ), A is the integrated value in the range of chemical shift 7.15 ppm to 7.23 ppm, B is the integrated value in the range of chemical shift 7.32 ppm to 7.42 ppm, C is the chemical shift from 7.42 ppm It is an integrated value in the range of 7.49 ppm.)
3. 3. The aromatic polyether copolymer according to 1 or 2, wherein the integral ratio Z represented by the following formula (I _Z ) is 0% in the ¹ H-NMR spectrum.
Z [%]={(D/2)/(A/8+B/4)}×100 (I _Z )
(In formula (I _Z ), A is the integrated value in the chemical shift range from 7.15 ppm to 7.23 ppm, B is the integrated value in the chemical shift range from 7.32 ppm to 7.42 ppm, D is the chemical shift from 7.89 ppm It is an integrated value in the range of 7.93 ppm.)
4. 4. The aromatic polyether copolymer according to any one of 1 to 3, wherein the integral ratio Y represented by the following formula (I _Y ) is 0.1 to 99.9% in the ¹ H-NMR spectrum.
Y [%] = {(A/8)/(A/8+B/4)} x 100 (I _Y )
(In formula (I _Y ), A is the integrated value in the chemical shift range from 7.15 ppm to 7.23 ppm, and B is the integrated value in the chemical shift range from 7.32 ppm to 7.42 ppm.)
5. 5. The aromatic polyether copolymer according to any one of 1 to 4, which has an exothermic peak width of 60° C. or less due to crystallization observed in differential scanning calorimetry.
6. 6. The aromatic polyether copolymer according to any one of 1 to 5, which has a melt flow rate of 100 g/10 min or less.
7. A method for producing an aromatic polyether copolymer, comprising reacting a dihalogenobenzophenone, a dihydric phenol, and a dihydric phenyl ether.
8. 8. The method for producing an aromatic polyether copolymer according to 7, wherein the dihalogenobenzophenone is difluorobenzophenone.
9. 9. The method for producing an aromatic polyether copolymer according to 8, wherein the difluorobenzophenone is 4,4'-difluorobenzophenone.
10. 10. The method for producing an aromatic polyether copolymer according to any one of 7 to 9, wherein the dihydric phenol is hydroquinone.
11. 11. The method for producing an aromatic polyether copolymer according to any one of 7 to 10, wherein the divalent phenyl ether is 4,4'-dihydroxydiphenyl ether.
12. Adjusting the molar ratio of the divalent phenyl ether to the total of the divalent phenol and the divalent phenyl ether subjected to the reaction to adjust the thermophysical properties of the produced aromatic polyether copolymer, 12. A method for producing an aromatic polyether copolymer according to any one of 7 to 11.
13. 13. The method for producing an aromatic polyether copolymer according to 12, wherein the crystallization temperature _Tc of the aromatic polyether copolymer is adjusted as the thermophysical property.
14. 14. The method for producing an aromatic polyether copolymer according to 12 or 13, wherein an exothermic peak width due to crystallization observed in differential scanning calorimetry of the aromatic polyether copolymer as the thermophysical property is adjusted.
15. A method for adjusting thermophysical properties of an aromatic polyether copolymer containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2),
By adjusting the molar ratio of the repeating unit represented by the formula (2) to the total of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2), the aromatic poly The above method, comprising adjusting the thermophysical properties of the ether copolymer.

16. 16. The method for adjusting thermophysical properties of an aromatic polyether copolymer according to 15, wherein the crystallization temperature _Tc of the aromatic polyether copolymer is adjusted as the thermophysical property.
17. 17. The method for adjusting the thermophysical properties of the aromatic polyether copolymer according to 15 or 16, wherein the exothermic peak width due to crystallization observed in differential scanning calorimetry of the aromatic polyether copolymer as the thermophysical property is adjusted. .

According to the present invention, it is possible to provide an aromatic polyether copolymer with excellent workability, a method for producing an aromatic polyether copolymer, and a method for adjusting thermophysical properties of an aromatic polyether copolymer.

¹ H-NMR spectrum measured in Example 2. FIG.

Hereinafter, the aromatic polyether copolymer, the method for producing the aromatic polyether copolymer, and the method for adjusting the thermophysical properties of the aromatic polyether copolymer of the present invention will be described in detail.
In addition, in this specification, the upper limit value and the lower limit value described with respect to the numerical range can be arbitrarily combined.
It is also possible to combine two or more of the individual embodiments of the aspects according to the invention described below that are not mutually exclusive, and embodiments combining two or more embodiments are also 1 is an embodiment of an aspect according to the invention;

1. Aromatic polyether copolymer An aromatic polyether copolymer according to one aspect of the present invention includes a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2) .

The repeating unit represented by formula (1) and the repeating unit represented by formula (2) are different from each other, and correspond to the repeating unit represented by formula (2) in the aromatic polyether copolymer. The partial structure is regarded as a repeating unit represented by formula (2) and not regarded as a repeating unit represented by formula (1).

According to the aromatic polyether copolymer according to this aspect, an effect of excellent workability can be obtained.
In the aromatic polyether copolymer according to this aspect, the molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (2) (for example, as a "peak area ratio" described later) is By adjusting, the thermophysical properties of the aromatic polyether copolymer can be adjusted. The processability can be improved by adjusting the thermophysical properties toward desired values according to various processing conditions.
The aromatic polyether copolymer according to this embodiment has thermophysical properties such as crystallization temperature T _c , glass transition temperature T _g , melting point T _m , difference between crystallization temperature T _c and melting point T _m (T _m −T _c ) and an exothermic peak width due to crystallization observed in differential scanning calorimetry (details will be described later, but it corresponds to the crystallization speed). One or more selected from the group can be adjusted.

For the aromatic polyether copolymer according to this aspect, for example, when molding an injection-molded article having a simple structure (when the structure of the mold is simple), the crystallization temperature _Tc is increased to give priority to production efficiency. When molding an injection-molded article with a complicated structure (when the mold has a complicated structure), the crystallization temperature _Tc can be lowered to give priority to molding accuracy.

In the aromatic polyether copolymer according to this aspect, even if the crystallization temperature _Tc is changed by the molar ratio described above, the glass transition temperature _Tg and the melting point _Tm change relatively slowly. From another point of view, the aromatic polyether copolymer according to this aspect can be adjusted to the difference between the crystallization temperature _Tc and the glass transition temperature _Tg , and the crystallization temperature The difference between _Tc and melting point _Tm can be adjusted respectively. This also contributes to the improvement of workability.

The aromatic polyether copolymer according to this aspect can reduce the difference between the crystallization temperature _Tc and the melting point _Tm , for example, by increasing the crystallization temperature _Tc . As a result, when the molten aromatic polyether copolymer is processed (for example, molded with a mold), the temperature holding time for sufficiently promoting crystallization can be shortened, and the molding cycle can be shortened. As a result, productivity can be increased, workability is excellent, and characteristics of a crystalline resin can be favorably imparted to a processed product (for example, a molded product).

In addition, the aromatic polyether copolymer according to this aspect can increase the difference between the crystallization temperature _Tc and the melting point _Tm , for example, by lowering the crystallization temperature _Tc . As a result, when processing the molten aromatic polyether copolymer (for example, molding with a mold), it is possible to prevent the initiation of crystallization during processing (for example, during filling into a mold). . Also, the molding temperature (for example, the temperature of the mold) can be lowered. As a result, the processability is excellent, and the characteristics of a crystalline resin can be favorably imparted to a processed product (for example, a molded product).

As described above, the aromatic polyether copolymer according to this aspect can be applied to various processing conditions with high versatility, and can exhibit excellent processability depending on the processing conditions.

Whether the aromatic polyether copolymer contains the repeating unit represented by formula (1) and the repeating unit represented by formula (2) is confirmed by the method described in Examples.

The molar ratio between the repeating unit represented by formula (1) and the repeating unit represented by formula (2) is not particularly limited. This molar ratio can be adjusted appropriately so as to obtain the desired crystallization temperature _Tc .

As one index of the molar ratio (or one expression of the molar ratio), the integral ratio Y represented by the following formula (I _Y ) in ¹ H-NMR measurement of the aromatic polyether copolymer can be used. can.
Y [%] = {(A/8)/(A/8+B/4)} x 100 (I _Y )
(In formula (I _Y ), A is the integrated value in the chemical shift range from 7.15 ppm to 7.23 ppm, and B is the integrated value in the chemical shift range from 7.32 ppm to 7.42 ppm.)
A peak derived from the repeating unit represented by formula (2) is observed in the integral range corresponding to the integral value A (chemical shift range from 7.15 ppm to 7.23 ppm).
A peak derived from the repeating unit represented by formula (1) is observed in the integral range corresponding to the integral value B (chemical shift range from 7.32 ppm to 7.42 ppm).
The integral ratio Y is the ratio of the repeating units represented by the formula (2) to the total of the repeating units represented by the formula (1) and the repeating units represented by the formula (2) contained in the aromatic polyether copolymer. Match the molar ratio.

The integral ratio Y can be appropriately adjusted so that the aromatic polyether copolymer is imparted with desired thermophysical properties.
In one embodiment, the integral ratio Y is greater than 0% and less than 100%, preferably 0.1-99.9%, preferably 5-95%.
In one embodiment, the integral ratio Y is, for example, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% , 65%, 70%, 75%, 80%, 85%, 90%, 95% or 99% or 0%, 0.1%, 0.5%, 1% above and below these point values, respectively, Ranges up to and including 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 9.5%, 9.9% or 10%. This range can be selected within a range in which the integral ratio Y exceeds 0% and is less than 100%. (For example, the point value is 50%, and the range including 5% above and 10% below the point value is 40 to 55%.)
The integral ratio Y is a value measured by the method described in Examples.

The integral ratio Y is preferably 0.1-49.9%, more preferably 3-25%. As a result, the aromatic polyether copolymer not only has excellent processability, but also exhibits excellent toughness.

The crystallization temperature _Tc of the aromatic polyether copolymer is not particularly limited, and can be appropriately adjusted by the integral ratio Y. Normally, the crystallization temperature _Tc can be lowered by increasing the integral ratio Y, and the crystallization temperature _Tc can be increased by decreasing the integral ratio Y. This tendency becomes stronger when the integral ratio X, which will be described later, exceeds 0%.
In one embodiment, the crystallization temperature _Tc of the aromatic polyether copolymer is 260°C or higher and 300°C or lower.
The crystallization temperature _Tc is a value measured by the method described in Examples.

The glass transition temperature _Tg of the aromatic polyether copolymer is not particularly limited, and can be appropriately adjusted by the integral ratio Y. Increasing the integral ratio Y tends to lower the glass transition temperature _Tg , and decreasing the integral ratio Y tends to raise the glass transition temperature _Tg . This tendency becomes stronger when the integral ratio X, which will be described later, exceeds 0%.
In one embodiment, the glass transition temperature T _g of the aromatic polyether copolymer is 130° C. or higher and 150° C. or lower.
The glass transition temperature _Tg is a value measured by the method described in Examples.

The melting point _Tm of the aromatic polyether copolymer is not particularly limited, and can be appropriately adjusted by the integral ratio Y. Normally, the melting point _Tm can be lowered by increasing the integral ratio Y, and the melting point _Tm can be increased by decreasing the integral ratio Y. This tendency becomes stronger when the integral ratio X, which will be described later, exceeds 0%.
In one embodiment, the aromatic polyether copolymer has a melting point T _m of 320° C. or higher and 350° C. or lower.
The melting point _Tm is a value measured by the method described in Examples.

The difference (T _m −T _c ) between the crystallization temperature T _c and the melting point T _m of the aromatic polyether copolymer is not particularly limited, and can be appropriately adjusted by the integral ratio Y. Increasing the integral ratio Y tends to increase the difference (T _m −T _c ), and decreasing the integral ratio Y tends to decrease the difference (T _m −T _c ). This tendency becomes stronger when the integral ratio X, which will be described later, exceeds 0%.
In one embodiment, the difference (T _m −T _c ) is 52° C. or higher or 53° C. or higher and is 60° C. or lower.

The exothermic peak width due to crystallization observed in differential scanning calorimetry (DSC) of the aromatic polyether copolymer is not particularly limited, and can be appropriately adjusted by the integration ratio Y. The exothermic peak width tends to increase as the integral ratio Y increases, and the exothermic peak width tends to decrease as the integral ratio Y decreases. This tendency becomes stronger when the integral ratio X, which will be described later, exceeds 0%. The exothermic peak width corresponds to the crystallization speed of the aromatic polyether copolymer, and it can be said that the smaller the width, the faster the crystallization speed.
In one embodiment, the exothermic peak width due to crystallization observed in differential scanning calorimetry (DSC) of the aromatic polyether copolymer is 15° C. or less. As a result, the crystallization speed of the aromatic polyether copolymer can be improved, and the processability can be further improved. The lower limit of the exothermic peak width is not particularly limited, and is, for example, 7°C or higher.
The exothermic peak width is a value measured by the method described in Examples.

In one embodiment, the aromatic polyether copolymer has a ¹ H-NMR spectrum in which the integral ratio X represented by the following formula (I _X ) exceeds 0%.
X [%] = {(C/2)/(A/8+B/4)} x 100 ( _IX )
(In formula (I _X ), A is the integrated value in the range of chemical shift 7.15 ppm to 7.23 ppm, B is the integrated value in the range of chemical shift 7.32 ppm to 7.42 ppm, C is the chemical shift from 7.42 ppm It is an integrated value in the range of 7.49 ppm.)

The integral ratio X represented by the formula (I _X ) will be described.
A peak derived from the repeating unit represented by formula (2) is observed in the integral range corresponding to the integral value A (chemical shift range from 7.15 ppm to 7.23 ppm).
A peak derived from the repeating unit represented by formula (1) is observed in the integral range corresponding to the integral value B (chemical shift range from 7.32 ppm to 7.42 ppm).
In the integral range corresponding to the integral value C (chemical shift range from 7.42 ppm to 7.49 ppm), a peak derived from fluorine atoms bonded to the main chain end of the aromatic polyether copolymer is observed. .
The fact that the integral ratio X exceeds 0% indicates the presence of an aromatic polyether copolymer having a fluorine atom bonded to at least one terminal of the main chain.
The integral ratio X is a value measured by the method described in Examples.
As a method of obtaining an aromatic polyether copolymer having an integral ratio X of more than 0%, a method of using a monomer containing a fluorine atom (for example, difluorobenzophenone, etc.) as a raw material for the aromatic polyether copolymer is mentioned. be done.

When the integral ratio X exceeds 0%, the molar ratio (or the integral ratio Y) between the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) and each thermophysical property described above becomes more linear, and each thermophysical property can be adjusted with high accuracy.

In one embodiment, the aromatic polyether copolymer has an integral ratio Z represented by the following formula (I _Z ) of 0% in the ¹ H-NMR spectrum.
Z [%]={(D/2)/(A/8+B/4)}×100 (I _Z )
(In formula (I _Z ), A is the integrated value in the chemical shift range from 7.15 ppm to 7.23 ppm, B is the integrated value in the chemical shift range from 7.32 ppm to 7.42 ppm, D is the chemical shift from 7.89 ppm It is an integrated value in the range of 7.93 ppm.)

The integral ratio Z represented by the formula (I _Z ) will be explained.
For the integral values A and B, the explanation given for the integral ratio X is used.
In the integration range corresponding to the integrated value D (chemical shift range from 7.89 ppm to 7.93 ppm), a peak derived from chlorine atoms bonded to the main chain end of the aromatic polyether copolymer is observed. .
The fact that the integral ratio Z exceeds 0% indicates the presence of an aromatic polyether copolymer having a chlorine atom bonded to at least one terminal of the main chain.
The integral ratio Z is a value measured by the method described in Examples.

When the integral ratio Z is 0%, that is, when the main chain end of the aromatic polyether copolymer does not have a chlorine atom bonded thereto, the effects of the present invention are exhibited more favorably.
As a method for making the integral ratio Z 0%, there is a method in which a monomer containing a chlorine atom (eg, dichlorobenzophenone, etc.) is not used as a raw material for the aromatic polyether copolymer.

The melt flow rate of the aromatic polyether copolymer is not particularly limited.
In one embodiment, the melt flow rate of the aromatic polyether copolymer is 1500 g/10 min or less, 1000 g/10 min or less, 500 g/10 min or less, 300 g/10 min or less, 200 g/10 min or less, 100 g/10 min or less, 80 g/ 10 min or less, 50 g/10 min or less, 30 g/10 min or less, 20 g/10 min or less, or 10 g/10 min or less, and 0.0001 g/10 min or more, 0.0005 g/10 min or more, or 0.001 g/10 min or more.
The melt flow rate of the aromatic polyether copolymer is preferably 100 g/10 min or less. An aromatic polyether copolymer having a melt flow rate of 100 g/10 min or less has a sufficiently high molecular weight and is therefore suitable for pelletization by an extruder or the like. Such pellets can be preferably applied to uses such as injection molding.
The melt flow rate is a value measured by the method described in Examples.

The terminal structure of the aromatic polyether copolymer is not particularly limited, and may be any structure, such as a hydrogen atom or a halogen atom. The halogen atom includes, for example, fluorine atom, bromine atom, iodine atom and the like, and fluorine atom is preferable. Especially when the terminal structure of the aromatic polyether copolymer contains a fluorine atom, each of the above thermophysical properties (specifically, the crystallization temperature T _c , the glass transition temperature T _g , the melting point T _m , the crystallization temperature T _c and melting point T _m (T _m - T _c ) and exothermic peak width due to crystallization observed in differential scanning calorimetry), thermophysical properties suitable for various processing conditions can be flexibly adjusted. can be given to

Also, the terminal structure of the aromatic polyether copolymer may be, for example, the terminal structure represented by the following formula (3).

The method of introducing the terminal structure represented by formula (3) into the aromatic polyether copolymer is not particularly limited.

Among the ends of the molecular chains constituting the aromatic polyether copolymer, the ends having the terminal structure represented by formula (3) are represented by the following formulas (4) or (5), for example.

That is, in the aromatic polyether copolymer, the terminal structure represented by formula (3) can form the terminal represented by formula (4) or (5). The carbonyl groups in formulas (4) and (5) can correspond to the carbonyl groups in formula (1) or (2).

In one embodiment, the aromatic polyether copolymer does not contain repeating units other than the repeating units represented by formula (1) and the repeating units represented by formula (2). However, the end of the molecular chain can have a terminal structure as described above.

In one embodiment, the aromatic polyether copolymer has a structure other than the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2), as long as the effect of the present invention is not impaired. Including units. Other structural units are not particularly limited, and include, for example, repeating units represented by formula (1) or formula (2) in which the linking position is different (the linking position is not para-position).

In one embodiment,
(i) the entire aromatic polyether copolymer,
(ii) a portion excluding the terminal structure from the entire aromatic polyether copolymer, or (iii) the repeating unit represented by the formula (1) for the total of all repeating units constituting the aromatic polyether copolymer And the total ratio (% by mass) of the repeating units represented by formula (2) is 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more , 97% by mass or more, 99% by mass or more, 99.5% by mass or more, or 100% by mass.

2. Method for Producing Aromatic Polyether Copolymer A method for producing an aromatic polyether copolymer according to one aspect of the present invention includes reacting a dihalogenobenzophenone, a dihydric phenol, and a dihydric phenyl ether. .

Dihalogenobenzophenone, dihydric phenol, and dihydric phenyl ether are monomers for producing aromatic polyether copolymers by polymerization.

In the method for producing an aromatic polyether copolymer according to one aspect of the present invention, the molar ratio of dihydric phenol and divalent phenyl ether to be subjected to the reaction (for example, the total of dihydric phenol and divalent phenyl ether By adjusting the molar ratio of the divalent phenyl ether), the thermophysical properties of the aromatic polyether copolymer obtained by polymerizing these monomers can be adjusted. Therefore, the effect of being able to produce an aromatic polyether copolymer with excellent workability can be obtained. For specific examples of thermophysical properties that can be adjusted in this embodiment, the description of the aromatic polyether copolymer according to one embodiment of the present invention is used.

In one embodiment, the dihalogenobenzophenone is 4,4'-dihalogenobenzophenone.
In one embodiment, the dihydric phenol is hydroquinone.
In one embodiment, the divalent phenyl ether is 4,4'-dihydroxydiphenyl ether.

In one embodiment, by using 4,4'-dihalogenobenzophenone as the dihalogenobenzophenone, hydroquinone as the dihydric phenol, and 4,4'-dihydroxydiphenyl ether as the dihydric phenyl ether, An aromatic polyether copolymer according to one aspect can be produced. Here, 4,4'-dihalogenobenzophenone and hydroquinone are linked to form a repeating unit represented by formula (1), and 4,4'-dihalogenobenzophenone and 4,4'-dihydroxydiphenyl ether By linking, a repeating unit represented by formula (2) is formed.

The 4,4'-dihalogenobenzophenone is not particularly limited, and the two halogen atoms may be the same or different. The two halogen atoms can each independently be a fluorine atom, a bromine atom or an iodine atom.

In one embodiment, the dihalogenobenzophenone is difluorobenzophenone. Here, the difluorobenzophenone is preferably 4,4'-difluorobenzophenone. As a result, an aromatic polyether copolymer having an integral ratio X of more than 0% is obtained.

An aromatic polyether copolymer is obtained by reacting (polymerizing) these monomers in a reaction mixture containing dihalogenobenzophenone, dihydric phenol, and dihydric phenyl ether as monomers.
In one embodiment, when the total substance amount of dihydric phenol and divalent phenyl ether to be subjected to the reaction is amol, and the substance amount of dihalogenobenzophenone is bmol, b/a≧1.00, preferably b /a>1.00, more preferably b/a>1.001, still more preferably b/a>1.002.

In one embodiment, the reaction mixture includes a solvent. The solvent is not particularly limited, and for example, a neutral polar solvent can be used. Examples of neutral polar solvents include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethyl Benzoamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, Nn-propyl-2-pyrrolidone, Nn- Butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5- trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-6-methyl-2-piperidone, N-methyl-3-ethylpiperidone, dimethylsulfoxide, diethylsulfoxide, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, N,N'-dimethylimidazolidinone, diphenylsulfone and the like. The reaction mixture can contain one or more solvents.

In one embodiment, the reaction mixture includes a base. The base is not particularly limited, and examples thereof include alkali metal salts and the like. Examples of alkali metal salts include alkali metal carbonates, alkali metal hydrogen carbonates, and the like. Examples of alkali metal carbonates include potassium carbonate, lithium carbonate, rubidium carbonate, and cesium carbonate. Examples of alkali metal hydrogencarbonates include lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, rubidium hydrogencarbonate, and cesium hydrogencarbonate. The reaction mixture can contain one or more bases.

In one embodiment, the blending amount of the base in the reaction mixture (the total blending amount when blending two or more bases) is when the total blending amount of the dihydric phenol and the divalent phenyl ether is 100 mol parts. , 100 mol parts or more, and 180 mol parts or less, 160 mol parts or less, 140 mol parts or less, or 120 mol parts or less. If the total amount of the bases is 100 mol parts or more, the reaction time can be shortened. If the total amount of the bases is 180 mol parts or less, the formation of gel components can be suppressed.

In one embodiment, the molar ratio of divalent phenyl ether to the total of divalent phenol and divalent phenyl ether subjected to the reaction (percentage: also referred to as "molar ratio y") is more than 0 mol% and less than 100 mol%, It is preferably 0.1 to 99.9 mol %, preferably 5 to 95 mol %.

The total concentration of dihalogenobenzophenone, dihydric phenol and dihydric phenyl ether in the reaction mixture (based on the blending amount) is not particularly limited.
In one embodiment, the total concentration of dihalogenobenzophenone, dihydric phenol and dihydric phenyl ether in the reaction mixture (based on the blending amount) is 1.0 mol/l or more, 1.2 mol/l or more, 1.3 mol/l 1.4 mol/l or more, or 1.5 mol/l or more, and 6.0 mol/l or less, 5.0 mol/l or less, or 4.0 mol/l or less.

In one embodiment, monomers other than dihalogenobenzophenone, dihydric phenol and dihydric phenyl ether are not used as the monomers subjected to the reaction described above.

In one embodiment, the monomers subjected to the reaction described above may contain monomers other than dihalogenobenzophenone, dihydric phenol, and dihydric phenyl ether to the extent that the effects of the present invention are not impaired. . Other monomers include, for example, a terminal blocking agent (eg, one or more selected from the group consisting of 4-phenoxyphenol and 4-halogenodiphenyl ether) capable of introducing a terminal structure represented by the above formula (3), and the like. are mentioned.

In one embodiment, the total amount (% by mass) of dihalogenobenzophenone, dihydric phenol and divalent phenyl ether is 50% by mass or more, 60% by mass or more, relative to the amount of all monomers in the reaction mixture, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, 99.5% by mass or more, or 100% by mass.

The reaction mixture may or may not contain components other than dihalogenobenzophenone, dihydric phenol, dihydric phenyl ether, base and solvent.

In one embodiment, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.9% by mass or more of the reaction mixture at the start of the reaction Or substantially 100% by weight is dihalogenobenzophenone, dihydric phenol, dihydric phenyl ether, base and solvent.
In addition, in the case of "substantially 100% by mass", unavoidable impurities may be included.

The reaction of dihalogenobenzophenone, dihydric phenol, and dihydric phenyl ether can be carried out under an inert gas atmosphere. The inert gas is not particularly limited, and examples thereof include nitrogen gas and argon gas.

In one embodiment, the reaction mixture is heated during the reaction of the dihalogenobenzophenone, dihydric phenol, and dihydric phenyl ether. The maximum temperature (maximum temperature) of the reaction mixture during the reaction is not particularly limited as long as it is the temperature at which the aromatic polyether copolymer is produced, and may be, for example, 250 to 350°C.

3. Method for adjusting thermophysical properties of aromatic polyether copolymer.
A method for adjusting the thermophysical properties of an aromatic polyether copolymer according to one aspect of the present invention includes an aromatic A method for adjusting the thermophysical properties of a polyether copolymer, which is represented by the formula (2) for the sum of the repeating units represented by the formula (1) and the repeating units represented by the formula (2) and adjusting the molar ratio of the repeating units to adjust the thermophysical properties of the aromatic polyether copolymer.

In this embodiment, the thermophysical properties include, for example, the crystallization temperature T _c , the glass transition temperature T _g , the melting point T _m , the difference between the crystallization temperature T _c and the melting point T _m (T _m −T _c ), and the differential scanning calorific value One or more selected from the group consisting of exothermic peak width due to crystallization observed in the measurement can be adjusted.
In one embodiment, as the thermophysical property, one or more selected from the group consisting of the crystallization temperature _Tc and the exothermic peak width due to crystallization observed in differential scanning calorimetry can be adjusted.
An aromatic polyether copolymer whose thermophysical properties are adjusted by the method for adjusting thermophysical properties of an aromatic polyether copolymer according to this aspect exhibits an effect of excellent workability.

In this aspect, the method for adjusting the molar ratio of the repeating unit represented by formula (2) to the total of the repeating unit represented by formula (1) and the repeating unit represented by formula (2) includes: A method of adjusting the ratio of monomers (eg, 4,4'-dihalogenobenzophenone, hydroquinone and 4,4'-dihydroxydiphenyl ether) used in producing the aromatic polyether copolymer can be used. In particular, by adjusting the molar ratio of hydroquinone and 4,4'-dihydroxydiphenyl ether (for example, the molar ratio of 4,4'-dihydroxydiphenyl ether to the sum of hydroquinone and 4,4'-dihydroxydiphenyl ether), Adjusting the molar ratio of the repeating unit represented by the formula (2) to the total of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) contained in the aromatic polyether copolymer can do.

As for the method for producing the aromatic polyether copolymer used in this aspect, the above description of the method for producing the aromatic polyether copolymer according to one aspect of the present invention is used. The molar ratio may be adjusted by adjusting the integral ratio Y, which is one index of the molar ratio.

4. Applications The aromatic polyether copolymer according to one aspect of the present invention described above, the aromatic polyether copolymer produced by the method for producing the aromatic polyether copolymer according to one aspect of the present invention, and An aromatic polyether copolymer whose thermophysical properties are adjusted by a method for adjusting thermophysical properties of an aromatic polyether copolymer according to one aspect of the present invention (hereinafter collectively referred to as “aromatic Group polyether copolymer α”) is not particularly limited. The aromatic polyether copolymer α can be preferably applied to various processing due to its excellent workability.

It is preferable to subject the aromatic polyether copolymer α to molding as an example of processing. As an example of molding, there is a method of molding the aromatic polyether copolymer α in a molten state and then cooling and solidifying it. A molded article can be produced by molding the aromatic polyether copolymer α. For molding, known methods such as injection molding, extrusion molding, and blow molding can be used. Also, the aromatic polyether copolymer α can be press-molded, and a known method such as a cold press method or a hot press method can be used. Furthermore, the aromatic polyether copolymer α can be used in 3D printer ink and molded by a 3D printer. The aromatic polyether copolymer α may or may not be subjected to a method of forming a three-dimensional object from powder by selective sintering using electromagnetic radiation.

As an example of processing, the aromatic polyether copolymer α may be used to form a composite material containing the aromatic polyether copolymer α and fibers. The fibers are not particularly limited, and examples thereof include fibers of inorganic compounds. Examples of inorganic compound fibers include glass fibers and carbon fibers. In the composite material, the fibers may be dispersed in the aromatic polyether copolymer α, or the fibers (for example, in the form of cloth) may be impregnated with the aromatic polyether copolymer α. A cloth is composed of fibers arranged in a plane. The cloth can be, for example, woven, nonwoven, unidirectional, or the like. A unidirectional material is composed of fibers aligned in one direction. The composite material may be subjected to molding as described above.

Examples of the present invention are described below, but the present invention is not limited by these examples.

(Example 1)
In a 300 ml separable flask, 0.1641 mol of difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd., abbreviated as "DFBP") and 0.1568 mol of hydroquinone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., abbreviated as "HQ") are added as monomers. 0.0049 mol of 4,4′-dihydroxydiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., abbreviated as “DHPE”) was added. Here, the molar ratio y of DHPE to the sum of HQ and DHPE is 3 mol %. Into this separable flask, 0.1860 mol of potassium carbonate (K ₂ CO ₃ ) (manufactured by Junsei Chemical Co., Ltd., special grade) was added as a base, and 140 g of diphenyl sulfone was added as a solvent.

A ribbon heater was wound around the top of the separable flask, and glass wool was wound thereon to keep it warm. In addition, the entire lower portion of the separable flask was wrapped with a mantle heater. Under nitrogen (flow rate: 0.1 L/min), the reaction mixture in the separable flask was heated and stirred using a mechanical stirrer.
The ribbon heater was set to 150°C and the mantle heater to 165°C, and after heating for 30 minutes while stirring at a stirring speed of 100 rpm, the stirring speed was changed to 210 rpm, and the reaction mixture was heated to 200°C over 30 minutes. .
After the temperature was raised, the temperature was maintained at 200°C for 1 hour, and the temperature was again raised to 250°C over 30 minutes.
After maintaining the temperature at 250° C. for 1 hour, the stirring speed was changed to 250 rpm, and the temperature was raised to 300° C. over 30 minutes.
After raising the temperature and maintaining the temperature at 300° C. for 2 hours, the reaction was terminated and the mother liquor was taken out. The recovered product was pulverized and washed with acetone and water to obtain a polymer.

<Evaluation method>
(1) Structural Analysis The obtained polymer (sample) was identified and primary structurally analyzed by ¹ H-NMR under the following measurement conditions.
[Measurement condition]
・Magnet: Ascend500
・Spectrometer: AVANCE III HD
Probe: TCI cryoprobe with a diameter of 5 mm Accumulation times: 256 Waiting time: 10 seconds Sample preparation: 0.6 mL of methanesulfonic acid was added to about 20 mg of the sample and stirred for 1 hour. 0.4 mL of heavy dichloromethane was added thereto to prepare a measurement sample.

Integral ratio X, integral ratio Y, and integral ratio Z in ¹ H-NMR measurement of the polymer were obtained based on integral values A, B, C, and D below.
The integral value A is obtained by connecting the intensity of the chemical shift 7.15 ppm and the intensity of 7.42 ppm with a straight line (baseline), and the intensity based on this baseline (the intensity when the intensity of the baseline is 0) It was obtained as an integrated value in the chemical shift range of 7.15 ppm to 7.23 ppm. If no peak is observed in the chemical shift range from 7.15 ppm to 7.23 ppm, the integrated value A is assumed to be 0.
The integral value B is obtained by connecting the intensity of the chemical shift 7.15 ppm and the intensity of 7.42 ppm with a straight line (baseline), and the intensity based on this baseline (the intensity when the intensity of the baseline is 0) It was obtained as a value integrated in the chemical shift range from 7.32 ppm to 7.42 ppm. When no peak is observed in the chemical shift range from 7.32 ppm to 7.42 ppm, the integrated value B is set to 0.
The integral value C is obtained by connecting the intensity of the chemical shift 7.42 ppm and the intensity of 7.49 ppm with a straight line (baseline), and the intensity based on this baseline (the intensity when the intensity of the baseline is 0) It was obtained as a value integrated in the chemical shift range from 7.42 ppm to 7.49 ppm. If no peak is observed in the chemical shift range from 7.42 ppm to 7.49 ppm, the integrated value C is assumed to be 0.
The integrated value D is obtained by connecting the intensity of the chemical shift 7.89 ppm and the intensity of 7.93 ppm with a straight line (baseline), and the intensity based on this baseline (the intensity when the intensity of the baseline is 0) It was obtained as a value integrated in the chemical shift range from 7.89 ppm to 7.93 ppm. When no peak is observed in the chemical shift range of 7.89 ppm to 7.93 ppm, the integrated value D is set to 0.
It was confirmed that the polymer contained the repeating unit represented by formula (1) and the repeating unit represented by formula (2) by checking that the integral ratio Y was more than 0% and less than 100%.

(2) Measurement of thermophysical properties (differential scanning calorimetry (DSC))
5 mg of the obtained polymer (sample) was weighed into an aluminum pan and subjected to temperature scanning measurement using a differential scanning calorimeter (“DSC8500” manufactured by PerkinElmer).
The temperature scan was performed by increasing the temperature of the sample from 50°C to 420°C at a rate of 20°C/min (first temperature increase) with nitrogen flowing at 20 ml/min, holding at 420°C for 1 minute, 420°C. C. to 50.degree. C. at -20.degree. C./min (first temperature decrease), hold at 50.degree. gone.

The crystallization temperature _Tc was determined by reading the exothermic peak due to crystallization observed during the first temperature drop. The exothermic peak width was obtained as the difference between the "extrapolation start point" and the "extrapolation end point" of the exothermic peak due to crystallization during the first temperature drop. Here, in the case of measurement at the time of temperature decrease, the "extrapolation start point" is the point (temperature) where the tangent line at the point of maximum slope on the high temperature side of the peak intersects with the baseline, and the "extrapolation end point" is the point (temperature) where the tangent to the point of maximum slope on the low temperature side of the peak intersects the baseline. Here, the difference between "extrapolation start point" - "extrapolation end point" was determined using thermal analysis software "Pyris" manufactured by PerkinElmer.
The glass transition temperature _Tg was obtained as the temperature at the midpoint of the transition (the midpoint of the displacement) by reading the baseline shift due to the glass transition observed during the second heating.
The melting point _Tm was obtained as the peak top temperature by reading the endothermic peak due to melting observed during the second heating.

(3) Melt flow rate (MFR)
The melt flow rate of the resulting polymer (sample) was measured using a melt indexer (L-220) manufactured by Tateyama Kagaku High Technologies Co., Ltd. in accordance with JIS K 7210-1: 2014 (ISO 1133-1: 2011). , was measured under the following measurement conditions.
[Measurement condition]
・Measurement temperature: 380°C
・Measurement load: 2.16 kg
・Cylinder inner diameter: 9.550 mm
・Die inner diameter: 2.095 mm
・Die length: 8.000 mm
・Piston head length: 6.35mm
・Piston head diameter: 9.474mm
·operation:
Samples were previously dried at 150° C. for 2 hours or longer. The sample was put into the cylinder, the piston was inserted, and it was preheated for 6 minutes. A load was applied and the piston guide was disengaged to force the molten sample out of the die. Samples were cut at given ranges of piston travel and given times (t [s]) and weighed (m [g]). MFR was obtained from the following equation. MFR [g/10 min] = 600/t x m

(4) Tensile test (tensile fracture nominal strain)
A sample (polymer) dried at 180° C. for 2 hours or more was prepared, and an ISO5A dumbbell (2 mmt) was injection molded with a Minijet Pro manufactured by Thermo Fisher Scientific (cylinder temperature 380° C., mold temperature 180° C., injection pressure 500 bar, holding pressure 500 Bar, holding pressure time 15 seconds).
The resulting dumbbells were subjected to a tensile test at a test speed of 20 mm/min under a 50% environment at 23° C. using an Instron Universal Testing Machine Model 5567 at a chuck distance of 50 mm to measure the nominal tensile strain at break. did. The nominal tensile strain at break was measured as the nominal tensile strain immediately before the stress decreased to 10% or less of the tensile strength.

(Example 2)
Example 1 except that the amount of HQ added was changed to 0.1455 mol, the amount of DHPE added was changed to 0.01617 mol, and the molar ratio y of DHPE to the total of HQ and DHPE was set to 10 mol%. A polymer was obtained in the same manner as in 1. Table 1 shows the results of evaluation in the same manner as in Example 1.

(Example 3)
Example 1 except that the amount of HQ added was changed to 0.1213 mol, the amount of DHPE added was changed to 0.0404 mol, and the molar ratio y of DHPE to the total of HQ and DHPE was set to 25 mol%. A polymer was obtained in the same manner as in 1. Table 1 shows the results of evaluation in the same manner as in Example 1. Also, the ¹ H-NMR spectrum is shown in FIG.

(Example 4)
Example 1 except that the amount of HQ added was changed to 0.0809 mol, the amount of DHPE added was changed to 0.0809 mol, and the molar ratio y of DHPE to the total of HQ and DHPE was set to 50 mol%. A polymer was obtained in the same manner as in 1. Table 1 shows the results of evaluation in the same manner as in Example 1.

(Example 5)
Example 1 except that the amount of HQ added was changed to 0.0404 mol, the amount of DHPE added was changed to 0.1213 mol, and the molar ratio y of DHPE to the total of HQ and DHPE was set to 75 mol%. A polymer was obtained in the same manner as in 1. Table 1 shows the results of evaluation in the same manner as in Example 1.

(Comparative example 1)
In Example 1, the same as Example 1 except that the amount of HQ added was changed to 0.1617 mol, the addition of DHPE was omitted, and the molar ratio y of DHPE to the total of HQ and DHPE was set to 0 mol%. to obtain a polymer. Table 1 shows the results of evaluation in the same manner as in Example 1.

<Evaluation>
From Table 1, adjusting the molar ratio of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) contained in the aromatic polyether copolymer (for example, "integral ratio Y" thermophysical properties such as the crystallization temperature T _c , the glass transition temperature T _g , the melting point T _m , the difference between the crystallization temperature T _c and the melting point T _m (T _m −T _c ), and the differential scanning It can be seen that the exothermic peak width due to crystallization observed in calorimetry can be adjusted. From this, it can be seen that according to the present invention, an aromatic polyether copolymer having excellent workability can be obtained.
Further, since the larger the molar ratio y, which is the charged monomer ratio, the larger the integral ratio Y, there is a correlation.

Although several embodiments and/or examples of the present invention have been described above in detail, those of ordinary skill in the art may modify these exemplary embodiments and/or examples without departing substantially from the novel teachings and advantages of the present invention. It is easy to make many modifications to the examples. Accordingly, many of these variations are included within the scope of the present invention.
The documents mentioned in this specification and the contents of the applications from which this application has priority under the Paris Convention are incorporated in their entirety.

Claims

An aromatic polyether copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).
2. The aromatic polyether copolymer according to claim 1, wherein the integral ratio X represented by the following formula (I X ) exceeds 0% in the 1 H-NMR spectrum.
X [%] = {(C/2)/(A/8+B/4)} x 100 ( IX )
(In formula (I X ), A is the integrated value in the range of chemical shift 7.15 ppm to 7.23 ppm, B is the integrated value in the range of chemical shift 7.32 ppm to 7.42 ppm, C is the chemical shift from 7.42 ppm It is an integrated value in the range of 7.49 ppm.)
3. The aromatic polyether copolymer according to claim 1, wherein the integral ratio Z represented by the following formula (I Z ) is 0% in the 1 H-NMR spectrum.
Z [%]={(D/2)/(A/8+B/4)}×100 (I Z )
(In formula (I Z ), A is the integrated value in the chemical shift range from 7.15 ppm to 7.23 ppm, B is the integrated value in the chemical shift range from 7.32 ppm to 7.42 ppm, D is the chemical shift from 7.89 ppm It is an integrated value in the range of 7.93 ppm.)
The aromatic polyether copolymer according to any one of claims 1 to 3, wherein in the 1 H-NMR spectrum, the integral ratio Y represented by the following formula (I Y ) is 0.1 to 99.9%. .
Y [%] = {(A/8)/(A/8+B/4)} x 100 (I Y )
(In formula (I Y ), A is the integrated value in the chemical shift range from 7.15 ppm to 7.23 ppm, and B is the integrated value in the chemical shift range from 7.32 ppm to 7.42 ppm.)
The aromatic polyether copolymer according to any one of claims 1 to 4, wherein the exothermic peak width due to crystallization observed in differential scanning calorimetry is 60°C or less.
The aromatic polyether copolymer according to any one of claims 1 to 5, which has a melt flow rate of 100 g/10 min or less.
A method for producing an aromatic polyether copolymer, comprising reacting a dihalogenobenzophenone, a dihydric phenol, and a dihydric phenyl ether.
The method for producing an aromatic polyether copolymer according to claim 7, wherein the dihalogenobenzophenone is difluorobenzophenone.
The method for producing an aromatic polyether copolymer according to claim 8, wherein the difluorobenzophenone is 4,4'-difluorobenzophenone.
The method for producing an aromatic polyether copolymer according to any one of claims 7 to 9, wherein the dihydric phenol is hydroquinone.
The method for producing an aromatic polyether copolymer according to any one of claims 7 to 10, wherein the divalent phenyl ether is 4,4'-dihydroxydiphenyl ether.
Adjusting the molar ratio of the divalent phenyl ether to the total of the divalent phenol and the divalent phenyl ether subjected to the reaction to adjust the thermophysical properties of the produced aromatic polyether copolymer, A method for producing an aromatic polyether copolymer according to any one of claims 7 to 11.
The method for producing an aromatic polyether copolymer according to claim 12, wherein the crystallization temperature Tc of the aromatic polyether copolymer is adjusted as the thermophysical property.
14. The method for producing an aromatic polyether copolymer according to claim 12 or 13, wherein an exothermic peak width due to crystallization observed in differential scanning calorimetry of the aromatic polyether copolymer is adjusted as the thermophysical property.
A method for adjusting thermophysical properties of an aromatic polyether copolymer containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2),
By adjusting the molar ratio of the repeating unit represented by the formula (2) to the total of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2), the aromatic poly The above method, comprising adjusting the thermophysical properties of the ether copolymer.
16. The method for adjusting the thermophysical properties of an aromatic polyether copolymer according to claim 15, wherein the crystallization temperature Tc of the aromatic polyether copolymer is adjusted as the thermophysical property.
The thermophysical properties of the aromatic polyether copolymer according to claim 15 or 16, wherein the exothermic peak width due to crystallization observed in differential scanning calorimetry of the aromatic polyether copolymer is adjusted as the thermophysical properties. adjustment method.