JPH01315417A - Production of aromatic ether ketone polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having excellent mechanical strength and heat-resistance and high glass transition point, by reacting dihydroxytetraphenylmethane with a plurality of specific raw material compounds in a neutral polar solvent. CONSTITUTION:The objective polymer can be produced by reacting (A) a 4,4'- dihalobenzophenone of formula (X is halogen) (preferably 4,4'- difluorobenzophenone, etc.), (B) 4,4'-dihydroxytetraphenylmethane, (C) an alkali metal compound (preferably sodium carbonate, etc.) and (D) a metal compound containing an element selected from the elements of the groups Ib, IIb and VIII of the periodic table (preferably cuprous oxide, etc.) in a neutral polar solvent (preferably N-methylpyrrolidone). The reaction is preferably carried out in an inert atmosphere under reduced pressure or normal pressure or thereabout at 180-250 deg.C for 0.8-5hr.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing an aromatic ether ketone polymer, and more specifically, to fields related to, for example, the mechanical field, the electronic/electrical field, and materials around nuclear reactors. The present invention relates to a method for producing an aromatic ether ketone polymer that can be suitably used in a wide range of fields such as the present invention.

[Conventional technology and issues] In recent years, it has been used as a so-called engineering resin.

Materials with various chemical structures are used in a wide range of industrial fields, but even these have not yet reached full satisfaction, and the development of new materials, especially engineering resins with excellent heat resistance, is desired. ing.

As one of these engineering resins, there is an aromatic ether ketone polymer, for example, in JP-A-53-970
In Publication No. 94.

JP-A No. 54-90296 discloses a repeating unit consisting of a repeating unit represented by:

and, A copolymer consisting of is shown.

However, although these have excellent properties in that they have a high thermal decomposition temperature, they have a low glass transition temperature (Tg) and have the problem of not being able to maintain rigidity in a temperature range exceeding this glass transition temperature. There was a point.

Therefore, attempts have been made to synthesize aromatic ether ketone polymers that have a particularly high glass transition temperature and can maintain rigidity over a wide temperature range compared to conventional aromatic ether ketone polymers.

For example, the present inventor attempted a production method using 4°4'-dihydroxytetraphenylmethane as one of the raw materials for an aromatic ether ketone polymer.

However, the reactivity of the hydroxyl group in 4,4'-dihydroxytetraphenylmethane is extremely poor, and raising the molecular weight of the polymer using known production methods poses a new problem in that it takes a significant amount of time. .

The present invention has been made to solve the above problems.

That is, an object of the present invention is to use 4,4'-dihydroxytetraphenylmethane to produce an aromatic ether ketone polymer having excellent mechanical strength, sufficiently high heat resistance, and especially a high glass transition temperature. To provide a method for producing an aromatic ether ketone polymer, which can be easily produced by polymerization, and which can increase the molecular weight of the aromatic ether ketone polymer in a short time when synthesizing the aromatic ether ketone polymer. be.

[Means for solving the problem] The present inventors
As a result of intensive research to solve the above problems, 4.
Mechanical strength and heat resistance are improved by reacting 4'-dihalobenzophenone, 4,4'-dihydroxytetraphenylmethane, an alkali metal compound, and a specific metal compound in a neutral polar solvent. It is possible to easily prepare an aromatic ether ketone polymer having excellent properties such as a high glass transition temperature. Furthermore, when synthesizing the aromatic ether ketone polymer, the molecular weight of the polymer can be They discovered that it is possible to increase this in a short period of time, and have completed the present invention.

That is, the structure of the present invention is 1 formula (I) (However, X in the formula represents a halogen atom.

The two Xs may be the same or different,
) 4,4'-dihalobenzophenone and 4.4
''-dihydroxytetraphenylmethane, alkali metal compounds, and Groups 1b, 5, and 1 of the periodic table.
selected from the group consisting of elements belonging to the group This is a method for producing an aromatic ether ketone polymer, which is characterized by using a metal compound containing at least one element and reacting it in a neutral polar solvent.

The present invention will be explained in detail below.

The 4,4'-dihalobenzophenone has the following formula (I) (However, X in formula 1 represents a halogen atom.

The two Xs may be the same or different,
).

The halogen atom in the 4,4'-dihalobenzophenone is not particularly limited, but among these, fluorine and chlorine atoms are preferred in consideration of reactivity, economical efficiency, and the like.

Specific examples of the 4,4'-dihalobenzophenone include 4,4'-difluorobenzophenone, 4,
．． 4'-dichlorobenzophenone, 4-chloro-4'-
Examples include fluorobenzophenone. Among these, 4゜4'-difluorobenzophenone, 4
．． 4'-dichlorobenzophenone and the like are preferred.

Incidentally, these 4,4'-dihalobenzophenones may be used alone or alternatively.

Two or more types may be used in combination.

The 4,4′-dihydroxytetraphenylmethane is
It can be used as is as it is.

In the present invention, a third component may be used in addition to the 4,4'-dihalobenzophenone and the 4,4'-dihydroxytetraphenylmethane to advance the polymerization reaction.

The third component may be, for example, (in the formula, R1 represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and ftR represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, a cyclohexyl group, or a halogen atom). Dihydric phenols represented by ) can be mentioned.

Dihydric phenols represented by the above formula (II) [hereinafter, this may be referred to as dihydric phenols (II). ]
Specific examples include hydroquinone, resorcinol, catechol, l,5-dihydroxynaphthalene,
2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)sulfone , bis(4-hydroxyphenyl) sulfide, 2.2-bis(4-hydroxyphenyl)propane, 2.2-bis(3-phenyl-4-hydroxyphenyl)propane, 2゜2-bis(3-chloro- 4-hydroxyphenyl)propane, 2.2-bis(3-phenyl-4-hydroxyphenyl)propane, 2.2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 3.3-bis(4 -hydroxyphenyl)pentane, l-phenyl-1,1-bis(4-hydroxyphenyl)ethane, l,1-diphenyl-1,1-bis(
Examples include 4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexane, and bis(4-hydroxyphenyl)methane.

Note that these dihydric phenols (n) may be used alone or in combination of two or more as a mixture.

Examples of the alkali metal compounds include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Examples include cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, and the like. Among these, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate are preferred. These alkali metal compounds may be used alone or in combination of two or more of them. good.

In the present invention, an element (
There are no particular restrictions on the metal elements (hereinafter simply referred to as metal elements) as long as they belong to Groups ■, ■, and Groups 1 of the periodic table, such as iron, cobalt, nickel, copper, and zinc. , gold, silver, cadmium, mercury, etc. Among these, preferred are iron, cobalt, nickel, copper, and zinc.

The effect of the metal element, together with the alkali metal compound, is that the 4.4'-dihalobenzophenone, 4.
It seems to have the function of promoting polymerization with 4'-dihydroxytetraphenylmethane.

Examples of the metal compound containing the metal element include oxides of the metal element, hydroxides, halides, cyanides, thiocyanates, sulfates, nitrates, and carbonates of the metal element.

Metal salts such as bicarbonates, chlorates, perchlorates, bromates, phosphates, arsenites, carboxylates, etc.

Examples include metal complexes such as metal carbonyls of serious metal elements. Further, metal compounds containing two or more of the above metal elements, such as metal oxides, metal salts, metal complexes, etc., can also be used.

Among these, preferred are metal oxides, chlorides, and carboxylates containing one of the above metal elements.

Examples of metal oxides containing one of the above metal elements include zinc oxide, cobalt oxide (■), cobalt oxide (m), iron oxide (■), iron oxide (■), copper oxide (I),
Examples include copper oxide (■) and nickel oxide (n).

Among these, copper oxide (■) is preferred.

Examples of metal chlorides containing one of the above metal elements include zinc chloride, cobalt chloride (■), and iron chloride (■).
, iron chloride (■), copper chloride (■), copper chloride (■), nickel chloride (n), and the like.

Among these, preferred are zinc chloride, cobalt chloride (■), iron chloride (■), copper chloride (I), and nickel chloride (■).

As a carboxylic acid salt containing one of the above metal elements,
Examples include aliphatic carboxylates, aromatic carboxylates, and the like of the metal elements.

Among these, preferred are aliphatic monocarboxylic acid salts, and more preferred are rmm gold metal element acetates.

Examples of the acetate include zinc acetate, cobalt acetate (■), iron acetate (■), iron acetate (■), and copper acetate (I).
, copper acetate (■), nickel acetate (n), and the like.

Among these, preferred are zinc acetate, cobalt acetate (■), iron acetate (■), iron acetate (m), copper acetate (1), copper acetate (■), and nickel acetate (II). .

The metal compound is usually preferably used as an anhydride, but if desired, it can also be used as a hydrate, a concentrated aqueous solution, or other water-containing compound.

It is desirable that the water added to the reaction system and the water produced by the reaction be appropriately removed from the reaction system during one reaction (condensation reaction) or prior to the reaction.

Further, the metal compounds may be used alone, or two or more of them may be used in combination in any ratio, such as a mixture.

As the neutral polar solvent, known ones can be used, and specifically, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and sulfolane.

Diphenylsulfone and the like can be suitably used.

Among these, N-methylpyrrolidone, sulfolane and the like are preferred, with N-methylpyrrolidone and the like being particularly preferred.

These neutral polar solvents may be used alone, or two or more may be used in combination as a mixed solvent, or they may be used for azeotropic removal of water from other inert solvents, especially from the reaction system. It can also be used as a mixed solvent with aromatic solvents such as benzene, toluene, and xylene.

According to the present invention, the aromatic ether ketone polymer synthesized is a homopolymer having a repeating unit represented by formula (m) (III) (hereinafter referred to as
(hereinafter referred to as a homopolymer) and a copolymer (hereinafter referred to as a copolymer) consisting of formula (m) and one or more repeating units, that is, comonomer units different from formula (m). As the copolymer.

For example, the repeating unit represented by formula (m) and the formula (I
V) (ff) (However, R' in the formula represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and R2 represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, a cyclohexyl group, or a halogen atom, ), and copolymers consisting of repeating units represented by:

The above-mentioned homopolymer is one of the above-mentioned 4.4'-
Using any one kind or arbitrary two or more kinds of dihalobenzophenones, as the other one of the raw material monomers,
4. A method of condensation polymerization using 4'-dihydroxytetraphenylmethane by heating in the neutral polar solvent in the presence of the alkali metal compound and the metal compound containing the metal element, etc. It can be suitably synthesized by.

In addition, as a variation of the above ■.

(2) A method in which a part of 4,4'-dihydroxytetraphenylmethane and a part of the alkali metal compound are substituted with an alkali metal salt of 4,4'-dihydroxytetraphenylmethane in (2) above; (2) A method in (2) above; In this method, it is also possible to adopt a method in which all of 4,4'-dihydroxytetraphenylmethane and part or all of the alkali metal compound are replaced by an alkali metal salt of 4,4'-dihydroxytetraphenylmethane. .

In the method (2) above, the ratio of the 4,4'-dihalobenzophenone used is usually 0.98 to 1.02 mol, preferably 1.00 to 1.02 mol, per 1 mol of 4,4'-dihydroxytetraphenylmethane. It is 1.01 mol.

In the method (2) above, the proportion of the neutral polar solvent to be used cannot be uniformly defined as it varies depending on the type and proportion of the monomers used, the reaction conditions, etc.
It is preferable to use the monomers at a ratio such that the total monomer concentration is usually 0.5 to 4 mol/mole.

In addition, when using the method (1) or (2) above, the usage ratio of each component is the same as that of the method (2) above.

In addition, the copolymer can be prepared by converting a part of 4,4'-dihydroxytetraphenylmethane into the dihydric phenols (1) in the method (2) above.
It can be suitably synthesized by a method in which one or a mixture of two or more of n) is used instead.

In addition, as a modification of the above ■.

■ In the method (■) above, a part of 4,4'-dihydroxytetraphenylmethane is replaced by an alkali metal salt of 4,4'-dihydroxytetraphenylmethane, or ■ one of the dihydric phenols (n) A method in which part or all of 4,4'-dihydroxytetraphenylmethane is replaced by an alkali metal salt of dihydric phenol gR (Il), or the above methods (1) and (2) are carried out simultaneously. It is also possible to adopt a method in which all of the dihydric phenols (n) are replaced by an alkyl metal salt of 4,4'-dihydroxytetraphenylmethane and an alkali metal salt of the dihydric phenols (■). .

In the method (2) above, the dihydric phenol (II)
The amount of 4,4'-dihydroxytetraphenylmethane to be used is determined by the ratio of the repeating unit represented by the formula (m) and the repeating unit represented by the formula (EV) in the resulting copolymer, or The total molar amount of units is 1
00 mol%, 1 to 99 mol%, preferably 1
The ratio is set to 0 to 90 mol%.

In the method (2) above, the ratio of the total amount of the 4,4'-dihalobenzophenone to be used is the 4,4'-dihydroxytetraphenylmethane and the dihydric phenol a (I
For a total of 311 moles of I), usually 0.98 he1
．． 02 mol, preferably 1.0 mol. oo to 1.01 mol.

In the method O, the proportion of the metal compound containing the metal element is usually o, oos, based on the total equivalent of the 4,4'-dihydroxytetraphenylmethane and the dihydric phenol (II). ~5 equivalents, preferably 0.01 to 1 equivalent.

In the present invention, when carrying out the polymerization reaction, there are no particular restrictions on the order or method of mixing the above-mentioned components, and the components may be mixed simultaneously and subjected to the reaction, or they may be mixed in stages. It may be subjected to a reaction.

As the polymerization method, a known solution polymerization method can be applied.

There is no particular restriction on the polymerization method, and it is possible to adopt a -stage or multi-stage polymerization, a batch method, a continuous method, a semi-continuous method, or a method combining one or more of these.

The temperature at which the reaction (condensation reaction) is carried out is usually I50 to 35.
The temperature is preferably 0°C, preferably within the range of 180 to 250°C. The reaction time for carrying out the condensation reaction is
The time may vary depending on the type of metal used, the type of metal compound containing the metal element, the ratio used, the reaction temperature, etc., so it cannot be specified uniformly, or it is usually 0.5 to 10 hours, preferably 0.8 hours. ~5 o'clock 1m.

There is no particular restriction on the reaction pressure, and the reaction may be carried out under reduced pressure, normal pressure or increased pressure, but it is usually preferable to carry out the reaction between reduced pressure and around normal pressure.

The reaction atmosphere is usually nitrogen or argon.

It is preferable to use an inert atmosphere such as under an inert gas flow such as helium or under reduced pressure exhaust.

An aromatic ether ketone polymer can be synthesized in the manner described above.

The synthesized polymer is separated from the raw Jti and the mixture by using a known post-treatment method, and after performing appropriate purification operations such as washing, it is recovered as an aromatic ether ketone polymer of desired purity. I can do it.

As a post-treatment method, for example, the polymerization reaction product mixture is cooled to around room temperature, the polymer is precipitated using an appropriate solvent such as acetone, the polymer is pulverized, and the polymer is washed with hot water or methanol. , drying methods can be suitably employed.

The present invention facilitates the production of aromatic ether ketone polymers having excellent properties such as excellent mechanical strength and heat resistance, and especially a high glass transition temperature, using industrially easily available production raw materials Furthermore, when synthesizing the aromatic ether ketone polymer, the present invention is a method for producing an aromatic ether ketone polymer which is extremely excellent in practical use and can increase the molecular weight of the polymer in a short period of time.

[Example] (Example 1) In a reactor with an internal volume of 100 sJL equipped with a Dean-Stark trap, a stirring device and an argon gas blowing tube, 22.038 g of 4,4'-difluorobenzophenone was added.
g (0.10 mol) and 4.4-dihydroxytetraphenylmethane: +5.243 g (0.10 mol)
, potassium carbonate 27.6g (0.2 mol), copper chloride (
I) 0.21 g (2.1 mmol) and 150 μm of N-methylpyrrolidone as a neutral polar solvent were added and dissolved at room temperature while flowing argon gas.
Next, put the reactor in an oil bath and heat it to 195℃ for 5 minutes.
The temperature was raised over 0 minutes, a small amount of toluene was added, the mixture was refluxed for 1 hour, the toluene was gradually removed, and the mixture was reacted at 200°C over 2 hours.

After the reaction was completed, the reaction product was cooled to room temperature, washed with acetone, and pulverized using a pulverizer. It was washed with water and dried to obtain 51 g of polymer powder (yield: 96%). The concentration of this polymer in p-chlorophenol as a solvent is 0.2.
The reduced viscosity [η5plc] of a solution of g/dl measured at 60°C (the same applies in the following examples) is 1.85 dJL
/g.

The glass transition temperature of this polymer was measured by differential scanning calorimetry, and 201'C1 thermogravimetric analysis showed that it was thermally decomposed in air at a temperature rate of 10°C/min (the same applies to the following examples). The starting temperature (5% weight dehumidification temperature) was measured and found to be 562°C.

Regarding the obtained polymer, infrared absorption spectrum, NMR
When the spectrum and the like were measured, it was confirmed that this polymer was an aromatic ether ketone homopolymer consisting of the following overlapping units.

The infrared absorption spectrum of this polymer is shown in FIG. 1.
The absorption of is based on the stretching vibration of the carbonyl group (C-O) and the ether bond (-0-), respectively.

(Example 2) Copper (II) oxide was used in place of copper (I) chloride in Example 1.
The same procedure as Example 1 was carried out except that 0.167 g (2.1 mmol) was used and the reaction time was 5 hours.

The weight of the obtained polymer was 50 g (yield: 94%), and the reduced viscosity [ηs p'/c ] of this polymer was 1.
It was 14d/g.

When the structure of this polymer was investigated in the same manner as in Example 1, it was found to be a homopolymer consisting of repeating units similar to those shown in Example 1.

(Example 3) Copper acetate (II) was used instead of copper (I) chloride in Example 1.
0. The same procedure as in Example 1 was carried out, except that 18 g (2.1 mmol) was used and the reaction time was 1.5 hours.

The amount of the obtained polymer was 52 g (yield: 98%), and the reduced viscosity [ηsp/cl] of this polymer was 1.86 db/g.

When the structure of this polymer was investigated in the same manner as in Example 1, it was found to be a homopolymer consisting of repeating units similar to those shown in Example 1.

(Example 4) Copper chloride (n) o, 3 in place of copper chloride (I) in Example 1
4 g (2.1 mmol) and a reaction time of 5
The experiment was carried out in the same manner as in Example 1, except for changing the time.

The amount of the obtained polymer was 52 g (yield 98%), and the reduced viscosity [ηsp/cl] of this polymer was 1.39 dl.
It was 1g.

The structure of this polymer was investigated in the same manner as in Example 1, and it was found to be a homopolymer consisting of the same eel-gae units as shown in Example 1.

(Example 5) Zinc chloride 0.286 was replaced with copper(I) chloride in Example 1.
Example 1 was carried out in the same manner as in Example 1, except that g (2.1 mmol) was used and the reaction time was 3 hours.

The weight of the obtained polymer was 51 g (yield: 96%), and the reduced viscosity [ηsp/cl] of this polymer was 1.58.
It was d sentences/g.

When the structure of this polymer was investigated in the same manner as in Example 1, it was found to be a homopolymer consisting of repeating units similar to those shown in Example 1.

(Example 6) Cobalt chloride (■
) 0.273 g (2.1 mmol) was used and the reaction time was 1.5 hours, but the same procedure as Example 1 was carried out.

The amount of the obtained polymer was 52 g (yield 98%), and the reduced viscosity [ηsp/c] of this polymer was 1.64 dl.
/g.

When the structure of this polymer was investigated in the same manner as in Example 1, it was found to be a homopolymer consisting of repeating units similar to those shown in Example 1.

(Example 7) Nickel chloride (II) was used instead of copper chloride (1) in Example 1.
) 0.27 g (2.1 mmol) was used and the reaction time was 1.5 hours, but the same procedure as Example 1 was carried out.

The amount of the obtained polymer was 52 g (yield 98%), and the reduced viscosity [ηsp/c] of this polymer was 1.67 db/g.

When the structure of this polymer was investigated in the same manner as in Example 1, it was found to be a homopolymer consisting of repeating units similar to those shown in Example 1.

[Effects of the Invention] According to the present invention, an aromatic ether ketone polymer having excellent properties such as excellent heat resistance and particularly a high glass transition temperature can be produced using manufacturing raw materials that are easy to obtain industrially. , an aromatic ether ketone polymer which can be easily produced under mild conditions and which is extremely advantageous in practical terms because it can increase the molecular weight of the aromatic ether ketone subpolymer in a short time when synthesizing the aromatic ether ketone subpolymer. We can provide a manufacturing method for

[Brief explanation of the drawing]

FIG. 1 is a chart showing the infrared absorption spectrum of the polymer obtained in Example 1. Patent applicant Idemitsu Kosan Co., Ltd.

Claims (1)

[Claims] (1) The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (However, X in the formula represents a halogen atom, and the two Xs may be the same or different. .) 4,4'-dihalobenzophenone and 4,4
'-dihydroxytetraphenylmethane, alkali metal compounds, and groups Ib, IIb and IIb of the periodic table.
1. A method for producing an aromatic ether ketone polymer, which comprises reacting a metal compound containing at least one element selected from the group consisting of elements belonging to Group VIII in a neutral polar solvent.