JP2003238662A - Method for producing polyarylene - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method in which a high molecular weight polyarylene having a weight average molecular weight of 30,000 or more that can exhibit sufficient mechanical properties can be produced with stability. <P>SOLUTION: The method for producing a polyarylene having a weight average molecular weight of 30,000 or more comprises undergoing a reaction while controlling the upper limit temperature of the reaction to 100°C or below in the coupling polymerization using an aromatic dihalide compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing polyarylene, and more particularly to a method for stably producing high molecular weight polyarylene.

[0002]

2. Description of the Related Art Aromatic polymers are used for various purposes because they have excellent heat resistance. Among them, polyarylene obtained by directly bonding aromatic rings to each other and polymerizing the polyarylene has excellent heat resistance and mechanical properties. It is attracting attention because it is used. As a method for producing polyarylene, a method is known in which an aromatic dihalide compound is polymerized by a reductive coupling reaction in the presence of a catalyst. However, in this polymerization method, a polymerization temperature around 50 ° C. is usually preferable,
There is a description that a temperature range of 25 to 100 ° C can be adopted (U
SP. 5403675). However, even if the polymerization reaction is controlled at 50 ° C, a high molecular weight product cannot be obtained. In order to obtain a high molecular weight compound, the reaction conditions should be controlled more precisely and the weight average molecular weight of the polyarylene should be 30 or less.
It was difficult to raise the temperature to 000 or more, and the mechanical properties were insufficient, and even a molded product could not be obtained in some cases.

[0003]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a method capable of stably producing a high molecular weight polyarylene having a weight average molecular weight of 30,000 or more and capable of exhibiting sufficient mechanical properties. To do.

[0004]

Means for Solving the Problems In the coupling polymerization using an aromatic dihalide compound, the present invention preferably controls the upper limit temperature of the reaction to 100 ° C. or lower, and preferably,
The present invention provides a method for producing a high molecular weight polyarylene, which comprises reacting so as to maintain a temperature range of 100 to 60 ° C. In the present invention, examples of the aromatic dihalide compound include compounds represented by the following general formulas (1) to (5).

General formula (1)

[Chemical 9] General formula (2)

[Chemical 10] General formula (3)

[Chemical 11] General formula (4)

[Chemical 12] General formula (5)

[Chemical 13] [In the above formula, R to R'may be the same or different from each other and represent a halogen atom excluding a fluorine atom, and R ^{1 to} R ¹⁵
And R ^{27 to} R ³⁰ may be the same or different and each represents at least one atom or group selected from the group consisting of hydrogen atom, fluorine atom, alkyl group, fluorine-substituted alkyl group, allyl group and aryl group. X represents a divalent electron-withdrawing group, Y represents a divalent electron-donating group, W represents a phenyl group, a naphthyl group and a group represented by the following general formulas (6) to (8). Represents at least one group selected from the group consisting of: n is 0 to 100, m is 0, 1
Or 2. General formula (6)

[Chemical 14] General formula (7)

[Chemical 15] General formula (8)

[Chemical 16] (In the formula, R ^{1 to} R ¹⁵ and R ^{27 to} R ³⁰ may be the same or different from each other and are selected from the group consisting of hydrogen atom, fluorine atom, alkyl group, fluorine-substituted alkyl group, allyl group and aryl group. And at least one atom or group, A represents an electron-withdrawing divalent group, and q represents 0 or 1.)]

Specific examples of the monomer represented by the above general formula (1) include 4,4'-bis (4-chlorobenzoyl) diphenyl ether, 4,4'-bis (4-chlorobenzoylamino) diphenyl ether, 4,4'-bis (4-chlorophenylsulfonyl) diphenyl ether, 4,4'-bis (4-chlorophenyl) diphenyl ether dicarboxylate, 4,4'-bis [(4-chlorophenyl) -1,1,1,3 , 3,3-Hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-chlorophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [( 4-
Chlorophenyl) tetrafluoroethyl] diphenyl ether, compounds in which chlorine atom is replaced by bromine atom or iodine atom in these compounds, compounds in which halogen atom substituted in 4-position of these compounds is substituted in 3-position, and further in these compounds Examples thereof include compounds in which at least one of the groups substituted at the 4-position of diphenyl ether is substituted at the 3-position.

Further, as the monomer represented by the general formula (1), 2,2-bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl] -1,1,1,3,3,
3-hexafluoropropane, bis [4- {4- (4-
Chlorobenzoyl) phenoxy} phenyl] sulfone,
And a compound represented by the following formula.

[0008]

[Chemical 17] Further, in the general formula (A), a monomer in which n is 2 or more
(A) is, for example, an electron-donating group B in the general formula (A).
Which is a combination of bisphenol, which is a source of etheric oxygen, which is an electron-withdrawing group A,> C═O, —SO ₂ —, and / or> C (CF ₃ ) ₂ ; 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-hydroxyphenyl) ketone, 2,2-bis (4-hydroxy) The substitution reaction of an alkali metal salt of bisphenol such as phenyl) sulfone with an excess amount of an active aromatic halogen compound such as 4,4-dichlorobenzophenone and bis (4-chlorophenyl) sulfone is performed as N-
Methyl-2-pyrrolidone, N, N-dimethylacetamide,
It can be obtained by sequentially polymerizing the above monomers in the presence of a polar solvent such as sulfolane. Examples of such a monomer (A) include compounds represented by the following formula.

[0009]

[Chemical 18]

[0010]

[Chemical 19]

[0011]

[Chemical 20] In the above, n is 2 or more, preferably 2 to 100.

Specific examples of the monomer represented by the above general formula (2) include compounds represented by the following formula.

[Chemical 21]

Specific examples of the monomer represented by the above general formula (3) include p-dichlorobenzene, p-dimethylsulfonoxybenzene, 2,5-dichlorotoluene and 2,5-dimethylsulfonyloxybenzene. 2,
5-dichloro-p-xylene, 2,5-dichlorobenzotrifluoride, 1,4-dichloro-2,3,5,6-tetrafluorobenzene, and in these compounds, chlorine atom is replaced with bromine atom or iodine atom And other compounds. Specific examples of the monomer represented by the general formula (4) include, for example, 4,4′-dimethylsulfonoxybiphenyl, 4,4′-dimethylsulfonoxy-3,3′-dipropenylbiphenyl, 4, 4'-dibromobiphenyl, 4,4'-diiodobiphenyl, 4,4 '
-Dimethylsulfonyloxy-3,3'-dimethylbiphenyl, 4,4'-dimethylsulfonyloxy-3,3'-difluorobiphenyl, 4,4'-dimethylsulfonyloxy-3,3'5,5 ' -Tetrafluorobiphenyl, 4,4 '
-Dibromooctafluorobiphenyl, 4,4'-dimethylsulfonyloxyoctafluorobiphenyl and the like. Specific examples of the monomer represented by the general formula (5) include m-dichlorobenzene, m-dimethylsulfonyloxybenzene, 2,4-dichlorotoluene, 3,5-dichlorotoluene and 2,6-dichloro. Toluene, 3,5-dimethylsulfonyloxytoluene, 2,6
-Dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 3,5-dichlorobenzotrifluoride, 1,3-dibromo-2,4,5,6-tetrafluorobenzene, and chlorine atom in these compounds Examples thereof include compounds in which is replaced with a bromine atom or an iodine atom.

The catalyst used in the production of polyarylene is a catalyst system containing a transition metal compound. The catalyst system includes a transition metal salt and a compound which becomes a ligand (hereinafter, referred to as "ligand component"). Or a transition metal complex (including a copper salt) in which a ligand is coordinated, and a reducing agent as essential components, and in order to further increase the polymerization rate,
"Salt" may be added. Here, as the transition metal salt, nickel compounds such as nickel chloride, nickel bromide, nickel iodide, and nickel acetylacetonate; palladium compounds such as palladium chloride, palladium bromide, palladium iodide; iron chloride, iron bromide Iron compounds such as iron iodide; cobalt compounds such as cobalt chloride, cobalt bromide and cobalt iodide. Of these, nickel chloride and nickel bromide are particularly preferable.
Further, as the ligand component, triphenylphosphine,
2,2'-bipyridine, 1,5-cyclooctadiene, 1,
3-bis (diphenylphosphino) propane etc. are mentioned. Of these, triphenylphosphine, 2,
2'-bipyridine is preferred. The compound that is the ligand component may be used alone or in combination of two or more.

Further, examples of the transition metal complex having a ligand coordinated include nickel chloride bis (triphenylphosphine), nickel bromide bis (triphenylphosphine), nickel iodide bis (triphenylphosphine), Nickel nitrate bis (triphenylphosphine),
Nickel chloride (2,2'-bipyridine), nickel bromide (2,2'-bipyridine), nickel iodide (2,2'-bipyridine), nickel nitrate (2,2'-bipyridine), bis (1, 5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium, etc. are mentioned. Of these, nickel chloride bis (triphenylphosphine) and nickel chloride (2,2′-bipyridine) are preferable. Examples of the reducing agent that can be used in the above catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium, calcium and the like. Of these, zinc, magnesium and manganese are preferable. These reducing agents can be further activated and used by bringing them into contact with an acid such as an organic acid.

As the "salt" which can be used in the above catalyst system, sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide and sodium sulfate, potassium fluoride, potassium chloride, odor, etc. Examples thereof include potassium compounds such as potassium iodide, potassium iodide and potassium sulfate; ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide and tetraethylammonium sulfate. Of these, sodium bromide, sodium iodide, potassium bromide, tetraethylammonium bromide and tetraethylammonium iodide are preferred.
The ratio of each component to be used is such that the transition metal salt or transition metal complex is usually 0.00 relative to 1 mol of the above-mentioned monomers in total.
The amount is 01 to 10 mol, preferably 0.01 to 0.5 mol. If it is less than 0.0001 mol, the polymerization reaction may not proceed sufficiently, while if it exceeds 10 mol, the molecular weight may decrease. When a transition metal salt and a ligand component are used in the catalyst system, the ratio of the ligand component used is usually 0.1 to 100 with respect to 1 mol of the transition metal salt.
The molar amount is preferably 1 to 10 mol. If it is less than 0.1 mol, the catalytic activity may be insufficient, while 10
If it exceeds 0 mol, the molecular weight may decrease. The ratio of the reducing agent used is usually 0.1 to 100 mol, preferably 1 to 10 mol, based on 1 mol of the total amount of the above monomers.
It is a mole. If it is less than 0.1 mol, polymerization may not proceed sufficiently, and if it exceeds 100 mol, purification of the resulting polymer may be difficult. Furthermore, when a "salt" is used, its use ratio is usually 0.001 to 100 mol, preferably 0.01 to 1 mol, based on 1 mol of the total of the above monomers. If it is less than 0.001 mol, the effect of increasing the polymerization rate may be insufficient,
If it exceeds the mol, it may be difficult to purify the resulting polymer.

Polymerization solvents that can be used in the present invention include, for example, tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone. And so on. Of these, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide,
N-methyl-2-pyrrolidone is preferred. It is preferable to use these polymerization solvents after drying them sufficiently. The total concentration of the above monomers in the polymerization solvent is usually
It is 1 to 90% by weight, preferably 5 to 40% by weight. In addition, the polymerization temperature at the time of polymerization is 100 ° C.
Below, it is preferably 60 to 90 ° C. The polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours. The upper limit temperature reached is the maximum temperature change of the temperature rise due to the heat of polymerization in the reactor during the polymerization process. Further, the time required to reach the upper limit temperature is preferably 10 minutes or more. According to the method of the present invention, a polyarylene having a polystyrene equivalent weight average molecular weight of 30,000 or more can be easily produced.

[0018]

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

Example 1 370.6 g (1080 mmo) of 2,5-dichloro-4′-phenoxybenzophenone was placed in a 3 L three-necked flask equipped with a stirring blade, a thermometer, a reflux condenser and a nitrogen inlet tube.
l), 4,4'-dichlorobenzophenone 30.1 g
(120 mmol), 4-chlorobenzophenone 0.7
8 g (3.6 mmol), bis (triphenylphosphine) nickel dichloride 23.6 g (36.0 mmo)
l), sodium iodide 23.4 g (156 mmo)
l), 125.9 g of triphenylphosphine (480 m
mol) and 188.3 g (2880 mmol) of zinc were taken, heated to 70 ° C. in an oil bath, and vacuum dried for 2 hours. After replacement with dry nitrogen, N-methylpyrrolidone 1500 m
L was added and the mixture was heated with stirring in an oil bath at 70 ° C. to start polymerization. The temperature of the reaction solution immediately after the start was 35 ° C.
After this, the reaction solution generated heat as the polymerization proceeded, and reached 15 ° C. and reached 70 ° C. I removed the oil bath here and stopped heating. Further, when the temperature reached 80 ° C. 19 minutes after the start, the flask was placed in an ice water bath to be cooled. This cooling was performed while adjusting the temperature so as to be in the range of 82 to 87 ° C. After 25 minutes, the heat generated by the polymerization subsided and the temperature did not rise. Here again, 80 ℃
The polymerization was continued while the flask was attached to the oil bath of No. 2 and heated. The viscosity of the solution increased at 40 minutes. After 3 hours, the polymerization solution was poured into 30 L of methanol containing 10 vol% concentrated hydrochloric acid. The precipitated polymer was taken out, dried and then dissolved in 9 L of tetrahydrofuran, and the insoluble portion was filtered. The obtained solution was reprecipitated in 30 L of methanol to obtain 303 g of a polymer (yield 96%). GPC of this polymer
The polystyrene reduced number average molecular weight (Mn) was 49,200 and the weight average molecular weight (Mw) was 141,000.
Met. The molecular weight distribution (Mw / Mn) was 2.87. The temperature change in the polymerization reactor during this polymerization experiment reaction is shown in FIG.

Example 2 In a 2 L three-necked flask equipped with a stirring blade, a thermometer, a reflux condenser, and a nitrogen inlet tube, 2,5-dichloro-4 '-(4
-Phenoxyphenoxy) benzophenone 130.0 g
(298 mmol), chlorobenzoylation at both ends [4,
4'-Dichlorobenzophenone-2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane] condensate (number average molecular weight 11500)
131.9 g (11.5 mmol), bis (triphenylphosphine) nickel dichloride 6.08 g (9.2
9 mmol), 6.04 g of sodium iodide (40.3
mmol), 32.5 g of triphenylphosphine (12
4 mmol) and 48.6 g (744 mmol) of zinc were taken, heated to 70 ° C. in an oil bath, and vacuum dried for 2 hours. After replacement with dry nitrogen, N-methylpyrrolidone 580 mL
Was added, and the mixture was heated with stirring in an oil bath at 80 ° C. to initiate polymerization. The temperature of the reaction liquid immediately after the start was 44 ° C. Thereafter, the reaction solution generated heat as the polymerization proceeded, and reached 75 ° C. 13 minutes later. I removed the oil bath here and stopped heating. Further, when the temperature reached 80 ° C. 17 minutes after the start, the flask was placed in an ice water bath to be cooled. This cooling was performed while adjusting the temperature so as to fall within the range of 77 to 83 ° C. After 50 minutes, the heat generated by the polymerization has subsided,
The temperature no longer rises. Here, again, the flask was attached to an oil bath at 80 ° C., and the polymerization was continued while heating. The viscosity of the solution increased at 70 minutes. After 3 hours, the polymerization solution was poured into 20 L of methanol containing 10 vol% concentrated hydrochloric acid. After taking out the precipitated polymer and drying it,
It was dissolved in 3 L of tetrahydrofuran and the insoluble portion was filtered.
The obtained solution was reprecipitated in 20 L of methanol to obtain a polymer 2
24 g (yield 93%) was obtained. The polystyrene-converted Mn of this polymer by GPC was 46,400 and Mw was 14
It was 0000. The molecular weight distribution (Mw / Mn) is 3.
It was 02. The temperature change in the polymerization reactor during this polymerization experiment reaction is shown in FIG.

Comparative Example 1 In the same manner as in Example 1, a monomer, a catalyst and a solvent were charged and polymerization was started. The temperature of the reaction solution immediately after starting is 40 ° C.
Met. After this, the reaction temperature increased as the polymerization proceeded. After 12 minutes, when the temperature reached 90 ° C, the oil bath was removed and heating was stopped. Thereafter, cooling with an ice-water bath was not performed, and stirring was continued at room temperature of 23 ° C. The reaction temperature rises sharply, 100 ° C. 13 minutes after the start and 1 ° C. at 16 minutes.
Reached 30 ° C. With this peak, the temperature gradually decreased to 100 ° C. in 35 minutes and 80 ° C. in 50 minutes.
Here, the flask was again attached to the oil bath at 80 ° C., and the polymerization was continued while heating. However, no remarkable increase in solution viscosity could be observed. After 3 hours, the polymer was isolated in the same manner as in Example 1. 286 g (yield 90%) of polymer were obtained. Mn of this polymer in terms of polystyrene by GPC
Was 6,700 and Mw was 12,000. Since the polymerization temperature became too high, the molecular weight decreased. The molecular weight distribution (Mw / Mn) was 1.79. The temperature change in the polymerization reactor during this polymerization experiment reaction is shown in FIG. Pore reached temperature: ° C (min)

Comparative Example 2 Monomers, a catalyst and a solvent were charged in the same manner as in Example 1 to initiate polymerization. The temperature of the reaction solution immediately after the start is 37 ° C
Met. After 15 minutes, when the reaction temperature reached 50 ° C, the oil bath was removed, and the polymerization was continued while being kept in a 20 ° C water bath. After this, the temperature rises very slowly,
After 57 minutes, reached 57 ° C. After that, the temperature began to drop, so that it was placed in an oil bath of 60 ° C. and the reaction temperature was maintained at 55 ° C. to continue the polymerization. The viscosity of the polymerization solution did not increase. After 3 hours, the polymer was isolated in the same manner as in Example 1. 283 g of polymer (yield 89%) was obtained. The Mn of this polymer was 5,400 and the Mw was 11,000. The molecular weight distribution (Mw / Mn) was 2.03. Since the polymerization temperature was set too low, the molecular weight decreased. The temperature change in the polymerization reactor during this polymerization experiment reaction is shown in FIG. Pore reached temperature: ° C (min)

Comparative Example 3 In the same manner as in Example 2, a monomer, a catalyst and a solvent were charged and polymerization was started. The temperature of the reaction solution immediately after starting is 47 ° C.
Met. After this, the reaction temperature increased as the polymerization proceeded. After 12 minutes, when the temperature reached 80 ° C, the oil bath was removed and heating was stopped. After that, stirring was continued without cooling with an ice water bath. The reaction temperature rises sharply, 16
The temperature reached 100 ° C. in minutes and 127 ° C. in 22 minutes. At this peak, the temperature dropped, reaching 100 ° C. for 40 minutes and 80 ° C. for 56 minutes. Here, the flask was again attached to the oil bath at 80 ° C., and the polymerization was continued while heating. After 3 hours, the polymer was isolated in the same manner as in Example 2. Polymer 207
g (yield 86%) was obtained. The polystyrene-converted Mn of this polymer measured by GPC was 11,100 and Mw was 28,
It was 100. Molecular weight distribution (Mw / Mn) is 2.53
Met. Since the polymerization temperature became too high, the molecular weight decreased. The temperature change in the polymerization reactor during this polymerization experiment reaction is shown in FIG. Pore reached temperature: ° C (min)

[0024]

According to the present invention, high molecular weight polyarylene can be stably produced.

[Brief description of drawings]

FIG. 1 is a graph showing a temperature change in a polymerization reaction liquid in Examples and Comparative Examples.

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Claims (3)

[Claims] 1. A method for producing a polyarylene having a polymerization average molecular weight of 30,000 or more, which is characterized in that, in the coupling polymerization using an aromatic dihalide compound, the upper limit temperature of the reaction is controlled to 100 ° C. or lower to carry out the reaction. 2. In a coupling polymerization using an aromatic dihalide compound, the upper limit temperature of the reaction is 60 ° C. to 1
A method for producing a polyarylene having a polymerization average molecular weight of 30,000 or more, which comprises controlling the reaction within a range of 00 ° C. 3. The aromatic dihalide compound has the following general formula:
At least 1 selected from the compounds represented by (1) to (5)
The method for producing a polyarylene according to claim 1 or 2, wherein General formula (1) General formula (2) General formula (3) General formula (4) General formula (5) [In the above formula, R to R'may be the same or different from each other and represent a halogen atom excluding a fluorine atom, and R ^{1 to} R ¹⁵
And R ^{27 to} R ³⁰ may be the same or different and each represents at least one atom or group selected from the group consisting of hydrogen atom, fluorine atom, alkyl group, fluorine-substituted alkyl group, allyl group and aryl group. X represents a divalent electron-withdrawing group, Y represents a divalent electron-donating group, W represents a phenyl group, a naphthyl group and a group represented by the following general formulas (6) to (8). Represents at least one group selected from the group consisting of: n is 0 to 100, m is 0, 1
Or 2. General formula (6) General formula (7) General formula (8) (In the formula, R ^{1 to} R ¹⁵ and R ^{27 to} R ³⁰ may be the same or different from each other and are selected from the group consisting of hydrogen atom, fluorine atom, alkyl group, fluorine-substituted alkyl group, allyl group and aryl group. And at least one atom or group, A represents an electron-withdrawing divalent group, and q represents 0 or 1.)]