JPH05163350A - Polyarylene sulfide sulfone and its production - Google Patents

Abstract

PURPOSE:To provide a new polyarylene sulfide sulfone polymer of excellent heat resistance. CONSTITUTION:A polyarylene sulfide sulfone of a melt viscosity of 0.20-0.60, obtained by reacting an aromatic dihalosulfone with a bisphenol fluorene, an alkali metal salt and a source of sulfur. An aromatic dihalosulfone is reacted with bisphenol fluorene in a molar ratio of 99/1-60/40 in the presence of an alkali metal hydroxide or an alkyl metal salt in an organic amide solvent and/or an organic sulfone solvent to form an oligomer containing halogen atoms at both ends. A least one source of sulfur selected from among an alkali metal sulfide, an alkali metal hydrosulfide and hydrogen sulfide is added to the reaction mixture and reacted with the oligomer at 175-235 deg.C for 1-20hr. Thus, a resin having a high glass transition temperature and excellent heat decomposition resistance can be obtained. This process is industrially advantageous in that a polymer having a high glass transition temperature which can be varied can be obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyarylene sulfide sulfone polymer and a process for producing the same.

[0002]

BACKGROUND OF THE INVENTION Sulfur-containing aromatic polymers such as polyether sulfones, polyarylene sulfide ketones,
Polyarylene sulfide sulfone, polyarylene sulfide, and the like have already been put to practical use in various fields because they have excellent mechanical properties at high temperatures and also have good chemical resistance and electrical properties.

[0003]

However, although the sulfur-containing aromatic polymer has the excellent performance as described above and the characteristics that it is easy to process,
In recent years, the number of fields of application requiring higher heat resistance is increasing, and therefore, the emergence of a polymer that retains the above excellent properties and has higher heat resistance is particularly desired from various fields.

The inventors of the present invention have conducted various investigations with the aim of obtaining a novel polyarylene sulfide sulfone polymer having excellent heat resistance and satisfying the above requirements. As a result, the bisphenol fluorene structure has a molecular structure. The present invention has been accomplished by finding that a polymer partially contained in a chain meets the above-mentioned object and further establishing a method for producing this polymer.

[0005]

That is, the polyarylene sulfide sulfone of the present invention is a polyarylene sulfide sulfone obtained by the reaction of aromatic dihalosulfone, bisphenolfluorene, an alkali metal salt and a sulfur source. And the composition ratio of bisphenolfluorene is 99/1 to 60 /
It is characterized by being 40 (mol / mol).

The method for producing a polyarylene sulfide sulfone according to the present invention is a method in which an aromatic dihalosulfone and bisphenolfluorene are mixed in an amide-based and / or sulfone-based organic solvent at a ratio of 99/1 to 60/40 (mol / mol). By reacting in the presence of an alkali metal hydroxide or an alkyl metal salt to form an oligomer that becomes a halogen at both ends, and then at least one selected from alkali metal sulfide, alkali metal hydrosulfide and hydrogen sulfide. Sulfur source is added and the temperature is 175 to 235 ° C.
It is characterized by reacting for 0 hours.

The polyarylene sulfide sulfone of the present invention has a bisphenolfluorene structure, that is, a 9,9-bis (4-hydroxyphenyl) fluorene structure in the molecular chain, and a polyarylene sulfide sulfone structure containing such a bisphenolfluorene structure. It has been revealed that the arylene sulfide sulfone has excellent heat resistance as compared with the corresponding polyarylene sulfide sulfone-based polymer containing no bisphenolfluorene structure.

Therefore, the polyarylene sulfide sulfone of the present invention maintains various physical properties such as mechanical properties and electrical properties up to a high temperature and has good dimensional stability. It has become possible to use it for other purposes.

Moreover, generally, a resin having excellent heat resistance is difficult to process, but the polyarylene sulfide sulfone of the present invention can be melt-molded, and a melt-molding method such as injection molding or extrusion molding is used. A molded product that requires high dimensional accuracy can be formed easily and easily.

The composition ratio of aromatic dihalosulfone, which is the main constituent of the polyarylene sulfide sulfone of the present invention, to bisphenolfluorene is 99/1 to 60/4.
Within the range of 0 (mol / mol), preferably 95/5
It is within the range of 70/30 (mol / mol). If the proportion of bisphenolfluorene is less than 1 mol%, the heat resistance improving effect of the obtained polymer will not be sufficiently exhibited, and 4
If it exceeds 0 mol%, the chemical resistance is impaired, which is not preferable.

The solution viscosity of the polyarylene sulfide sulfone of the present invention is in the range of 0.20 to 0.60,
It is preferably in the range of 0.25 to 0.50. If the solution viscosity is less than 0.20, the heat resistance of the resulting polymer will not be sufficiently exhibited, and if it exceeds 0.60, the melt moldability will be significantly deteriorated, which is not preferable.

The solution viscosity referred to in the present invention is 30 ° C.
Is a value measured by a viscometer using a solution prepared by dissolving 1 g of the polymer in 100 ml of N-methyl-2-pyrrolidone (hereinafter referred to as NMP).

The polyarylene sulfide sulfone of the present invention can be obtained by the production method described below.

That is, the polyarylene sulfide sulfone of the present invention containing a bisphenolfluorene structure in the polymer main chain can be prepared in a two-step process.

In the first step, bisphenol fluorene and a substantial excess of aromatic dihalosulfone are added in the presence of an alkali metal base, optionally in the presence of an alkali metal carboxylate, to an amide-based and / or sulfone-based organic solvent. By reacting in, a polyether sulfone oligomer essentially having halogens at both ends is obtained.

Then, in the second step, a sulfur source such as sodium sulfide is added to the reaction mixture and the polymerization reaction is continued to obtain a high molecular weight polyarylene sulfide sulfone having excellent heat resistance.

The bisphenol fluorene used in the method of the present invention acts as a dialkali metal salt in the actual reaction. Therefore, it is possible to separately produce and use a dialkali metal salt of bisphenolfluorene, or to proceed the reaction while forming a salt before or at the same time as the polymerization reaction.

Specific examples of the aromatic dihalosulfone compound used in the method of the present invention include bis (p-chlorophenyl) sulfone, bis (p-fluorophenyl) sulfone, bis (p-bromophenyl) sulfone and bis ( P-iodophenyl) sulfone, bis (2-methyl-)
4-chlorophenyl) sulfone, bis (2,5-dimethyl-4-chlorophenyl) sulfone, p-chlorophenyl p-bromophenyl sulfone, bis (3-isopropyl-4-iodophenyl) sulfone, bis (2,5-dipropyl-) 4-chlorophenyl) sulfone, bis (2-
Examples thereof include butyl-4-fluorophenyl) sulfone and bis (2,3,5,6-tetramethyl-4-chlorophenyl) sulfone. These can be used alone or as a mixture of two or more kinds. ..
Bis (p-chlorophenyl) sulfone can be mentioned as a particularly preferred aromatic dihalosulfone.

Specific examples of the alkali metal base used in the method of the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate and potassium carbonate. These can be used alone or as a mixture of two or more kinds. A particularly preferred alkali metal base is sodium carbonate.

Specific examples of the sulfur source used in the method of the present invention include alkali metal hydrosulfides such as sodium hydrosulfide and potassium hydrosulfide, alkali metal sulfides such as sodium sulfide and potassium sulfide, and hydrogen sulfide. These can be used alone or as a mixture of two or more kinds.

In the production method of the present invention, a specific alkali metal carboxylate can be added to the reaction system if necessary for the purpose of controlling the degree of polymerization of the produced polymer. , Lithium acetate, sodium acetate, potassium acetate, lithium propionate, sodium propionate, potassium benzoate, sodium benzoate and the like.
It can also be used as a mixture of more than one kind. A particularly preferred alkali metal carboxylate is sodium acetate.

Specific examples of the amide organic solvent and the sulfone organic solvent used in the method of the present invention include:
Formamide, acetamide, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-ethylpropionamide, N, N-
Dipropyl butyramide, 2-pyrrolidone, NMP, ε
-Caprolactam, dimethyl imidazolidinone, dimethyl benzamide, dimethyl sulfoxide, diethyl sulfoxide, sulfolane, diphenyl sulfone, dimethyl sulfone and diethyl sulfone, etc. can be mentioned, and these can be used alone or as a mixture of two or more kinds. .. NMP can be mentioned as an organic solvent particularly preferably used in the present invention.

As described above, the preferred production method for obtaining the polyarylene sulfide sulfone of the present invention is a two-step polymerization method comprising two steps. In this polymerization process, the composition ratio of the main constituent components is realized. There are several ways.

That is, the usual method is to add aromatic dihalosulfone and bisphenol fluorene according to a predetermined composition ratio at the time of adding the raw materials in the first step.
When the purpose is to highly polymerize the resulting polymer, the dihalo-terminated polyethersulfone oligomer formed in the initial stage of the first step is close to the aromatic dihalosulfone / bisphenolfluorene = 2/1 molar ratio. It is also possible to employ a method of reacting under the conditions, and then additionally adding necessary raw materials so as to obtain a polymer having a predetermined constitutional ratio. The molar ratio of alkali metal base / bisphenolfluorene can be appropriately selected, but it is usually within the range of 2/1 to 25/1, and preferably 10/1 to 20/1.

There is no particular restriction on the amount of the amide-based and / or sulfone-based organic solvent used, but it is usually in the range of 5 to 15 mol, preferably 6 per mol of the aromatic dihalosulfone. 10 to 10 mol. First
When the alkali metal carboxylate is added in the step, the amount of the alkali metal carboxylate added may be changed according to the purpose, but is usually within the range of 0.5 to 3 mol with respect to 1 mol of the aromatic dihalosulfone. And preferably in the range of 1 to 2 mol.

In the production method of the present invention, the amount of the sulfur source added in the second step is (difference between the number of moles of aromatic dihalosulfone and the number of moles of bisphenolfluorene) / the molar ratio of sulfur source is from 2/1 to It is in the range of 0.8 / 1, preferably 1.25 / 1 to 0.9 / 1, and most preferably 1.05 / 1 to 0.95 / 1.

In the second step, it is also necessary to control the amount of water present in the polymerization system, which amount is at least about 3.5 moles per mole of sulfur source, and 1 mole. A good polymer can be obtained by adding water in an amount of more than about 0.5 mol based on the amide-based and / or sulfone-based organic solvent.

Since water may be contained in the sulfur source and the alkali metal base in the form of a hydrate in some cases, it is necessary to consider their amounts.

When NMP is used as the solvent, it is desirable that the molar ratio of (total moles of water including water of hydrate) / (total moles of NMP) exceeds about 0.5, and preferably. Is in the range of 0.75 to 2.5, and more preferably in an amount of the range of 1 to 2.

In the first step of the production method of the present invention, the order of addition of the raw materials is not particularly limited, and aromatic dihalosulfone, bisphenolfluorene, alkali metal base, amide-based and / or sulfone-based organic solvent, and if necessary, The alkali metal carboxylates to be used may be mixed in any order.

Then, in the subsequent second step, the sulfur source, the alkali metal carboxylate, and, if necessary, the remaining alkali metal salt and solvent are added.

The reaction temperature of the first step is not particularly limited, but can be selected in the range of 150 to 250 ° C., preferably 165-225 ° C., and optimally 175-2.
It is within the range of 00 ° C.

Subsequently, the reaction temperature in the second step is usually 17
Within the range of 5 to 235 ° C., preferably 190 to 2
15 ° C, and optimally in the range 195-205 ° C.

When the reaction temperature is lower than the above temperature range, the desired reaction hardly progresses at a practically practical rate, and it is difficult to obtain a polymer having a required molecular weight. On the other hand, when the reaction temperature is higher than the above temperature range, side reactions other than the intended reaction cannot be ignored, and the resulting polymer is significantly colored.

The reaction time for each of the two-step process may vary depending on the reaction temperature, but it is usually within 24 hours, and preferably the conditions can be set within 8 hours.

In the method of the present invention, the reaction of the second step is allowed to proceed for a predetermined time, and then the reaction mixture is usually cooled,
The produced polymer may be recovered. Here, for the purpose of facilitating the recovery of the polymer, it is possible to add an appropriate amount of water, NMP or a mixture thereof to the reaction mixture after the heating is stopped.

The polyarylene sulfide sulfone produced by the method of the present invention can be prepared by a conventional method such as filtration,
It can be purified by subsequent washing.

In the present invention, the polymer recovered, if necessary, is treated with an aqueous solution of zinc acetate having a concentration of 0.1 to 5% to obtain 15
By performing the treatment at a temperature of 0 to 200 ° C. for 0.5 to 2 hours, a polyarylene sulfide sulfone having excellent melt stability can be obtained.

According to the above-mentioned method for producing a polyarylene sulfide sulfone of the present invention, the glass transition temperature of the obtained polymer can be controlled and changed to various temperatures at a high level, which is industrially advantageous.

The polyarylene sulfide sulfone obtained by the method of the present invention can be molded by a molding method such as compression molding, extrusion molding and injection molding similar to the usual thermoplastic resins.

Typical molding conditions of the polymer are shown in the case of extrusion and injection molding.
The temperature is 400 ° C., preferably 250 to 380 ° C.

In molding, it is possible to further lower the molding temperature from the above range by adding a plasticizer, a stabilizer and the like. There is no restriction on the size and shape of the molded product, and besides the normal molded product, a film, a sheet-shaped product, a component having a precision fine structure, and the like can be easily molded by a general molding method.

In the polyarylene sulfide sulfone of the present invention, if necessary, a fibrous and / or granular reinforcing material is added in an amount of not more than 200 parts by weight, usually 10 to 150 parts by weight, per 100 parts by weight of the polymer. It is possible to improve the properties such as strength, rigidity, heat resistance and dimensional stability.

As the fiber reinforcing material, glass fiber,
Alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, metal fibers, carbon fibers and the like can be mentioned.

As the granular reinforcing material, silicates such as wollastonite, sericite, kaolin, mica, clay, bentonite, talc and alumina silicate, metals such as alumina, silicon chloride, magnesium oxide, zirconium oxide and titanium oxide are used. Examples thereof include oxides, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, boron nitride, silicon carbide and silica, which may be hollow.

Two or more kinds of these reinforcing materials can be used in combination, and if necessary, they can be used after being pretreated with a coupling agent such as a silane-based or titanium-based coupling agent.

Further, the polyarylene sulfide sulfone of the present invention contains the usual additives such as antioxidants, heat stabilizers, lubricants, UV inhibitors, colorants, flame retardants, etc. within a range that does not impair the effects of the present invention. And small amounts of other polymers can be added.

Further, the polyarylene sulfide sulfones of the present invention can be cured by crosslinking and / or chain extension to give a cured product having high thermal stability and good chemical resistance.

Molded articles obtained from the polyarylene sulfide sulfone of the present invention are various parts in the electrical and electronic fields, housings, automobile parts, interior materials for aircraft, sliding parts, gears, insulating materials, dental materials and It can be used in a wide range of fields such as steam sterilization containers.

The present invention will be described in more detail below with reference to Examples and Comparative Examples.

[0051]

【Example】

Example 1 A 1-liter stainless steel autoclave was charged with screws (4
-Chlorophenyl) sulfone 143.59 g (0.5 mol), sodium carbonate 53.0 g (0.5 mol), NM
P198.26 g (2.0 mol) and 9,9-bis (4-hydroxyphenyl) fluorene 10.51 g
(0.03 mol) was charged and the reaction system was replaced with nitrogen.
The temperature was raised to 200 ° C. with stirring at 400 rpm, and the reaction was carried out for 3 hours.

Then, the autoclave was cooled to 40 to 60 ° C., and then the reaction product of the second step, that is, 41.02 g (0.5 mol) of sodium acetate and 2 parts of sodium hydrosulfide were added.
6.35 g (0.47 mol), NMP 198.26 g
(2.0 mol) and 81.0 g (4.5 mol) of water were charged, the temperature of the autoclave was gradually heated to 200 ° C., and the reaction was carried out for 3 hours.

Then, after completion of the reaction, the autoclave was cooled to room temperature, and the slurry-like reaction mixture was filtered off.

Then, the recovered solid product was washed with hot ion-exchanged water three times and dried at 140 ° C. under vacuum to obtain 130.2 g of a white polymer.

The solution viscosity of this polymer was 0.38.

Further, the peak of the infrared absorption spectrum obtained by performing infrared analysis is IR (KBr, c
m ^-1 ): 3080, 1580, 1510, 1480,
1390, 1320, 1280, 1250, 1160,
1110, 1080, 1020, 830, 760, and the relationship between the position of the peak and the bond is shown below.

1250 cm ^-1 : -O-stretching vibration Example 2 9,9-bis (4-hydroxyphenyl) fluorene 1
7.52 g (0.05 mol) and sodium hydrosulfide 2
The reaction and post-treatment were carried out in the same manner as in Example 1 except that 5.23 g (0.45 mol) was used.
5.6 g was obtained.

The solution viscosity of this polymer was 0.34.

Example 3 A 1-liter stainless steel autoclave was charged with screws (4
-Chlorophenyl) sulfone 143.59 g (0.5 mol), 50% by weight aqueous sodium hydroxide solution 17.6 g
(0.22 mol), NMP 198.26 g (2.0 mol) and 9,9-bis (4-hydroxyphenyl) fluorene 35.04 g (0.1 mol) were charged, and the reaction system was replaced with nitrogen. The temperature was raised to 200 ° C. with stirring at 400 rpm, and the reaction was carried out for 3 hours.

Then, after cooling the autoclave to 40 to 60 ° C., the reaction product in the second step, that is, 16.0 g (0.4 mol) of sodium hydroxide and 2.
12 g (0.02 mol), sodium acetate 41.02 g
(0.4 mol), sodium hydrosulfide 23.54 g (0.
42 mol), 198.26 g (2.0 mol) of NMP and 81.0 g (4.5 mol) of water were charged, and the temperature of the autoclave was gradually heated to 200 ° C. and reacted for 4 hours.

Then, after completion of the reaction, the autoclave was cooled to room temperature, and the slurry-like reaction mixture was filtered off.

Then, the recovered solid product was washed with hot ion-exchanged water 3 times and dried at 140 ° C. under vacuum to obtain 148.0 g of a white polymer.

The solution viscosity of this polymer was 0.33.

Comparative Example 1 11.41 g (0.05 mol) of bisphenol A (2,2-bis (4-hydroxyphenyl) propane) was used instead of 9,9-bis (4-hydroxyphenyl) fluorene. Was subjected to the reaction and post-treatment in the same manner as in Example 2 to obtain 129.6 g of a white polymer.

The solution viscosity of this polymer was 0.31.

Comparative Example 2 Example 2 was repeated except that 12.51 g (0.05 mol) of bisphenol sulfur (bis (4-hydroxyphenyl) sulfone) was used instead of 9,9-bis (4-hydroxyphenyl) fluorene. Reaction and post-treatment were carried out in the same manner as in, to obtain 128.2 g of a white polymer.

The solution viscosity of this polymer was 0.22.

Comparative Example 3 A 1-liter stainless steel autoclave was charged with screws (4
-Chlorophenyl) sulfone 143.59 g (0.5 mol), sodium carbonate 53.0 g (0.5 mol) sodium acetate 41.02 g (0.5 mol), NMP396.
5 g (4.0 mol), 81.0 g (4.5 mol) of water and 28.03 g (0.5 mol) of sodium hydrosulfide were charged, and the reaction system was replaced with nitrogen.

The temperature was increased to 200 while stirring at 400 rpm.
The mixture was gradually heated to ℃ and reacted for 3 hours.

After completion of the reaction, the autoclave was cooled to room temperature and the slurry-like reaction mixture was filtered off.

Then, the recovered solid product was washed with hot ion-exchanged water three times and dried at 140 ° C. under vacuum to obtain 121.7 g of a white polymer.

The solution viscosity of this polymer was 0.36.

Examples 4, 5 and 6 Using the polyarylene sulfide sulfone polymers obtained in Examples 1, 2 and 3, respectively, temperature: 300 ° C., pressure: 50 Kgf / cm ² , time: 5 minutes press A press sheet having a thickness of 0.3 to 0.4 mm was created under the conditions. Table 1 shows the properties of the obtained sheet.

Table 1 also shows the results of measuring the glass transition temperature (Tg) of the obtained sheet by the differential scanning calorimetry method.

Table 1 Polymers used Properties of press sheet Glass transition temperature Example 4 Example 1 Transparent toughness 213 ° C. Example 5 Example 2 Transparent toughness 219 ° C. Example 6 Example 3 Transparent toughness 225 ° C. Comparative example 4 5, 6 Each of the polymers obtained in Comparative Examples 1, 2, and 3 was used, with a temperature of 300 ° C., a pressure of 50 Kgf / cm ² , and a pressing condition of 5 minutes, and a thickness of 0.3 to 0. A 4 mm press sheet was prepared. Table 2 shows the properties of the obtained sheet.

Table 2 also shows the results of measuring the glass transition temperature (Tg) of the obtained sheet by the differential scanning calorimetry method.

Table 2 Polymers used Properties of press sheet Glass transition temperature Comparative example 4 Comparative example 1 Transparent brittleness 208 ° C. Comparative example 5 Comparative example 2 Foaming 196 ° C. Comparative example 6 Comparative example 3 Transparent brittleness 209 ° C.

[0078]

As described in detail above, the polyarylene sulfide sulfone of the present invention is a resin having a particularly high glass transition temperature and excellent thermal decomposition resistance.

Further, the polyarylene sulfide sulfone of the present invention is a polymer which is usually amorphous, has excellent moldability such as transparency, toughness and melt moldability, and is also excellent in flame retardancy.

Therefore, the polyarylene sulfide sulfone of the present invention can be suitably used in a wide range of fields such as parts of various machines and appliances as well as parts of electric and electronic fields, and is a very industrially useful material. Is.

Further, according to the method for producing a polyarylene sulfide sulfone of the present invention, the glass transition temperature of the obtained polymer can be controlled and changed to various temperatures at a high level, which is industrially advantageous.

Claims (3)

[Claims] 1. A polyarylene sulfide sulfone obtained by the reaction of aromatic dihalosulfone, bisphenolfluorene, an alkali metal salt and a sulfur source,
Polyarylene sulfide, wherein the composition ratio of the aromatic dihalosulfone and the bisphenolfluorene is 99/1 to 60/40 (mol / mol), and the solution viscosity is in the range of 0.20 to 0.60. Sulfone. 2. The polyarylene sulfide sulfone according to claim 1, wherein the composition ratio of aromatic dihalosulfone and bisphenolfluorene is 95/5 to 70/30 (mol / mol). 3. An amide-based and / or sulfone-based organic solvent containing an aromatic dihalosulfone and bisphenolfluorene in a ratio of 99/1 to 60/40 (mol / mol), of an alkali metal hydroxide or an alkyl metal salt. By reacting in the presence of an oligomer to form halogens at both ends, then at least one sulfur source selected from alkali metal sulfides, alkali metal hydrosulfides and hydrogen sulfide is added, and the temperature is from 175 to 235 ° C. 1 to 20
The method for producing a polyarylene sulfide sulfone according to claim 1 or 2, wherein the reaction is carried out for a time.