JPH05310941A - Formed article composed of aromatic polyether sulfone copolymer - Google Patents

Abstract

PURPOSE:To obtain the subject formed article having a heat-distortion temperature falling within a specific range and excellent heat-resistance and mechanical strength and useful for mechanical parts, electrical and electronic parts, etc., by melt-forming a specific polyether sulfone copolymer. CONSTITUTION:The objective formed article having a heat-distortion temperature(HDT) of 175-235 deg.C is produced by the melt-forming of an aromatic polyether sulfone copolymer having a weight-average molecular weight of 10,000-500,000 and composed of (A) 25-75wt.% of a recurring unit of formula I (R is 1-6C alkyl or 6-8C aryl; (m) is 0-3) having a phenolphthalein structure and (B) 75-25wt.% of a recurring unit of formula II having a bisphenol A structure.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aromatic polyether sulfone copolymer having a phenolphthalein structure. More specifically, the present invention relates to a melt-formed product of a polyethersulfone resin which has excellent mechanical strength and heat resistance and is suitable for a wide range of industrial applications such as mechanical parts, electric / electronic parts and automobile parts.

[0002]

2. Description of the Related Art Aromatic polyether sulfones obtained by polycondensing bisphenol A with an aromatic dihalosulfone compound in the presence of a basic catalyst and a method for producing the same are described, for example, in JP-B-42-7799 and JP-B-45-21318.
It is publicly known such as in British Patent 1708234.

Aromatic polyether sulfones obtained by polycondensing phenolphthalein with an aromatic dihalosulfone compound in the presence of a basic catalyst and a method for producing the same are described in, for example, Chinese Patent CN85-101721 (Che).
m. Abstr. , 107 (22): 199181).

[0004]

The aromatic polyether sulfone obtained by polycondensation of bisphenol A and bis (p-chlorophenyl) sulfone, which is known in the above-mentioned literature, has a low glass transition point of 190 ° C. and is a heat-resistant material. As a result, I am not satisfied. On the other hand, the glass transition point of aromatic polyether sulfone obtained by polycondensation of phenolphthalein and bis (p-chlorophenyl) sulfone is 258.
It has a high temperature as high as 0 ° C and is satisfactory in heat resistance, but has extremely low toughness and is not satisfactory as a molding material. Further, it is known that the sulfone-based polymer is decomposed at a high temperature, especially around 400 ° C. to generate a slight amount of sulfurous acid gas to damage the molding machine and the mold. The above-mentioned two kinds of aromatic polyether sulfones are no exception and have a problem that sulfurous acid gas is generated at a high temperature. Therefore, as a result of diligent studies to obtain a molding material having excellent heat resistance and toughness and a small amount of sulfurous acid gas generated at the time of high temperature molding, the present inventors have conducted polycondensation of phenolphthalein and bisphenol A with an aromatic dihalosulfone compound. It was found that the copolymer obtained as a result shows extremely excellent heat resistance and toughness, and that a copolymer having a ratio of phenolphthalein structure within a certain range produces a small amount of sulfurous acid gas. The invention was completed.

[0005]

That is, the present invention provides 25 to 75% by weight of a repeating unit having a phenolphthalein structure substantially represented by the general formula I, and a general formula
A repeating unit having a bisphenol A structure represented by II consisting of 75 to 25% by weight and having a weight average molecular weight of 100.
A molded article made of an aromatic polyethersulfone copolymer having a heat distortion temperature (HDT) of 175 to 235 ° C., which is obtained by melt-molding an aromatic polyethersulfone copolymer having an amount of 00 to 500,000.

[0006]

[Chemical 3]

[Chemical 4] (However, R in the formula represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms, and m represents an integer of 0 to 3.) Aromatic polyether used in the present invention The sulfone copolymer contains phenolphthalein and a bisphenol A structure in its molecular chain, and such an aromatic polyether sulfone resin containing a phenolphthalein and a bisphenol A structure has excellent heat resistance. It became clear. Therefore, the resin molded article of the present invention has various physical properties such as mechanical properties and electrical properties, which are maintained at high temperatures.
In addition, since it has good dimensional stability, it can be used in many applications that were difficult to use in the past. Moreover, although such a resin having excellent heat resistance is generally difficult to process, the aromatic polyether sulfone resin used in the present invention can be melt-molded and is usually molded by injection molding or extrusion molding. It is possible to easily and efficiently manufacture a molded product required to have high dimensional accuracy by using the melt molding processing method. Furthermore, since the aromatic polyether sulfone copolymer used in the present invention does not decompose at high temperature and generates a small amount of sulfurous acid gas, continuous melt molding for a long time without damaging an extruder, a molding machine cylinder, a mold or the like. Became possible.

The aromatic polyether sulfone copolymer used in the present invention is produced by polycondensation of phenolphthalein, bisphenol A and an aromatic dihalosulfone compound.

The bisphenol compound used in the present invention is substantially phenolphthalein and bisphenol A.
And acts as a dialkali metal salt in the actual reaction. Therefore, it is possible to separately produce and use a dialkali metal salt of phenolphthalein and bisphenol A, or to proceed the reaction while forming a salt before or at the same time as the polymerization reaction. If the copolymer of the present invention does not impair the mechanical properties and heat resistance of the bisphenol compound, the bisphenol compound may be used up to about 1% by weight.
4'-biphenol, 4,4'-dihydroxydiphenyl sulfone, 1,1-bis (4-hydroxyphenyl)
It may be substituted with cyclohexane, bis (4-hydroxyphenyl) methane, hexafluoroisopropylidenediphenol, or the like.

The constitutional ratio of the repeating unit represented by the general formula I (the structural unit derived from phenolphthalein and the aromatic dihalosulfone compound), which is a constitutional component of the aromatic polyether sulfone copolymer of the present invention, ranges from 25 to 25. It is in the range of 75% by weight, preferably in the range of 30 to 70% by weight. In addition, the other constituent component of the general formula II
The constitutional ratio of the repeating unit represented by (a structural unit derived from bisphenol A and an aromatic dihalosulfone compound) is in the range of 75 to 25% by weight, preferably 7
It is in the range of 0 to 30% by weight. If the proportion of the structural unit derived from phenolphthalein and the aromatic dihalosulfone compound is less than 25% by weight, the heat resistance improving effect of the resulting polymer is not sufficiently exhibited, which is not preferable. When the proportion of the structural unit derived from the dihalosulfone compound exceeds 75% by weight, the heat resistance is satisfactory but the toughness decreases, which is not preferable.

The aromatic dihalosulfone compound used in the method for producing the aromatic polyether sulfone copolymer of the present invention is represented by the general formula III, and specific examples include bis (p-chlorophenyl) sulfone, Screw (p
-Fluorophenyl) sulfone, bis (2-methyl-4)
-Chlorophenyl) sulfone, bis (2,5-dimethyl-4-chlorophenyl) sulfone, bis (2,5-dipropyl-4-chlorophenyl) sulfone, bis (2-butyl-4-fluorophenyl) sulfone, bis (2,2
3,5,6-Tetramethyl-4-chlorophenyl) sulfone and the like can be mentioned, and these can be used alone or as a mixture of two or more kinds. A particularly preferred aromatic dihalosulfone compound is bis (p-
Examples thereof include chlorophenyl) sulfone and bis (p-fluorophenyl) sulfone. Further, within a range not impairing the mechanical properties and heat resistance of the copolymer of the present invention, up to about 1% by weight of the aromatic dihalosulfone compound used is 2,4′-dichlorodiphenylsulfone or 2,4 ′.
-Substitution with difluorobenzophenone is acceptable.

[0011]

[Chemical 5] (However, X in the formula represents fluorine or chlorine, and R
Represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms, and m represents an integer of 0 to 3. ) The amount of the aromatic dihalosulfone compound suitable for the production of the aromatic polyether sulfone copolymer used in the present invention is such that the aromatic dihalosulfone is 0.1 mol per 1 mol of the bisphenol compound (phenolphthalein + bisphenol A). 95-1.1 mol, preferably 0.98-1.0
It is used in an amount of 5 mol, more preferably 1 to 1.02 mol. If the amount is less than 0.95 mol or more than 1.1 mol, the equivalence to the bisphenol compound cannot be maintained and it becomes difficult to obtain the target polymer having a high molecular weight, which is not suitable.

Specific examples of the alkali metal or alkaline earth metal base used in the polycondensation of the aromatic polyether sulfone copolymer include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and water. Cesium oxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium carbonate,
Sodium carbonate, potassium carbonate, sodium hydrogen carbonate,
Examples thereof include potassium hydrogen carbonate, and these can be used alone or as a mixture of two or more kinds. Preferred bases are sodium carbonate, potassium carbonate,
Sodium hydroxide and potassium hydroxide. The alkali metal or alkaline earth metal base used in the present invention may be used as a solid or as an aqueous solution. When an aqueous solution is used, the dehydration step with an azeotropic solvent may be performed sufficiently.

The amount of the base used for producing the aromatic polyether sulfone copolymer is 0.8 to 5 equivalents, preferably 1 to 3 equivalents, and more preferably 1 to 1 equivalent to the bisphenol compound used. It is used in the range of 5 equivalents. When the amount of the base used is less than 0.8 equivalent, a high degree of polymerization cannot be obtained, and when the amount of the base used is more than 5 equivalents, side reactions other than the intended polymerization reaction are ignored. It is not preferable because it is impossible to do so and the resulting polymer is significantly colored.

Specific examples of the aprotic polar solvent used in the production of the aromatic polyether sulfone copolymer include formamide, acetamide, N-methylformamide, N, N-dimethylformamide, N, N-. Dimethylacetamide, N-ethylpropionamide,
N, N-dipropylbutyramide, 2-pyrrolidone, N
-Methyl-2-pyrrolidone, ε-caprolactam, 1,
Examples thereof include 3-dimethyl-2-imidazolidinone, dimethylbenzamide, dimethyl sulfoxide, diethyl sulfoxide, sulfolane, diphenyl sulfone, dimethyl sulfone and diethyl sulfone. These may be used alone or as a mixture of two or more kinds. You can Solvents that are preferably used in the present invention are amide solvents, especially N-methyl-2-pyrrolidone (NM
P), N, N-dimethylformamide (DMF), N,
N-dimethylacetamide (DMAc) and 1,3-dimethyl-2-imidazolidinone are preferable.

The amount of the aprotic polar solvent suitable for producing the aromatic polyether sulfone copolymer is from 0.05 to 0.05 based on the weight of the bisphenol compound used.
It is usually used in the range of 20 times. More preferably,
The amount is in the range of 0.1 to 10 times, and the amount used varies depending on the type of solvent and other reaction conditions. When the amount is less than 0.05 times, the effect as a solvent is not recognized, and even if the produced polymer has a low molecular weight, it precipitates, so that a practical high molecular weight polymer is obtained. I will not be able to. On the other hand, when the amount of the solvent is more than 20 times, the monomer concentration decreases, so that only a mixture of low molecular weight oligomers and, in some cases, cyclic oligomers can be obtained.

Specific examples of the azeotropic solvent used in producing the aromatic polyether sulfone copolymer include benzene,
Examples thereof include aromatic hydrocarbons such as toluene and xylene, and aromatic halogen compounds such as chlorobenzene and dichlorobenzene. These can be used alone or as a mixture of two or more kinds, and are appropriately selected depending on reaction conditions. Just select it. In particular, toluene having a low boiling point is preferable because the energy cost at the time of recovery is low.

The amount of the azeotropic solvent suitable for producing the aromatic polyether sulfone copolymer can be determined from the amount of water present in the reaction system and the azeotropic composition. In dehydration using an azeotropic solvent, water is distilled out together with the azeotropic solvent, the distillate is cooled and concentrated, and the water and the azeotropic solvent are separated into two layers. If the separated azeotropic solvent layer is refluxed in the reaction system, the azeotropic solvent is effectively used, so that the dehydration can be completed without using a large excess of the azeotropic solvent.

In the production of the aromatic polyether sulfone copolymer, the order of adding the raw materials is not particularly limited, and any one of phenolphthalein, bisphenol A, aromatic dihalosulfone compound, base, aprotic solvent and azeotropic solvent may be used. May be mixed in this order, and the aromatic dihalosulfone compound may be added after completion of the dehydration reaction.

The initial dehydration reaction temperature varies depending on the kind and amount of the azeotropic solvent used, but is usually 100 to 250.
It is appropriate to select the range of ℃, preferably 120
Within the range of 180 ° C. The subsequent polymerization reaction temperature is also not particularly limited because it changes depending on the type and amount of the aprotic solvent used, but is usually within the range of 30 to 300 ° C., and NMP is typically used as the aprotic polar solvent. In a specific embodiment, preferably 100 to 200
C, and optimally in the range 160-200C.
When the reaction temperature is lower than 30 ° C., the intended reaction hardly proceeds at a rate practically practical, and it is difficult to obtain a polymer having a required molecular weight. On the other hand, the reaction temperature is 300
When the temperature is higher than 0 ° C, side reactions other than the intended reaction cannot be ignored, and the resulting polymer becomes significantly colored. Usually, the reaction is carried out at normal pressure, but if distillation of the solvent poses a problem, the reaction may be carried out under pressure.

The time required for the azeotropic dehydration of the present invention varies depending on the amount of water present in the reaction system, the amount of the azeotropic solvent used, and the like, but from the practical viewpoint, it is preferably within 10 hours, and further 5 More preferably, it is completed within the time. Furthermore, the time required for the polymerization reaction may vary depending on the reaction temperature, but it is usually within 24 hours, and preferably the conditions can be set within 8 hours.

When the polymerization rate is extremely high and it is difficult to control the degree of polymerization, one of the monomers is used in excess, or a monofunctional compound such as 4-fluorobenzophenone or 4-chlorophenylphenyl sulfone is used. The reaction may be carried out by adding it as a molecular weight modifier.

The reaction atmosphere for carrying out the reaction in the production of the aromatic polyether sulfone copolymer is preferably oxygen-free, and good results can be obtained by carrying out the reaction in nitrogen or other inert gas. The metal salt of phenolphthalein is easily oxidized when heated in the presence of oxygen, which hinders the intended polymerization reaction, makes it difficult to increase the molecular weight, and causes coloring of the polymer.

After the polymerization for a predetermined time, the reaction mixture is cooled to stop the polymerization reaction. At this time, the viscosity of the reaction product becomes high and the reaction product may solidify depending on the type of the reaction solvent. Therefore, it may be effective to dilute the reaction product with an inert solvent before or during cooling.

The aromatic polyether sulfone copolymer is
It can be purified by a conventional method, for example, filtration and subsequent washing.

The aromatic polyether sulfone copolymer used in the present invention has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using N-methylpyrrolidone as a solvent and polystyrene as a standard substance. ) Is 10,000 to 500,000, preferably 15,000 to 350,000, and more preferably 200.
It is in the range of 00 to 300,000. This M
When w is less than 10000, the mechanical strength of the polymer is lowered or the heat resistance becomes insufficient, which is not preferable. When Mw is larger than 500000,
It is not suitable because the moldability is significantly reduced.

The molded article of the present invention can be produced by melt molding, and ordinary injection molding, extrusion molding, press molding, blow molding, compression molding, transfer molding and the like can be used.

When a molded article is produced using an aromatic polyether sulfone copolymer, a fibrous and / or granular reinforcing material is added, if necessary, to 200 parts by weight per 100 parts by weight of the aromatic polyether sulfone copolymer. It is possible to add it in a range not exceeding the weight part, and it is possible to improve strength, rigidity, heat resistance, dimensional stability and the like by usually adding in the range of 10 to 150 parts by weight.

Examples of the fibrous reinforcing material include glass fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber and carbon fiber.

Further, 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. 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 aromatic polyether sulfone copolymer of the present invention is added with usual additives such as an antioxidant, a heat stabilizer, a lubricant, an anti-UV agent, a colorant, a flame retardant and a small amount of another kind of polymer. Can be used.

[0031]

EXAMPLES The present invention will be described in detail with reference to the following examples and comparative examples, but the present invention is not limited thereto.

The weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC),
The measurement was performed using N-methylpyrrolidone as a solvent and polystyrene as a standard substance. Glass transition temperature (Tg)
Is the median of the inflection points observed when the temperature is raised at a rate of 20 ° C./min using a DSC (differential scanning calorimeter).

Test pieces for measuring various mechanical properties were measured with an injection molding machine at a cylinder temperature of 300 to 400 ° C.
Melt molding was performed at a mold temperature of 80 to 200 ° C. Tensile properties, bending properties, Izod impact value (with notch), heat distortion temperature (HDT) are ASTM D-638 and D-79, respectively.
0, D-256, D-648.

Regarding the amount of sulfurous acid gas generated at a high temperature, a part (3 g) of the molded product was cut out and heated in a test tube at 450 ° C. for 1 hour, and then the generated gas was tetrachloromercury (II).
It was absorbed in an acid salt solution and quantified by an absorptiometric method in which this was developed with pararose aniline and formalin (New Experimental Chemistry Course, Volume 9, Analytical Chemistry [I], 218-9p, edited by The Chemical Society of Japan, Maruzen). .. The results are shown as the amount of sulfurous acid gas (ppm) generated per 1 g of the molded product.

Example 1 30 L internal volume equipped with a Dean Stark trap filled with toluene, a stirrer and an argon gas blowing tube
0.955 kg of phenolphthalein in the reaction vessel of
(3.00 mol), bisphenol A 1.598 kg
(7.00 mol), 2.900 kg (10.10 mol) of bis (p-chlorophenyl) sulfone, 1.589 kg (11.50 mol) of potassium carbonate and 10 L of N-methylpyrrolidone were added, and these raw materials were mixed at room temperature. In, the mixture was stirred while flowing argon gas to obtain an N-methylpyrrolidone solution.

The reaction vessel was placed in an oil bath and heated to 180 ° C., 1.5 L of toluene was added and refluxed for 1 hour. After removing toluene, the temperature was raised to 200 ° C. and stirred for 3 hours. After cooling, the reaction mixture was poured into a large amount of methanol acidified with dilute hydrochloric acid to precipitate a polymer, which was washed 3 times with hot water and dried at 100 ° C. under reduced pressure to give a polymer 4.58.
0 kg was obtained.

When the infrared spectrum of the obtained polymer was measured, the stretching vibration of the methyl group at 2950 cm ^-1 was 1.
At 780 cm ⁻¹ , characteristic absorption due to C═O stretching vibration of the lactone ring portion of phenolphthalein was observed at 1250 cm ^{−1 due} to —O— stretching vibration.

Furthermore, the weight average molecular weight Mw = 13600
0, Tg = 218 ° C. Table 1 shows the results of measurement of mechanical properties by melt injection molding this polymer to prepare various test pieces. Table 1 also shows the amount of sulfurous acid gas generated at 450 ° C.

Example 2 1.592 kg (5.00 mol) of phenolphthalein
The reaction and post-treatment were carried out in the same manner as in Example 1 except that 1.141 kg (5.00 mol) of bisphenol A was used to obtain 4.740 kg of a polymer. The characteristic absorption in the infrared spectrum of the obtained polymer is almost the same as that of the polymer obtained in Example 1, and Mw = 13400.
0, Tg = 229 ° C. Table 1 shows the mechanical properties and the amount of sulfurous acid gas generated at 450 ° C.

Example 3 2.228 kg (7.00 mol) of phenolphthalein
Then, the reaction and post-treatment were carried out in the same manner as in Example 1 except that 0.685 kg (3.00 mol) of bisphenol A was used to obtain 4.920 kg of a polymer. The infrared spectrum absorption of the obtained polymer is almost the same as that of the polymer obtained in Example 1, Mw = 135000, Tg = 2.
It was 40 ° C. Table 1 shows the mechanical properties and the amount of sulfurous acid gas generated at 450 ° C.

Example 4 Instead of bis (p-chlorophenyl) sulfone, 2.568 kg (1 of bis (p-fluorophenyl) sulfone
0.10 mol) and 1.219 kg (11.50 mol) of sodium carbonate instead of potassium carbonate were used, the reaction and post-treatment were carried out in the same manner as in Example 1 to obtain polymer 4.
520 kg was obtained. The infrared spectrum absorption of the polymer obtained is the same as that of the polymer obtained in Example 1, and M
It was w = 140,000 and Tg = 218 ° C. Table 1 shows the mechanical properties and the amount of sulfurous acid gas generated at 450 ° C.

Example 5 1.616 kg (20.20 mol) of a 50% aqueous solution of sodium hydroxide was used instead of potassium carbonate, and dimethyl sulfoxide (DMSO) 8 was used instead of N-methylpyrrolidone.
The reaction and post-treatment were carried out in the same manner as in Example 1 except that 0 L was used to obtain 4.420 kg of a polymer. The infrared spectrum absorption of the obtained polymer is the same as that of the polymer obtained in Example 1, Mw = 105000, Tg = 218.
It was ℃. Table 1 shows the mechanical properties and the amount of sulfurous acid gas generated at 450 ° C.

Example 6 Molecular weight regulator 4-chlorophenylphenyl sulfone 3
The same reaction and post-treatment as in Example 1 were carried out except that 7.9 g (0.15 mol) was added, and 4.510 kg of polymer
Got The infrared spectrum absorption was the same as that of the polymer obtained in Example 1, Mw = 84000 and Tg = 218 ° C. Table 1 shows the mechanical properties and the amount of sulfurous acid gas generated at 450 ° C.

Example 7 The same reaction and post-treatment as in Example 1 were carried out except that N, N-dimethylacetamide (DMAc) was used as the solvent instead of N-methylpyrrolidone, and polymer 4.54 was used.
0 kg was obtained. The infrared spectrum absorption is the same as the polymer obtained in Example 1, Mw = 129000, Tg = 2.
It was 18 ° C. Table 1 shows the mechanical properties and the amount of sulfurous acid gas generated at 450 ° C.

Example 8 The same reaction and post-treatment as in Example 1 were carried out except that 1,3-dimethyl-2-imidazolidinone was used as the solvent instead of N-methylpyrrolidone, and polymer 4.500 was used.
I got kg. The infrared spectrum absorption is the same as that of the polymer obtained in Example 1, Mw = 130,000, Tg = 21.
It was 8 ° C. Table 1 shows the mechanical properties and the amount of sulfurous acid gas generated at 450 ° C.

Comparative Example 1 30 L internal volume equipped with a Dean-Stark trap filled with toluene, a stirrer and an argon gas blowing tube
3.183 kg of phenolphthalein in the reaction vessel of
(10.00 mol), 2.900 kg (10.10 mol) of bis (p-chlorophenyl) sulfone, 1.589 kg (11.50 mol) of potassium carbonate and 10 L of N-methylpyrrolidone were added, and these raw material components were mixed at room temperature. In, the mixture was stirred while flowing argon gas to obtain an N-methylpyrrolidone solution.

The reaction vessel was placed in an oil bath and heated to 180 ° C., 1.5 L of toluene was added and refluxed for 1 hour. After removing toluene, the temperature was raised to 200 ° C. and the mixture was stirred for 3 hours. After cooling, the reaction mixture was poured into a large amount of methanol acidified with dilute hydrochloric acid to precipitate a polymer, which was then washed with hot water three times and dried at 100 ° C. under reduced pressure to give a polymer of 5.20.
0 kg was obtained.

Further, the GPC molecular weight was measured and found to be Mw = 145000 and Tg = 258 ° C. Table 1 shows the mechanical properties and the amount of sulfurous acid gas generated at 450 ° C.

Comparative Example 2 Using "UDEL" P-1700 (manufactured by Amoco),
The mechanical properties of the injection-molded product and the amount of sulfur dioxide gas generated at 450 ° C. were measured. The measurement results are shown in Table 1. Also, Tg
= 190 ° C.

[0050]

[Table 1] From Examples 1 to 3 and Comparative Examples 1 to 2, the aromatic polyether sulfone copolymers of the present invention have a glass transition temperature (T
It can be seen that g) is high, and therefore the heat distortion temperature (HDT) is also high. The mechanical properties are also high, and the balance between strength and toughness is extremely good. On the other hand, it can be seen that Comparative Example 1 has a high heat distortion temperature (HDT) and a high mechanical strength, but has a low toughness and is extremely brittle. Further, Comparative Example 2 has a drawback that the heat distortion temperature (HDT) and the mechanical strength are low although the toughness is large and the toughness is very strong. Further, when comparing the amount of sulfur dioxide gas generated at 450 ° C., Comparative Examples 1 and 2 are at a high level, but Examples 1 to 3 show a low value. Less damage.

From the results of Examples 1 and 4, it is understood that the same effect can be obtained even if the halogen of the aromatic dihalosulfone compound is changed from chlorine to fluorine. Example 1,
From the results of 5, it is understood that the same effect can be obtained even if the base is changed from carbonate to caustic or an aqueous solution is used. From the results of Examples 1 and 6, it can be seen that the molecular weight can be reduced by adding a small amount of the monohalogen compound during the polymerization, but the physical properties of the molded product are not affected. From Examples 1, 7, and 8, the solvent at the time of polymerization was NM.
It can be seen that even if P is changed to DMAc or 1,3-dimethyl-2-imidazolidinone, the same effect can be obtained.

[0052]

The article obtained by melt-molding the aromatic polyether sulfone copolymer of the present invention has a heat distortion temperature (HD
It has excellent cost performance because it uses bisphenol A and phenolphthalein, which have high T) and are inexpensive general-purpose chemicals.

The aromatic polyether sulfone copolymer is amorphous and is a polymer having excellent moldability such as transparency, toughness and melt moldability. Therefore, it is an industrially extremely useful material because it can be suitably used in a wide range of fields such as various parts of electric and electronic fields as well as parts materials of various machines and appliances. Further, since the decomposition at a high temperature is small and the amount of sulfur dioxide gas generated at the time of melt molding is small, a molded product can be manufactured without damaging the mold even when continuously molding for a long time.

Claims (4)

[Claims] 1. Substantially 25 to 75% by weight of a repeating unit having a phenolphthalein structure represented by the general formula I and 75 to 25% by weight of a repeating unit having a bisphenol A structure represented by the general formula II, A molded article made of an aromatic polyether sulfone copolymer having a heat distortion temperature (HDT) of 175 to 235 ° C. obtained by melt-molding an aromatic polyether sulfone copolymer having a weight average molecular weight of 10,000 to 500,000. [Chemical 1] [Chemical 2] (However, R in the formula represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms, and m represents an integer of 0 to 3.) 2. The molding according to claim 1, wherein the aromatic polyether sulfone copolymer is produced by polycondensing phenolphthalein, bisphenol A and an aromatic dihalosulfone compound in an aprotic polar solvent. Goods. 3. The molded article according to claim 2, wherein the aprotic polar solvent is an amide solvent. 4. The aprotic polar solvent is at least one selected from N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and 1,3-dimethyl-2-imidazolidinone. Item 2. A molded article according to item 2.