Aromatic polysulfone

Abstract

To provide aromatic polysulfone suppressing thickening under a high temperature environment.SOLUTION: Aromatic polysulfone includes a repeating unit S1 derived from a compound expressed by formula (S1), and a repeating unit S2 expressed by formula (S2). A percentage content of the repeating unit S1 is 0.10 mol% or more and less than 1.50 mol%, with regard to all repeating units of the aromatic polysulfone. In the formulas, R1, R2 and R3 independently denote a hydrogen atom or a methyl group. R5 and R6 independently denote a halogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and m and n independently denote an integer of 0 to 4. If there are a plurality of R5 or R6, they may be the same or different.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to aromatic polysulfones. [Background technology]

[0002] Aromatic polysulfones have a high glass transition temperature (Tg) and are used in many fields, such as electronic materials, as they have excellent heat resistance. For example, Patent Document 1 discloses that by using at least 20 mol % of trimethylhydroquinone, based on the total amount of dihydroxy components, as a monomer constituting aromatic polysulfone, the resulting polymer exhibits high thermal stability and is suitable as a membrane material. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2020-525600 Summary of the Invention [Problem to be solved by the invention]

[0004] Aromatic polysulfones generally have a high Tg and require high processing temperatures. Therefore, if aromatic polysulfone remains in a molding machine, the high processing temperature can cause partial polymerization of the aromatic polysulfone, resulting in increased molecular weight and thickening. When the aromatic polysulfone thickens, stable molding becomes difficult, and the molding machine must be disassembled and cleaned, resulting in reduced productivity.

[0005] An object of the present disclosure is to provide an aromatic polysulfone that is inhibited from thickening at high temperatures (for example, 400°C). [Means for solving the problem]

[0006] The present disclosure encompasses the following aspects.

[0007] [1] An aromatic polysulfone comprising a repeating unit S1 derived from a compound represented by the following formula (S1) and a repeating unit S2 represented by the following formula (S2), wherein the content of the repeating unit S1 relative to all repeating units of the aromatic polysulfone is 0.10 mol % or more but less than 1.50 mol %: [ka] (In formula (S1), R 1 , R 2 and R 3 each independently represents a hydrogen atom or a methyl group. [ka] (In formula (S2), R 5 and R 6 R each independently represents a halogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and m and n each independently represent an integer of 0 to 4. 5 or R 6 If there are multiple, they may be the same or different.)

[0008] [2] The aromatic polysulfone according to [1], wherein the content of the repeating unit S1 relative to the total repeating units is 0.10 mol % or more and 0.50 mol % or less.

[0009] [3] The aromatic polysulfone according to [1] or [2], wherein the compound represented by formula (S1) is trimethylhydroquinone or 2,3-dimethylhydroquinone. [Effects of the Invention]

[0010] According to the present disclosure, it is possible to provide an aromatic polysulfone in which thickening at high temperatures such as 400°C is suppressed. DETAILED DESCRIPTION OF THE INVENTION

[0011] <Aromatic polysulfone> The aromatic polysulfone of this embodiment is an aromatic polysulfone containing a repeating unit S1 derived from a compound represented by the following formula (S1) and a repeating unit S2 represented by the following formula (S2), and the content of the repeating unit S1 relative to all repeating units of the aromatic polysulfone is 0.10 mol % or more and less than 1.50 mol %. [ka] (In formula (S1), R 1 , R 2 and R 3 each independently represents a hydrogen atom or a methyl group. [ka] (In formula (S2), R 5 and R 6 R each independently represents a halogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and m and n each independently represent an integer of 0 to 4. 5 or R 6 When there are multiple, they may be the same or different.

[0012] In this specification, the term "derived from" means that the chemical structure of the molecular structure changes at the site where a new bond is formed during polymerization due to the polymerization of the raw material monomer, but no other structural changes occur. The term "derived from" as used herein is a concept that also encompasses cases where the polymerizable derivative of the raw material monomer is used as the origin.

[0013] [Repeating unit S1] The content of the repeating unit S1 relative to all repeating units of the aromatic polysulfone is preferably 0.10 mol % or more and 0.50 mol % or less.

[0014] The compound represented by the above formula (S1) is Methylhydroquinone (R 1 ~R 3 is a hydrogen atom) 2,3-dimethylhydroquinone (R 1 is a methyl group, R2 and R 3 is a hydrogen atom) 2,5-dimethylhydroquinone (R 2 is a methyl group, R 1 and R 3 is a hydrogen atom) 2,6-dimethylhydroquinone (R 3 is a methyl group, R 1 and R 2 is a hydrogen atom) Trimethylhydroquinone (R 1 and R 2 is a methyl group, R 3 is a hydrogen atom) Tetramethylhydroquinone (R 1 ~R 3 is a methyl group) Among these, trimethylhydroquinone or 2,3-dimethylhydroquinone is preferred.

[0015] [Repeating unit S2] In the above formula (S2), R 5 and R 6 The alkyl group in may be linear or branched. Specific examples include a methyl group, an ethyl group, a 1-propyl group, an isopropyl group, a 1-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-hexyl group.

[0016] In the above formula (S2), R 5 and R 6 The alkenyl group in the above-mentioned alkyl group may be exemplified by the above-mentioned alkyl group in which a single bond (CC) between any two carbon atoms is replaced with a double bond (C=C), and the position of the double bond is not limited.

[0017] In the above formula (S2), m and n are each preferably 0.

[0018] The aromatic polysulfone preferably has a content of repeating units S2 of 0.11 mol% or more, more preferably 0.12 mol% or more, and preferably 1.00 mol% or less, and more preferably 0.50 mol% or less, based on all repeating units constituting the aromatic polysulfone. The content of repeating units S2 may be 0.10 mol% to 1.00 mol%, 0.10 mol% to 0.50 mol%, 0.11 mol% to 1.50 mol%, 0.11 mol% to 1.00 mol%, 0.11 mol% to 0.50 mol%, 0.12 mol% to 1.50 mol%, 0.12 mol% to 1.00 mol%, or 0.12 mol% to 0.50 mol%.

[0019] The aromatic polysulfone may have other repeating units in addition to the repeating unit S1 and the repeating unit S2. The aromatic polysulfone preferably has only the repeating unit S1 and the repeating unit S2.

[0020] <<Method for producing aromatic polysulfone>> The aromatic polysulfone can be produced by a production method comprising a step of reacting, in an aprotic polar solvent, monomers containing at least one compound represented by the following formula (S2a), at least one compound represented by the following formula (S2b), and a compound represented by the formula (S1), wherein the content of the compound represented by formula (S1) relative to all monomers is 0.10 mol % or more but less than 1.50 mol %.

[0021] [ka] (In formula (S2a), R 5 , R 6 , m and n are R in the above formula (S2), 5 , R 6 , m, and n.)

[0022] [ka] (In formula (S2b), R5 , R 6 , m and n are R in the above formula (S2), 5 , R 6 , m and n. In formula (S2b), X 1 and X 2 Each of X independently represents a halogen atom. 1 and X 2 may be the same or different.)

[0023] The step of reacting the monomer is preferably carried out using an alkali metal carbonate. The alkali metal carbonate may be a carbonate, which is a normal salt, a bicarbonate (hydrogen carbonate), which is an acidic salt, or a mixture of both. As the carbonate, sodium carbonate or potassium carbonate is preferably used, and as the hydrogen carbonate, sodium bicarbonate or potassium bicarbonate is preferably used.

[0024] Examples of aprotic polar solvents include dimethyl sulfoxide, 1-methyl-2-pyrrolidone, sulfolane (1,1-dioxothiane), 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, and diphenyl sulfone.

[0025] The polymerization temperature varies depending on the type of aprotic polar solvent used, but is generally about 180°C to 300°C.

[0026] The molecular weight of the obtained aromatic polysulfone is evaluated by the reduced viscosity, which can be measured by the following method.

[0027] [Measurement of reduced viscosity] 1 g of aromatic polysulfone is dissolved in N,N-dimethylformamide to a volume of 1 dL (solution concentration: 1 g / dL). The viscosity (η) of the resulting aromatic polysulfone solution is measured at 25°C using an Ostwald-type viscometer.

[0028] In addition, the viscosity (η0) of the solvent N,N-dimethylformamide is measured at 25°C using an Ostwald-type viscometer. The specific viscosity η sp = ((η-η0) / η0).

[0029] Specific viscosity η sp is divided by the solution concentration of the aromatic polysulfone solution to determine the reduced viscosity (unit: dL / g).

[0030] The aromatic polysulfone described above, which contains "repeating units derived from the compound represented by formula (S1)", is prevented from thickening in a high-temperature environment.

[0031] The degree of thickening of the aromatic polysulfone in a high-temperature environment is evaluated by measuring the melt viscosity of the aromatic polysulfone and calculating the "melt viscosity ratio" representing the degree of thickening from the obtained value. The melt viscosity of the aromatic polysulfone can be measured by the following method.

[0032] [Melt viscosity measurement] The melt viscosity of the aromatic polysulfone is determined from a viscosity curve obtained using a dynamic viscoelasticity measuring device (Rheometer CVO model manufactured by Bohlin Instruments) with parallel plates under the following conditions: As an example, the measurement temperature is set to 400°C, but the measurement temperature can be changed. Using this measurement method, the melt viscosity (A) after a holding time of 5 minutes and the melt viscosity (B) after a holding time of 30 minutes are determined. (conditions) Measurement temperature: 400℃ Distortion: 0.05% Frequency: 1Hz Plate spacing: 0.8 mm Holding time: 30 minutes

[0033] By calculating the melt viscosity ratio (melt viscosity (B) / melt viscosity (A)) from the measurement results, the degree of thickening of the aromatic polysulfone at the measurement temperature can be evaluated. When the melt viscosity ratio is 1 or less, it can be evaluated that the aromatic polysulfone does not thicken at the measurement temperature, and stable molding is possible at the measurement temperature. When the melt viscosity ratio exceeds 1, it can be evaluated that the aromatic polysulfone thickens at the measurement temperature, and stable molding at the measurement temperature may become difficult.

[0034] <<Molded body>> The above-mentioned aromatic polysulfone can be suitably used as a material for molded articles that require heat resistance.

[0035] Examples of such molded articles include electrical and electronic components such as connectors, sockets, IC sockets, burn-in sockets, relay parts, coil bobbins, optical pickups, oscillators, printed wiring boards, circuit boards, semiconductor packages, and computer-related parts; semiconductor manufacturing process-related parts such as IC trays and wafer carriers; home electrical appliance parts such as VTRs, televisions, irons, air conditioners, stereos, vacuum cleaners, refrigerators, rice cookers, and lighting fixtures; lighting fixture parts such as lamp reflectors and lamp holders; audio product parts such as compact discs, laser discs (registered trademark), and speakers; ferrules for optical cables, telephone parts, facsimile parts, and communication equipment parts such as modems; separation claws and heaters. Copier and printer related parts such as photocopier holders; mechanical parts such as impellers, fan gears, gears, bearings, motor parts and cases; automotive parts such as automotive mechanism parts, engine parts, engine room parts, electrical parts, and interior parts; cooking utensils such as microwave cooking pots and heat-resistant tableware; heat insulation and soundproofing materials such as flooring and wall materials, support materials such as beams and pillars, building materials such as roofing materials, or civil engineering and construction materials; parts for aircraft, spacecraft, and space equipment; radiation facility components such as nuclear reactors, marine facility components, cleaning jigs, optical equipment parts, valves, pipes, nozzles, filters, membranes, medical equipment parts and medical materials, sensor parts, sanitary equipment, sporting goods, leisure goods, and cable ties.

[0036] The molded article can be obtained by melt-molding the mixture of aromatic polysulfone with, if necessary, known additives such as fillers and stabilizers, and other resin materials, using methods such as injection molding, blow molding, vacuum molding, and press molding, with injection molding being preferred.

[0037] According to the aromatic polysulfone having the above-mentioned constitution, it is possible to provide an aromatic polysulfone in which the increase in viscosity at high temperatures such as 400°C is suppressed.

[0038] Although the preferred embodiments of the present disclosure have been described above, the present disclosure is not limited to these examples. The combinations and the like shown in the above examples are merely examples, and various modifications can be made based on design requirements and the like within the scope of the present disclosure. [Example]

[0039] The present disclosure will be described below with reference to examples, but the present disclosure is not limited to these examples.

[0040] In the present examples, physical properties were measured according to the following descriptions.

[0041] [Measurement of reduced viscosity] The reduced viscosity of the aromatic polysulfone was measured according to the description in [Measurement of reduced viscosity] above.

[0042] [Melt viscosity measurement] The melt viscosity of the aromatic polysulfone was measured according to the above-mentioned [Melt Viscosity Measurement]. The measurement temperature was 400°C. Using this measurement method, the melt viscosity (A) after a holding time of 5 minutes and the melt viscosity (B) after a holding time of 30 minutes were determined.

[0043] In the examples and comparative examples, the following monomers were used. Monomer L: 4,4'-dichlorodiphenyl sulfone Monomer M: 4,4'-dihydroxydiphenyl sulfone Monomer N: Trimethylhydroquinone Monomer O: 2,3-dimethylhydroquinone Monomer P: Hydroquinone

[0044] [Example 1] A polymerization vessel equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a condenser with a receiver at its tip was charged with 65.39 g of Monomer L, 54.92 g of Monomer M, 0.08 g of Monomer N, and 106.70 g of diphenyl sulfone as a polymerization solvent, and the temperature was raised to 180°C while circulating nitrogen gas through the system. To the resulting solution, 31.62 g of potassium carbonate was added, and the temperature was gradually raised to 290°C, and the reaction was continued at 290°C for an additional 3 hours.

[0045] The resulting reaction solution was cooled to room temperature to solidify, and then finely pulverized. The resulting powder was washed with warm water, then washed with a mixed solvent of acetone and methanol, and further dried by heating at 150°C to obtain a white powder of aromatic polysulfone of Example 1.

[0046] Monomer N corresponds to the "compound represented by formula (S1)" in the present disclosure. The content of repeating units S1 relative to all repeating units of the aromatic polysulfone of Example 1 was 0.13 mol%.

[0047] The reduced viscosity and melt viscosity of the obtained aromatic polysulfone were measured by the above-mentioned measurement methods, and the melt viscosity ratio (melt viscosity (B) / melt viscosity (A)) was calculated from the measurement results.

[0048] [Example 2] Except for changing the amounts charged to 54.79 g of Monomer M, 0.17 g of Monomer N, and 106.63 g of diphenyl sulfone, the aromatic polysulfone of Example 2 was obtained in the same manner as in Example 1. The content of repeating unit S1 relative to all repeating units of the aromatic polysulfone of Example 2 was 0.25 mol%.

[0049] [Example 3] Except for changing the amounts charged to 54.51 g of Monomer M, 0.33 g of Monomer N, and 106.48 g of diphenyl sulfone, the aromatic polysulfone of Example 3 was obtained in the same manner as in Example 1. The content of repeating unit S1 relative to all repeating units of the aromatic polysulfone of Example 3 was 0.50 mol%.

[0050] [Example 4] An aromatic polysulfone of Example 4 was obtained in the same manner as in Example 1, except that the amounts of Monomer M and diphenyl sulfone were changed to 54.51 g and 106.44 g, respectively, and that 0.08 g of Monomer N was changed to 0.30 g of Monomer O.

[0051] Monomer O corresponds to the "compound represented by formula (S1)" in the present disclosure. The content of repeating units S1 relative to all repeating units of the aromatic polysulfone of Example 4 was 0.50 mol%.

[0052] [Comparative Example 1] Except for changing the amounts charged to 55.06 g of monomer M, 0 g of monomer N, and 106.78 g of diphenyl sulfone, the aromatic polysulfone of Comparative Example 1 was obtained in the same manner as in Example 1. The content of repeating unit S1 relative to all repeating units of the aromatic polysulfone of Comparative Example 1 was 0.00 mol%.

[0053] Comparative Example 2 Except for changing the amounts charged to 65.26 g of Monomer L, 55.06 g of Monomer M, 0 g of Monomer N, and 106.61 g of diphenyl sulfone, an aromatic polysulfone of Comparative Example 2 was obtained in the same manner as in Example 1. The content of repeating unit S1 relative to all repeating units of the aromatic polysulfone of Comparative Example 2 was 0.00 mol%.

[0054] Comparative Example 3 Except for changing the amounts charged to 55.01 g of Monomer M, 0.03 g of Monomer N, and 106.75 g of diphenyl sulfone, an aromatic polysulfone of Comparative Example 3 was obtained in the same manner as in Example 1. The content of repeating unit S1 relative to all repeating units of the aromatic polysulfone of Comparative Example 3 was 0.05 mol%.

[0055] Comparative Example 4 Except for changing the amounts charged to 53.41 g of Monomer M, 1.00 g of Monomer N, and 105.90 g of diphenyl sulfone, an aromatic polysulfone of Comparative Example 4 was obtained in the same manner as in Example 1. The content of repeating units S1 relative to all repeating units of the aromatic polysulfone of Comparative Example 4 was 1.50 mol%.

[0056] Comparative Example 5 Except for changing the amounts charged to 49.56 g of Monomer M, 3.35 g of Monomer N, and 103.87 g of diphenyl sulfone, the aromatic polysulfone of Comparative Example 5 was obtained in the same manner as in Example 1. The content of repeating unit S1 relative to all repeating units of the aromatic polysulfone of Comparative Example 5 was 5.00 mol%.

[0057] When the melt viscosity of the obtained aromatic polysulfone was measured, the melt viscosity increased significantly, so the measurement was stopped midway and it was deemed impossible to measure.

[0058] Comparative Example 6 Except for changing the amounts of monomer M to 54.51 g and diphenyl sulfone to 106.36 g and changing 0.08 g of monomer N to 0.24 g of monomer P, an aromatic polysulfone of Comparative Example 6 was obtained in the same manner as in Example 1. The content of repeating unit S1 relative to all repeating units of the aromatic polysulfone of Comparative Example 6 was 0.00 mol%.

[0059] The results are shown in Table 1 below.

[0060] [Table 1]

[0061] As a result of the evaluation, the aromatic polysulfones of Examples 1 to 4 all had a melt viscosity ratio of 1 or less, and no increase in viscosity was confirmed under the measurement conditions. It can be evaluated that all of the aromatic polysulfones of Examples 1 to 4 can be stably molded at the measurement temperature.

[0062] In contrast, the aromatic polysulfones of Comparative Examples 1 to 3 and 6, in which the content of the compound represented by formula (S1) relative to all repeating units was less than 0.10 mol %, and Comparative Example 4, in which the content was 1.50 mol % or more, had melt viscosity ratios exceeding 1, confirming an increase in viscosity under the measurement conditions. The aromatic polysulfone of Comparative Example 5 was confirmed to have increased viscosity to the extent that the melt viscosity could not be measured.

[0063] The above results confirm that the present disclosure is useful.

Claims

1. a repeating unit S1 derived from a compound represented by the following formula (S1); An aromatic polysulfone comprising a repeating unit S2 represented by the following formula (S2): The aromatic polysulfone has a content of the repeating unit S1 of 0.10 mol % or more and less than 1.50 mol % based on all repeating units of the aromatic polysulfone. 【Chemical 1】 (In formula (S1), R １ , R ２ and R ３ each independently represents a hydrogen atom or a methyl group) 【Chemistry 2】 (In formula (S2), R ５ and R ６ R each independently represents a halogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and m and n each independently represent an integer of 0 to 4. ５ or R ６ If there are multiple, they may be the same or different.)

2. 2. The aromatic polysulfone according to claim 1, wherein the content of the repeating unit S1 relative to all the repeating units is 0.10 mol % or more and 0.50 mol % or less.

3. 3. The aromatic polysulfone according to claim 1, wherein the compound represented by formula (S1) is trimethylhydroquinone or 2,3-dimethylhydroquinone.

Images