An aromatic sulfone-benzophenone copolymer, and a preparation method and application thereof

Abstract

This invention provides an aromatic sulfone-benzophenone copolymer, its preparation method, and its applications. The aromatic sulfone-benzophenone copolymer comprises aromatic sulfone polymer segments and polybenzophenone segments. Based on the mass of the aromatic sulfone-benzophenone copolymer as 100%, the mass of benzophenone residues in the aromatic sulfone-benzophenone copolymer is 4.8~16.2%. The aromatic sulfone-benzophenone copolymer exhibits excellent water-boiling resistance while maintaining good toughness.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to an aromatic sulfone-benzophenone copolymer, its preparation method, and its application. Background Technology

[0002] Aromatic sulfone polymers are high-temperature resistant, transparent thermoplastic engineering plastics with outstanding thermal properties, excellent chemical resistance, excellent high-temperature creep resistance, superior dimensional stability, extremely low smoke and toxic gas emissions, and good electrical properties. With the continuous improvement of aromatic sulfone polymer materials, their applications are becoming increasingly widespread, finding applicability in aerospace, medical and health, food, home appliances, electronics, and energy and chemical industries. Particularly in food contact and medical and health applications, the requirements for material performance are becoming increasingly stringent. Especially in high-end medical applications, resistance to high-temperature steam or high-temperature water sterilization is a prerequisite.

[0003] However, aromatic sulfone polymers still experience a decrease in strength and a decline in chemical resistance when used in high-temperature steam or water environments for extended periods. In other words, their long-term water resistance needs to be further improved, and their long-term performance requires further enhancement.

[0004] Therefore, developing an aromatic sulfone polymer with excellent water-boiling resistance is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide an aromatic sulfone-benzophenone copolymer, its preparation method, and its applications. The aromatic sulfone-benzophenone copolymer exhibits excellent water resistance while maintaining good toughness.

[0006] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides an aromatic sulfone-benzophenone copolymer, wherein the aromatic sulfone-benzophenone copolymer comprises aromatic sulfone polymer segments and polybenzophenone segments; and the mass of benzophenone residues in the aromatic sulfone-benzophenone copolymer is 4.8 to 16.2% based on 100% of the mass of the aromatic sulfone-benzophenone copolymer.

[0007] In this invention, by introducing polybenzophenone segments into the main chain of an aromatic sulfone polymer through copolymerization, a certain amount of crystalline segments are introduced into the molecular structure of the polymer. This not only ensures good toughness but also helps to improve the water resistance of the aromatic sulfone polymer. When the mass percentage of the benzophenone residues is less than 4.8%, the improvement in water resistance is not significant; when it is greater than 16.2%, the toughness of the material deteriorates.

[0008] In this invention, based on the mass of the aromatic sulfone-benzophenone copolymer as 100%, the mass of benzophenone residues in the aromatic sulfone-benzophenone copolymer is 4.8% to 16.2%, for example, it can be 4.9%, 5%, 5.2%, 5.5%, 5.8%, 6%, 6.2%, 6.5%, 6.8%, 7%, 7.2%, 7.5%, 7.8%, 8%, 8.2%, 8.5%, 8.8%, 9%, 9.2%, 9.5%, 9.8%, 10%, 10.2%, 10.5%, 10.8%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, or any range of the above values; more preferably, it is 6.5% to 12%.

[0009] In this invention, the proportion of benzophenone residues in the aromatic sulfone-benzophenone copolymer is expressed as a percentage of the monomer addition mass to the total mass of the raw materials (i.e., the total mass of the aromatic sulfone polymer and the benzophenone compound).

[0010] Preferably, the aromatic sulfone polymer segments are derived from aromatic sulfone polymers.

[0011] Preferably, the aromatic sulfone polymer comprises polyphenylene sulfone resin (PPSU).

[0012] In this invention, the polyphenylene sulfone resin comprises a first structural unit and a second structural unit; the first structural unit is derived from a sulfone compound, and the second structural unit is derived from a polyhydroxy compound; the sulfone compound comprises at least one of 4,4′-dichlorodiphenyl sulfone and 4,4′-difluorodiphenyl sulfone; the polyhydroxy compound comprises at least one of 4,4′-biphenylhydrazine and bisphenol A.

[0013] Preferably, the molecular weight distribution index of the aromatic sulfone polymer is 1.5 to 3.5, for example, it can be 1.6, 1.7, 1.8, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4 or any of the above values, more preferably 2 to 3.

[0014] In this invention, if the molecular weight distribution index of the aromatic sulfone polymer is too small, the resin toughness will be slightly worse; if it is too large, the water boiling resistance will decrease, and the resin toughness will also decrease.

[0015] In this invention, the weight-average molecular weight of the aromatic sulfone-benzophenone copolymer is 32,000 to 65,000.

[0016] In this invention, the weight-average molecular weight and molecular weight distribution index can be obtained by gel permeation chromatography (GPC). Specifically, polystyrene is used as a standard, tetrahydrofuran is used as the mobile phase, and the sample concentration is 0.1~10 mg / mL (e.g., 5 mg / mL). The weight-average molecular weight and molecular weight distribution index are determined by gel permeation chromatography.

[0017] Preferably, the polybenzophenone segments are derived from benzophenone compounds containing hydroxyl and halogen end groups, that is, the benzophenone compounds have a hydroxyl end and a halogen end.

[0018] In this invention, the halogen includes any one of F, Cl, Br, and I.

[0019] Preferably, the benzophenone compounds containing hydroxyl and halogen end groups include at least one of 4-chloro-4′-hydroxybenzophenone and 4-fluoro-4′-hydroxybenzophenone.

[0020] In this invention, the aromatic sulfone-benzophenone copolymer includes at least one of AB diblock copolymer, ABA triblock copolymer, and ABA′ triblock copolymer; wherein A and A′ are each independently a polybenzophenone segment; and B is an aromatic sulfone polymer segment.

[0021] Preferably, the molar percentage content of the AB diblock copolymer, ABA triblock copolymer and / or ABA′ triblock copolymer in the aromatic sulfone-benzophenone copolymer is ≥90%, for example, ≥95%.

[0022] In this invention, A and A′ have different molecular weights; A and A′ each independently contain at least one polybenzophenone segment; for example, they may contain two polybenzophenone segments or three polybenzophenone segments, etc.

[0023] In a second aspect, the present invention provides a method for preparing the aromatic sulfone-benzophenone copolymer according to the first aspect, the method comprising the following steps: The aromatic sulfone polymer was reacted with a benzophenone compound to obtain the aromatic sulfone-benzophenone copolymer.

[0024] In the above preparation method, benzophenone compounds undergo self-condensation to form polybenzophenone segments.

[0025] In this invention, the aromatic sulfone polymer can be obtained commercially or prepared using conventional methods. For example, the aromatic sulfone polymer can be prepared using the following method, which includes the following steps: (1) A sulfone compound is reacted with a polyhydroxy compound to form a salt, and the salt product is obtained; (2) The salt-forming product is subjected to a polymerization reaction to obtain the aromatic sulfone polymer.

[0026] In this invention, the molar ratio of the polyhydroxy compound to the sulfone compound is 1:(1~3), for example, it can be 1:1.02, 1:1.05, 1:1.08, 1:1.1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, 1:2.8, 1:3 or any range of the above values; the salt-forming reaction is carried out in a solvent, the solvent including but not limited to sulfolane; the mass of the solvent is 2 to 3 times the total mass of the sulfone compound and the polyhydroxy compound, for example, it can be 2 times, 2.2 times, 2.4 times, 2.6 times, 2.8 times, 3 times or any range of the above values; the raw materials for the salt-forming reaction also include The mixture includes salt-forming agents and / or azeotropic agents; the salt-forming agents include, but are not limited to, sodium carbonate and / or potassium carbonate; the mass of the salt-forming agent is 15-30% of the total mass of the sulfone compound and the polyhydroxy compound, for example, it can be 16%, 18%, 20%, 22%, 24%, 26%, 28% or any of the above values; the azeotropic agents include, but are not limited to, toluene and / or xylene; the mass of the azeotropic agent is 0.05-1 times the total mass of the sulfone compound and the polyhydroxy compound, for example, it can be 0.05 times, 0.06 times, 0.08 times, 0.1 times, 0.2 times, 0.3 times, 0.4 times, 0.6 times, 0.8 times, 1 times or any of the above values.

[0027] In this invention, the salt formation reaction in step (1) is carried out in the presence of a protective atmosphere, which includes, but is not limited to, nitrogen; the temperature of the salt formation reaction is 180~210℃ and the time is 4~6h; during the salt formation reaction, the azeotropic agent continuously discharges the reaction water through azeotroping until no water is discharged, at which point the salt formation reaction ends and the azeotropic agent is distilled off; the polymerization reaction in step (2) is carried out at a temperature of 220~250℃ and for 2~6h.

[0028] In this invention, after the polymerization reaction in step (2) is completed, a post-processing step is also included; the post-processing includes sequentially subjecting the product obtained from the polymerization reaction to acidic water precipitation, crushing with a crusher, boiling with deionized water for at least 1 hour, centrifuging and filtering, repeating the above steps until the filtrate does not become turbid when tested with silver nitrate, indicating that the by-product salt has been washed away, and then removing the water from the purified polymer under vacuum drying to obtain the aromatic sulfone polymer.

[0029] Preferably, the mass ratio of the aromatic sulfone polymer to the benzophenone compound is 1:(0.05~0.2), wherein the specific value of (0.05~0.2) can be, for example, 0.06, 0.08, 0.1, 0.12, 0.14, 0.16, 0.18 or any of the above values.

[0030] Preferably, the reaction of the aromatic sulfone polymer with the benzophenone compound is carried out in the presence of a salt-forming agent.

[0031] Preferably, the mass of the salt-forming agent is 3 to 16% of the mass of the aromatic sulfone polymer, for example, it can be 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or any of the above values.

[0032] Preferably, the salt-forming agent includes at least one of sodium carbonate, potassium carbonate, and sodium bicarbonate.

[0033] In this invention, the reaction between the aromatic sulfone polymer and the benzophenone compound is carried out in a solvent and an azeotropic agent. The solvent includes, but is not limited to, sulfolane. The mass of the solvent is 2.5 to 3.5 times the total mass of the aromatic sulfone polymer and the phenolic monomer, for example, 2.6 times, 2.8 times, 3 times, 3.2 times, 3.4 times, or any of the above values. The azeotropic agent includes, but is not limited to, toluene and / or xylene. The mass of the azeotropic agent is 0.05 to 1 times the total mass of the aromatic sulfone polymer and the phenolic monomer, for example, 0.05 times, 0.06 times, 0.08 times, 0.1 times, 0.2 times, 0.3 times, 0.4 times, 0.6 times, 0.8 times, 1 times, or any of the above values.

[0034] Preferably, the reaction temperature is 235~285℃, for example, it can be 238℃, 240℃, 250℃, 255℃, 260℃, 265℃, 270℃, 275℃, 280℃ or any range between the above values.

[0035] Preferably, the reaction time is 1 to 5 hours, for example, 2 hours, 3 hours, 4 hours, etc.

[0036] In this invention, after the aromatic sulfone polymer reacts with the benzophenone compound, the reaction further includes adding a solvent to cool down, ending the reaction, and then sequentially subjecting the product to precipitation with a DMF / water mixture (if specifically indicated, the volume ratio can be 1:1), crushing with a crusher, boiling the DMF / water mixture for at least 1 hour, centrifuging and filtering, repeating this process at least 5 times, then boiling with deionized water for at least 1 hour, centrifuging and filtering, and repeating the above steps until the filtrate does not become turbid when tested with silver nitrate, indicating that the byproduct salts have been washed away. Finally, the purified polymer is dried under vacuum to remove moisture, thus obtaining the aromatic sulfone-benzophenone copolymer.

[0037] Thirdly, the present invention provides a polysulfone composition comprising the aromatic sulfone-benzophenone copolymer described in the first aspect.

[0038] In this invention, aromatic sulfone-benzophenone copolymers can be compounded with other components to form polysulfone compositions according to actual needs, thereby meeting different performance requirements.

[0039] In this invention, the mass percentage of the aromatic sulfone-benzophenone copolymer in the polysulfone composition is ≥50%.

[0040] Preferably, the other components include fillers and / or additives.

[0041] In this invention, the filler content in the polysulfone composition is ≤50% by mass; the additive content in the polysulfone composition is ≤10% by mass.

[0042] In this invention, the filler includes, but is not limited to, at least one of silica, kaolin, calcium carbonate, talc, montmorillonite, mica, wollastonite, glass fiber, and carbon fiber.

[0043] In this invention, the additives include, but are not limited to, at least one of lubricants, coupling agents, antioxidants, antistatic agents, light stabilizers, and flame retardants.

[0044] In this invention, the lubricant includes, but is not limited to, at least one of polyethylene wax, polypropylene wax, paraffin wax, organosiloxane, silicone, and polytetrafluoroethylene.

[0045] In this invention, the coupling agent includes silane coupling agents, which include, but are not limited to, at least one of the following: aminosilane coupling agents (such as γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane), epoxysilane coupling agents (such as γ-glycidoxypropyltrimethoxysilane), vinylsilane coupling agents (such as vinyltriethoxysilane, vinyltrimethoxysilane), methacryloxysilane coupling agents (γ-methacryloxypropyltrimethoxysilane), and mercaptosilane coupling agents (such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane).

[0046] In this invention, the antioxidants include primary antioxidants and / or secondary antioxidants; the primary antioxidants include, but are not limited to, any one or a combination of at least two of 2,6-di-tert-butyl-p-cresol (BHT), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis(4-methyl-6-nonylphenol), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, and pentaerythritol tetra(3,5-di-tert-butyl-4-hydroxyhydrocinnamate); the secondary antioxidants include, but are not limited to, tri(nonylphenyl) phosphite and / or dilauryl thiodipropionate.

[0047] In this invention, the antistatic agent includes, but is not limited to, at least one of hexadecyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, sodium dodecylbenzenesulfonate, dodecylaminopropionic acid, alkyldimethyl betaine, polyether ester amide, and polyaniline.

[0048] In this invention, the light stabilizer includes, but is not limited to, at least one of benzotriazole UV absorbers (such as UV-P, UV-327, UV-326), benzophenone UV absorbers (such as UV-531, UV-9), triazine UV absorbers (such as UV-1164, UV-400), and hindered amine light stabilizers (such as Chimassorb 944, Tinuvin 770, Tinuvin 622).

[0049] In this invention, the flame retardant includes, but is not limited to, at least one of aluminum hydroxide, magnesium hydroxide, melamine cyanurate, ammonium polyphosphate, tricresyl phosphate, triphenyl phosphate, resorcinol bis(diphenyl phosphate), and aluminum diethylphosphinate.

[0050] Fourthly, the present invention provides an article comprising the aromatic sulfone-benzophenone copolymer described in the first aspect or a polysulfone composition described in the second aspect.

[0051] Preferably, after the product is boiled in water at 150°C for 100 hours, the elongation at break is retained at ≥75%.

[0052] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific point values ​​included in the range.

[0053] Compared with the prior art, the beneficial effects of the present invention are as follows: The aromatic sulfone-benzophenone copolymer provided by the present invention improves the water resistance of the aromatic sulfone polymer by introducing polybenzophenone segments into the main chain of the aromatic sulfone polymer through copolymerization; and by controlling the mass ratio of benzophenone residues within a specific range, the toughness and water resistance of the material can be balanced. Detailed Implementation

[0054] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention.

[0055] In this invention, the methods for testing weight-average molecular weight and molecular weight distribution index are as follows: Polystyrene was used as the standard, tetrahydrofuran was used as the mobile phase, and the polymer concentration was 5 mg / mL. The weight-average molecular weight and molecular weight distribution index of the samples were determined by gel permeation chromatography.

[0056] In this invention, the proportion of benzophenone residues in the aromatic sulfone-benzophenone copolymer is expressed as a percentage of the monomer addition mass to the total mass of the raw materials (i.e., the total mass of the aromatic sulfone polymer and the benzophenone compound).

[0057] All materials used in this invention are commercially available or prepared using conventional methods. Unless otherwise specified, the materials used in this invention are as follows: Sulfolane: Solvent, purity >99.8%.

[0058] 4,4′-Dichlorodiphenyl sulfone: a reactive monomer with a purity >99.5%.

[0059] 4,4′-Biphenyldiol: a reactive monomer with a purity >99.5%.

[0060] 4-Chloro-4′-hydroxybenzophenone: a reactive monomer with a purity >99.5%.

[0061] Xylene: Azeotropic agent, isomer grade.

[0062] Sodium carbonate: Salt-forming agent, purity >99.5%.

[0063] Preparation Example 1 This preparation example provides a polyphenylene sulfone resin, and the preparation method of the polyphenylene sulfone resin is as follows: In a 100L reactor protected with high-purity nitrogen, 36 kg of sulfolane, 8.84 kg of 4,4′-dichlorodiphenyl sulfone (30.8 mol), and 5.59 kg of 4,4′-biphenylhydrazine (30 mol) were quantitatively added. The mixture was stirred and heated, and 3.5 kg of sodium carbonate and 3 kg of xylene were added. Solution polycondensation was employed, and the temperature was maintained between 180 and 210 °C for 6 h. During the reaction, the azeotropic agent xylene continuously discharged reaction water through azeotropic action until no more water was discharged, at which point the salt formation reaction was complete, and xylene was distilled off. The reaction system was then heated to 240 °C and maintained for 2.5 h. Stirring and heating were stopped, and the resulting material was precipitated into strips in acidic water. After crushing, the material was obtained as a powder, then boiled in deionized water for 1 h, centrifuged, and filtered. This process was repeated 10 times until the filtrate remained unchanged when tested with silver nitrate. The purified product was then dried under vacuum to remove moisture, yielding polyphenylsulfone (PPSU) resin, thus obtaining the aromatic sulfone polymer. GPC test molecular weight distribution PDI=2.20.

[0064] Preparation Example 2 This preparation example provides a polyphenylene sulfone resin with a PDI of 2.8. The preparation method differs from that of Preparation Example 1 in that the resin is kept at 180~210℃ for 5 hours, while the other steps are the same as those in Preparation Example 1.

[0065] Preparation Example 3 This preparation example provides a polyphenylene sulfone resin with a PDI of 3.4. The preparation method differs from that of Preparation Example 1 in that the resin is kept at 180~210℃ for 4 hours, while the other steps are the same as those in Preparation Example 1.

[0066] Preparation Example 4 This preparation example provides a polyphenylene sulfone resin with a PDI of 1.6. The preparation method differs from that of Preparation Example 1 in that the temperature is maintained between 180 and 210°C for 10 hours, while the other steps are the same as those in Preparation Example 1.

[0067] Example 1 This embodiment provides an aromatic sulfone-benzophenone copolymer, which includes an aromatic sulfone polymer segment and a benzophenone segment. The aromatic sulfone polymer segment is derived from PPSU provided in Preparation Example 1, and its PDI is 2.2. The benzophenone segment is derived from 4-chloro-4′-hydroxybenzophenone. Based on the mass of the aromatic sulfone-benzophenone copolymer as 100%, the mass of benzophenone residues in the aromatic sulfone-benzophenone copolymer is 5.0% (denoted as M).

[0068] The preparation method of the aromatic sulfone-benzophenone copolymer includes: quantitatively adding 10 kg of PPSU resin provided in Preparation Example 1 to a 100 L reactor under high-purity nitrogen protection, adding 30 kg of sulfolane, 1 kg of xylene and 0.4 kg of sodium carbonate, and then adding 0.53 kg of 4-chloro-4′-hydroxybenzophenone, heating to 250 °C and maintaining for 2 h. During the reaction, the azeotropic agent xylene continuously removes reaction water through azeotropic action until no water is discharged, and then distilling off the xylene. Afterward, 5 kg of solvent sulfolane is added to cool down and the reaction is terminated. Stirring and heating are stopped, and the obtained polymer material is precipitated into strips in DMF / water, crushed by a crusher to obtain powder, boiled in DMF / deionized water for 1 h, centrifuged and filtered, repeated 5 times, then boiled in deionized water for 1 h and repeated 5 times, until the filtrate does not become turbid when tested with silver nitrate, indicating that the byproduct salts have been completely washed away. The purified polymer is dried under vacuum to remove moisture, thus obtaining the copolymer resin, which is the aromatic sulfone-benzophenone copolymer.

[0069] Examples 2-6, Comparative Examples 1-3 Examples 2-6 and Comparative Examples 1-3 each provide an aromatic sulfone-benzophenone copolymer. The difference between them and Example 1 is that the source of the aromatic sulfone polymer chain segment, PDI, and the mass percentage M of benzophenone residues are different, as shown in Tables 1 and 2.

[0070] The difference between the preparation methods of the aromatic sulfone-benzophenone copolymers provided in Examples 2-6 and Comparative Examples 2-3 and Example 1 is that the amount of 4-chloro-4′-hydroxybenzophenone and salt-forming agent (sodium carbonate) added is different. Other raw materials, dosages and process steps are the same as in Example 1.

[0071] Comparative Example 4 provides a polysulfone containing a benzophenone group. The preparation method of the polysulfone differs from that of Example 1 only in that 4-chloro-4′-hydroxybenzophenone is replaced with an equal mass of 4,4′-dichlorobenzophenone. All other aspects are the same as those in Example 1.

[0072] Performance testing (1) Mechanical property testing Impact strength of cantilever beam notched: determined according to ISO 180:2023, type A notch.

[0073] Elongation at break: determined according to ISO 527-2, under test conditions of 23℃ and tensile rate of 10 mm / min.

[0074] (2) Water boiling resistance The ISO standard specimens of mechanical properties obtained by injection molding of polymers provided in the examples and comparative examples were placed in pure water, heated to 150°C, and kept at a constant temperature for 100 hours. Their elongation at break was tested, and the elongation at break retention rate was calculated. Elongation at break retention rate = elongation at break after boiling / elongation at break before boiling × 100%.

[0075] The specific test results are shown in Tables 1 and 2.

[0076] Table 1 Table 2 As shown in Tables 1 and 2, the aromatic sulfone-benzophenone copolymer provided by this invention, by introducing polybenzophenone segments into the main chain of the aromatic sulfone polymer through copolymerization, is beneficial to improving the water resistance and strength of the aromatic sulfone polymer; and by controlling the mass ratio of polybenzophenone segments (i.e., benzophenone residues) within a specific range, both the toughness and water resistance of the material can be taken into account; after being boiled in water at 150°C for 100 hours, the aromatic sulfone-benzophenone copolymer retains an elongation at break of ≥75%, exhibiting good water resistance; it also has a high cantilever beam notched impact strength, ≥54 kJ / m 2 .

[0077] As can be seen from Example 1 and Comparative Example 1, compared with PPSU resin, the aromatic sulfone-benzophenone copolymer provided by the present invention has significantly improved water resistance and has little impact on toughness.

[0078] As can be seen from Example 1 and Comparative Examples 2 and 3, the mass percentage of benzophenone residues in the aromatic sulfone-benzophenone copolymer is not within a specific range, resulting in poor water resistance or reduced toughness.

[0079] As can be seen from Example 1 and Comparative Example 4, it is not an aromatic sulfone-benzophenone copolymer, but benzophenone is used as a coupling agent to connect PPSU segments, resulting in a polymer with poor water boiling resistance.

[0080] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. An aromatic sulfone-benzophenone copolymer, characterized in that, The aromatic sulfone-benzophenone copolymer comprises aromatic sulfone polymer segments and polybenzophenone segments; Based on the mass of the aromatic sulfone-benzophenone copolymer as 100%, the mass of benzophenone residues in the aromatic sulfone-benzophenone copolymer is 4.8~16.2%.

2. The aromatic sulfone-benzophenone copolymer according to claim 1, characterized in that, Based on the mass of the aromatic sulfone-benzophenone copolymer as 100%, the mass of benzophenone residues in the aromatic sulfone-benzophenone copolymer is 6.5~12%.

3. The aromatic sulfone-benzophenone copolymer according to claim 1, characterized in that, The aromatic sulfone polymer segments are derived from aromatic sulfone polymers; Preferably, the aromatic sulfone polymer comprises polyphenylene sulfone resin.

4. The aromatic sulfone-benzophenone copolymer according to claim 3, characterized in that, The molecular weight distribution index of the aromatic sulfone polymer is 1.5 to 3.5, more preferably 2 to 3.

5. The aromatic sulfone-benzophenone copolymer according to claim 1, characterized in that, The polybenzophenone segments are derived from benzophenone compounds containing hydroxyl and halogen end groups; Preferably, the benzophenone compounds containing hydroxyl and halogen end groups include at least one of 4-chloro-4′-hydroxybenzophenone and 4-fluoro-4′-hydroxybenzophenone.

6. The aromatic sulfone-benzophenone copolymer according to claim 1, characterized in that, The aromatic sulfone-benzophenone copolymer includes at least one of AB diblock copolymer, ABA triblock copolymer, and ABA′ triblock copolymer; wherein A and A′ are each independently a polybenzophenone segment; and B is an aromatic sulfone polymer segment. Preferably, the molar percentage of AB diblock copolymer, ABA triblock copolymer and / or ABA′ triblock copolymer in the aromatic sulfone-benzophenone copolymer is ≥90%.

7. A method for preparing an aromatic sulfone-benzophenone copolymer according to any one of claims 1 to 6, characterized in that, The preparation method includes the following steps: The aromatic sulfone polymer was reacted with a benzophenone compound to obtain the aromatic sulfone-benzophenone copolymer.

8. The preparation method according to claim 7, characterized in that, The mass ratio of the aromatic sulfone polymer to the benzophenone compound is 1:(0.05~0.2); Preferably, the reaction is carried out in the presence of a salt-forming agent; Preferably, the mass of the salt-forming agent is 3-16% of the mass of the aromatic sulfone polymer; Preferably, the salt-forming agent includes at least one of sodium carbonate, potassium carbonate, and sodium bicarbonate; Preferably, the reaction temperature is 235~285℃; Preferably, the reaction time is 1 to 5 hours.

9. A polysulfone composition, characterized in that, The polysulfone composition comprises the aromatic sulfone-benzophenone copolymer according to any one of claims 1 to 6.

10. An article characterized in that, The article comprises the aromatic sulfone-benzophenone copolymer according to any one of claims 1 to 6 or the polysulfone composition according to claim 9; Preferably, after the product is boiled in water at 150°C for 100 hours, the elongation at break is retained at ≥75%.

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