A poly(arylsulfoether) resin for film production and a method for producing the same

Abstract

The present application relates to a kind of polyarylsulfonyl ether resin for film preparation and its preparation method. The technology of simultaneously adding special functional group-containing arylsulfonyl ether polymer before the condensation polymerization process of polyarylsulfonyl ether resin is carried out, and then condensation polymerization is carried out. The present application makes full use of the affinity of these special functional groups with di-functional phenolic group and alkali metal in inorganic salt respectively, to promote the combination of the two. In addition, using the affinity of special functional group-containing polyarylsulfonyl ether molecular chain and di-functional halogenated arylsulfonyl monomer, the combination of the three is promoted, which plays a similar role to high molecular coupling agent, thereby greatly reducing the content of small molecular weight oligomer. Compared with the prior art, the polyarylsulfonyl ether prepared by the present application can become very clear, transparent and completely true solution state when dissolved in DMF, and can be stably maintained for more than 20 days, thereby ensuring that various film preparation processes can be successfully implemented, so that polyarylsulfonyl ether can achieve its maximum application value.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a polyarylsulfone ether resin for film formation and its preparation method. Background Technology

[0002] Polyarylsulfone ether plastics are a class of amorphous aromatic thermoplastic polymers whose repeating polymer unit structures contain both arylsulfone bonds (-SO2-) and aryl ether bonds linked together. Industrially valuable polyarylsulfone ether plastics mainly include polysulfone (abbreviated as PSF, PSU, PSO, etc., hereinafter referred to as PSU), polyethersulfone (abbreviated as PES), polyphenylene sulfone (abbreviated as PPSF, PPSU, PPSO, etc., hereinafter referred to as PPSU), and polysulfide sulfone (abbreviated as PTES).

[0003] The sulfone and ether bonds in polyarylsulfone ethers endow these polymers with toughness, transparency, and high heat resistance. The sulfone bonds in the polymer backbone provide stiffness and hardness, while the continuous aromatic ring structure grants them resistance to high-temperature oxidation. Furthermore, the presence of flexible ether bonds in the backbone contributes to their toughness and impact resistance. Their heat distortion temperature ranges from 174 to 221°C, and their continuous operating temperature ranges from 160 to 190°C, with some varieties even reaching continuous operating temperatures above 205°C. These plastics also possess intrinsic flame retardant properties, producing very little smoke even when burning. In addition, these plastics exhibit high chemical resistance, meeting stringent safety requirements. It is evident that polyarylene ether plastics are a class of special engineering plastics characterized by high thermal stability, good transparency, excellent hydrolytic stability, low molding shrinkage, good biocompatibility, moderate electrical and mechanical properties, and excellent resistance to acids, alkalis, alcohols, aliphatic hydrocarbons, and salt solutions. They are fully comparable to high-quality engineering plastics such as polyether ether ketone (PEEK) and polyether ketone ketone (PEKK). In particular, the applications of polyarylene ether plastics in seawater desalination, ultrapure water filtration in the IC field, and membrane separation fields such as artificial kidneys are particularly outstanding, further highlighting their application value.

[0004] However, the preparation of polyarylsulfone ethers presents certain technical challenges, particularly in the preparation of polyarylsulfone ether resins for membrane applications, which presents significant technical barriers and hinders the development of polyarylsulfone ether resins in this most valuable application area. The most commonly used membrane-forming technique is the solution method, which requires dissolving the polyarylsulfone ether resin in solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), or N-methylpyrrolidone (NMP) before membrane formation. This necessitates that the polyarylsulfone ether resin solution remain highly clear, transparent, and stable throughout the entire processing cycle, exhibiting a truly complete solution state. Unfortunately, most products produced using existing polymerization technologies fail to meet this requirement. Some research reports suggest that this is due to the presence of small molecule oligomers in the polymer; see Selvaraj Sam, Geoffrey S. Underwooda, Eric M. Dickinson, Patrick J. Schieleke, Allan S. Hay. Polysulfone with lower levels of cyclic dimer: Use of MALDI-TOF in the study of cyclic oligomers, Desalination, 2002, 144, 15-20. During the research process leading to the technical solution of this application, the inventors discovered that these small molecules are primarily ABA, ABAB, and ABABA type small molecule oligomers (where A represents a difunctional phenol and B represents a difunctional halide sulfone); see [reference needed]. Figure 1 GPC spectra. Moreover, if the total peak area of ​​these small molecule oligomers exceeds 2.6% of the total peak area of ​​the system (determined by GPC analysis), it will cause the film-forming solution to become turbid within a short period of time, and this turbidity will worsen over time, eventually even becoming a combination of gel and pure solvent. It is evident that the harm caused by these small molecule oligomers is very serious; even if polyarylsulfone ether resins are synthesized and their mechanical properties are not inferior, the presence of these small molecule oligomers makes them unusable in film-forming processes. Unfortunately, no inventions on how to eliminate these small molecule oligomers have been publicly reported to date.

[0005] For example, Chinese patent CN 116218220A discloses a polyphenylsulfone composition, comprising, by weight, the following components: 95-99 parts of polyphenylsulfone resin; 0.1-5 parts of polyarylamide liquid crystal polymer; and 0.05-0.3 parts of acid scavenger. The polyphenylsulfone resin, by molar percentage, is derived from the following monomers: 10-35 mol% of 4,4'-biphenylhydrazine; 15-40 mol% of bisphenol monomers containing amide groups; and 45-55 mol% of 4,4'-dichlorodiphenyl sulfone. The main innovation of this scheme lies in adding 0.1-5 parts of polyarylamide liquid crystal polymer to the polymerizing monomers to increase the hydrophilicity of polyphenylsulfone, and adding 0.15% of acid scavenger to simplify the polycondensation process. However, it does not clearly contribute to whether this resin can completely eliminate small molecule oligomers and form a clear, transparent, and stable polyarylsulfone ether resin solution.

[0006] For example, Chinese patent CN 116589680 A discloses a method for preparing aromatic polymers, which includes polymerizing a halogenated monomer and a second monomer in the presence of an alkali, a solvent, and a desiccant. The second monomer includes a phenolic monomer, a thiophenolic monomer, or an amine monomer. The main innovation of this method lies in the fact that the monomer type is not limited to phenolic groups, but can also include thiophenolic or amine groups; it is not limited to dichlorophenyl sulfone, but can use various chlorophenyl sulfones, and even fluorophenyl sulfones. Furthermore, a desiccant is added during the reaction. It is believed that using a cheap and readily available desiccant to absorb the water generated during the polymerization reaction eliminates the need for a desiccant or a desiccant process, and reduces the content of non-soluble solids, thereby achieving low-cost and high-efficiency synthesis of a series of aromatic polymers. However, this invention also makes no clear contribution to whether small molecule oligomers can be completely eliminated to prepare a clear, transparent, and stable polyarylsulfone ether plastic solution for use in film-forming processes.

[0007] For example, Chinese patent CN118271618A discloses a method for preparing polyarylsulfone ethers based on a double-end-capping method. Using difunctional phenols and difunctional halosulfones as raw materials, a condensation polymerization reaction is carried out in an organic solvent and in the presence of an inorganic caustic alkali or inorganic caustic salt to prepare polyarylsulfone ethers. After the molecular weight of the polyarylsulfone ether reaches a predetermined value, a halogen-free phenolic metal end-capping agent is added to the polymerization system to remove the halogen end groups and control the molecular weight distribution of the polymer. After the condensation polymerization reaches the predetermined molecular weight, a highly active phenol-free metal aromatic end-capping agent is added to the polymerization system to remove the phenolic metal end groups and terminate the condensation polymerization reaction. Furthermore, the end-capping process allows the polyarylsulfone ether to contain necessary functional groups to meet the requirements of different application fields. Although this invention uses a highly active end-capping agent, which can eliminate some small molecule oligomers and thus effectively prolong the time for the polyarylsulfone ether plastic solution to become clear, transparent, and stable, there is still a certain gap compared to meeting the requirements of film-forming processes.

[0008] Therefore, in the field of membrane separation, where polyarylsulfone ether plastics have the greatest application value, it is necessary to maintain the intrinsic properties of polyarylsulfone ether while ensuring that it remains clear, transparent, and stable in solvents such as DMF for more than 20 days as a true solution. However, most current polymerization technologies cannot achieve this. This problem has naturally attracted the attention of the scientific and industrial communities, who are working to change this situation. This invention is part of these efforts. Summary of the Invention

[0009] The purpose of this invention is to overcome the defect of the classic polyarylsulfone ether synthesis technology, which is prone to generating small molecule oligomers, and to reduce the total peak area of ​​these small molecule oligomers to less than 1.6% of the total peak area of ​​the system (determined by GPC analysis). This allows the polyarylsulfone ether to dissolve in solvents, especially in DMF, into a very clear, transparent, and completely true solution state, which can be stably maintained for more than 20 days, so as to ensure that various film-forming processes can be implemented smoothly.

[0010] Based on this, the present invention provides a method for preparing polyarylsulfone ether resin for film forming.

[0011] The core technical solution adopted in this invention is to simultaneously add an aryl sulfone ether polymer containing special functional groups before the condensation polymerization process, and then carry out the condensation polymerization. This application fully utilizes the affinity of these special functional groups for difunctional phenolic groups and alkali metals in inorganic salts, respectively, to promote their combination. In addition, it utilizes the affinity of the polyaryl sulfone ether molecular chain containing special functional groups for difunctional halosulfone monomers to promote the combination of the three, acting as a polymer coupling agent, thereby significantly reducing the content of low molecular weight oligomers.

[0012] Therefore, the core of this invention is: first, a sulfone ether polymer containing special functional groups must be synthesized, and then added to the monomer raw material of the classic polysulfone ether condensation polymerization as a functional coupling agent, and then condensation polymerization is carried out to finally obtain a polysulfone ether resin with a total peak area of ​​small molecule oligomers that is less than 1.6% of the total peak area of ​​the system (GPC determination results).

[0013] The objective of this invention can be achieved through the following technical solutions:

[0014] The present invention first provides an aryl sulfone ether polymer containing a special functional group, which is obtained by condensation polymerization reaction of a difunctional aromatic phenol monomer, a difunctional halogenated aryl sulfone monomer, a difunctional aromatic phenol monomer with a special functional group and a difunctional halogenated aryl sulfone monomer with a special functional group.

[0015] The difunctional aromatic phenol monomer of the special functional group is selected from one or more of the following structures:

[0016]

[0017] In the structure of the difunctional aromatic phenol monomer of the special functional group, one, two, three or four positions of 1, 2, 3, 4 are –CN substituents, and one, two, three or four positions of a, b, c, d are –NO2 substituents.

[0018] The difunctional halosulfone monomer of the special functional group is selected from one of the following structures:

[0019]

[0020] In the difunctional halogenated sulfone monomer structure of the special functional group, one, two, three, or four positions at positions 1, 2, 3, and 4 are –CN substituents, and one, two, three, or four positions at positions a, b, c, and d are –NO2 substituents.

[0021] In one embodiment of the present invention, when preparing the sulfone ether polymer containing a special functional group by polymerization of a difunctional aromatic phenol monomer, a difunctional halogenated sulfone monomer, a difunctional aromatic phenol monomer with a special functional group and a difunctional halogenated sulfone monomer with a special functional group, the molar ratio of phenol to halogen is (0.8-1):1, preferably, the molar ratio of phenol to halogen is 1:1.

[0022] In one embodiment of the present invention, when preparing the sulfone ether polymer containing a special functional group by polymerizing a difunctional aromatic phenol monomer, a difunctional halogenated sulfone monomer, a difunctional aromatic phenol monomer with a special functional group, and a difunctional halogenated sulfone monomer with a special functional group, the molar content of the difunctional aromatic phenol monomer with the special functional group is no more than 5% of the total molar content of the difunctional aromatic phenol monomer and the difunctional aromatic phenol monomer with the special functional group, and the molar content of the difunctional halogenated sulfone monomer with the special functional group is no more than 5% of the total molar content of the difunctional halogenated sulfone monomer and the difunctional halogenated sulfone monomer with the special functional group. This ensures that these special functional groups are more widely dispersed and uniformly distributed along the molecular chain. Furthermore, it also helps to reduce production costs.

[0023] In one embodiment of the present invention, the difunctional aromatic phenol is selected from one or more combinations of the following structures:

[0024]

[0025]

[0026] In one embodiment of the present invention, the difunctional halosulfone is selected from one or more combinations of the following structural formulas:

[0027]

[0028] In one embodiment of the present invention, the weight-average molecular weight of the arylsulfone ether polymer containing special functional groups is 50,000 to 100,000.

[0029] The present invention further provides a method for preparing the arylsulfone ether polymer containing the special functional group, comprising the following steps:

[0030] S11. Salt formation and polycondensation reaction: Using difunctional aromatic phenol monomers and difunctional halosulfone monomers as raw materials, and adding the sulfone ether polymer containing the special functional group, a polycondensation polymerization reaction is carried out in an organic solvent in the presence of an inorganic caustic alkali or an inorganic caustic salt. The inorganic caustic alkali or inorganic caustic salt first reacts with the difunctional aromatic phenol monomer to generate a phenol metal salt, and then reacts with the halogen atom in the difunctional halosulfone monomer to remove the haloalkali metal salt and form the polycondensation product polysulfone ether.

[0031] S12. Cooling to terminate the reaction: After the condensation polymerization reaches the predetermined molecular weight, the reaction is terminated by cooling. Inorganic salts are removed by precipitation and filtration to obtain the arylsulfone ether polymer containing the special functional group.

[0032] In the preparation of sulfolane polymers containing special functional groups, the molar content of the difunctional aromatic phenol monomers containing special functional groups does not exceed 5% of the total molar content of both difunctional aromatic phenol monomers and difunctional aromatic phenol monomers containing special functional groups, and the molar content of the difunctional halosulfolane monomers containing special functional groups does not exceed 5% of the total molar content of both difunctional halosulfolane monomers and difunctional halosulfolane monomers containing special functional groups. This ensures that these special functional groups are more widely dispersed and uniformly distributed along the molecular chain. Secondly, it also helps to reduce production costs.

[0033] In the preparation of arylsulfone ether polymers containing special functional groups, the equivalent number of the inorganic caustic base or inorganic caustic salt is 1-1.5 times the equivalent number of phenol.

[0034] The inorganic caustic base or inorganic caustic salt is selected from one or a combination of the following substances:

[0035] LiOH, NaOH, KOH, CsOH, Na2O, K2O, Cs2O, Na2O2, K2O2, Na2CO3, K2CO3, Cs2CO3, NaHCO3, KHCO3, CsHCO3, Li3PO4, Na3PO4, K3PO4, Cs3PO4, Na2HPO4, Cs2HPO4 or K2HPO4;

[0036] The organic solvent is selected from one or a combination of the following substances: dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, and cyclohexanone.

[0037] The preparation of the aryl sulfone ether polymer containing special functional groups provided by the present invention can refer to the preparation of conventional polyaryl sulfone ether resins, or refer to the following method for preparing polyaryl sulfone ether resins for film forming.

[0038] This invention further provides a method for preparing polyarylsulfone ether resin for film forming, comprising the following steps:

[0039] S21. Salt formation and polycondensation reaction: Using difunctional aromatic phenol monomers, difunctional halosulfone monomers, and the above-mentioned sulfone ether polymers containing special functional groups as raw materials, a polycondensation reaction is carried out in an organic solvent in the presence of an inorganic caustic alkali or an inorganic caustic salt. The inorganic caustic alkali or inorganic caustic salt first reacts with the difunctional aromatic phenol monomer to generate a phenol metal salt, and then reacts with the halogen atom in the difunctional halosulfone monomer to remove the haloalkali metal salt and form the polycondensation product polysulfone ether.

[0040] S22. Termination of condensation polymerization: After the condensation polymerization reaches the predetermined molecular weight, a highly active phenol-removing metal aromatic end-capping agent is added to the polymerization system. The reaction is carried out for 1-2 hours. The halogen atoms in the structure of the highly active phenol-removing metal aromatic end-capping agent react with the phenol metal to remove the phenol metal end groups, thereby terminating the condensation polymerization reaction. During the end-capping process, the polyarylsulfone ether is end-capped with aromatic end groups. Then, the system is cooled, cooled down, and precipitated. Finally, the alkali halide metal salts are filtered out to obtain polyarylsulfone ether resin for film preparation.

[0041] In the preparation method of polyarylsulfone ether resin for film forming provided by the present invention, the addition of arylsulfone ether polymers containing special functional groups not only significantly reduces the content of small molecule oligomers in polyarylsulfone ether, but also significantly increases the polymerization rate.

[0042] In one embodiment of the present invention, the highly active phenol-removing metal aromatic end-capping agent in step S22 is selected from one or more of the following structural formulas, wherein n is a natural number from 0 to 16.

[0043]

[0044] In the preparation method of polyarylsulfone ether resin for membrane fabrication provided by the present invention, the content of the arylsulfone ether polymer containing special functional groups does not exceed 15% of the solid content of the polyarylsulfone ether resin for membrane fabrication.

[0045] In the preparation method of polyarylsulfone ether resin for film forming provided by the present invention, in step S22, not only is the polyarylsulfone ether end-group made aromatic during the end-capping process, but also the prepared polyarylsulfone ether resin for film forming contains necessary functional groups according to the structure of the aromatic end-capping agent.

[0046] In the preparation method of the polyarylsulfone ether resin for film forming in this application, an arylsulfone ether polymer containing special functional groups is added during the polycondensation reaction. The affinity of these special functional groups with difunctional phenolic groups and alkali metals in inorganic salts is fully utilized to promote their combination. In addition, the affinity of the polyarylsulfone ether molecular chain containing special functional groups with difunctional halogenated arylsulfone monomers is utilized to promote the combination of the three, playing a role similar to a polymer coupling agent, thereby significantly reducing the content of low molecular weight oligomers.

[0047] To enable conventional polyarylene ether sulfone resins to be used in film fabrication, the core of this invention lies in adding an arylene ether sulfone polymer containing a special functional group before polymerization in the conventional polymerization process. The polymerization of this arylene ether sulfone polymer containing the special functional group is identical to the preparation of the polyarylene sulfone ether resin itself, except for the addition of monomers containing the special functional group.

[0048] However, simply adding difunctional aromatic phenol monomers and difunctional halosulfone monomers with special functional groups during the polymerization of polyarylsulfone ether resins is ineffective. Therefore, the proposed method requires the addition of arylsulfone ether polymers with special functional groups during the polymerization of polyarylsulfone ether resins to eliminate small molecule oligomers. In other words, it is necessary to utilize the coupling effect of macromolecules containing special functional groups on the polymer chain to significantly reduce the content of small molecular weight oligomers.

[0049] Since the sulfone ether polymer containing special functional groups mainly uses the same difunctional aromatic phenol monomers and dihalosulfone monomers as the main raw materials for preparing polysulfone ether resin for membranes, the addition of the sulfone ether polymer containing special functional groups to the polymerization system of polysulfone ether resin for membranes in this application will not affect the performance of the main polysulfone ether resin.

[0050] In one embodiment of the present invention, when preparing polyarylsulfone ether resin for film forming, the relationship between the amount of difunctional aromatic phenol and difunctional halosulfone is: the molar ratio of phenol to halogen is (0.8-1):1, preferably, the molar ratio of phenol to halogen is 1:1.

[0051] In one embodiment of the present invention, the equivalent number of the inorganic caustic alkali or inorganic caustic salt is 1-1.5 times the equivalent number of phenol.

[0052] In one embodiment of the present invention, the inorganic caustic alkali or inorganic caustic salt is selected from one or a combination of the following substances:

[0053] LiOH, NaOH, KOH, CsOH, Na2O, K2O, Cs2O, Na2O2, K2O2, Na2CO3, K2CO3, Cs2CO3, NaHCO3, KHCO3, CsHCO3, Li3PO4, Na3PO4, K3PO4, Cs3PO4, Na2HPO4, Cs2HPO4 or K2HPO4.

[0054] In one embodiment of the present invention, the organic solvent is selected from one or a combination of the following substances: dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, and cyclohexanone.

[0055] In one embodiment of the present invention, the theoretical dosage of the highly active phenol-removing metal aromatic end-capping agent is shown in formula (1).

[0056]

[0057] Where: W is the amount of capping agent used, in weight unit; M is the set molecular weight of polyarylsulfone ether; V is the mass of the theoretical repeating unit of polyarylsulfone ether; N is the number of theoretical repeating unit structures converted from the raw materials of difunctional aromatic phenol and difunctional halosulfone; Q is the mass of the two end groups after deducting the repeating unit from the set molecular weight; C is the molar mass of the capping agent.

[0058] In one embodiment of the present invention, during the salt formation and polycondensation reaction in step S11 of the preparation of arylsulfone ether polymer containing special functional groups or in step S21 of the preparation of polyarylsulfone ether resin for film forming, an inert gas is required for gas phase protection, wherein the inert gas is selected from Ar, N2, etc.

[0059] In one embodiment of the present invention, during the salt formation and polycondensation reaction in step S11 of the preparation of the aryl sulfone ether polymer containing a special functional group or in step S21 of the preparation of the polyaryl sulfone ether resin for film formation, the phenolic alkali metal reacts with the halogen atoms in the haloaryl sulfone to obtain the reaction byproducts water and alkali halide metal salts. The remaining parts of the molecules bond with each other to form macromolecules, causing the molecular weight of the polyaryl sulfone ether to gradually increase. The byproduct water evaporates and is removed from the system, while the alkali halide metal salt precipitates and is removed from the polymerization system.

[0060] In one embodiment of the present invention, in step S12 of the preparation of the arylsulfone ether polymer containing special functional groups or in step S22 of the preparation of the polyarylsulfone ether resin for film forming, the method for determining whether the molecular weight of the polyarylsulfone ether reaches the predetermined value is as follows: during the polymerization process, samples are continuously taken, and the viscosity of the obtained samples is tested in a fixed solvent and concentration. The molecular weight of the polyarylsulfone ether can be determined based on its viscosity.

[0061] The present invention further provides a polyarylsulfone ether resin for film formation prepared by the above preparation method.

[0062] In one embodiment of the present invention, the membrane is dissolved in a solvent using polyarylsulfone ether resin, and then the membrane is formed.

[0063] In one embodiment of the present invention, the solvent is DMF.

[0064] Compared with the prior art, the advantages and beneficial effects of the present invention are mainly reflected in the following aspects:

[0065] 1) Existing technologies for preparing polyarylsulfone ether resins for membranes, once dissolved in solvents such as DMF, DMAc, and NMN, cause the polyarylsulfone ether resin solution to become turbid, precipitate, or even form peptones within a short period due to the presence of numerous small-molecule oligomers in the polymer, rendering it unusable. This invention adds an arylsulfone ether polymer containing special functional groups before the classic condensation polymerization process, and then performs condensation polymerization. By fully utilizing the coupling effect of this arylsulfone ether polymer containing special functional groups, the content of small-molecule oligomers is significantly reduced, lowering the total mass of small-molecule oligomers to below 1.6% of the mass of the resulting polyarylsulfone ether resin (determined based on GPC peak area analysis). This results in the polyarylsulfone ether dissolving in solvents, especially DMF, becoming a very clear, transparent, and completely true solution with a stable time exceeding 20 days, ensuring the smooth implementation of various membrane fabrication processes and maximizing the application value of the polyarylsulfone ether.

[0066] 2) In the existing synthesis process of polysulfone ether resins, a phenolic metal end group is always present. This severely hinders the application of polysulfone ether membranes in the IC field and ultrapure water filtration, and also induces precipitation of polysulfone ether resin in the membrane fabrication process. Although there are examples of using chloromethane for end-capping in classic synthesis methods, the boiling point of chloromethane is much lower than the polymerization temperature, which inevitably leads to the escape of chloromethane into the gas phase. This not only results in very low utilization and inability to be measured, but also causes these toxic gases to pollute the environment. It is particularly noteworthy that due to its high reactivity, it can even break the polysulfone ether bonds that are still in the transition state, generating more small molecule oligomers. The technical solution provided in this application uses an aromatic highly active end-capping agent with a boiling point higher than the polymerization temperature. This not only has high utilization and can be accurately measured, but also avoids environmental pollution. More importantly, its activity is slightly higher than that of halosulfones that have already formed large molecular end groups, making it easier to react with difficult-to-react small molecule oligomers to form large molecules, thereby reducing the content of small molecule oligomers and improving the stability of the membrane formation solution.

[0067] 3) Since the synthesis of polysulfone ethers is basically carried out by condensation polymerization, which involves the combination and removal of a halogen atom of a difunctional halosulfone with a phenol metal atom of a difunctional aromatic phenol metal, and the subsequent bonding of the removed molecular chains, the molecular weight distribution during the condensation polymerization process is difficult to control. This makes it difficult to ensure that the product or film has sufficient strength, processing flowability, and sufficient extensibility. However, this application adds a certain molecular weight of sulfone ether polymer containing special functional groups before starting the polymerization, and then carries out the condensation polymerization. This inevitably produces some higher molecular weight molecular chains, thereby achieving the requirement of expanding the molecular weight distribution.

[0068] 4) In the application of polyarylsulfone ether membrane separation, besides requiring a relatively stable membrane preparation solution, the polyarylsulfone ether resin membrane also needs to have different permeability to certain substances for different applications. This necessitates modifications to the polyarylsulfone ether molecular structure. For example, improving the hydrophilicity, carbonyl affinity, or amide affinity of specific sites in the molecular structure is required. Classical polymerization techniques typically involve adding other monomers to achieve copolymerization, which often alters the intrinsic properties of the polyarylsulfone ether and is less effective than using more dynamic end groups. The proposed solution uses end-capping agents with corresponding functional groups, achieving the desired outcome through a simple end-capping reaction. Attached Figure Description

[0069] Figure 1 The results of GPC analysis of the small molecule oligomers in Comparative Example 2, which could only remain turbid for 3 days, are shown. Figure 2 The results are from the GPC analysis of the small molecule oligomers in Example 2, which remained turbid for more than 45 days. Detailed Implementation

[0070] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0071] Comparative Example 1:

[0072] In a 50L pilot-scale reactor equipped with a distillation apparatus, 20 mol of biphenyl hydroquinone, 24 mol of sodium carbonate, 20.05 mol of dichlorodiphenyl sulfone, and 12.8L of N-methylpyrrolidone as solvent were added sequentially. Simultaneously, the stirrer was turned on at a speed of 120 rpm, and pure nitrogen was introduced for gas phase protection. Then, the heater for the circulating heat transfer oil in the reactor jacket was turned on, allowing the temperature to gradually increase. At 180℃, the temperature was maintained for 2 hours to complete the salt formation reaction. The temperature was then raised to 203℃, maintaining a reflux ratio R of approximately 1.1 in the distillation apparatus to remove moisture from the byproducts while polymerization continued for 4 hours. When the rotational viscosity of the melt in a 25% (mass percentage, the same below) dimethylacetamide solution at 40°C reaches 3000 mPa·s (measured by a rotational viscometer, the same below, i.e., the molecular weight of polyarylsulfone ether is controlled to reach the predetermined value), add 35.81 g of biphenyl benzyl chloride according to formula (1) and continue the reaction for 2 h. Then stop heating and stirring, and let the polymerization system cool down naturally while allowing the polymer solution to stand and precipitate. When the system drops to 120°C, maintain a constant temperature until the polymer solution precipitates the byproduct salt, potassium chloride, and the upper layer becomes a clear solution. Then separate and take out the upper clear polymer solution.

[0073] The clear polymer solution in the upper layer was concentrated, and some of the solvent was extracted. The concentrate was then circulated and ground in deionized water to form a fine powder mixed with water. After centrifugation to remove water, the mixture was dried under reduced pressure at 170°C using a ribbon dryer to obtain a dry powder of polyarylsulfone ether polymer. Then, at a total concentration of 0.2%,... 1790 / Under the protection of antioxidant 168, using Granulation of polyarylsulfone ether granules was obtained using a co-rotating parallel twin-screw extruder with a capacity of 35 and an L / D ratio of 40 at temperature settings of 150℃, 200℃, 225℃, 250℃, 260℃, 270℃, 280℃, 290℃, 300℃, and 300℃. The performance of the granules is shown in Table 1, where the ABA oligomer content represents the content of oligomers with a "phenol-phenyl sulfone-phenol" trimonomer unit structure.

[0074] Comparative Example 2:

[0075] Similar to Comparative Example 1, 20 mol of bisphenol A, 24 mol of potassium carbonate, 20.05 mol of dichlorodiphenyl sulfone, and 12.8 L of N-dimethylacetamide as solvent were added sequentially to a 50 L pilot-scale reactor equipped with a distillation apparatus. Simultaneously, the stirrer was turned on at a speed of 120 r / min, and pure nitrogen was introduced for gas phase protection. Then, the heater of the circulating heat transfer oil in the reactor jacket was turned on to gradually increase the temperature. At 130 °C, the temperature was maintained for 2 hours to complete the salt formation reaction. The temperature was then raised to 165 °C, maintaining a reflux ratio R of approximately 1.1 in the distillation apparatus to remove byproduct moisture while polymerization continued for 4 hours. Heating and stirring were stopped when the rotational viscosity of the melt in a 25% dimethylacetamide solution at 40 °C reached 2800, allowing the polymerization system to cool naturally and the polymer solution to settle. After the system is cooled to 120°C, it is kept at a constant temperature until the polymer solution precipitates out the byproduct salt, potassium chloride, and the upper layer becomes a clear solution. Then, the clear upper polymer solution is separated and removed.

[0076] The clear polymer solution from the top layer was partially solvent-extracted. The concentrated solution was then circulated and ground in deionized water to form a fine powder mixed with water. After centrifugation to remove water, the solution was dried under reduced pressure at 170°C using a ribbon dryer to obtain a dry powder of polyarylsulfone ether polymer. Then, at a total concentration of 0.2%,... 1790 / Under the protection of antioxidant 168, granulation was performed using a φ35 twin-screw extruder to obtain polyarylsulfone ether granules. Its performance testing and GPC analysis of the low molecular weight oligomers are shown in Table 1 and Table 2, respectively. Figure 1 As shown.

[0077] Example 1:

[0078] The first step is the synthesis of arylsulfone ether polymers containing special functional groups:

[0079] In a 50L pilot-scale reactor equipped with a distillation apparatus, 19.4 mol of biphenyl hydroquinone, 24 mol of sodium carbonate, 19.45 mol of dichlorodiphenyl sulfone, 0.03 mol of 2,2′-dinitrobisphenol A, 0.03 mol of 3,3′-dinitrodichlorodiphenyl sulfone, and 12.8L of N-methylpyrrolidone as solvent were added sequentially. Simultaneously, the stirrer was turned on at a speed of 120 rpm, and pure nitrogen was introduced for gas phase protection. Then, the heater of the circulating heat transfer oil in the reactor jacket was turned on, and the temperature was gradually increased. When the temperature reached 180℃, it was maintained for 2 hours to complete the salt formation reaction. Then, the temperature was raised to 203℃, and the reflux ratio R of the distillation apparatus was maintained at approximately 1.1 to remove moisture from the by-products while polymerization continued for 4 hours. When the rotational viscosity of the melt in a 25% dimethylacetamide solution at 40°C reaches 3000, heating and stirring are stopped, and the polymerization system is allowed to cool naturally while the polymer solution is allowed to settle. When the system cools to 120°C, the temperature is maintained until byproduct salts precipitate from the polymer solution and a clear solution appears on the upper layer. The clear upper polymer solution is then separated and removed.

[0080] The clear polymer solution in the upper layer is concentrated, and part of the solvent is extracted. The concentrate is then circulated and ground in deionized water to form a fine powder and water mixture. After centrifugation to remove water, the mixture is dried under reduced pressure at 170°C using a ribbon dryer to obtain a dry powder of aryl sulfone ether polymer containing special functional groups, namely aryl sulfone ether polymer A containing special functional groups.

[0081] Synthesis of polyarylsulfone ether resin for membrane fabrication:

[0082] In a 50L pilot-scale reactor equipped with a distillation apparatus, 20 mol of biphenyl hydroquinone, 24 mol of sodium carbonate, 20.05 mol of dichlorodiphenyl sulfone, 478 g of aryl sulfone ether polymer A containing a special functional group, and 13 L of N-methylpyrrolidone as solvent were added sequentially. Simultaneously, the stirrer was turned on at a speed of 120 r / min, and pure nitrogen was introduced for gas phase protection. Then, the heater of the circulating heat transfer oil in the reactor jacket was turned on, allowing the temperature to gradually increase. At 180℃, the temperature was maintained for 2 hours to complete the salt formation reaction. The temperature was then raised to 203℃, maintaining a reflux ratio R of approximately 1.1 in the distillation apparatus to remove byproduct moisture while polymerization continued for 4 hours. When the rotational viscosity of the melt in a 25% dimethylacetamide solution at 40℃ reached 2800, chloromethane was introduced, and the reaction continued for another 2 hours. When the rotational viscosity of the melt in a 25% dimethylacetamide solution at 40°C reaches 3000, heating and stirring are stopped, and the polymerization system is allowed to cool naturally while the polymer solution is allowed to settle. When the system cools to 120°C, the temperature is maintained until the polymer solution precipitates out the byproduct salt, sodium chloride, and a clear solution appears on the upper layer. The clear upper polymer solution is then separated and removed.

[0083] The clear polymer solution from the top layer was partially solvent-extracted. The concentrated solution was then circulated and ground in deionized water to form a fine powder mixed with water. After centrifugation to remove water, the solution was dried under reduced pressure at 170°C using a ribbon dryer to obtain a dry powder of polyarylsulfone ether polymer. Then, at a total concentration of 0.2%,... 1790 / Under the protection of antioxidant 168, granulation was carried out using a φ35 twin-screw extruder to obtain polyarylsulfone ether granules for film making. The performance test results are shown in the table.

[0084] Example 2:

[0085] The first step is the synthesis of arylsulfone ether polymers containing special functional groups:

[0086] In a 50L pilot-scale reactor equipped with a distillation apparatus, 19.4 mol of bisphenol A, 24 mol of potassium carbonate, 19.45 mol of dichlorodiphenyl sulfone, 0.03 mol of 2,2′-diacetonitrile bisphenol A, 0.03 mol of 3,3′-diacetonitrile dichlorodiphenyl sulfone, and 12.8L of N-dimethylacetamide as solvent were added sequentially. Simultaneously, the stirrer was turned on at a speed of 120 rpm, and pure nitrogen was introduced for gas phase protection. Then, the heater of the circulating heat transfer oil in the reactor jacket was turned on, and the temperature was gradually increased. At 130℃, the temperature was maintained for 2 hours to complete the salt formation reaction. Then, the temperature was raised to 170℃, and the reflux ratio R of the distillation apparatus was maintained at approximately 1.1 to remove moisture from the byproducts while polymerization continued for 4 hours. When the rotational viscosity of the melt in a 25% dimethylacetamide solution at 40°C reaches 2900, heating and stirring are stopped, and the polymerization system is allowed to cool naturally while the polymer solution is allowed to settle. When the system cools to 120°C, the temperature is maintained until the polymer solution precipitates out the byproduct salt and a clear solution appears on the upper layer. The clear polymer solution on the upper layer is then separated and removed.

[0087] The clear polymer solution in the upper layer is concentrated, and part of the solvent is extracted. The concentrate is then circulated and ground in deionized water to form a fine powder mixed with water. After centrifugation to remove water, the solution is dried under reduced pressure at 170°C using a ribbon dryer to obtain a dry powder of aryl sulfone ether polymer containing special functional groups, namely aryl sulfone ether polymer B containing special functional groups.

[0088] Synthesis of polyarylsulfone ether resin for membrane fabrication:

[0089] In a 50L pilot-scale reactor equipped with a distillation apparatus, 18 mol of bisphenol A, 21.6 mol of sodium carbonate, 18.05 mol of dichlorodiphenyl sulfone, 886 g of arylsulfone ether polymer B containing a special functional group, and 12.8 L of dimethylacetamide as solvent were added sequentially. Simultaneously, the stirrer was turned on at a speed of 120 r / min, and pure nitrogen was introduced for gas phase protection. Then, the heater of the circulating heat transfer oil in the reactor jacket was turned on to gradually increase the temperature. At 130℃, the temperature was maintained for 2 hours to complete the salt formation reaction. The temperature was then raised to 170℃, maintaining a reflux ratio R of approximately 1.1 in the distillation apparatus, while simultaneously removing moisture from the byproducts and continuing polymerization for 4 hours. Heating and stirring were stopped when the rotational viscosity of the melt in a 25% dimethylacetamide solution at 40℃ reached 2800, allowing the polymerization system to cool naturally and the polymer solution to settle. After the system is cooled to 120°C, it is kept at a constant temperature until the polymer solution precipitates out the byproduct salt and the upper layer becomes a clear solution. Then, the clear upper polymer solution is separated and removed.

[0090] The clear polymer solution in the upper layer was concentrated, and some of the solvent was extracted. The concentrate was then circulated and ground in deionized water to form a fine powder mixed with water. After centrifugation to remove water, the mixture was dried under reduced pressure at 170°C using a ribbon dryer to obtain a dry powder of polyarylsulfone ether polymer. Then, at a total concentration of 0.2%,... 1790 / Under the protection of antioxidant 168, granulation was performed using a φ35 twin-screw extruder to obtain polyarylsulfone ether granules for film formation. Its performance testing and GPC analysis of the low molecular weight oligomers are shown in Table 1 and Table 2, respectively. Figure 2 As shown.

[0091] Example 3:

[0092] Similar to Example 2, 18 moles of bisphenol A, 21.6 moles of sodium carbonate, 18.05 moles of dichlorodiphenyl sulfone, 886 g of arylsulfone ether polymer B containing special functional groups, and 12.8 L of dimethylacetamide as solvent were added sequentially to a 50 L pilot-scale reactor equipped with a distillation apparatus. Simultaneously, the stirrer was turned on at a speed of 120 r / min, and pure nitrogen was introduced for gas phase protection. Then, the heater of the circulating heat transfer oil in the reactor jacket was turned on to gradually increase the temperature. When the temperature reached 130 °C, it was maintained for 2 h to complete the salt formation reaction. Then, the temperature was raised to 170 °C, maintaining a reflux ratio R of approximately 1.1 in the distillation apparatus, while removing moisture from the byproducts and continuing polymerization for 4 h. When the rotational viscosity of the melt in a 25% dimethylacetamide solution at 40 °C reached 2800, 25.31 g of p-methylbenzyl chloride was added according to formula (1), and the reaction continued for 2-3 h. Then stop heating and stirring, and allow the polymerization system to cool naturally while the polymer solution settles. Once the system reaches 120°C, maintain a constant temperature until the polymer solution precipitates out the byproduct salt and a clear solution appears on the upper layer. Then separate and remove the clear polymer solution from the upper layer.

[0093] The clear polymer solution in the upper layer was concentrated, and some of the solvent was extracted. The concentrate was then circulated and ground in deionized water to form a fine powder mixed with water. After centrifugation to remove water, the mixture was dried under reduced pressure at 170°C using a ribbon dryer to obtain a dry powder of polyarylsulfone ether polymer. Then, at a total concentration of 0.2%,... 1790 / Under the protection of antioxidant 168, granules of polyarylsulfone ether for film production were obtained by granulation using a φ35 twin-screw extruder. Its performance is shown in the table below.

[0094] Table 1. Performance of polyarylsulfone ether granules in comparative examples and embodiments.

[0095]

[0096] In Table 1, the following parameters are specified: Tensile properties: Test method refers to GB / T 1040.2-2006 (Type 1A); Impact strength: Test method refers to GB / T 9341-2008; Glass transition temperature: Test method refers to ASTM D3418-15; Contact angle: Test method refers to GB / T 30447-2013; Metal content: Atomic spectroscopy.

[0097] Depend on Figure 1 , Figure 2 As shown in Table 1, in Comparative Example 2, the best representative example without the present invention, the total content of small molecule oligomers could only be reduced to 2.63% (GPC peak area ratio), and therefore its clarity in DMF solution could only be maintained for 3 days. In contrast, the method of the present invention, which involves adding an aryl sulfone ether polymer containing special functional groups before the classic condensation polymerization process and then performing condensation polymerization, can directly reduce the total content of small molecule oligomers to 1.55% (GPC peak area ratio), and thus maintains its clarity in DMF solution for at least 45 days. Furthermore, in Example 3, due to the use of a selected aromatic end-capping agent, the total amount of small molecule oligomers was further reduced to 1.4%; in contrast, in Example 1, after chloromethane end-capping, the total amount of small molecule oligomers was actually higher than in the comparative example. It is conceivable that such polyaryl sulfone ether resin can be readily used in any film-forming process. This allows polyarylsulfone ether resins to play a greater role in high-value applications such as seawater desalination membranes and biofiltration membranes.

[0098] The polyarylsulfone ether resin prepared by this invention can be used for film formation by solution film formation method. Specifically, the polyarylsulfone ether resin prepared by this invention is dissolved in solvents such as DMF, DMAc, and NMP (especially DMF solvent), and then film is formed using conventional methods.

[0099] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A sulfolane polymer containing a special functional group, characterized in that, It is obtained by condensation polymerization of difunctional aromatic phenol monomers, difunctional halosulfone monomers, difunctional aromatic phenol monomers with special functional groups and difunctional halosulfone monomers with special functional groups. The difunctional aromatic phenol monomer of the special functional group is selected from one or more of the following structures: In the structure of the difunctional aromatic phenol monomer of the special functional group, one, two, three or four positions of 1, 2, 3, 4 are –CN substituents, and one, two, three or four positions of a, b, c, d are –NO2 substituents. The difunctional halosulfone monomer of the special functional group is selected from one of the following structures: In the difunctional halogenated sulfone monomer structure of the special functional group, one, two, three, or four positions at positions 1, 2, 3, and 4 are –CN substituents, and one, two, three, or four positions at positions a, b, c, and d are –NO2 substituents.

2. The arylsulfone ether polymer containing a special functional group according to claim 1, characterized in that, When preparing the sulfone ether polymer containing the special functional group by polymerization of difunctional aromatic phenol monomers, difunctional halosulfone monomers, difunctional aromatic phenol monomers with special functional groups and difunctional halosulfone monomers with special functional groups, the molar ratio of phenol to halogen is (0.8-1):1, preferably, the molar ratio of phenol to halogen is 1:

1. When preparing the sulfone ether polymer containing a special functional group by polymerization of difunctional aromatic phenol monomers, difunctional halogenated sulfone monomers, difunctional aromatic phenol monomers containing special functional groups and difunctional halogenated sulfone monomers containing special functional groups, the molar content of the difunctional aromatic phenol monomers containing special functional groups shall not exceed 5% of the total molar content of the difunctional aromatic phenol monomers and difunctional aromatic phenol monomers containing special functional groups, and the molar content of the difunctional halogenated sulfone monomers containing special functional groups shall not exceed 5% of the total molar content of the difunctional halogenated sulfone monomers and difunctional halogenated sulfone monomers containing special functional groups.

3. The arylsulfone ether polymer containing a special functional group according to claim 1, characterized in that, The difunctional aromatic phenol is selected from one or more of the following structures: The difunctional halosulfone is selected from one or more of the following structural formulas:

4. The method for preparing an arylsulfone ether polymer containing a special functional group as described in claim 1, characterized in that, Includes the following steps: S11, Salt formation and condensation reaction: Using difunctional aromatic phenol monomers, difunctional halosulfone monomers, difunctional aromatic phenol monomers with special functional groups, and difunctional halosulfone monomers with special functional groups as raw materials, a condensation polymerization reaction is carried out in an organic solvent in the presence of an inorganic caustic alkali or inorganic caustic salt. The inorganic caustic alkali or inorganic caustic salt first reacts with the difunctional aromatic phenol monomer to generate a phenol metal salt, and then reacts with the halogen atom in the difunctional halosulfone monomer to remove the haloalkali metal salt and form the condensation product polyarylsulfone ether. S12. Cooling to terminate the reaction: After the condensation polymerization reaches the predetermined molecular weight, the reaction is terminated by cooling. Inorganic salts are removed by precipitation and filtration to obtain the arylsulfone ether polymer containing the special functional group.

5. The method for preparing an arylsulfone ether polymer containing a special functional group according to claim 4, characterized in that, The molar content of the difunctional aromatic phenol monomer with special functional group does not exceed 5% of the total molar content of the difunctional aromatic phenol monomer and the difunctional aromatic phenol monomer with special functional group, and the molar content of the difunctional halosulfone monomer with special functional group does not exceed 5% of the total molar content of the difunctional halosulfone monomer and the difunctional halosulfone monomer with special functional group. The equivalent number of the inorganic caustic alkali or inorganic caustic salt is 1 to 1.5 times that of the phenol equivalent number; The inorganic caustic base or inorganic caustic salt is selected from one or a combination of the following substances: LiOH, NaOH, KOH, CsOH, Na2O, K2O, Cs2O, Na2O2, K2O2, Na2CO3, K2CO3, Cs2CO3, NaHCO3, KHCO3, CsHCO3, Li3PO4, Na3PO4, K3PO4, Cs3PO4, Na2HPO4, Cs2HPO4 or K2HPO4; The organic solvent is selected from one or a combination of the following substances: dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, and cyclohexanone.

6. A method for preparing a polyarylsulfone ether resin for film forming, characterized in that, Includes the following steps: S21. Salt formation and polycondensation reaction: Using difunctional aromatic phenol monomers and difunctional halosulfone monomers as raw materials, and adding the sulfone ether polymer containing the special functional group, a polycondensation polymerization reaction is carried out in an organic solvent in the presence of an inorganic caustic alkali or an inorganic caustic salt. The inorganic caustic alkali or inorganic caustic salt first reacts with the difunctional aromatic phenol monomer to generate a phenol metal salt, and then reacts with the halogen atom in the difunctional halosulfone monomer to remove the haloalkali metal salt and form the polycondensation product polysulfone ether. S22. Termination of condensation polymerization: After the condensation polymerization reaches the predetermined molecular weight, a highly active phenol-removing metal aromatic end-capping agent is added to the polymerization system. The reaction is carried out for 1-2 hours. The halogen atoms in the structure of the highly active phenol-removing metal aromatic end-capping agent react with the phenol metal to remove the phenol metal end groups, thereby terminating the condensation polymerization reaction. During the end-capping process, the polyarylsulfone ether is end-capped with aromatic end groups. Then, the system is cooled, cooled down, and precipitated. Finally, the alkali halide metal salt is filtered out to obtain polyarylsulfone ether resin for film preparation. The difunctional aromatic phenol monomer, the difunctional halosulfone monomer as defined in claim 3, or the sulfone ether polymer containing the special functional group is as described in any one of claims 1-3.

7. The method for preparing a polyarylsulfone ether resin for film forming according to claim 6, characterized in that, The amount of the polymer containing special functional aryl sulfone ethers added shall not exceed 15% of the total mass of the polyaryl sulfone ether resin for membranes.

8. The method for preparing a polyarylsulfone ether resin for film forming according to claim 6, characterized in that, The highly active phenol-removing metal aromatic end-capping agent in step S22 is selected from one or more of the following structural formulas, where n is a natural number from 0 to 16; The theoretical dosage of the highly active phenol-removing metal aromatic end-capping agent is shown in formula (1). Where: W is the amount of capping agent used, in weight unit; M is the set molecular weight of polyarylsulfone ether; V is the mass of the theoretical repeating unit of polyarylsulfone ether; N is the number of theoretical repeating unit structures converted from the raw materials of difunctional aromatic phenol and difunctional halosulfone; Q is the mass of the two end groups after deducting the repeating unit from the set molecular weight; C is the molar mass of the capping agent.

9. The method for preparing a polyarylsulfone ether resin for film forming according to claim 6, characterized in that, When preparing polyarylsulfone ether resin for film forming, the relationship between the amount of difunctional aromatic phenol and difunctional halosulfone is: the molar ratio of phenol to halogen is (0.8-1):1, preferably, the molar ratio of phenol to halogen is 1:1; During the salt formation and condensation reaction, inert gas is required for gas phase protection. The equivalent number of the inorganic caustic alkali or inorganic caustic salt is 1 to 1.5 times that of the phenol equivalent number; The inorganic caustic base or inorganic caustic salt is selected from one or a combination of the following substances: LiOH, NaOH, KOH, CsOH, Na2O, K2O, Cs2O, Na2O2, K2O2, Na2CO3, K2CO3, Cs2CO3, NaHCO3, KHCO3, CsHCO3, Li3PO4, Na3PO4, K3PO4, Cs3PO4, Na2HPO4, Cs2HPO4 or K2HPO4; The organic solvent is selected from one or a combination of the following substances: dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, and cyclohexanone.

10. A polyarylsulfone ether resin for film formation, characterized in that, The polyarylsulfone ether resin used for film preparation is prepared by the preparation method described in claim 6 and can be used to prepare polyarylsulfone ether films.

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