Synthesis method of polyarylether resin

Abstract

The invention discloses a synthesis method of polyarylether resin, belongs to the technical field of high polymer materials, and particularly relates to a preparation method of special engineering plastic polyarylether resin. According to the method, the polyarylether is synthesized by adopting the organic solvent, a water-carrying agent is not added, the content of the organic solvent is adjustable, the solid content is adjustable, and the molecular collision speed can be regulated, so that the polymerization reaction can be completed more quickly. Compared with a sample polymer containing a water-carrying agent, the molecular weight is larger, the heat resistance is better, and the mechanical property is higher. The method does not contain polymerization reaction of a water-carrying agent, is more environment-friendly, saves energy consumption, and can be widely applied to industrial production.

Description

Technical Field

[0001] The present invention belongs to the field of polymer materials and relates to a synthesis method for preparing polyaryl ether materials such as non-crystalline polyarylether sulfone and soluble polyether ketone. Background Art

[0002] Polyaryl ether materials refer to aromatic polymers containing groups such as benzene rings, phenoxybenzenes, and sulfone groups or ketone groups. For such polymers, the molecular chains are relatively rigid, and they have good mechanical properties and thermal properties. Relatively mature industrial products include polyethersulfone, polyphenylene sulfone, bisphenol A polysulfone, and amorphous polyether ketone. These resins have extensive applications in the fields of food, medical device and drug administration, electronics and electrical, walking machinery, aerospace, and petrochemical industry. The synthesis methods of polyaryl ether materials can be divided into electrophilic routes and nucleophilic routes, each having its own advantages. Among commercial products, for the same variety, products of both routes are available. The output of the polymerization products of the nucleophilic route occupies an absolute dominant position, and the nucleophilic route is the main synthesis route of polyaryl ether materials.

[0003] The nucleophilic route of polyaryl ether is the polymerization reaction of bisphenol and dihalide. Under the action of a salt-forming agent, a nucleophilic substitution reaction occurs. The salt-forming agent can be a strong base such as hydroxide or a weak base such as carbonate, and the main by-products are water and inorganic halide salts. During the polymerization process of the polyaryl ether reaction, the removal of water is the key to the forward progress of the reaction.

[0004] For the nucleophilic polycondensation reaction of polyaryl ether, depending on the monomer activity, solubility, and salt-forming agent activity, etc., the final polymerization temperature is between 120°C and 250°C. Depending on the solubility of the polymer and the reaction temperature, the polymerization solvent is generally a high-temperature resistant solvent, including N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, isoquinoline, etc.

[0005] Many current polymerization processes of polyethersulfone and soluble polyaryletherketone polymers generally use a water-carrying agent to remove the water produced by the reaction from the reaction system. The water-carrying agent is generally incompatible with water. At high temperatures, water and the water-carrying agent form an azeotrope. The water-carrying agent circulates into the reaction system, and the water is removed and separated to allow the reaction to proceed in the normal phase. Different solvents are used in nucleophilic polycondensation reactions, and the water-carrying agents are also different. When N, N-dimethylacetamide (DMAc) is used as a solvent, toluene is generally used as a water-carrying agent (CN117384381A); when a high-boiling point solvent such as cyclopentane sulfone (TMS) is used, xylene is used as a water-carrying agent (CN117247544A, CN116836391A); when N-methylpyrrolidone (NMP) is used as a solvent, toluene or xylene can be used as a water-carrying agent (CN117209367A). At the same time, the reaction belongs to a gradual polycondensation reaction, which has a long reaction time, high energy consumption, and high temperature reaction is also easy to cause monomer oxidation, affecting the color. The polymerization time of CN1176970A, CN1231302A, and CN1268526A is more than 10 hours.

[0006] In recent years, methods for synthesizing polyarylether without using a water-containing agent have also been gradually studied. Many patents use high-temperature solvents, and utilize the difference in vapor pressure and boiling point between solvents and water to remove water at high temperatures. Solvents such as diphenyl sulfone and cyclopentane (CN113980275A) can be selected. These methods have low water removal efficiency and long reaction time. Patent document CN116120556A uses a method of nitrogen conduit and gas distributor to blow water out of the reaction system using a large amount of nitrogen. There is no industrial device for this method yet.

[0007] There are also some methods to increase the polymerization rate of polyarylether, mainly using organic amine salts, organic acid salts, pyridine derivatives, etc. as phase transfer catalysts to increase the reaction rate (CN104277221A, CN104371105A, CN116178721A, CN118126268A, CN117069652A). These methods introduce components with high prices and are difficult to remove, which affects product performance.

[0008] Based on the prior art, when using water-soluble solvents (such as TMS, NMP and DMAc) in the nucleophilic polycondensation reaction of polyarylethersulfone and soluble polyaryletherketone, water-carrying agents are used to remove water so that the reaction proceeds in the forward direction. The method of azeotropic reaction of water and organic solvent is used to accelerate the removal of water solvent. If a water-carrying agent is not used, the water removal is not complete, the reaction time is longer, and the reaction cannot obtain a high molecular weight polymer. The water-carrying agents used in these polymerization reactions are extremely carcinogenic and have great harm to the environment; and in the final polymerization solution, the residual xylene and other reagents are extremely harmful to the workers when the material is discharged at high temperature, causing xylene to deposit in the workers' bodies.

[0009] In addition, the commonly used organic azeotropic water-carrying agents are flammable and explosive, belonging to Class A hazardous chemicals, and have high requirements for the production environment and equipment. In the nucleophilic polycondensation reaction of polyarylether sulfone and soluble polyarylether ketone materials, except for the water-carrying agent, the other materials are Class C hazardous chemicals at most. The polymerization reaction without a water-carrying agent will be easier to produce and have lower costs. Summary of the Invention

[0010] To improve the above technical problems, the present invention provides a method for preparing polyarylether, including: mixing and reacting a dihalo monomer, a bisphenol monomer, a composite salt, and a solvent to obtain the polyarylether;

[0011] The dihalo monomer is selected from Each X is the same or different and is independently selected from halogens, such as F, Cl; E is selected from C(O), S(O)2; m is selected from 1, 2, 3, 4;

[0012] The bisphenol monomer is selected from A is selected from a single bond, S(O)2, the following groups unsubstituted or optionally substituted by one, two, or more Ra: sub-C 1-6 alkyl, C 6-14 arylene, 3-14 membered heteroarylene; each Ra is the same or different and is independently selected from oxo, halogen, C 1-6 alkyl, halo-C 1-6 alkyl;

[0013] The composite salt includes the following three salts:

[0014] (1) Alkali metal carbonate;

[0015] (2) Alkali metal hydroxide;

[0016] (3) And sodium sulfite;

[0017] According to an embodiment of the present invention, the dihalo monomer is selected from:

[0018]

[0019] According to an embodiment of the present invention, the bisphenol monomer is selected from A is selected from a single bond, S(O)2, the following groups unsubstituted or optionally substituted by one, two, or more Ra: methylene, C 10-13 arylene (such as fluorene-9,9-diyl), 5-9 membered heteroarylene (such as ); each Ra is the same or different and is independently selected from oxo, methyl, trifluoromethyl;

[0020] According to an embodiment of the present invention, the bisphenol monomer is selected from:

[0021]

[0022] According to an embodiment of the present invention, the alkali metal carbonate is selected from at least one of sodium carbonate, potassium carbonate, and cesium carbonate.

[0023] According to an embodiment of the present invention, the alkali metal hydroxide is selected from at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide.

[0024] According to an embodiment of the present invention, the molar ratio of the alkali metal carbonate, alkali metal hydroxide, and sodium sulfite in the composite salt is (4 - 20):1:(0.0001 - 0.1); for example, (5 - 15):1:(0.001 - 0.01), (8 - 12):1:(0.002 - 0.008), such as 9.6:1:0.0047, 13.3:1:0.0042.

[0025] According to an embodiment of the present invention, the molar ratio of the bisphenol monomer to the composite salt is 1:(0.8 - 2), for example, 1:(1.05 - 1.4), such as 1:1.2, 1:1.3.

[0026] According to an embodiment of the present invention, the molar ratio of the dihalo monomer to the bisphenol monomer is (0.5 - 2):1, for example, (0.8 - 1.5):1, such as 0.85:1, 0.9:1, 0.95:1, 1:1.

[0027] According to an embodiment of the present invention, the solvent is selected from at least one of sulfolane (TMS), dimethyl sulfoxide (DMSO), N,N - dimethylacetamide (DMAc), and N - methylpyrrolidone (NMP).

[0028] According to an embodiment of the present invention, the weight ratio of the total weight of the dihalo monomer and the bisphenol monomer to the weight of the solvent is 1:(0.5 - 2), for example, 1:(0.8 - 1.5). Preferably, at the initial stage of the reaction, the weight ratio of the total weight of the dihalo monomer and the bisphenol monomer to the weight of the solvent is 1:(0.8 - 1.1), and the solvent is added according to the viscosity of the reaction solution to make the viscosity of the reaction solution not higher than 2500 Pa·s, for example, not higher than 2000 Pa·s.

[0029] According to an embodiment of the present invention, hydrazine hydrate can also be added in the preparation method.

[0030] According to an embodiment of the present invention, the polyarylether is obtained by mixing and reacting the dihalo monomer, bisphenol monomer, composite salt, hydrazine hydrate, and solvent.

[0031] According to an embodiment of the present invention, the volume of the hydrazine hydrate is one - hundred - thousandth to two - ten - thousandths of the volume of the solvent, for example, two - hundred - thousandths to one - ten - thousandth.

[0032] According to an embodiment of the present invention, the temperature of the reaction is 100°C to 240°C, for example 120°C to 180°C, such as 130°C, 140°C, 150°C, 160°C, 170°C.

[0033] According to an embodiment of the present invention, the time of the reaction is 0.5 - 6 h, for example 1 - 4 h.

[0034] According to an embodiment of the present invention, the preparation method further includes the step of supplementing and adding a solvent when the reaction viscosity increases, and the viscosity of the reaction solution is not higher than 2500 Pa·s, for example not higher than 2000 Pa·s.

[0035] According to an embodiment of the present invention, the amount of the supplemented and added solvent is at least the amount of the solvent lost during the reaction process.

[0036] According to an embodiment of the present invention, the polyarylether is polyarylethersulfone or polyaryletherketone, for example soluble non-crystalline polyarylethersulfone or polyaryletherketone.

[0037] According to an embodiment of the present invention, the preparation method includes the following steps: mixing a dihalogen monomer, a bisphenol monomer, a composite salt, and optionally added hydrazine hydrate in a solvent, heating, maintaining at 120°C to 180°C for 0.5 to 2 h; maintaining at 150°C to 230°C for 1 to 4 h, when the reaction viscosity is relatively high, supplementing and adding a solvent, determining the polymerization end point according to the viscosity of the polymerization solution, and performing post-treatment to obtain the polyarylether.

[0038] According to an embodiment of the present invention, the preparation method includes the following steps: mixing a dihalogen monomer, a bisphenol monomer, a composite salt, and hydrazine hydrate in a solvent, heating, maintaining at 120°C to 180°C for 0.5 to 2 h; maintaining at 150°C to 230°C for 1 to 4 h, when the reaction viscosity is relatively high, supplementing and adding a solvent, determining the polymerization end point according to the viscosity of the polymerization solution, and performing post-treatment to obtain the polyarylether.

[0039] According to an embodiment of the present invention, the post-treatment includes injecting the reaction solution into water, pulverizing, filtering, extracting the polymerization solvent and inorganic salts with distilled water, and drying the obtained product to obtain the polyarylether.

[0040] According to an embodiment of the present invention, the preparation method includes the following steps:

[0041] Under the protection of inert gas, add a solvent into a reaction kettle, then add a composite salt, hydrazine hydrate, a dihalogen monomer and a bisphenol monomer, and heat. Keep the temperature at 120°C to 180°C for 0.5 to 1 hour. At this time, a gas distills out. Add a condenser 1 at the gas phase outlet. The temperature of the condenser 1 is 110 to 180°C, so that the organic solvent returns to the reaction kettle while water distills out of the reaction system. The gas phase continues to enter a condenser 2, and the temperature of the condenser 2 is room temperature to recover the uncondensed substances. According to the activity of the polymerization monomers and the type of solvent, keep the temperature at 150°C to 230°C for 1 to 4 hours. Measure the weight of the distilled liquid at the outlet end of the reaction kettle. When the reaction viscosity is relatively high, gradually add an appropriate amount of solvent to the reaction kettle. Determine the polymerization end point according to the viscosity of the polymerization solution. After reaching the target viscosity, inject the polymerized solution that has completed the reaction into water, crush it, filter it, and extract the polymerization solvent and inorganic salts with distilled water. Dry the obtained polymer powder to obtain the target polyarylether material.

[0042] According to the embodiments of the present invention, achieving the target viscosity means that the number average molecular weight of the product is 20,000 to 160,000 g / mol.

[0043] The present invention also provides the application of the preparation method in the industrial preparation of polyarylether materials.

[0044] Beneficial effects

[0045] (1) The present invention provides a nucleophilic polycondensation method for polyarylethers. By designing the composition of the basic composite salt, the polymerization reaction can be quickly completed without a water-carrying agent. At the same time, it avoids the physical damage of production personnel caused by residual high carcinogens such as toluene (usually used as a water-carrying agent) during the discharging process after polymerization, and avoids the high explosion-proof requirements for flammable and explosive substances such as toluene.

[0046] (2) The method of the present invention can improve the influence of oxygen on the color caused by the lack of reflux of the water-carrying agent.

[0047] (3) The present invention can achieve a rapid polymerization reaction, reduce the polymerization cost, and reduce the influence of long-term heating at high temperature on the reaction color. The polymer generated by the present invention has good color, mechanical properties and transparency. Description of the drawings

[0048] Figure 1 : Thermogravimetric diagrams of the polysulfones synthesized in Example 1 and Example 2: a. Example 1, b. Example 2

[0049] Figure 2 : Tensile properties of the polysulfone resins synthesized in Example 1 and Example 2: a. Example 1, b. Example 2

[0050] Term definitions and explanations

[0051] Unless otherwise specified, the definitions of groups and terms recited in the specification and claims of this application, including their definitions as examples, exemplary definitions, preferred definitions, definitions recited in tables, definitions of specific compounds in the examples, etc., can be combined and combined with each other arbitrarily. The defined groups and compound structures after such combination and combination should be understood to be within the scope recited in the specification and / or claims of this application.

[0052] Unless otherwise specified, the numerical ranges recited in this specification and claims are equivalent to at least recording each specific integer value therein. For example, the numerical range "1-14" is equivalent to recording each integer value in the numerical range "1-14", namely 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14.

[0053] It should be understood that in the description of one, two or more, "more" should mean greater than 2, for example, an integer greater than or equal to 3, such as 3, 4, 5, 6, 7, 8, 9 or 10.

[0054] The term "halogen" means fluorine, chlorine, bromine and iodine.

[0055] The term "C 1-6 alkyl" should be understood to mean straight-chain and branched-chain alkyls having 1, 2, 3, 4, 5 or 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, etc. or their isomers.

[0056] The term "C 6-14 aryl" should be understood to preferably mean a monocyclic, bicyclic (such as fused ring, bridged ring, spiro ring) or tricyclic hydrocarbon ring having 6 to 14 carbon atoms with monovalent aromatic or partially aromatic properties, which can be a monocyclic aromatic ring or a polycyclic aromatic ring fused together. The term "C 6-14 aryl" should be understood to preferably mean a monocyclic, bicyclic or tricyclic hydrocarbon ring having 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms with monovalent aromatic or partially aromatic properties ("C 6-14 aryl"), especially a ring having 6 carbon atoms ("C6 aryl"), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C9 aryl"), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10"aryl"), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl"), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl"), such as anthryl. When the C 6-20 aryl is substituted, it may be mono-substituted or multi-substituted. And there is no restriction on the substitution site, for example, it may be ortho-substituted, para-substituted or meta-substituted.

[0057] The term "3- to 14-membered heterocyclic group" refers to a saturated or unsaturated non-aromatic ring or ring system. For example, it is a 4-, 5-, 6- or 7-membered monocyclic ring, a 7-, 8-, 9-, 10-, 11- or 12-membered bicyclic ring (such as a fused ring, a bridged ring, a spiro ring) or a 10-, 11-, 12-, 13-, 14- or 15-membered tricyclic ring system, and contains at least one, for example, 1, 2, 3, 4, 5 or more heteroatoms selected from O, S and N, wherein N and S may also be optionally oxidized to various oxidation states to form the state of nitrogen oxide, -S(O)- or -S(O)2-. Preferably, the heterocyclic group may be selected from "3- to 10-membered heterocyclic group". The term "3- to 10-membered heterocyclic group" means a saturated or unsaturated non-aromatic ring or ring system and contains at least one heteroatom selected from O, S and N. The heterocyclic group may be connected to the rest of the molecule through any one of the carbon atoms or a nitrogen atom (if present). The heterocyclic group may include fused or bridged rings and spiro rings. In particular, the heterocyclic group may include, but is not limited to: a 4-membered ring, such as azetidinyl, oxetanyl; a 5-membered ring, such as tetrahydrofuranyl, dioxolanyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a 6-membered ring, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl or trithianyl; or a 7-membered ring, such as diazepanyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclic group may be bicyclic, for example, but not limited to a 5,5-membered ring, such as hexahydrocyclopenta[c]pyrrol-2(1H)-yl ring, or a 5,6-membered bicyclic ring, such as hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl ring. The heterocyclic group may be partially unsaturated, that is, it may contain one or more double bonds, for example, but not limited to dihydrofuranyl, dihydropyranyl, 2,5-dihydro-1H-pyrrolyl, 4H-[1,3,4]thiadiazinyl, 1,2,3,5-tetrahydrooxazolyl or 4H-[1,4]thiazinyl, or it may be benzo-fused, for example, but not limited to dihydroisoquinolinyl.

[0058] The term "sub*ylene" refers to a divalent group, such as sub-C 1-6 alkyl, C 6-14 arylene, 3- to 14-membered subheterocyclic group, wherein, C 1-6 alkyl, C6-14 An aryl group or a 3- to 14-membered heterocyclic group has the definitions described above. Detailed implementation manners

[0059] The technical solutions of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only for illustrative explanation of the present invention and should not be construed as limiting the protection scope of the present invention.

[0060] All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention. Unless otherwise specified, the raw materials and reagents used in the following embodiments are commercially available products or can be prepared by known methods.

[0061] Example 1:

[0062] Under the protection of an inert gas, 50 kg of N,N-dimethylacetamide was added, 6 ml of hydrazine hydrate (80% content), 14.15 kg of potassium carbonate, 0.6 kg of potassium hydroxide, 6.3 g of sodium sulfite, 25.9978 kg of 4,4'-dichlorodiphenyl sulfone, and 20.5467 kg of bisphenol A were added. Stir and heat to 160 °C, with the temperature of the condenser being 165 °C. React for 1 hour, weigh the distilled weight as 6.6 kg, supplement 5 kg of pure DMAc at 160 °C, change the temperature of condenser 1 to 140 °C, raise the reaction temperature to 167 °C, set the condenser temperature to 158 °C, and continue to react for 2.6 hours. The weight of the distilled solution is 0.5 kg. According to the viscosity of the reaction solution, when it exceeds 2000 Pa·s, solvent is supplemented. It is supplemented 6 times, with 7 kg of pure DMAc at 150 °C each time. Discharge into pure water, pulverize, purify 9 times with pure water, filter and dry to prepare 40 kg of resin, with a yield of 99%.

[0063] Example 2:

[0064] Example 2 is a comparative experiment, using toluene as a water-carrying agent.

[0065] Under the protection of an inert gas, 94 kg of N,N-dimethylacetamide, 14.15 kg of potassium carbonate, 0.6 kg of potassium hydroxide, 3 kg of toluene, 25.9978 kg of 4,4'-dichlorodiphenyl sulfone, and 20.5467 kg of bisphenol A were added. Stir and heat, and use a water separator to carry out water, with the condenser refluxing. After reacting for 2 hours, toluene and water were released, raise the reaction temperature to 167 °C, with the condenser refluxing, react for 2.6 hours, discharge into pure water, pulverize, purify 9 times with pure water, filter and dry to prepare 35.16 kg of resin, with a yield of 87%. The sample was too brittle to prepare mechanical property test specimens.

[0066] Example 3:

[0067] Change 4,4'-dichlorodiphenyl sulfone in Example 1 to 4,4'-difluorobenzophenone.

[0068] Under the protection of inert gas, add 45 kg of N,N-dimethylacetamide, 6 ml of hydrazine hydrate (80% content), 14.15 kg of potassium carbonate, 0.6 kg of potassium hydroxide, 6.3 g of sodium sulfite, 19.62 kg of 4,4'-difluorobenzophenone, and 20.5467 kg of bisphenol A. Stir and heat up to 160 °C. The temperature of the condenser is 165 °C. React for 1 hour. Weigh the distilled weight as 6.5 kg. Add 5 kg of pure DMAc at 160 °C. Change the temperature of condenser 1 to 140 °C. Heat up the reaction to 167 °C. Set the condenser temperature to 158 °C. Continue to react for 2.6 hours. The weight of the distilled solution is 0.45 kg. According to the viscosity of the reaction solution, when it exceeds 2000 Pa·s, add solvent. Add 8 kg of pure DMAc at 150 °C in 5 times. Discharge into pure water, crush, purify 9 times with pure water, filter and dry to prepare 35.8 kg of resin with a yield of 98%.

[0070] Table 1 Molecular weight test of polymers prepared in each example

[0071] M(n) M(w) DPI Example 1 60300 138690 2.3 Example 2 18300 31100 1.7 Example 3 139400 262200 1.9

[0072] Among them, Mn is the number average molecular weight, Mw is the weight average molecular weight, and DPI is the dispersity

[0073] The above has given an exemplary description of the implementation manners of the technical solutions of the present disclosure. It should be understood that the protection scope of the present disclosure is not limited to the above implementation manners. Any modifications, equivalent replacements, improvements, etc. made by those skilled in the art within the spirit and principle of the present disclosure shall be included within the protection scope of the claims of this application.

Claims

1. A method for preparing a polyaryl ether, comprising: The polyarylether is obtained by mixing a dihalo monomer, a bisphenol monomer, a composite salt and a solvent and reacting them; The dihalo monomer is selected from Each X is the same or different and is independently selected from halogens, such as F, Cl; E is selected from C(O), S(O)2; m is selected from 1, 2, 3, 4; The bisphenol monomer is selected from A is selected from a single bond, S(O)2, and the following groups which are unsubstituted or optionally substituted by one, two or more Ra groups: sub-C 1-6 alkyl, C 6-14 arylene, 3- to 14-membered heterocyclylene; each Ra is the same or different and is independently selected from oxo, halogen, C 1-6 alkyl, halo-C 1-6 alkyl; The composite salt includes the following three salts: (1) Alkali metal carbonate; (2) Alkali metal hydroxide; (3) And sodium sulfite.

2. The preparation method according to claim 1, characterized in that, The dihalo monomer is selected from:

3. The preparation method according to claim 1 or 2, characterized in that, The bisphenol monomer is selected from A is selected from a single bond, S(O)2, and the following groups which are unsubstituted or optionally substituted by one, two or more Ra: methylene, C 10-13 arylene (such as fluorenylene), 5- to 9-membered heteroarylene (such as ); each Ra is the same or different and is independently selected from oxo, methyl, trifluoromethyl; Preferably, the bisphenol monomer is selected from:

4. The preparation method according to any one of claims 1-3, characterized in that, The alkali metal carbonate is selected from at least one of sodium carbonate, potassium carbonate and cesium carbonate; Preferably, the alkali metal hydroxide is selected from at least one of lithium hydroxide, sodium hydroxide and potassium hydroxide.

5. The preparation method according to any one of claims 1-4, characterized in that, The molar ratio of the alkali metal carbonate, the alkali metal hydroxide and the sodium sulfite in the composite salt is (4-20):1:(0.0001-0.1); for example, (5-15):1:(0.001-0.01), (8-12):1:(0.002-0.008); Preferably, the molar ratio of the bisphenol monomer to the composite salt is 1:(0.8-2), for example, 1:(1.05-1.4); Preferably, the molar ratio of the dihalo monomer to the bisphenol monomer is (0.5-2):1, for example, (0.8-1.5):

1.

6. The preparation method according to any one of claims 1-5, characterized in that, The solvent is selected from at least one of sulfolane (TMS), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP); Preferably, the weight ratio of the total weight of the dihalo monomer and the bisphenol monomer to the weight of the solvent is 1:(0.5-2), for example, 1:(0.8-1.5); Preferably, hydrazine hydrate can also be added in the preparation method; Preferably, the volume of the hydrazine hydrate is one ten-thousandth to two ten-thousandths of the volume of the solvent, for example, two ten-thousandths to one ten-thousandth.

7. The preparation method according to any one of claims 1-6, characterized in that, The temperature of the reaction is 100°C to 240°C, for example, 120°C to 180°C; Preferably, the reaction time is 0.5-6h, for example, 1-4h; Preferably, the preparation method further includes the step of supplementing and adding a solvent when the reaction viscosity increases; preferably, the increase in the reaction viscosity means that the viscosity of the reaction solution is not higher than 2500 Pa·s, for example, not higher than 2000 Pa·s. Preferably, the amount of the supplemented solvent is at least the amount of the solvent lost during the reaction; Preferably, the polyarylether is polyarylether sulfone or polyarylether ketone, for example, soluble non-crystalline polyarylether sulfone or polyarylether ketone.

8. The preparation method according to any one of claims 1-7, characterized in that, The preparation method includes the following steps: Mixing a dihalo monomer, a bisphenol monomer, a composite salt, and optionally added hydrazine hydrate in a solvent, heating, maintaining at 120°C to 180°C for 0.5 to 2h; maintaining at 150°C to 230°C for 1 to 4h, when the reaction viscosity is high, supplement and add a solvent, determine the polymerization end point according to the viscosity of the polymerization solution, and perform post-treatment to obtain the polyarylether.

9. The preparation method according to any one of claims 1-8, characterized in that, The preparation method includes the following steps: Under the protection of inert gas, a solvent is added to the reaction kettle, and a composite salt, hydrazine hydrate, a dihalo monomer and a bisphenol monomer are added. Then, it is heated and maintained at 120°C to 180°C for 0.5 to 1 h. At this time, a gas distills out. A condenser 1 is added at the gas phase outlet, and the temperature of the condenser 1 is 110 to 180°C, so that the organic solvent returns to the reaction kettle, while water distills out of the reaction system. The gas phase continues to enter the condenser 2, and the temperature of the condenser 2 is room temperature, and the uncondensed substances are recovered. According to the activity of the polymerization monomer and the type of solvent, it is maintained at 150°C to 230°C for 1 to 4 h. Measure the weight of the distilled liquid at the outlet end of the reaction kettle. When the reaction viscosity is relatively high, an appropriate amount of solvent is gradually added to the reaction kettle. Determine the polymerization end point according to the viscosity of the polymerization solution. After reaching the target viscosity, the completed polymerization solution is injected into water, pulverized, filtered, and the polymerization solvent and inorganic salts are extracted with distilled water. The obtained polymer powder is dried to obtain the target polyarylether material; Preferably, the reaching of the target viscosity means that the number average molecular weight of the product is 20,000 to 160,000 g / mol.

10. Use of the preparation method according to any one of claims 1-9 in the industrial preparation of polyarylether materials.

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