Preparation method of active end group polyarylether sulfone

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of active end group polyarylether sulfone. The preparation method of the active end group polyarylether sulfone comprises the following steps: mixing a dihalogenated aromatic sulfone monomer, an alkaline reagent and an aprotic polar solvent, adding an aromatic dihydroxyl monomer in batches for polymerization reaction, and desalting to obtain a polyarylether sulfone system; the temperature of the polymerization reaction is 120 to 240 DEG C; the number of times of adding the aromatic dihydroxyl monomer to carry out the polymerization reaction is more than three; and mixing the polyarylether sulfone system with an end-capping reagent, and carrying out an end-capping reaction to obtain the polyarylether sulfone. According to the preparation method of the polyarylether sulfone provided by the invention, through fine synthesis of step-by-step polymerization, reaction temperature control, effective control of reaction rate and inhibition of hydrolysis rate of raw materials, the obtained polyarylether sulfone is high in purity, proper in active end group content and good in solution color and luster, and has a better toughening effect when being combined with epoxy resin.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a method for preparing active terminal polyarylethersulfone. Background Art

[0002] Polyarylethersulfone is a non-crystalline amber transparent polymer compound containing sulfone groups and aromatic ring structures on the main chain of the molecule. It has good mechanical properties, heat resistance, creep resistance, flame retardancy, electrical properties, chemical resistance and non-toxicity. These properties enable polyarylethersulfone to maintain stable performance in harsh environments such as high temperature, high pressure and strong corrosion, so it is widely used in various fields.

[0003] Polyarylethersulfone can be used as a toughening agent for epoxy resins. It is generally divided into inactive-end polyarylethersulfone and active-end polyarylethersulfone. The active end groups include hydroxyl, amino, etc. When inactive-end polyarylethersulfone is blended with epoxy resin system, polyarylethersulfone is dispersed in epoxy resin matrix in the form of irregular particles of different sizes to form a semi-interpenetrating network structure, which can improve the impact strength, tensile strength and elongation at break of the material. When active-end polyarylethersulfone is added to epoxy resin system, epoxy resin and polyarylethersulfone can be chemically connected together through active end groups during mixing, and the resulting epoxy resin material has better performance.

[0004] The related technology uses a one-step synthesis method to synthesize active end-group polyarylethersulfone, adding 4,4'-dichlorodiphenylsulfone, excess bisphenol S and alkaline reagent into the reaction solvent at one time for temperature polymerization. During the process, 4,4'-dichlorodiphenylsulfone is hydrolyzed, causing it to lose its reaction activity. The imbalance of the reaction raw material ratio results in a large number of small molecules or cyclic polymers in the system, the active end group content is uncontrollable, and the polymer color and purity are not ideal. Summary of the invention

[0005] The object of the present invention is to provide a method for preparing active terminal polyarylethersulfone. The active terminal polyarylethersulfone obtained by the preparation method provided by the present invention has high purity and controllable active terminal content, and thus has better epoxy resin toughening effect.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a method for preparing active terminal polyarylethersulfone, comprising the following steps:

[0008] A dihalogenated aromatic sulfone monomer, an alkaline reagent and a non-protonic polar solvent are mixed, an aromatic dihydroxy monomer is added in batches for polymerization reaction, and a desalting treatment is performed to obtain a polyarylethersulfone system; the polymerization reaction temperature is 120 to 240° C. The number of times the aromatic dihydroxy monomer is added for polymerization reaction is more than 3 times; the molar ratio of the aromatic dihydroxy monomer to the dihalogenated aromatic sulfone monomer is 1 to 1.3:1;

[0009] The polyarylethersulfone system and a capping agent are mixed to carry out a capping reaction to obtain the polyarylethersulfone; the capping agent comprises one or more of an aromatic dihydroxy monomer, a halogenated alkane, a halogenated benzyl, an aminophenol and 4-(4-hydroxyaniline)phenol; and the temperature of the capping reaction is 60 to 210°C.

[0010] Preferably, the step of adding the aromatic dihydroxy monomer in batches to carry out the polymerization reaction comprises the following steps:

[0011] Mixing a first aromatic dihydroxy monomer, a dihalogenated aromatic sulfone monomer, an alkaline agent and a non-protonic polar solvent, performing a first polymerization reaction, and removing water to obtain a first polyarylethersulfone system;

[0012] The first polyarylethersulfone system and the second aromatic dihydroxy monomer are mixed to perform a second polymerization reaction, and water is discharged to obtain a second polyarylethersulfone system;

[0013] The second polyarylethersulfone system and the third aromatic dihydroxy monomer are mixed and subjected to a third polymerization reaction to obtain a polyarylethersulfone system; the molar ratio of the first aromatic dihydroxy monomer, the second aromatic dihydroxy monomer and the third aromatic dihydroxy monomer is 45-80:10-52:0.5-1.5.

[0014] Preferably, the aromatic dihydroxy monomer includes one or more of dihydroxybenzene, bis(hydroxyphenyl)alkane, dihydroxydiphenyl sulfone, biphenylene glycol and dihydroxydiphenyl ether;

[0015] The dihalogenated aromatic sulfone monomers include 4,4'-dichlorodiphenyl sulfone and / or 4,4'-difluorodiphenyl sulfone.

[0016] Preferably, the temperature of the first polymerization reaction is 120-210°C;

[0017] The temperature of the second polymerization reaction is 150 to 240° C.;

[0018] The temperature of the third polymerization reaction is 220-240°C.

[0019] Preferably, the molar ratio of the first aromatic dihydroxy monomer to the end-capping agent is 10 to 100:1.

[0020] Preferably, the alkaline agent comprises an alkali metal weak acid salt and / or a base; and the molar ratio of the alkaline agent to the aromatic dihydroxy monomer is 1 to 2.5:1.

[0021] Preferably, the aprotic polar solvent comprises dimethyl sulfoxide, dimethyl sulfone, diphenyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, sulfolane, tetrahydrothiophene-1-monoxide, N,N-dimethylacetamide, N,N-dimethylformamide or N-methylpyrrolidone.

[0022] Preferably, the polymerization reaction time is 1.5 to 12 hours; the end-capping reaction time is 0.5 to 2 hours.

[0023] Preferably, the polymerization reaction and the end-capping reaction are independently carried out in nitrogen or an inert gas.

[0024] Preferably, the desalination treatment comprises filtration.

[0025] The invention provides a method for preparing active terminal polyarylethersulfone, comprising the following steps: mixing dihalogenated aromatic sulfone monomers, alkaline reagents and aprotic polar solvents, adding aromatic dihydroxy monomers in batches to carry out polymerization reaction, and performing desalting treatment to obtain a polyarylethersulfone system; the polymerization reaction temperature is 120-240°C; the number of times the aromatic dihydroxy monomers are added to carry out polymerization reaction is more than 3 times; the molar ratio of the aromatic dihydroxy monomers to the dihalogenated aromatic sulfone monomers is 1-1.3:1; mixing the polyarylethersulfone system and an end-capping agent, carrying out an end-capping reaction to obtain the polyarylethersulfone; the end-capping agent comprises one or more of an aromatic dihydroxy monomer, a halogenated alkane, a halogenated benzyl, an aminophenol and 4-(4-hydroxyaniline)phenol; and the end-capping reaction temperature is 60-210°C. The polyarylethersulfone preparation method provided by the present invention has a refined design for the synthesis process, controls the reaction temperature through the refined synthesis of step-by-step polymerization, effectively controls the reaction rate, enables water to be removed in time, suppresses the hydrolysis rate of the raw material, is beneficial to the control of the molecular weight and the active end group content, and the obtained polyarylethersulfone has high purity, appropriate active end group content, good solution color, good bonding performance with epoxy resin, and better toughening effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0027] Figure 1 This is a physical picture of the active end group polyarylethersulfone system at the end point of the end-capping reaction in Example 1;

[0028] Figure 2 This is a physical picture of the polyarylethersulfone system at the end point of the polymerization reaction in Comparative Example 1;

[0029] Figure 3 This is a physical picture of the active end group polyarylethersulfone system at the end point of the end-capping reaction in Example 2;

[0030] Figure 4 This is a physical picture of the polyarylethersulfone system at the end point of the end-capping reaction in Comparative Example 2;

[0031] Figure 5 This is a physical picture of the active end group polyarylethersulfone system at the end point of the end-capping reaction in Example 3;

[0032] Figure 6 This is a physical picture of the polyarylethersulfone system at the end point of the end-capping reaction in Comparative Example 3;

[0033] Figure 7 This is a physical picture of the active end group polyarylethersulfone system at the end point of the end-capping reaction in Example 4;

[0034] Figure 8 This is a physical picture of the polyarylethersulfone system at the end point of the polymerization reaction in Comparative Example 4. DETAILED DESCRIPTION

[0035] The present invention provides a method for preparing active terminal polyarylethersulfone, comprising the following steps:

[0036] A dihalogenated aromatic sulfone monomer, an alkaline reagent and a non-protonic polar solvent are mixed, an aromatic dihydroxy monomer is added in batches for polymerization reaction, and a desalting treatment is performed to obtain a polyarylethersulfone system; the polymerization reaction temperature is 120 to 240° C. The number of times the aromatic dihydroxy monomer is added for polymerization reaction is more than 3 times; the molar ratio of the aromatic dihydroxy monomer to the dihalogenated aromatic sulfone monomer is 1 to 1.3:1;

[0037] The polyarylethersulfone system and a capping agent are mixed to carry out a capping reaction to obtain the polyarylethersulfone; the capping agent comprises one or more of an aromatic dihydroxy monomer, a halogenated alkane, a halogenated benzyl, an aminophenol and 4-(4-hydroxyaniline)phenol; and the temperature of the capping reaction is 60 to 210°C.

[0038] In the present invention, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art.

[0039] The invention mixes dihalogenated aromatic sulfone monomers, alkaline reagents and non-protonic polar solvents, adds aromatic dihydroxy monomers in batches to carry out polymerization reaction, and performs desalination treatment to obtain a polyarylethersulfone system.

[0040] In the present invention, the step of adding aromatic dihydroxy monomers in batches to carry out polymerization reaction comprises the following steps:

[0041] Mixing a first aromatic dihydroxy monomer, a dihalogenated aromatic sulfone monomer, an alkaline agent and a non-protonic polar solvent, performing a first polymerization reaction, and removing water to obtain a first polyarylethersulfone system;

[0042] The first polyarylethersulfone system and the second aromatic dihydroxy monomer are mixed to perform a second polymerization reaction, and water is discharged to obtain a second polyarylethersulfone system;

[0043] The second polyarylethersulfone system and the third aromatic dihydroxy monomer are mixed and subjected to a third polymerization reaction to obtain a polyarylethersulfone system; the molar ratio of the first aromatic dihydroxy monomer, the second aromatic dihydroxy monomer and the third aromatic dihydroxy monomer is 45-80:10-52:0.5-1.5.

[0044] In the present invention, the aromatic dihydroxy monomer includes one or more of hydroquinone, bis(hydroxyphenyl)alkane, dihydroxydiphenyl sulfone, biphenyl and dihydroxy diphenyl ether; the hydroquinone may be hydroquinone, catechol, or resorcinol; the bis(hydroxyphenyl)alkane may be 2,2-bis(4'-hydroxyphenyl)propane; the dihydroxy diphenyl sulfone may be bisphenol S; the biphenyl may be 4,4'-biphenyl; the dihydroxy diphenyl ether may be 4,4'-dihydroxy diphenyl ether; in a specific embodiment, the first aromatic dihydroxy monomer, the second aromatic dihydroxy monomer and the third aromatic dihydroxy monomer may independently be bisphenol S.

[0045] In the present invention, the dihalogenated aromatic sulfone monomer includes 4,4'-dichlorodiphenyl sulfone and / or 4,4'-difluorodiphenyl sulfone, and in a specific embodiment, it can be 4,4'-dichlorodiphenyl sulfone; the molar ratio of the aromatic dihydroxy monomer to the dihalogenated aromatic sulfone monomer can be 1 to 1.3:1, and in a specific embodiment, it can be 1.02:1, 1.1:1 or 1.15:1.

[0046] In the present invention, the alkaline agent includes an alkali metal weak acid salt and / or a base; the alkali metal weak acid salt includes one or more of sodium bicarbonate, potassium bicarbonate, potassium carbonate and sodium carbonate, and in a specific embodiment, it can be sodium carbonate; the base includes potassium hydroxide and / or sodium hydroxide; the molar ratio of the alkaline agent to the aromatic dihydroxy monomer can be 1 to 2.5:1, and in a specific embodiment, it can be 1.3:1, 1.5:1 or 2:1.

[0047] In the present invention, the aprotic polar solvent includes dimethyl sulfoxide, dimethyl sulfone, diphenyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, cyclopentane, tetrahydrothiophene-1-monoxide, N,N-dimethylacetamide, N,N-dimethylformamide or N-methylpyrrolidone, and in a specific embodiment, it can be cyclopentane; the mass ratio of the total mass of the first aromatic dihydroxy monomer and the dihalogenated aromatic sulfone monomer to the first polymerization reaction system can be 10% to 50%, and in a specific embodiment, it can be 20%, 25%, 31% or 40%.

[0048] The present invention does not have any special limitation on the mixing process, and the raw materials can be completely dissolved in a manner well known to those skilled in the art.

[0049] In the present invention, the polymerization reaction time can be 1.5 to 12 hours, and in a specific embodiment, it can be 5 hours, 7 hours or 9 hours; the temperature of the first polymerization reaction can be 120 to 210°C, and in a specific embodiment, it can be 150°C or 180°C; the time can be 0.5 to 2 hours, and in a specific embodiment, it can be 1 hour; the first polymerization reaction is carried out in nitrogen or an inert gas.

[0050] In the present invention, the second aromatic dihydroxy monomer can be a second aromatic dihydroxy monomer solution; the solvent of the solution is the same as the aprotic polar solvent and is not repeated here; the concentration of the second aromatic dihydroxy monomer solution is 1% to 50%, and in a specific embodiment, it can be 15% or 30%.

[0051] The present invention does not have any special limitation on the mixing process, and the raw materials can be completely dissolved in a manner well known to those skilled in the art.

[0052] In the present invention, the temperature of the second polymerization reaction can be 150-240°C, and in a specific embodiment, can be 180°C or 210°C; the time can be 0.5-2h, and in a specific embodiment, can be 1h; the second polymerization reaction is carried out in nitrogen or an inert gas.

[0053] In the present invention, the molar ratio of the first aromatic dihydroxy monomer, the second aromatic dihydroxy monomer and the third aromatic dihydroxy monomer can be 45-80:10-52:0.5-1.5, and in a specific embodiment, can be 50:48:1; the third aromatic dihydroxy monomer can be a third aromatic dihydroxy monomer solution; the solvent of the solution is the same as the aprotic polar solvent, which is not repeated here; the concentration of the third aromatic dihydroxy monomer solution is 1%-50%, and in a specific embodiment, can be 15% or 30%. In the present invention, the third polymerization is to carry out end group replacement to ensure that the aromatic dihydroxy monomer theoretically completely converts the end group into the target end group to meet the needs of subsequent work.

[0054] In the present invention, the mixing may be performed by dripping a third aromatic dihydroxy monomer solution into the second polyarylethersulfone system; the dripping speed of the aromatic dihydroxy monomer solution may be 1 to 100 drops / s, and in a specific embodiment, may be 3 drops / s, 10 drops / s, 30 drops / s or 50 drops / s.

[0055] In the present invention, the temperature of the third polymerization reaction can be 220-240°C, and in a specific embodiment, it can be 230°C; the time can be 0.5-8h, and in a specific embodiment, it can be 6h; the third polymerization reaction is carried out in nitrogen or an inert gas; the viscosity of the reaction system after the third polymerization reaction is 80-1200mPa·s, and in a specific embodiment, it can be 500mPa·s. In the present invention, the polymerization reaction temperature is set in the above range to control the degree of reaction, so that the reaction cannot continue after a certain degree, to prevent the generation of super large molecular weight, and to avoid the extreme situation of producing super small molecules.

[0056] In the present invention, the desalination treatment includes filtration; the filtration can be mechanical pressure filtration; the mechanical pressure filtration; the pore size of the filter screen of the pressure filtration is 200-1000 mesh, in a specific embodiment, it can be 400 mesh or 600 mesh; the pressure is 0.1-0.4MPa, in a specific embodiment, it can be 0.2MPa; the filtration can also include dilution; the reagent used for the dilution is the same as the non-protonic polar solvent, which will not be repeated here; the solid content of the reaction system after the dilution is 15%-30%, in a specific embodiment, it can be 27%. The role of the dilution in the present invention is to reduce the temperature and reduce the solid content to facilitate desalination. The desalted polymer is more convenient for purification treatment in subsequent processes, and can save processes and costs compared to desalination after end-capping.

[0057] After obtaining the third polyarylethersulfone system, the present invention mixes the third polyarylethersulfone system with a capping agent to perform a capping reaction to obtain the polyarylethersulfone.

[0058] In the present invention, the end-capping agent includes one or more of an aromatic dihydroxy monomer, a halogenated alkane, a halogenated benzyl, an aminophenol and 4-(4-hydroxyaniline)phenol; the aromatic dihydroxy monomer is the same as the first aromatic dihydroxy monomer and is not described in detail here; the halogenated alkane includes methyl chloride and / or ethyl chloride; the halogenated benzyl includes one or more of benzyl chloride, benzyl bromide and benzyl iodide; the aminophenol includes one or more of p-aminophenol, m-aminophenol and o-aminophenol; in a specific embodiment, the end-capping agent can be one or more of bisphenol S, methyl chloride and p-aminophenol; the molar ratio of the first aromatic dihydroxy monomer to the end-capping agent is 10 to 100:1, and in a specific embodiment, it can be 50:1.

[0059] In the present invention, the mixing may be adding a capping agent to the third polyarylethersulfone system; when the capping agent is an aromatic dihydroxy monomer, the aromatic dihydroxy monomer may be added by dripping an aromatic dihydroxy monomer solution; the dripping speed may be 1 to 100 drops / s, and in a specific embodiment, may be 3 drops / s, 10 drops / s, 30 drops / s or 50 drops / s; when the capping agent is a gaseous capping agent, the capping agent may be added by passing a gaseous capping agent; the flow rate of the gaseous capping agent is 0.5 to 10 L / min, and in a specific embodiment, may be 1 L / min or 3 L / min.

[0060] In the present invention, the temperature of the end-capping reaction can be 60-210°C, and in a specific embodiment, it can be 80°C, 120°C, 150°C or 180°C; the time can be 0.5-2h, and in a specific embodiment, it can be 1h; the end-capping reaction is carried out in nitrogen or an inert gas. The temperature of the end-capping reaction is limited to this range to avoid volatilization or decomposition of the end-capping agent, and at the same time avoid depolymerization of the polymer and destruction of the polymer structure.

[0061] In the present invention, the end-capping reaction may further include acidification; the acidifying agent for the acidification includes inorganic acid and / or organic acid; the inorganic acid includes hydrochloric acid and / or carbonic acid; the organic acid includes one or more of oxalic acid, acetic acid and butyric acid; in a specific embodiment, the end-capping agent may be an acid, and in a specific embodiment, may be oxalic acid. The role of the acidification in the present invention is to convert the -ONa end group into -OH.

[0062] In the present invention, the end-capping reaction may further include dispersing, crushing, washing and drying in sequence; the dispersing solvent may be alcohol, water or an alcohol aqueous solution; the alcohol includes methanol, ethanol or isopropanol; the washing reagent may be water; the present invention does not have any special limitation on the dispersing, crushing, washing and drying process, and the process well known to those skilled in the art may be used.

[0063] The polyarylethersulfone preparation method provided by the present invention has a refined design for the synthesis process, and through the refined synthesis with step-by-step temperature control, the reaction rate is effectively controlled, and the hydrolysis rate of the raw material can be suppressed, which is beneficial to the control of the molecular weight and the active end group content. The obtained polyarylethersulfone has high purity, appropriate active end group content, good solution color, good bonding performance with epoxy resin, and better toughening effect.

[0064] The active terminal polyarylethersulfone obtained by the preparation method provided by the present invention has a polymerization degree of 1 to 300 and a molecular weight of 1000 to 120000. The terminal groups include hydroxyl and / or amino groups, and may also include one or more of aryl, halogen, alkoxy, -ONa and -OK. The hydroxyl and / or amino groups account for 10 to 100% of the total terminal groups.

[0065] In order to further illustrate the present invention, the preparation method of the active terminal polyarylethersulfone provided by the present invention is described in detail below in conjunction with the accompanying drawings and examples, but they should not be construed as limiting the scope of protection of the present invention.

[0066] Example 1

[0067] 127.6379 g (0.51 mol) of bisphenol S, 287.16 g (1.00 mol) of 4,4'-dichlorodiphenyl sulfone, 162.1647 g (1.53 mol) of sodium carbonate and 1083.6709 g (9.02 mol) of cyclopentane sulfone were added into a 3000 mL four-necked flask with mechanical stirring, the mass of bisphenol S and 4,4'-dichlorodiphenyl sulfone accounted for 25% of the total mass of the system, and nitrogen was replaced 3 times. Under nitrogen protection, the temperature was first raised to 180° C. and reacted for 1 hour. The system changed from white to yellow and then to white, to obtain the first polyarylethersulfone system;

[0068] After the first polyarylethersulfone system was drained of water, a sulfolane solution containing bisphenol S122.6325 g (0.49 mol) was added, the temperature was maintained at 200° C., and the reaction was carried out for 2 h to obtain a second polyarylethersulfone system;

[0069] After the obtained second polyarylethersulfone system was drained of water, the temperature was raised to 235°C, and a 25% sulfolane solution containing 2.5027 g (0.01 mol) of bisphenol S was added dropwise at a dropping speed of 3 drops / s. The reaction was continued for 6 hours until the reaction viscosity reached 500 mPa·S. 216.7342 g (1.80 mol) of sulfolane was added to dilute the system to a solid content of 27%, and mechanical pressure filtration was performed to remove salt under the conditions of a pressure of 0.2 MPa and a filter mesh aperture of 400 meshes to obtain a third polyarylethersulfone system;

[0070] The obtained third polyarylethersulfone system was cooled to 200°C, and a 25% cyclobutane sulfone solution containing 2.5027g (0.01mol) of bisphenol S was added at a dropping rate of 5 drops / s for end-capping. The reaction was carried out for 1h, and the temperature was again cooled to 80°C. 1.8007g (0.02mol) of oxalic acid was added for acidification for 0.5h. Finally, it was dispersed in pure water, crushed, washed with pure water, and dried to obtain active end-group polyarylethersulfone.

[0071] Comparative Example 1

[0072] 255.2758g (1.02mol) of bisphenol S, 287.1600g (1.00mol) of 4,4'-dichlorodiphenyl sulfone, 162.1647g (1.53mol) of sodium carbonate and 1083.6709g (9.02mol) of cyclopentane sulfone were added into a 3000mL four-necked flask with mechanical stirring, the mass of bisphenol S and 4,4'-dichlorodiphenyl sulfone accounted for 31% of the total mass of the system, nitrogen was replaced 3 times, and under nitrogen protection, the temperature was raised to 235°C, reacted for 8h, and desalted by mechanical pressure filtration, and 216.7342g (1.80mol) of cyclopentane sulfone was added for dilution. At this time, the solid content of the system was 27%, and the temperature was lowered to 80°C, and then 1.8007g (0.02mol) of oxalic acid was added for acidification, and finally, pure water dispersion, crushing, pure water washing, and drying were performed to obtain polyarylethersulfone.

[0073] Example 2

[0074] 127.6379 g (0.51 mol) of bisphenol S, 287.16 g (1.00 mol) of 4,4'-dichlorodiphenyl sulfone, 162.1647 g (1.53 mol) of sodium carbonate and 1083.6709 g (9.02 mol) of cyclopentane sulfone were added into a 3000 mL four-necked flask with mechanical stirring, the mass of bisphenol S and 4,4'-dichlorodiphenyl sulfone accounted for 25% of the total mass of the system, and nitrogen was replaced 3 times. Under nitrogen protection, the temperature was first raised to 180° C. and reacted for 1 hour. The system changed from white to yellow and then to white, to obtain the first polyarylethersulfone system;

[0075] After the first polyarylethersulfone system was drained of water, a sulfolane solution containing bisphenol S122.6325 g (0.49 mol) was added, the temperature was maintained at 200° C., and the reaction was carried out for 2 h to obtain a second polyarylethersulfone system;

[0076] After the obtained second polyarylethersulfone system was drained of water, the temperature was raised to 235°C, and a 25% sulfolane solution containing 2.5027 g (0.01 mol) of bisphenol S was added dropwise at a dropping speed of 3 drops / s. The reaction was continued for 6 hours until the reaction viscosity reached 500 mPa·S. 216.7342 g (1.80 mol) of sulfolane was added to dilute the system to a solid content of 27%, and mechanical pressure filtration was performed to remove salt under the conditions of a pressure of 0.2 MPa and a filter mesh aperture of 400 meshes to obtain a third polyarylethersulfone system;

[0077] The obtained third polyarylethersulfone system was cooled to 200°C, and a 25% cyclopentane sulfone solution containing 2.5027 g (0.01 mol) of bisphenol S was added at a dropping rate of 5 drops / s for end-capping. The reaction was continued for 1 hour, and the temperature was cooled to 120°C. Then, methyl chloride gas was introduced at 1 L / min for 10 minutes for secondary end-capping. Finally, the system was dispersed in pure water, crushed, washed with pure water, and dried to obtain active end-group polyarylethersulfone.

[0078] Comparative Example 2

[0079] 255.2758g (1.02mol) of bisphenol S, 287.1600g (1.00mol) of 4,4'-dichlorodiphenyl sulfone, 162.1647g (1.53mol) of sodium carbonate and 1083.6709g (9.02mol) of cyclopentane were added into a 3000mL four-necked flask with mechanical stirring, the mass of bisphenol S and 4,4'-dichlorodiphenyl sulfone accounted for 31% of the total mass of the system, nitrogen was replaced 3 times, and under nitrogen protection, the temperature was raised to 235°C, reacted for 8h, and desalted by mechanical pressure filtration, and 216.7342g (1.80mol) of cyclopentane was added for dilution, the solid content of the system was 27%, and the temperature was lowered to 120°C, and then methyl chloride gas was introduced at 1L / min for 10min for end-capping, and finally pure water dispersion, crushing, pure water washing, and drying were carried out to obtain polyarylethersulfone.

[0080] Example 3

[0081] 127.6379 g (0.51 mol) of bisphenol S, 287.16 g (1.00 mol) of 4,4'-dichlorodiphenyl sulfone, 163.7546 g (1.545 mol) of sodium carbonate and 1083.6709 g (9.02 mol) of cyclopentane sulfone were added into a 3000 mL four-necked flask with mechanical stirring, the mass of bisphenol S and 4,4'-dichlorodiphenyl sulfone accounted for 25% of the total mass of the system, and nitrogen was replaced 3 times. Under nitrogen protection, the temperature was first raised to 180° C. and reacted for 1 hour. The system changed from white to yellow and then to white, to obtain the first polyarylethersulfone system;

[0082] After the first polyarylethersulfone system was drained of water, a sulfolane solution containing bisphenol S122.6325 g (0.49 mol) was added, the temperature was raised to 200° C., and the reaction was carried out for 2 h to obtain a second polyarylethersulfone system;

[0083] After the obtained second polyarylethersulfone system was drained of water, the temperature was raised to 235° C., and a 25% sulfolane solution containing 7.5081 g (0.03 mol) of bisphenol S was added dropwise at a dropping speed of 3 drops / s. The reaction was continued for 6 hours until the reaction viscosity reached 500 mPa·S. 216.7342 g (1.80 mol) of sulfolane was added to dilute the system to a solid content of 27%, and mechanical pressure filtration was performed to remove salt under the conditions of a pressure of 0.2 MPa and a filter mesh aperture of 400 meshes to obtain a third polyarylethersulfone system;

[0084] The obtained third polyarylethersulfone system was cooled to 200°C, and a 25% cyclopentane sulfone solution containing 3.7541g (0.015mol) of bisphenol S was added at a dropping rate of 5 drops / s for end-capping. The reaction was carried out for 1h, and the temperature was cooled to 80°C. 6.5476g (0.06mol) of p-aminophenol was added for secondary end-capping for 0.5h. Finally, it was dispersed in pure water, crushed, washed with pure water, and dried to obtain active end-group polyarylethersulfone.

[0085] Comparative Example 3

[0086] 257.7785g (1.03mol) of bisphenol S, 287.1600g (1.00mol) of 4,4'-dichlorodiphenyl sulfone, 163.7546g (1.545mol) of sodium carbonate and 1083.6709g (9.02mol) of cyclopentane sulfone were added into a 3000mL four-necked flask with mechanical stirring, the mass of bisphenol S and 4,4'-dichlorodiphenyl sulfone accounted for 31% of the total mass of the system, nitrogen was replaced 3 times, and under nitrogen protection, the temperature was raised to 235°C, reacted for 8h, and desalted by mechanical pressure filtration, and 216.7342g (1.80mol) of cyclopentane sulfone was added for dilution, the solid content of the system was 27%, and the temperature was lowered to 80°C, and 6.5476g (0.06mol) of p-aminophenol was added for end-capping for 0.5h, and finally, it was dispersed in pure water, crushed, washed with pure water, and dried to obtain polyarylethersulfone.

[0087] Example 4

[0088] 127.6379 g (0.51 mol) of bisphenol S, 287.16 g (1.00 mol) of 4,4'-dichlorodiphenyl sulfone, 163.7546 g (1.545 mol) of sodium carbonate and 1083.6709 g (9.02 mol) of cyclopentane sulfone were added into a 3000 mL four-necked flask with mechanical stirring, the mass of bisphenol S and 4,4'-dichlorodiphenyl sulfone accounted for 25% of the total mass of the system, and nitrogen was replaced 3 times. Under nitrogen protection, the temperature was first raised to 180° C. and reacted for 1 hour. The system changed from white to yellow and then to white, to obtain the first polyarylethersulfone system;

[0089] After the first polyarylethersulfone system was drained of water, a sulfolane solution containing bisphenol S122.6325 g (0.49 mol) was added, the temperature was raised to 200° C., and the reaction was carried out for 2 h to obtain a second polyarylethersulfone system;

[0090] After the obtained second polyarylethersulfone system was drained of water, the temperature was raised to 235° C., and a sulfolane solution containing 7.5081 g (0.03 mol) of bisphenol S was added dropwise at a dropping rate of 3 drops / s. The reaction was continued for 6 hours until the reaction viscosity reached 500 mPa·S. 216.7342 g (1.80 mol) of sulfolane was added to dilute the system to a solid content of 27%, and mechanical pressure filtration was performed to remove salt under the conditions of a pressure of 0.2 MPa and a filter mesh aperture of 400 meshes to obtain a third polyarylethersulfone system;

[0091] The obtained third polyarylethersulfone system was cooled to 200°C, and a cyclopentane sulfone solution containing 3.7541 g (0.015 mol) of bisphenol S was added at a dropping rate of 5 drops / s for end-capping. The reaction was carried out for 1 hour, and finally, it was dispersed in pure water, crushed, washed with pure water, and dried to obtain active end-group polyarylethersulfone.

[0092] Comparative Example 4

[0093] 110.4765g (0.4414mol) of bisphenol S, 164.0914g (0.5714mol) of 4,4'-dichlorodiphenyl sulfone, 70.1805g (0.6621mol) of sodium carbonate and 541.8355g (4.51mol) of cyclopentane sulfone were added into a 1000mL four-necked flask with mechanical stirring, the mass of bisphenol S and 4,4'-dichlorodiphenyl sulfone accounted for 31% of the total mass of the system, nitrogen was replaced 3 times, the temperature was raised to 180°C under nitrogen protection, prepolymerized for 3h, filtered and desalted, and prepolymerized liquid 1 was obtained;

[0094] 147.3020 g (0.5886 mol) of bisphenol S, 123.0686 g (0.4286 mol) of 4,4'-dichlorodiphenyl sulfone, 93.5740 g (0.8829 mol) of sodium carbonate and 541.8355 g (4.51 mol) of cyclopentane sulfone were added into a 1000 mL four-necked flask with mechanical stirring, the mass of bisphenol S and 4,4'-dichlorodiphenyl sulfone accounted for 31% of the total mass of the system, nitrogen was replaced 3 times, the temperature was raised to 180°C under nitrogen protection, prepolymerized for 3 hours, filtered and desalted, and prepolymerized liquid 2 was obtained;

[0095] The obtained prepolymer solution 1 and the obtained prepolymer solution 2 are mixed, maintained at 240° C. for 6 hours, and finally dispersed in pure water, crushed, washed with pure water, and dried to obtain polyarylethersulfone.

[0096] Figures 1 to 8 The system physical pictures of the polyarylethersulfone obtained in Example 1, Comparative Example 1, Example 2, Comparative Example 2, Example 3, Comparative Example 3, Example 4 and Comparative Example 4 at the end point of the end-capping reaction are respectively shown.

[0097] Depend on Figures 1 to 8 It can be seen that the appearance of the polymer system in the preparation method provided by the present invention changes significantly after the reaction end point, proving that the end group has been changed.

[0098] Test Example 1

[0099] The molecular weight, viscosity and active end group content of the polyarylethersulfones obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were measured, wherein the molecular weight was measured by GPC, the viscosity was measured in a 25% DMAc solution at 40° C., and the active end group content was measured by non-aqueous potentiometric titration in a DMAc system. The test results are shown in Table 1.

[0100] Table 1 Molecular weight, viscosity and active end group content data of polyarylethersulfone obtained in Examples 1 to 4 and Comparative Examples 1 to 4

[0101] Molecular weight / Mw Viscosity / mPa·s Active end group content / ppm Comparative Example 1 54368 755 754 (Hydroxy) Example 1 62443 704 221(Hydroxy) Comparative Example 2 65355 726 <15(hydroxyl) Example 2 67259 733 215(Hydroxy) Comparative Example 3 60258 699 189 (amino) Example 3 61002 712 264 (amino) Comparative Example 4 67888 701 <15(hydroxyl) Example 4 62400 716 189 (Hydroxy)

[0102] The optimal active end group content in the toughened polyarylethersulfone is generally 100 to 300 ppm. As shown in Table 1, the polymerization method of Comparative Example 1 is not refined enough, resulting in a wide molecular weight distribution during the reaction, with many ultra-large molecules and small molecules; in Comparative Examples 2 and 4, there is an excess of sodium carbonate, and the -ONa content in the end group is high without end group treatment. Compared with the comparative example, the active end group content of the polyarylethersulfone prepared in the embodiment meets the end group content and better meets the use requirements.

[0103] Test Example 2

[0104] The polyarylethersulfone obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was dissolved in an epoxy resin system at a mass ratio of 10% at 120°C, vacuum degassed and poured into a mold, and cured according to the curing process to obtain a toughened epoxy resin material, which was prepared according to the national standard GB / T2567-2021. The mechanical properties and glass transition temperature (T g ), where the mechanical data were measured by a Jinjian domestic mechanical properties tester, and T was measured by differential scanning calorimetry (DSC). g .

[0105] Table 2 Mechanical properties and glass transition temperature data of polyarylethersulfone reinforced epoxy resin obtained in Examples 1 to 4 and Comparative Examples 1 to 4

[0106]

[0107]

[0108] As shown in Table 2, the active terminal polyarylethersulfone obtained in Examples 1 to 4 of the present invention combined with epoxy resin has a better toughening effect on epoxy resin than that of Comparative Examples 1 to 4.

[0109] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing active terminal polyarylethersulfone, characterized in that: The following steps are involved: A dihalogenated aromatic sulfone monomer, an alkaline reagent and a non-protonic polar solvent are mixed, an aromatic dihydroxy monomer is added in batches for polymerization reaction, and a desalting treatment is performed to obtain a polyarylethersulfone system; the polymerization reaction temperature is 120 to 240° C. The number of times the aromatic dihydroxy monomer is added for polymerization reaction is more than 3 times; the molar ratio of the aromatic dihydroxy monomer to the dihalogenated aromatic sulfone monomer is 1 to 1.3:1; The polyarylethersulfone system and a capping agent are mixed to carry out a capping reaction to obtain the polyarylethersulfone; the capping agent comprises one or more of an aromatic dihydroxy monomer, a halogenated alkane, a halogenated benzyl, an aminophenol and 4-(4-hydroxyaniline)phenol; and the temperature of the capping reaction is 60 to 210°C.

2. The preparation method according to claim 1, characterized in that: The step of adding aromatic dihydroxy monomers in batches to carry out polymerization reaction comprises the following steps: Mixing a first aromatic dihydroxy monomer, a dihalogenated aromatic sulfone monomer, an alkaline agent and a non-protonic polar solvent, performing a first polymerization reaction, and removing water to obtain a first polyarylethersulfone system; The first polyarylethersulfone system and the second aromatic dihydroxy monomer are mixed to perform a second polymerization reaction, and water is discharged to obtain a second polyarylethersulfone system; The second polyarylethersulfone system and the third aromatic dihydroxy monomer are mixed and subjected to a third polymerization reaction to obtain a polyarylethersulfone system; the molar ratio of the first aromatic dihydroxy monomer, the second aromatic dihydroxy monomer and the third aromatic dihydroxy monomer is 45-80:10-52:0.5-1.

5.

3. The preparation method according to claim 1 or 2, characterized in that: The aromatic dihydroxy monomer includes one or more of dihydroxybenzene, bis(hydroxyphenyl)alkane, dihydroxydiphenyl sulfone, biphenylene and dihydroxydiphenyl ether; The dihalogenated aromatic sulfone monomers include 4,4'-dichlorodiphenyl sulfone and / or 4,4'-difluorodiphenyl sulfone.

4. The preparation method according to claim 2, characterized in that: The temperature of the first polymerization reaction is 120-210° C.; The temperature of the second polymerization reaction is 150 to 240° C.; The temperature of the third polymerization reaction is 220-240°C.

5. The preparation method according to claim 1, characterized in that: The molar ratio of the first aromatic dihydroxy monomer to the end-capping agent is 10 to 100:

1.

6. The preparation method according to claim 1 or 2, characterized in that: The alkaline agent comprises an alkali metal weak acid salt and / or a base; the molar ratio of the alkaline agent to the aromatic dihydroxy monomer is 1 to 2.5:

1.

7. The preparation method according to claim 1 or 2, characterized in that: The aprotic polar solvent includes dimethyl sulfoxide, dimethyl sulfone, diphenyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, sulfolane, tetrahydrothiophene-1-monoxide, N,N-dimethylacetamide, N,N-dimethylformamide or N-methylpyrrolidone.

8. The preparation method according to claim 1 or 2, characterized in that: The polymerization reaction time is 1.5 to 12 hours; the end-capping reaction time is 0.5 to 2 hours.

9. The preparation method according to claim 1 or 2, characterized in that: The polymerization reaction and the end-capping reaction are independently carried out in nitrogen or an inert gas.

10. The preparation method according to claim 1, characterized in that: The desalination process includes filtration.

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