Polysulfone resin, preparation method thereof and polymer product

Abstract

The invention relates to polysulfone resin, a preparation method thereof and a polymer product. The preparation method of the polysulfone resin comprises the following steps: mixing a bisphenol monomer, dihalogenated diphenyl sulfone, a salt-forming agent, an organic solvent and a first end-capping reagent, and carrying out a salt-forming reaction and a polymerization reaction to obtain a reaction solution; in the bisphenol monomer and dihalogenated diphenyl sulfone, one component is excessive relative to the other component; adding a second end-capping reagent into the reaction liquid for end-capping reaction to obtain polysulfone resin; the first end-capping reagent is selected from a hydroxyl-containing organic compound or a halogen-containing organic compound; and the second end-capping reagent is selected from a compound which can react with hydroxyl and / or hydroxyl salt to generate ether. According to the preparation method, by controlling the feeding amount ratio of the bisphenol monomer to the dihalogenated diphenyl sulfone, the primary end capping is performed, the first end capping reagent is combined for secondary end capping to control the molecular weight, and then the active end groups of the polysulfone resin are reduced through the second end capping reagent, so that the thermal stability of the polysulfone resin is improved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a polysulfone resin and a preparation method thereof, and a polymer product. Background Art

[0002] Polysulfone resin is a high-performance thermoplastic engineering plastic with sulfone group (-SO2-) and aromatic ring structure in the main chain of the molecule. Its typical chemical structure is formed by the polymerization of bisphenol monomer and 4,4'-dichlorodiphenyl sulfone through nucleophilic substitution reaction. This structure makes polysulfone resin have excellent heat resistance, mechanical properties and chemical stability.

[0003] In traditional preparation methods, polysulfone resins are usually synthesized in a one-step process. However, in the one-step synthesis process, the prepared polysulfone resin has a large molecular weight and a wide molecular weight distribution, resulting in unstable resin performance; and there are a large number of unreacted active end groups in the polysulfone molecular chain, such as terminal chlorine, terminal hydroxyl and terminal hydroxyl salt. Unreacted terminal chlorine and terminal hydroxyl are prone to cause side reactions at high temperatures, reducing the thermal stability of the polysulfone resin; thus limiting the application range of the polysulfone resin. Summary of the invention

[0004] Based on this, it is necessary to provide a polysulfone resin with good thermal stability, a preparation method thereof, and a polymer product.

[0005] In a first aspect of the present application, a method for preparing a polysulfone resin is provided, comprising the following steps:

[0006] Mixing a bisphenol monomer, a dihalogenated diphenyl sulfone, a salt-forming agent, an organic solvent and a first end-capping agent, and performing a salt-forming reaction and a polymerization reaction to obtain a reaction solution; wherein one of the bisphenol monomer and the dihalogenated diphenyl sulfone is in excess relative to the other;

[0007] adding a second end-capping agent to the reaction solution to carry out an end-capping reaction to obtain a polysulfone resin;

[0008] The first end-capping agent is selected from an organic compound containing a hydroxyl group or an organic compound containing a halogen;

[0009] The second end-capping agent is selected from compounds that can react with hydroxyl groups and / or hydroxyl salts to form ethers.

[0010] In the preparation method, the molecular weight of the polysulfone resin is controlled, the molecular weight distribution width is reduced, and the performance stability of the polysulfone resin is improved by controlling the excessive feeding of one component among the bisphenol monomer and the dihalogenated diphenyl sulfone, using the monomer itself for preliminary end-capping, and then combining with the first end-capping agent for secondary end-capping during the polymerization reaction; further, after the polymerization reaction is completed, a second end-capping agent of a specific component is further added to react with the active hydroxyl groups existing in the molecular chain, thereby reducing the number of active terminal hydroxyl groups in the polysulfone resin, inhibiting the performance change of the polysulfone resin caused by the thermal degradation of the terminal group during the subsequent processing or use of the polysulfone resin, and improving the thermal stability of the polysulfone resin.

[0011] In some embodiments, the molar ratio of the bisphenol monomer to the dihalogenated diphenyl sulfone is a, and a satisfies the following relationship: 0.9≤a<1, or, 1<a≤1.1.

[0012] In some embodiments, the preparation method satisfies at least one of the following conditions:

[0013] (1) a satisfies the following relationship: 0.9≤a<1, and the first end-capping agent is selected from at least one of organic alcohols, phenolic compounds, organic alcohol potassium salts, organic alcohol sodium salts, phenol potassium salts and phenol sodium salts; or,

[0014] The a satisfies the following relationship: 1<a≤1.1, and the first end-capping agent is selected from at least one of a cyclic hydrocarbon compound containing a Cl element and a cyclic hydrocarbon compound containing a F element.

[0015] In some embodiments, a satisfies the following relationship: 0.9≤a<1, and the first end-capping agent is selected from at least one of naphthol, hydroquinone, naphthalene diol, phenol, at least one halogen-substituted phenol, at least one C1~C6 alkyl-substituted phenol, at least one C1~C6 alkyl-substituted hydroquinone, aminophenol, hydroxybiphenyl, dihydroxydiphenyl ether, hydroxyanisole, phenolphthalein, hydroxyquinoline, hydroxybenzophenone, methanol and ethanol; or,

[0016] The a satisfies the following relationship: 1<a≤1.1, and the first end-capping agent is selected from at least one of fluorobenzonitrile, fluoroacetophenone, fluoroquinoline, difluoroketone, fluoronaphthalene, fluorobenzamide, benzyl chloride, methylbenzyl chloride, aminobenzyl chloride, diphenylmethane, triphenylmethane, methoxybenzyl chloride, methylbenzyl chloride, 4-chloro, 4-hydroxypotassium diphenyl sulfone, chloropyridine, 2-chloro-N,N-dimethylacetamide, N,N-dimethyl-4-fluorobenzamide, chloropyrazine, chloropyrimidine, chloroquinoline, dimethylbenzene chloride, 4-chloro-1,8-naphthalene dicarboxylic anhydride, chlorodiphenyl sulfone, fluorobenzene and chlorophenolphthalein.

[0017] In some embodiments, the second capping agent is selected from at least one of diethyl sulfate, dimethyl sulfate, methyl chloride, ethyl bromide, iodopropane, tetramethylammonium hydroxide, methanesulfonic acid, methyl p-toluenesulfonate, N,N-dimethylformamide dimethyl acetal, triphenyl phosphate, trimethyl phosphate and dimethyl carbonate.

[0018] In some embodiments, the preparation method satisfies at least one of the following conditions:

[0019] (1) a satisfies the following relationship: 0.9≤a<1, and the molar ratio of the dihalogenated diphenyl sulfone to the first end-capping agent is (10-10000):1; or,

[0020] The a satisfies the following relationship: 1<a≤1.1, and the molar ratio of the bisphenol monomer to the first end-capping agent is (10-10000):1;

[0021] (2) The molar ratio of the bisphenol monomer to the second end-capping agent is (10-10000):1.

[0022] In some embodiments, the preparation method satisfies at least one of the following conditions:

[0023] (1) The temperature of the salt-forming reaction is 120°C to 240°C, and the time of the salt-forming reaction is 3 to 7 hours;

[0024] (2) The temperature of the polymerization reaction is 0°C to 50°C higher than the temperature of the salt-forming reaction;

[0025] (3) The polymerization reaction time is 1h~20h;

[0026] (4) The number average molecular weight of the polysulfone resin is 20,000 to 130,000.

[0027] (5) The temperature of the end-capping reaction is 50°C to 240°C; the time of the end-capping reaction is 1h to 20h.

[0028] In some embodiments, the preparation method satisfies at least one of the following conditions:

[0029] (1) The bisphenol monomer is at least one selected from bisphenol A, bisphenol S, bisphenol F, bisphenol Z, 4,4'-dihydroxybiphenyl and 2,2-bis(4-hydroxyphenyl)butane;

[0030] (2) the dihalogenated diphenyl sulfone is at least one selected from dichlorodiphenyl sulfone, difluorodiphenyl sulfone and dibromodiphenyl sulfone;

[0031] (3) The organic solvent is at least one selected from N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane and diphenyl sulfone;

[0032] (4) The salt-forming agent is at least one selected from sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.

[0033] The second aspect of the present application provides a polysulfone resin obtained according to the preparation method described in the first aspect.

[0034] The third aspect of the present application provides a polymer product, wherein the polymer product comprises the polysulfone resin described in the second aspect. DETAILED DESCRIPTION

[0035] The technical solution of the present application is further described in detail below in conjunction with specific embodiments. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0037] The term "alkyl" refers to a saturated hydrocarbon containing primary (normal) carbon atoms, or secondary carbon atoms, or tertiary carbon atoms, or quaternary carbon atoms, or a combination thereof. Phrases containing this term, for example, "C1~C6 alkyl" refers to an alkyl containing 1 to 6 carbon atoms, each occurrence of which can be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl or C6 alkyl. Suitable examples include, but are not limited to: methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu , s-butyl, -CH(CH3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3 )CH(CH3)2), 3-methyl-1-butyl (-CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3) 2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH(CH3)CH2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2) and 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2).

[0038] "Halogen" or "halo" refers to F, Cl, Br or I.

[0039] In one embodiment of the present application, a method for preparing a polysulfone resin is provided, comprising the following steps:

[0040] The bisphenol monomer, dihalogenated diphenyl sulfone, a salt-forming agent, an organic solvent and a first end-capping agent are mixed to perform a salt-forming reaction and a polymerization reaction to obtain a reaction solution; one of the bisphenol monomer and the dihalogenated diphenyl sulfone is in excess relative to the other component;

[0041] Adding a second end-capping agent into the reaction solution to carry out an end-capping reaction to obtain a polysulfone resin;

[0042] The first capping agent is selected from an organic compound containing a hydroxyl group or an organic compound containing a halogen;

[0043] The second capping agent is selected from compounds that can react with hydroxyl groups and / or hydroxyl salts to form ethers.

[0044] In the preparation method, the molecular weight of the polysulfone resin is controlled, the molecular weight distribution width is reduced, and the performance stability of the polysulfone resin is improved by controlling the excessive feeding of one component among the bisphenol monomer and the dihalogenated diphenyl sulfone, using the monomer itself for preliminary end-capping, and then combining with the first end-capping agent for secondary end-capping during the polymerization reaction; further, after the polymerization reaction is completed, a second end-capping agent of a specific component is further added to react with the active hydroxyl groups existing in the molecular chain, thereby reducing the number of active terminal hydroxyl groups in the polysulfone resin, inhibiting the performance change of the polysulfone resin caused by the thermal degradation of the terminal group during the subsequent processing or use of the polysulfone resin, and improving the thermal stability of the polysulfone resin.

[0045] In some embodiments, the molar ratio of the bisphenol monomer to the dihalogenated diphenyl sulfone is a, where a satisfies the following relationship: 0.9≤a<1, or 1<a≤1.1.

[0046] In some embodiments, a satisfies the following relationship: 0.9≤a<1, and the first end-capping agent is selected from an organic compound containing a hydroxyl group. When 0.9≤a<1, the dihalogenated diphenyl sulfone is excessive, and the dihalogenated diphenyl sulfone will appear at the chain end; when the organic compound end-capping agent containing a hydroxyl group is added, the dihalogenated diphenyl sulfone at the chain end can be used to reduce the terminal halogen group.

[0047] Furthermore, the first end-capping agent is selected from at least one of organic alcohols, phenolic compounds, organic alcohol potassium salts, organic alcohol sodium salts, phenol potassium salts and phenol sodium salts.

[0048] Furthermore, the first end-capping agent includes but is not limited to naphthol, hydroquinone, naphthalene diol, phenol, at least one halogen-substituted phenol, at least one C1~C6 alkyl-substituted phenol, at least one C1~C6 alkyl-substituted hydroquinone, aminophenol, hydroxybiphenyl, dihydroxydiphenyl ether, hydroxyanisole, phenolphthalein, hydroxyquinoline, hydroxybenzophenone, methanol and ethanol.

[0049] Further, the first end-capping agent includes, but is not limited to, at least one of 2-naphthol, 1-naphthol, 1,5-dihydroxynaphthalene, 4,4-dihydroxydiphenyl ether, trimethylhydroquinone, methylhydroquinone, tetramethylhydroquinone, 2-hydroxybiphenyl, 4-hydroxybiphenyl, phenol, hydroquinone, catechol, tribromophenol, 4-hydroxydiphenyl ether, p-aminophenol, p-tert-butylphenol, isopropylphenol, p-isopropylphenylphenol, m-aminophenol, p-hydroxyanisole, 2,6-dimethylphenol, p-methylphenol, o-cresol, p-chlorophenol, phenolphthalein, methanol, ethanol, 4-hydroxybenzophenone and 8-hydroxyquinoline.

[0050] In some embodiments, a satisfies the following relationship: 1<a≤1.1, and the first capping agent is selected from at least one of a cyclic hydrocarbon compound containing a Cl element and a cyclic hydrocarbon compound containing a F element.

[0051] Further, the first end-capping agent includes, but is not limited to, at least one of fluorobenzonitrile, fluoroacetophenone, fluoroquinoline, difluoroketone, fluoronaphthalene, fluorobenzamide, benzyl chloride, methylbenzyl chloride, aminobenzyl chloride, diphenylmethane, triphenylmethane, methoxybenzyl chloride, methylbenzyl chloride, 4-chloro, 4-hydroxypotassium diphenyl sulfone, chloropyridine, 2-chloro-N,N-dimethylacetamide, N,N-dimethyl-4-fluorobenzamide, chloropyrazine, chloropyrimidine, chloroquinoline, dimethylbenzene chloride, 4-chloro-1,8-naphthalene dicarboxylic anhydride, chlorodiphenyl sulfone, fluorobenzene and chlorophenolphthalein.

[0052] Further, the first end-capping agent includes, but is not limited to, 4-fluorobenzonitrile, 4-fluoroacetophenone, 8-fluoroquinoline, difluoroketone, 1-fluoronaphthalene, 3-fluorobenzamide, 4-fluorobenzamide, 2-fluorobenzamide, benzyl chloride, m-methylbenzyl chloride, aminobenzyl chloride, diphenylmethane, triphenylmethane, p-methoxybenzyl chloride, p-methylbenzyl chloride, 4-chloro, 4-hydroxy potassium diphenyl sulfone, 2-chloropyridine, 2-chloro-N,N-dimethylacetamide, N,N-dimethyl-4-fluorobenzamide, chloropyrazine, 2-chloropyrimidine, 2-chloroquinoline, 2,6-dimethylbenzene chloride, 4-chloro-1,8-naphthalene dicarboxylic anhydride, 4-chlorodiphenyl sulfone, fluorobenzene and chlorophenolphthalein. Preferably, the first end-capping agent is selected from at least one of 2-naphthol, 1-naphthol, 2-methoxybenzyl chloride, 3-methoxybenzyl chloride and 4-methoxybenzyl chloride.

[0053] In some embodiments, a satisfies the following relationship: when 0.9≤a<1, the molar ratio of dihalogenated diphenyl sulfone to the first end-capping agent is (10-10000): 1. Further, the molar ratio of dihalogenated diphenyl sulfone to the first end-capping agent is (10-100): 1. More preferably, the molar ratio of dihalogenated diphenyl sulfone to the first end-capping agent is (20-30): 1.

[0054] In some embodiments, a satisfies the following relationship: when 1<a≤1.1, the ratio of the molar amount of the bisphenol monomer to the molar amount of the first end-capping agent is (10-10000): 1. Further, the ratio of the molar amount of the bisphenol monomer to the molar amount of the first end-capping agent is (10-100): 1. More preferably, the ratio of the molar amount of the bisphenol monomer to the molar amount of the first end-capping agent is (20-30): 1.

[0055] In some embodiments, the second capping agent is selected from at least one of diethyl sulfate, dimethyl sulfate, methyl chloride, ethyl bromide, iodopropane, tetramethylammonium hydroxide, methanesulfonic acid, methyl p-toluenesulfonate, N,N-dimethylformamide dimethyl acetal, triphenyl phosphate, trimethyl phosphate and dimethyl carbonate.

[0056] In some embodiments, the molar ratio of the bisphenol monomer to the second end-capping agent is (10-10000): 1. Further, the molar ratio of the bisphenol monomer to the second end-capping agent is (10-100): 1. More preferably, the molar ratio of the bisphenol monomer to the second end-capping agent is (20-30): 1.

[0057] In some embodiments, the temperature of the salt-forming reaction is 120°C to 240°C. It is understood that the salt-forming reaction mainly occurs in the salt-forming reaction, in which the hydroxyl hydrogen atoms on the bisphenol monomer are replaced by the metal salt in the salt-forming agent; a phenolic hydroxyl salt is generated; and then the phenolic hydroxyl salt is polymerized with the dihalogenated diphenyl sulfone. As an example, the temperature of the salt-forming reaction can be 120°C, 140°C, 150°C, 160°C, 180°C, 200°C, 210°C, 220°C, 230°C or 240°C. Furthermore, the temperature of the above-mentioned salt-forming reaction can be a range value consisting of any two of the above-mentioned point values ​​as end values.

[0058] In some embodiments, the time of the salt-forming reaction is 3 hours to 7 hours. As an example, the time of the salt-forming reaction can be 3 hours, 4 hours, 5 hours, 6 hours or 7 hours. Further, the time of the salt-forming reaction can be a range value consisting of any two of the above point values ​​as end values.

[0059] In some embodiments, the temperature of the polymerization reaction is 0°C to 50°C higher than the temperature of the salt-forming reaction. As an example, the temperature of the polymerization reaction is 0°C, 10°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C or 50°C higher than the temperature of the salt-forming reaction. Further increasing the temperature of the polymerization reaction can significantly increase the polymerization reaction rate of the phenolic hydroxyl salt and the dihalogenated diphenyl sulfone polymerization, and a polymer of the target molecular weight can be obtained in a shorter time. Preferably, the temperature of the polymerization reaction is 20°C to 50°C higher than the temperature of the salt-forming reaction.

[0060] In some embodiments, the polymerization time is 1h~20h. As an example, the polymerization time can be 1h, 2h, 3h, 5h, 7h, 9h, 10h, 12h, 14h, 15h, 16h, 18h, 19h or 20h. Further, the polymerization time can be a range value consisting of any two of the above-mentioned point values ​​as end values. The molecular weight of the obtained polymer can be controlled by controlling the polymerization time. Preferably, the polymerization time is 5h~7h.

[0061] In some embodiments, the number average molecular weight of the polysulfone resin is 20,000 to 130,000.

[0062] In some embodiments, the temperature of the end-capping reaction is 50°C to 240°C. It is understood that the second end-capping agent reacts with the terminal hydroxyl group or the terminal hydroxyl salt in the polymer molecular chain, and the polymer stops polymerizing. As an example, the temperature of the end-capping reaction can be 50°C, 60°C, 80°C, 100°C, 120°C, 140°C, 150°C, 160°C, 180°C, 200°C, 210°C, 220°C, 230°C or 240°C. Further, the temperature of the end-capping reaction can be a range value consisting of any two of the above-mentioned point values ​​as end values. The utilization rate of the end-capping agent can be effectively improved by controlling the temperature of the end-capping reaction. Preferably, the temperature of the end-capping reaction is 80°C to 230°C.

[0063] In some embodiments, the time of the end-capping reaction is 0.25h to 20h. As an example, the time of the end-capping reaction can be 0.25h, 1h, 2h, 3h, 4h, 5h, 8h, 10h, 12h, 15h, 16h, 18h or 20h. Further, the time of the end-capping reaction can be a range value consisting of any two of the above point values ​​as end values. By controlling the time of the end-capping reaction, the end-capping can be completed within the economic time limit.

[0064] In some embodiments, the bisphenol monomer is selected from at least one of bisphenol A, bisphenol S, bisphenol F, bisphenol Z, 4,4'-dihydroxybiphenyl (BP), and 2,2-bis(4-hydroxyphenyl)butane.

[0065] In some embodiments, the halogen in the dihalogenated diphenyl sulfone may be at least one of fluorine, chlorine and bromine.

[0066] In some embodiments, the dihalogenated diphenyl sulfone is selected from at least one of dichlorodiphenyl sulfone, difluorodiphenyl sulfone and dibromodiphenyl sulfone. Preferably, the dihalogenated diphenyl sulfone is selected from 4,4-dichlorodiphenyl sulfone.

[0067] In some embodiments, the organic solvent is selected from at least one of N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, dimethylacetamide, sulfolane, and diphenyl sulfone.

[0068] In some embodiments, the salt-forming agent is selected from at least one of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide. Preferably, the salt-forming agent is selected from sodium carbonate.

[0069] In some embodiments, the preparation method further comprises the following step: removing the water generated during the salt-forming reaction. By removing the water, the hydrolysis of dihalogenated diphenyl sulfone can be inhibited, the polymerization effect of dihalogenated diphenyl sulfone and bisphenol monomer can be improved, and the generation of hydrolyzed terminal hydroxyl groups and terminal hydroxyl salts can be reduced.

[0070] In some embodiments, a protective gas is introduced at 120° C. to 240° C. to remove moisture generated during the salt-forming reaction.

[0071] In some embodiments, the protective gas is selected from nitrogen or argon.

[0072] In some embodiments, the preparation method further comprises: after the end-capping reaction is completed, performing a first filtration and a water precipitation treatment in sequence to obtain polymer resin particles. The purpose of the first filtration is mainly to remove the solid salt component in the polymer mixture. The water precipitation treatment is that the solubility of the polymer solution in water is low, and solids will precipitate when the liquid polymer is added to water.

[0073] In some embodiments, the preparation method further comprises: after the hydrolysis treatment, sequentially performing the steps of second filtration, washing, centrifugation and drying.

[0074] In some embodiments, washing is performed using pure water.

[0075] In some embodiments, drying is performed by negative pressure drying.

[0076] In another embodiment of the present application, a polysulfone resin is provided. The polysulfone resin is prepared by the above preparation method.

[0077] In yet another embodiment of the present application, a polymer product is provided, wherein the polymer product includes the above-mentioned polysulfone resin.

[0078] In some embodiments, polymer articles include, but are not limited to, hard disk drives, lamp covers, and rearview mirror housings.

[0079] In order to make the purpose, technical solutions and advantages of the present invention more concise and clear, the present invention is described with the following specific embodiments, but the present invention is by no means limited to these embodiments. The embodiments described below are only preferred embodiments of the present invention, which can be used to describe the present invention and cannot be understood as limiting the scope of the present invention. It should be pointed out that any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

[0080] In order to better illustrate the present invention, the present invention is further described below in conjunction with the embodiments. The following are specific embodiments.

[0081] Example 1

[0082] (1) Into an 8000 L reactor, 3600 kg of NMP solvent, 856 kg of bisphenol A, 1108 kg of 4,4-dichlorodiphenyl sulfone, 400 kg of sodium carbonate and 16 kg of 2-naphthol were added.

[0083] (2) Replace the air in the kettle with nitrogen. After the replacement is completed, heat it to 180°C and carry out salt formation reaction for 6 hours, and separate the water with nitrogen or argon; then heat it to 200°C and react for 5 hours. Then add 2 kg of end-capping agent N,N-dimethylformamide dimethyl acetal and react for 2 hours.

[0084] (3) The polymer solution is then filtered, desalted, and precipitated with water. The precipitated mixed material is filtered, washed with pure water 10 times, filtered to obtain a powder, dried in a negative pressure drying device to obtain a polysulfone powder resin, and then melt-extruded and granulated in an extruder to obtain a finished product.

[0085] Example 2

[0086] (1) Add 3600 kg of NMP solvent, 856 kg of bisphenol A, 1108 kg of 4,4-dichlorodiphenyl sulfone, 400 kg of sodium carbonate, and 16 kg of 2-naphthol into an 8000 L reactor.

[0087] (2) Replace the air in the kettle with nitrogen. After the replacement is completed, heat it to 180°C and carry out salt formation reaction for 6 hours, and separate the water with nitrogen or argon; then heat it to 200°C and react for 5 hours. Then add 2.6 kg of end-capping agent diethyl sulfate and react for 2 hours.

[0088] (5) The polymer solution is then filtered, desalted, and precipitated with water. The precipitated mixed material is filtered, washed with pure water 10 times, and the filtered powder is dried in a negative pressure drying device to obtain a polysulfone powder resin, which is then melt-extruded and granulated in an extruder to obtain a finished product.

[0089] Example 3

[0090] (1) Add 3600 kg of NMP solvent, 856 kg of bisphenol A, 1045 kg of 4,4-dichlorodiphenyl sulfone, 400 kg of sodium carbonate, and 15.2 kg of p-methoxybenzyl chloride into an 8000 L reactor.

[0091] (2) After the replacement with nitrogen is completed, the temperature is raised to 180°C, and the salt-forming reaction is carried out for 6 hours, and the water is separated by nitrogen or argon; then the temperature is raised to 200°C and the reaction is carried out for 5 hours. Then, 2 kg of the end-capping agent N,N-dimethylformamide dimethyl acetal is added and the reaction is carried out for 2 hours.

[0092] (3) The polymer solution is then filtered, desalted, and precipitated with water. The precipitated mixed material is filtered and washed with pure water 10 times. The filtered powder is dried in a negative pressure drying device to obtain a polysulfone powder resin, which is then melt-extruded and granulated in an extruder to obtain a finished product.

[0093] Example 4

[0094] (1) Add 3600 kg of NMP solvent, 856 kg of bisphenol A, 1045 kg of 4,4-dichlorodiphenyl sulfone, 400 kg of sodium carbonate, and 15.2 kg of p-methoxybenzyl chloride into an 8000 L reactor.

[0095] (2) Replace the air in the kettle with nitrogen. After the replacement is completed, heat it to 180°C and carry out salt formation reaction for 6 hours, and separate the water with nitrogen or argon; then heat it to 200°C and react for 5 hours. Then add 2.6 kg of end-capping agent diethyl sulfate and react for 2 hours.

[0096] (3) The polymer solution is then filtered, desalted, and precipitated with water. The precipitated mixed material is filtered and washed with pure water 10 times. The filtered powder is dried in a negative pressure drying device to obtain a polysulfone powder resin, which is then melt-extruded and granulated in an extruder to obtain a finished product.

[0097] Comparative Example 1

[0098] (1) Into an 8000 L reactor, 3600 kg of NMP solvent, 856 kg of bisphenol A, 1108 kg of 4,4-dichlorodiphenyl sulfone, 400 kg of sodium carbonate and 16 kg of 2-naphthol were added.

[0099] (2) The air in the reactor is replaced with nitrogen. After the replacement is completed, the temperature is raised to 180°C, and the salt-forming reaction is carried out for 6 hours. The water is separated by nitrogen or argon; then the temperature is raised to 200°C and the reaction is carried out for 5 hours.

[0100] (3) The polymer solution is then filtered, desalted, and precipitated with water. The precipitated mixed material is filtered and washed with pure water 10 times. The filtered powder is dried in a negative pressure drying device to obtain a polysulfone powder resin, which is then melt-extruded and granulated in an extruder to obtain a finished product.

[0101] Comparative Example 2

[0102] (1) Add 3600 kg of NMP solvent, 856 kg of bisphenol A, 1045 kg of 4,4-dichlorodiphenyl sulfone, 400 kg of sodium carbonate, and 15.2 kg of p-methoxybenzyl chloride into an 8000 L reactor.

[0103] (2) Replace the air in the kettle with nitrogen. After the replacement is completed, raise the temperature to 180°C and carry out salt-forming reaction for 6 hours, and use nitrogen or argon to separate the water; then raise the temperature to 200°C and react for 5 hours.

[0104] (3) The polymer solution is then filtered, desalted, and precipitated with water. The precipitated mixed material is filtered and washed with pure water 10 times. The filtered powder is dried in a negative pressure drying device to obtain a polysulfone powder resin, which is then melt-extruded and granulated in an extruder to obtain a finished product.

[0105] Comparative Example 3

[0106] (1) Add 3600 kg of NMP solvent, 856 kg of bisphenol A, 1108 kg of 4,4-dichlorodiphenyl sulfone, and 400 kg of sodium carbonate into an 8000 L reactor.

[0107] (2) Replace the air in the kettle with nitrogen. After the replacement is completed, raise the temperature to 180°C and carry out salt-forming reaction for 6 hours, and use nitrogen or argon to separate the water; then raise the temperature to 200°C and react for 5 hours.

[0108] (3) The polymer solution is then filtered, desalted, and precipitated with water. The precipitated mixed material is filtered, washed with pure water 10 times, and the filtered powder is dried in a negative pressure drying device to obtain a polysulfone powder resin, which is then melt-extruded and granulated in an extruder to obtain a finished product.

[0109] Comparative Example 4

[0110] (1) Add 3600 kg of NMP solvent, 856 kg of bisphenol A, 1045 kg of 4,4-dichlorodiphenyl sulfone, and 400 kg of sodium carbonate into an 8000 L reactor.

[0111] (2) Replace the air in the kettle with nitrogen. After the replacement is completed, raise the temperature to 180°C and carry out salt-forming reaction for 6 hours, and use nitrogen or argon to separate the water; then raise the temperature to 200°C and react for 5 hours.

[0112] (3) The polymer solution is then filtered, desalted, and precipitated with water. The precipitated mixed material is filtered and washed with pure water 10 times. The filtered powder is dried in a negative pressure drying device to obtain a polysulfone powder resin, which is then melt-extruded and granulated in an extruder to obtain a finished product.

[0113] When preparing polysulfone resin particles in various embodiments and comparative examples, the components added are shown in Table 1.

[0114] Table 1

[0115]

[0116] Performance Test:

[0117] Melt index: Tested according to ISO 1133 standard.

[0118] Chlorine content: tested by X-ray fluorescence spectrometry.

[0119] TGA test: NETZSCH STH 449F5 equipment was used for testing.

[0120] The performance test data of the polysulfone resin particles prepared in each embodiment and comparative example are shown in Table 2.

[0121] Table 2

[0122]

[0123] As can be seen from Table 2, Examples 1 to 4 adopt the technical solution of the present application to prepare polysulfone resins by a multiple end-capping method, and the chlorine content of the obtained polysulfone resins is only 164ppm~459ppm, and its environmental performance is good, and its corresponding dielectric constant is relatively low; the starting point of the TGA curve is 514°C~527°C, and it has high thermal stability.

[0124] When the polysulfone resin is prepared in Comparative Example 1, its preparation method is relatively consistent with that of Examples 1 and 2, and the main difference is that the second end-capping agent is not added in Comparative Example 2. The chlorine content of the polysulfone resin prepared by the comparative example is as high as 200ppm, which is higher than that of Examples 3 and 4; the starting point of the TGA curve is 509°C, which is lower than that of Examples 3 and 4. It shows that the thermal stability of the polysulfone resin prepared in Comparative Example 1 is not as good as that of Examples 2 and 3; the dielectric constant of the polysulfone resin prepared in Comparative Example 1 is higher than that of Examples 2 and 3.

[0125] When the polysulfone resin is prepared in Comparative Example 2, its preparation method is relatively consistent with Examples 3 and 4, and the main difference is that the second end-capping agent is not added in Comparative Example 1. The chlorine content of the polysulfone resin prepared is as high as 512ppm, which is higher than that of Examples 1 and 2; the starting point of the TGA curve is 507°C, which is lower than that of Examples 1 and 2. It shows that the thermal stability of the polysulfone resin prepared in Comparative Example 2 is not as good as that of Examples 1 and 2; the dielectric constant of the polysulfone resin prepared in Comparative Example 2 is higher than that of Examples 2 and 3.

[0126] When the polysulfone resins were prepared in Comparative Examples 3 and 4, no end-capping agent was added, and the chlorine content in the polysulfone resins prepared in Comparative Examples 3 and 4 was as high as 2000 ppm and 6000 ppm; the starting points of the TGA curves were at 439° C. and 499° C. Combined with the data of Examples 1 to 4, it can be seen that Examples 1 to 4 significantly improved the thermal stability and lower dielectric constant of the polysulfone resins.

[0127] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0128] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for those of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing a polysulfone resin, characterized in that: The steps include: Mixing a bisphenol monomer, a dihalogenated diphenyl sulfone, a salt-forming agent, an organic solvent and a first end-capping agent, and performing a salt-forming reaction and a polymerization reaction to obtain a reaction solution; wherein one of the bisphenol monomer and the dihalogenated diphenyl sulfone is in excess relative to the other; adding a second end-capping agent to the reaction solution to carry out an end-capping reaction to obtain a polysulfone resin; The first end-capping agent is selected from an organic compound containing a hydroxyl group or an organic compound containing a halogen; The second end-capping agent is selected from compounds that can react with hydroxyl groups and / or hydroxyl salts to form ethers.

2. The preparation method according to claim 1, characterized in that: The molar ratio of the bisphenol monomer to the dihalogenated diphenyl sulfone is a, and a satisfies the following relationship: 0.9≤a<1, or, 1<a≤1.

1.

3. The preparation method according to claim 2, characterized in that: The preparation method satisfies at least one of the following conditions: (1) a satisfies the following relationship: 0.9≤a<1, and the first end-capping agent is selected from at least one of organic alcohols, phenolic compounds, organic alcohol potassium salts, organic alcohol sodium salts, phenol potassium salts and phenol sodium salts; or, The a satisfies the following relationship: 1<a≤1.1, and the first end-capping agent is selected from at least one of a cyclic hydrocarbon compound containing a Cl element and a cyclic hydrocarbon compound containing a F element.

4. The preparation method according to claim 2, characterized in that: The a satisfies the following relationship: 0.9≤a<1, the first end-capping agent is selected from at least one of naphthol, hydroquinone, naphthalene diol, phenol, at least one halogen element substituted phenol, at least one C1~C6 alkyl substituted phenol, at least one C1~C6 alkyl substituted hydroquinone, aminophenol, hydroxybiphenyl, dihydroxydiphenyl ether, hydroxyanisole, phenolphthalein, hydroxyquinoline, hydroxybenzophenone, methanol and ethanol; or, The a satisfies the following relationship: 1<a≤1.1, and the first end-capping agent is selected from at least one of fluorobenzonitrile, fluoroacetophenone, fluoroquinoline, difluoroketone, fluoronaphthalene, fluorobenzamide, benzyl chloride, methylbenzyl chloride, aminobenzyl chloride, diphenylmethane, triphenylmethane, methoxybenzyl chloride, methylbenzyl chloride, 4-chloro, 4-hydroxypotassium diphenyl sulfone, chloropyridine, 2-chloro-N,N-dimethylacetamide, N,N-dimethyl-4-fluorobenzamide, chloropyrazine, chloropyrimidine, chloroquinoline, dimethylbenzene chloride, 4-chloro-1,8-naphthalene dicarboxylic anhydride, chlorodiphenyl sulfone, fluorobenzene and chlorophenolphthalein.

5. The preparation method according to any one of claims 1 to 4, characterized in that The second end-capping agent is selected from at least one of diethyl sulfate, dimethyl sulfate, methyl chloride, ethyl bromide, iodopropane, tetramethylammonium hydroxide, methanesulfonic acid, methyl p-toluenesulfonate, N,N-dimethylformamide dimethyl acetal, triphenyl phosphate, trimethyl phosphate and dimethyl carbonate.

6. The preparation method according to any one of claims 2 to 4, characterized in that The preparation method satisfies at least one of the following conditions: (1) a satisfies the following relationship: 0.9≤a<1, and the molar ratio of the dihalogenated diphenyl sulfone to the first end-capping agent is (10-10000):1; or, The a satisfies the following relationship: 1<a≤1.1, and the molar ratio of the bisphenol monomer to the first end-capping agent is (10-10000):1; (2) The molar ratio of the bisphenol monomer to the second end-capping agent is (20-10000):

1.

7. The preparation method according to any one of claims 1 to 4, characterized in that The preparation method satisfies at least one of the following conditions: (1) The temperature of the salt-forming reaction is 120°C to 240°C, and the time of the salt-forming reaction is 3 to 7 hours; (2) The temperature of the polymerization reaction is 0°C to 50°C higher than the temperature of the salt-forming reaction; (3) The polymerization reaction time is 1h~20h; (4) The number average molecular weight of the polysulfone resin is 20,000 to 130,000; (5) The temperature of the end-capping reaction is 50°C to 240°C; the time of the end-capping reaction is 1h to 20h.

8. The preparation method according to any one of claims 1 to 4, characterized in that The preparation method satisfies at least one of the following conditions: (1) The bisphenol monomer is at least one selected from bisphenol A, bisphenol S, bisphenol F, bisphenol Z and 4,4'-dihydroxybiphenyl; (2) the dihalogenated diphenyl sulfone is at least one selected from dichlorodiphenyl sulfone, difluorodiphenyl sulfone and dibromodiphenyl sulfone; (3) The organic solvent is at least one selected from N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane and diphenyl sulfone; (4) The salt-forming agent is at least one selected from sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.

9. A polysulfone resin, characterized in that Obtained according to the preparation method according to any one of claims 1 to 8.

10. A polymer product, characterized in that The polymer article comprises the polysulfone resin of claim 9.

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