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CN-122011390-A - Polyarylethersulfone and preparation method thereof

CN122011390ACN 122011390 ACN122011390 ACN 122011390ACN-122011390-A

Abstract

The invention provides polyarylethersulfone and a preparation method thereof. The preparation method comprises the steps of mixing a polar aprotic solvent, bisphenol monomers and alkaline substances, introducing protective gas, heating, dehydrating, cooling to T1, adding diphenyl sulfone monomers, carrying out a first-stage polymerization reaction at T1, and carrying out a second-stage polymerization reaction after adding a low-polarity solvent and heating to T2, thereby obtaining the polyarylethersulfone, wherein the low-polarity solvent is selected from one or more of n-hexane, cyclohexane, toluene, ethylbenzene, biphenyl and diphenyl ether. The invention reduces or partially inhibits the generation of cyclic oligomers during the reaction process, thereby obtaining the polyarylethersulfone with narrow molecular weight distribution and low content of cyclic polymer. The method provided by the invention is simple and feasible, is convenient to control, avoids complex product purification and separation processes, and is beneficial to industrialized implementation.

Inventors

  • TAO RUOYUAN
  • Jia Yanyu

Assignees

  • 中石油(上海)新材料研究院有限公司
  • 中国石油天然气股份有限公司

Dates

Publication Date
20260512
Application Date
20241112

Claims (20)

  1. 1. A method for preparing polyarylethersulfone, comprising the following steps: mixing a polar aprotic solvent, a bisphenol monomer and an alkaline substance, introducing a protective gas, heating, dehydrating, cooling to T1, adding a diphenyl sulfone monomer, and carrying out a first-stage polymerization reaction at T1; Adding a low-polarity solvent, heating to T2, and performing a second-stage polymerization reaction to obtain polyarylethersulfone; Wherein the low-polarity solvent is selected from one or more than two of normal hexane, cyclohexane, toluene, ethylbenzene, biphenyl and diphenyl ether.
  2. 2. The process according to claim 1, wherein the molar ratio of the polar aprotic solvent, bisphenol monomer, alkaline substance, diphenylsulfone monomer is (5-9): 1 (1-1.1): 1-1.05.
  3. 3. The production method according to claim 1, wherein the content of the low-polarity solvent is 5 to 25wt.% based on 100wt.% of the total weight of the polar aprotic solvent and the low-polarity solvent.
  4. 4. The production method according to claim 1 or 2, wherein the bisphenol monomer is selected from one or a combination of two or more of bisphenol a, bisphenol S, and biphenol.
  5. 5. The production method according to claim 1 or 2, wherein the diphenyl sulfone monomer is selected from one or a combination of two or more of 4,4' -dichlorodiphenyl sulfone, 4' -difluorodiphenyl sulfone and 4,4' -dibromodiphenyl sulfone.
  6. 6. The preparation method according to claim 1, wherein the polar aprotic solvent is selected from one or a combination of two or more of N-methylpyrrolidone, dimethylformamide, dimethylacetamide, DMSO, and sulfolane.
  7. 7. The preparation method according to claim 1, wherein the alkaline substance is one or a combination of two or more selected from sodium hydroxide, potassium carbonate and sodium carbonate.
  8. 8. The process according to claim 1, wherein T2-T1 is not less than 20 ℃.
  9. 9. The production method according to claim 1 or 8, wherein the T1 is 150 to 200 ℃; And/or, the T2 is 180-240 ℃.
  10. 10. The method of claim 9, wherein T1 is 150-180 ℃; And/or, the T2 is 180-220 ℃.
  11. 11. The production method according to claim 1, wherein the first-stage polymerization is carried out to such an extent that the conversion of phenolic hydroxyl groups in the bisphenol monomer becomes 95% or more.
  12. 12. The production process according to claim 11, wherein the first-stage polymerization is carried out to such an extent that the conversion of phenolic hydroxyl groups in the bisphenol monomer becomes 98% or more.
  13. 13. The production process according to claim 1, wherein the rate of temperature rise in the second-stage polymerization reaction is 0.4 to 1℃per minute.
  14. 14. The production process according to claim 1, wherein the second-stage polymerization reaction is carried out to such an extent that the conversion of the end groups of the phenolic hydroxyl groups in the bisphenol monomer becomes 99.2% or more.
  15. 15. The process of claim 14, wherein the second stage polymerization reaction is carried out to the extent that the conversion of the end groups of phenolic hydroxyl groups in bisphenol monomers reaches 99.5% -99.8%.
  16. 16. The preparation method of claim 1, wherein after the second-stage polymerization reaction is finished, a blocking agent is introduced, a polar aprotic solvent is added, the temperature is reduced to room temperature, solids in the system are removed by filtration, and the polyarylethersulfone is obtained by suction filtration and drying.
  17. 17. A polyarylethersulfone prepared by the method of preparing a polyarylethersulfone of any one of claims 1-16.
  18. 18. The polyarylethersulfone of claim 17, wherein the weight average molecular weight of the polyarylethersulfone is 40000-73000g/mol.
  19. 19. The polyarylethersulfone of claim 17, wherein the molecular weight distribution of the polyarylethersulfone is from 2.0 to 2.9.
  20. 20. The polyarylethersulfone of claim 17, wherein the content of cyclic oligomers in the polyarylethersulfone is 1.2wt% or less.

Description

Polyarylethersulfone and preparation method thereof Technical Field The invention relates to polyarylethersulfone and a preparation method thereof, and belongs to the technical field of high polymer materials. Background Polyarylethersulfone (polysulfone for short) is a high-performance polymer, has excellent heat resistance, mechanical properties and flame retardance, and is widely applied to the fields of automobiles, aerospace, medical equipment, household equipment, separation membranes and the like due to good characteristics. Currently, the industrialized polysulfone resin mainly comprises bisphenol A Polysulfone (PSU), polyether sulfone (PES) and polyphenylene sulfone (PPSU), and is generally prepared by catalyzing bisphenol monomers and dichlorodiphenyl sulfone under alkaline conditions and gradually polymerizing by a high-temperature solution method. In the solution polymerization process of polysulfone, a chain-linking reaction inevitably occurs, and the produced cyclic oligomer cannot further increase the molecular weight, resulting in deviation of the polycondensation reaction from the classical polycondensation model, leading to broadening of the molecular weight distribution of the final product, and further affecting the processing and usability of the resin. In addition, these cyclic oligomers can deposit on the walls of polysulfone solution storage containers to form hard scale that is difficult to remove, which is extremely insoluble in conventional organic solvents, difficult to dissolve and remove at high temperatures of 400 ℃, and severely affects the storage and use of polysulfone materials. Therefore, the cyclic oligomer content of the polysulfone is reduced, and the cyclizing side reaction is inhibited, so that the performance of the polysulfone is improved, and the method has important significance for widening the application of the polysulfone material. Disclosure of Invention In order to solve the technical problems, the invention aims to provide polyarylethersulfone and a preparation method thereof. The generation of cyclic oligomers can be reduced or partially suppressed during the reaction, resulting in polyarylethersulfones with a narrow molecular weight distribution and low content of cyclic polymers. In order to achieve the above object, in a first aspect, the present invention provides a method for preparing polyarylethersulfone, comprising the steps of: mixing a polar aprotic solvent, a bisphenol monomer and an alkaline substance, introducing a protective gas, heating, dehydrating, cooling to T1, adding a diphenyl sulfone monomer, and carrying out a first-stage polymerization reaction at T1; Adding a low-polarity solvent, heating to T2, and performing a second-stage polymerization reaction to obtain polyarylethersulfone; Wherein the low-polarity solvent is selected from one or more than two of normal hexane, cyclohexane, toluene, ethylbenzene, biphenyl and diphenyl ether. According to a specific embodiment of the present invention, the low polarity solvent is selected from one or a combination of two or more of n-hexane, cyclohexane, toluene and biphenyl. The invention adds low-polarity solvent in the second polymerization reaction (high temperature section) to reduce the solvent polarity of the reaction system, and the addition of the low-polarity solvent not only affects the reactivity and selectivity, but also changes the solubility of the product in the mixed system, so that the effect is optimal when the dosage of the mixed solvent reaches a certain optimal balance value, and the second-stage polymerization chain growth reaction is efficiently carried out at a higher temperature to further inhibit the cyclization reaction, thereby improving the selectivity of the linear chain growth reaction relative to the cyclization reaction, reducing the generation of low-molecular-weight cyclic oligomers in the polymer and reducing the molecular weight distribution of the polymerization product. According to a specific embodiment of the present invention, preferably, the molar ratio of the polar aprotic solvent, bisphenol monomer, alkaline substance, diphenyl sulfone monomer is (5-9): 1 (1-1.1): 1-1.05. According to a specific embodiment of the present invention, preferably, the low polar solvent is present in an amount of 5wt.% to 25wt.%, based on 100wt.% total weight of polar aprotic solvent and low polar solvent. According to a specific embodiment of the present invention, preferably, the bisphenol monomer is selected from one or a combination of two or more of bisphenol a, bisphenol S, biphenol. According to a specific embodiment of the present invention, preferably, the diphenyl sulfone monomer is selected from one or a combination of two or more of 4,4 '-dichlorodiphenyl sulfone, 4' -difluorodiphenyl sulfone and 4,4 '-dibromodiphenyl sulfone, and further preferably 4,4' -dichlorodiphenyl sulfone. According to a specific embodiment of the present invention, preferably, the