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CN-122011250-A - Synthetic method of vinyl polystyrene

CN122011250ACN 122011250 ACN122011250 ACN 122011250ACN-122011250-A

Abstract

The invention relates to a method for synthesizing vinyl polystyrene, which comprises the steps of 1) mixing an initiator, a solvent, a styrene compound and hydroxyethyl acrylate, stirring until the mixture is completely dissolved to obtain a premix, 2) adding the solvent into a three-port bottle, starting stirring, heating to 70-150 ℃ under an inert gas atmosphere, dropwise adding the premix, performing constant-temperature reaction for 30-100min after the dropwise adding is finished, 3) cooling to 10-70 ℃, adding a catalyst, stirring, dropwise adding methacrylic anhydride, acrylic anhydride, chloromethyl styrene or bromomethyl styrene under an inert gas atmosphere, performing constant-temperature reaction for 0.5-1.5h after the dropwise adding, reacting for 2-8h at 20-100 ℃, 4) adding water after the reaction is finished, adjusting the pH to 4-8, stirring, standing, separating out a water phase, evaporating water, precipitating in methanol or ethanol, and performing vacuum drying to obtain the vinyl polystyrene. The method has the advantages of mild reaction conditions, high production efficiency and high product purity, can realize effective regulation and control of the product performance, and meets the performance requirements of different fields on vinyl polystyrene.

Inventors

  • WANG KAI
  • ZHANG YUANSHENG
  • ZHANG DECHUANG
  • Jia tianhe
  • ZHANG KEYANG
  • LIU YAN
  • LU ZAIJUN
  • LIU XIAOKE
  • Lou Yuanchao
  • WANG HONGSHUI
  • BAI YUANYUAN
  • Tang Hongshi

Assignees

  • 濮阳市恩赢高分子材料有限公司

Dates

Publication Date
20260512
Application Date
20260115

Claims (10)

  1. 1. The synthesis method of the vinyl polystyrene is characterized by comprising the following steps of: 1) The preparation of premix, namely mixing and stirring an initiator, a solvent, a styrene compound and hydroxyethyl acrylate until the initiator, the solvent, the styrene compound and the hydroxyethyl acrylate are completely dissolved to obtain premix; 2) Adding solvent into a three-mouth bottle, stirring, heating to 70-150 ℃ under the inert gas atmosphere, dripping the premix, and reacting for 30-120min at constant temperature after the dripping is finished; 3) The esterification reaction, namely cooling to 10-70 ℃, adding a catalyst, stirring, dropwise adding methacrylic anhydride, acrylic anhydride, chloromethyl styrene or bromomethyl styrene in an inert gas atmosphere, carrying out constant temperature reaction for 0.5-1.5h after the dropwise addition, and then carrying out reaction for 2-8h at 20-100 ℃; 4) And (3) after the reaction is finished, adding water, adjusting the pH to 4-8, stirring, standing, separating out a water phase, then carrying out reduced pressure distillation on the residual organic phase, evaporating out excessive water, precipitating and separating out in methanol or ethanol, and carrying out vacuum drying to obtain the catalyst.
  2. 2. The method for synthesizing vinyl polystyrene according to claim 1, wherein in the step 1), the initiator is one or more selected from benzoyl oxide, azobisisobutyronitrile, azobisisoheptonitrile, azobiscyanovaleric acid, di-tert-butyl peroxide and dicumyl peroxide, and the initiator is 0.5-8% of the mass of the styrene compound.
  3. 3. The method for synthesizing vinyl polystyrene according to claim 1, wherein in step 1) and step 2), the solvent is at least one of toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, chlorobenzene, dimethyl sulfoxide, chloroform and tetrachloromethane, and the solvent is 1-3 times of the mass of the styrene compound.
  4. 4. The method for synthesizing vinyl polystyrene according to claim 1, wherein the styrene compound in step 1) is styrene, p-methylstyrene, p-ethylstyrene or α -methylstyrene, and the molar ratio of the styrene compound to hydroxyethyl acrylate is (1-12): 1.
  5. 5. The method for synthesizing vinyl polystyrene according to claim 1, wherein the molar ratio of methacrylic anhydride, acrylic anhydride, chloromethylstyrene, or bromomethylstyrene to hydroxyethyl acrylate in step 3) is 1 to 1.2.
  6. 6. The method for synthesizing vinyl polystyrene according to claim 1, wherein the catalyst in the step 3) is one or two selected from triethylamine, 4-dimethylaminopyridine and furan, and the catalyst is used in an amount of 0.5 to 3 times the molar amount of hydroxyethyl acrylate.
  7. 7. The method for synthesizing vinyl polystyrene according to claim 1, wherein in the step 4), a base is added to adjust the pH to 4 to 8, and the base is one or more selected from the group consisting of aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, sodium carbonate and potassium carbonate.
  8. 8. The method for synthesizing vinyl polystyrene according to claim 7, wherein the mass concentration of the aqueous sodium hydroxide solution and the aqueous potassium hydroxide solution is 10% to 20%.
  9. 9. Vinyl polystyrene prepared by the synthetic method of any one of claims 1-8.
  10. 10. Use of the vinyl polystyrene of claim 9 in the preparation of hydrocarbon resins.

Description

Synthetic method of vinyl polystyrene Technical Field The invention belongs to the technical field of high polymer material synthesis, and particularly relates to a synthesis method of vinyl polystyrene, which is mainly applied to the field of hydrocarbon resin, and is particularly suitable for scenes with low dielectric requirements on dielectric properties of materials, such as insulating materials, packaging materials and the like in the field of electronic information. Background With the rapid development of the electronic information industry, the performance requirements on the polymer materials are increasingly improved, and particularly in the high-frequency and high-speed signal transmission field, the polymer materials with low dielectric constants become one of the key requirements. Hydrocarbon resin is used as an important polymer material and has wide application in the fields of electronic packaging, printed circuit boards and the like, and vinyl polystyrene is used as an important component of hydrocarbon resin, and the synthesis process directly influences the dielectric property, mechanical property and processing property of hydrocarbon resin. At present, the existing vinyl polystyrene synthesis method has various defects, such as severe reaction conditions of partial synthesis process, high production cost caused by extremely high reaction temperature or special reaction equipment, low purity of products in the partial synthesis method, high impurity content, influence on the dielectric properties of subsequent hydrocarbon resins, long reaction time of the partial synthesis method, low production efficiency and difficulty in meeting the requirements of industrial mass production. In addition, the types of the initiator and the catalyst used in the existing synthesis method are single, the regulation and control capability on the reaction is poor, and the performance of the product is difficult to adjust according to actual requirements. Therefore, the development of the vinyl polystyrene synthesis method with mild reaction conditions, high production efficiency, high product purity and controllable performance has important practical significance. Disclosure of Invention The invention aims to overcome the defects of harsh reaction conditions, low production efficiency, low product purity, poor performance controllability and the like in the vinyl polystyrene synthesis method in the prior art, and provides a vinyl polystyrene synthesis method. The method has mild reaction conditions, high production efficiency and high product purity, does not need special equipment, can realize effective regulation and control of the product performance by selecting different types of initiators and catalysts, and meets the performance requirements of different fields on vinyl polystyrene. In order to achieve the above purpose, the invention adopts the following technical scheme: a method for synthesizing vinyl polystyrene, which comprises the following steps: 1) The preparation of premix, namely mixing and stirring an initiator, a solvent, a styrene compound and hydroxyethyl acrylate until the initiator, the solvent, the styrene compound and the hydroxyethyl acrylate are completely dissolved to obtain premix; 2) Adding the same solvent used in the step 1) into a three-mouth bottle, starting stirring, heating to 70-150 ℃ under the inert gas atmosphere, dropwise adding the premix within 50-160min after the temperature is stable, and performing constant-temperature reaction for 30-120min after the dropwise adding is finished to complete the polymerization reaction to obtain a polystyrene copolymer solution containing hydroxyl; 3) The esterification reaction is carried out, namely, the temperature is reduced to 10-70 ℃, a catalyst is added, the mixture is stirred and then methacrylic anhydride, acrylic anhydride, chloromethyl styrene or bromomethyl styrene is dripped in the inert gas atmosphere, the constant temperature reaction is carried out for 0.5-1.5h after the dripping is finished, the reaction is carried out for 2-8h at 20-100 ℃, and the esterification reaction is finished, thus obtaining a vinyl polystyrene crude product solution; 4) And (3) after the reaction is finished, adding water, regulating the pH value to be 4-8, slowly stirring for 30-90min to enable impurities in the crude product to be fully dissolved in the water, stopping stirring, and standing for 30-90min to enable the solution to be layered. Separating out the lower water phase, then carrying out reduced pressure distillation on the residual organic phase, evaporating out excessive water, precipitating and separating out in methanol or ethanol, and carrying out vacuum drying at 40 ℃ to obtain a pure vinyl polystyrene product. Specifically, in the step 1), the initiator is selected from one or more of benzoyl oxide (BPO), azobisisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), azodicyanovaleric acid (ACVA), di-tert-butyl peroxide