Search

CN-122011362-A - Polyaryletherketone copolymer with high Tg and low Tm, preparation method thereof and composite material

CN122011362ACN 122011362 ACN122011362 ACN 122011362ACN-122011362-A

Abstract

The invention relates to the technical field of high polymer synthesis, in particular to a polyaryletherketone copolymer with high Tg and low Tm, a preparation method thereof and a composite material; the preparation method comprises the steps of S1, deoxidizing a reaction device filled with difluorobenzophenone, dihydroxydiphenyl ether and a reaction solvent under mechanical stirring, preheating in a protective atmosphere to form a homogeneous system, adding a first salifying agent, heating to perform a prepolymerization reaction, S2, adding a diphenol monomer containing a diphenyl structure and a difluoropolyaryldiketone monomer into the reaction system, adding a second salifying agent, heating to perform a copolymerization reaction, S3, after the reaction is finished, performing post-treatment to precipitate out a polyaryletherketone copolymer with high Tg and low Tm, wherein the material has excellent melt flowability and filling capacity, and is suitable for injection molding complex precise structural members or thin-wall structural members.

Inventors

  • LI JUN
  • Tu zheng
  • TAN ZONGSHANG
  • LIU ZHE

Assignees

  • 江苏君华特种高分子材料股份有限公司
  • 山东君昊高性能聚合物有限公司

Dates

Publication Date
20260512
Application Date
20260202

Claims (9)

  1. 1. The preparation method of the polyaryletherketone copolymer with high Tg and low Tm is characterized by comprising the following steps: s1, deoxidizing the interior of a reaction device filled with difluorobenzophenone, dihydroxydiphenyl ether and a reaction solvent under mechanical stirring, preheating in a protective atmosphere to form a homogeneous system, adding a first salifying agent, and heating to perform a prepolymerization reaction; S2, adding a diphenol monomer containing a diphenyl structure and a difluoro polyaryldiketone monomer into the reaction system, adding a second salt forming agent, and heating to perform copolymerization reaction; S3, after the reaction is finished, carrying out post-treatment precipitation to obtain the high Tg and low Tm polyaryletherketone copolymer.
  2. 2. The method for producing a polyaryletherketone copolymer having both high Tg and low Tm according to claim 1, wherein the difluorobenzophenone is one or more selected from the group consisting of 4,4 '-difluorobenzophenone, 2' -difluorobenzophenone, 2,4 '-difluorobenzophenone, 3' -difluorobenzophenone; The dihydroxydiphenyl ether is selected from one or more of 4,4 '-dihydroxydiphenyl ether, 3- (4-hydroxyphenoxy) phenol and 2,2' -dihydroxydiphenyl ether; the diphenol monomer containing the diphenyl structure is selected from one or more of diphenyl diphenol, tetramethyl diphenyl diphenol and dimethyl diphenyl diphenol; The difluoro polyaryldione monomer is selected from one or more of 1, 3-bis (4-fluorobenzoyl) benzene and 1, 3-bis (4-fluorophenyl) propane-1, 3-dione.
  3. 3. The method for preparing a polyaryletherketone copolymer having both high Tg and low Tm according to claim 2, wherein the first salt former and the second salt former are both a combination of sodium carbonate and potassium carbonate, wherein the mass ratio of potassium carbonate in the first salt former is in the range of 0.1% to 1%, and the mass ratio of potassium carbonate in the second salt former is in the range of 0.3% to 1%.
  4. 4. The method for producing a polyaryletherketone copolymer having both high Tg and low Tm according to claim 3, wherein the first salt former is added in an amount of 50 to 65% of the sum of the molar amounts of difluorobenzophenone and dihydroxydiphenyl ether, and the second salt former is added in an amount of 28 to 45% of the sum of the molar amounts of diphenol monomer containing biphenyl structure and difluoropolyaryldiketone monomer.
  5. 5. The method for producing a polyaryletherketone copolymer having both high Tg and low Tm according to any one of claims 1 to 4, wherein the molar ratio of the difluorobenzophenone to the dihydroxydiphenyl ether and the diphenol monomer containing diphenyl structure to the difluoropolyaryldione monomer in S1 is 1.05 to 1.3:1, the molar ratio of the difluorobenzophenone to the dihydroxydiphenyl ether is 1.65 to 1.75:1, and the molar ratio of the diphenol monomer containing diphenyl structure to the difluoropolyaryldione monomer is 1 to 1.3:2.
  6. 6. The method for preparing a polyaryletherketone copolymer having both high Tg and low Tm according to any one of claims 1 to 4, wherein the reaction solvent is selected from diphenyl sulfone, the ratio of the reaction monomer to the reaction solvent is 1mol:720-1200g, and the reaction monomer comprises the difluorobenzophenone, the difluoropolyaryldione monomer, the dihydroxydiphenyl ether and the diphenol monomer containing diphenyl structure.
  7. 7. The method for producing a polyaryletherketone copolymer having both high Tg and low Tm according to any one of claims 1 to 4, wherein the pre-heating temperature is 145 to 165 ℃; the temperature of the prepolymerization reaction is 280-315 ℃ and the reaction time is 40min-2h; the temperature of the copolymerization reaction is in the range of 315-350 ℃ and the reaction time is 30min-1h; The temperature rising rate is controlled to be 1-3 ℃ per minute.
  8. 8. Polyaryletherketone copolymers having both a high Tg and a low Tm, characterized by being prepared by the preparation method according to any one of claims 1-7.
  9. 9. A composite material comprising as a base material a polyaryletherketone copolymer having both a high Tg and a low Tm prepared by the method according to any one of claims 1 to 7.

Description

Polyaryletherketone copolymer with high Tg and low Tm, preparation method thereof and composite material Technical Field The invention relates to the technical field of high polymer synthesis, in particular to a polyaryletherketone copolymer with high Tg and low Tm, a preparation method thereof and a composite material. Background Polyaryletherketone (PAEK) is a special engineering plastic with a molecular main chain composed of arylene, ether bonds and ketone bonds, and is typically represented by Polyetheretherketone (PEEK). PEEK has excellent mechanical properties, heat resistance (tg=143° C, tm =343 ℃) and chemical stability, and is widely used in aerospace, electronic and electrical fields, etc. However, the extremely high melting point (Tm) of PEEK results in processing temperatures as high as 370-420 ℃, which presents significant drawbacks of (1) high energy consumption, high cost, and huge processing energy consumption due to the need for special high temperature equipment. (2) The process window is narrow, thermal degradation and thermal oxidation aging are easy to occur at high temperature, the product performance is affected, and the rejection rate is increased. (3) The high melt viscosity makes it difficult to use in injection molding thin-walled articles, complex structures, or heat-sensitive overmolding scenes. The prior art has been explored to solve the above problems. For example, PAEKs other than low melting point have been developed by introducing rigid structures. However, these methods tend to lower the melting point while it is difficult to maintain or further raise the glass transition temperature (Tg), resulting in reduced high temperature service properties of the material. Thus, there has long been a technical contradiction in the art how to maintain its excellent high temperature properties without sacrificing or even increasing its glass transition temperature while significantly reducing the PAEK melting point and melt viscosity to improve processability. Disclosure of Invention In order to solve the technical problems, the invention provides a polyaryletherketone copolymer with high Tg and low Tm, a preparation method thereof and a composite material. The polyaryletherketone material with high glass transition temperature, low melting point temperature and low melt viscosity is obtained through the high molecular structural design and the step polymerization process, has excellent melt fluidity and filling capability, and is suitable for injection molding complex precise structural members or thin-wall structural members. In order to achieve the above purpose, the invention is realized by the following technical scheme: the first aspect of the present invention provides a method for preparing a polyaryletherketone copolymer having both high Tg and low Tm, comprising the steps of: s1, deoxidizing the interior of a reaction device filled with difluorobenzophenone, dihydroxydiphenyl ether and a reaction solvent under mechanical stirring, preheating in a protective atmosphere to form a homogeneous system, adding a first salifying agent, and heating to perform a prepolymerization reaction; S2, adding a diphenol monomer containing a diphenyl structure and a difluoro polyaryldiketone monomer into the reaction system, adding a second salt forming agent, and heating to perform copolymerization reaction; S3, after the reaction is finished, carrying out post-treatment precipitation to obtain the high Tg and low Tm polyaryletherketone copolymer. Further, the difluorobenzophenone is selected from one or more of 4,4 '-difluorobenzophenone, 2' -difluorobenzophenone, 2,4 '-difluorobenzophenone and 3,3' -difluorobenzophenone, and the dihydroxydiphenyl ether is selected from one or more of 4,4 '-dihydroxydiphenyl ether, 3- (4-hydroxyphenoxy) phenol and 2,2' -dihydroxydiphenyl ether. Further, the diphenol monomer containing the diphenyl structure is selected from one or more of diphenyl diphenol (such as 4,4 '-diphenyl diphenol), tetramethyl diphenyl diphenol (such as 3,5,3',5 '-tetramethyl-4, 4' -dihydroxydiphenyl) and dimethyl diphenyl diphenol (such as 3,3 '-dimethyl-4, 4' -diphenyl diphenol). Further, the difluoro polyaryldione monomer is selected from one or more of 1, 3-bis (4-fluorobenzoyl) benzene, 1, 3-bis (4-fluorophenyl) propane-1, 3-dione. Further, the first salt forming agent and the second salt forming agent are both combinations of sodium carbonate and potassium carbonate, wherein the mass ratio of the potassium carbonate in the first salt forming agent is in the range of 0.1-1%, and the mass ratio of the potassium carbonate in the second salt forming agent is in the range of 0.3-1%. Preferably, the mass ratio of the potassium carbonate in the first salt forming agent is in the range of 0.2% -0.4%, and the mass ratio of the potassium carbonate in the second salt forming agent is 0.4% -0.6%. The potassium carbonate mainly accelerates the reaction speed and reduces the polycondensati