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CN-122011344-A - Photo-thermal stable PTAA copolymer and preparation method thereof

CN122011344ACN 122011344 ACN122011344 ACN 122011344ACN-122011344-A

Abstract

The invention discloses a photo-thermal stable PTAA copolymer and a preparation method thereof, wherein the structural formula of the photo-thermal stable PTAA copolymer is as follows Wherein R is selected from Or At least one of which n is 0.03 to 0.26. The copolymer has PTAA conjugated main chain and piperazine side group, and can realize good processing property and improved photo-thermal stability.

Inventors

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Assignees

  • 链行走新材料科技(广州)有限公司

Dates

Publication Date
20260512
Application Date
20260416

Claims (10)

  1. 1. A photo-thermally stable PTAA copolymer, wherein the photo-thermally stable PTAA copolymer has a structural formula as shown in formula (I): Formula (I); wherein R is selected from Or (b) At least one of which n is 0.03 to 0.26.
  2. 2. The photo-thermally stable PTAA copolymer according to claim 1, wherein the photo-thermally stable PTAA copolymer has a number average molecular weight of 10-40 kda and a pdi of 1.2-3.0.
  3. 3. The photo-thermally stable PTAA copolymer according to claim 1, wherein R is selected from the group consisting of 。
  4. 4. A method for preparing a photo-thermally stable PTAA copolymer according to any of claims 1 to 3, comprising the steps of: Under the action of a palladium catalyst and an auxiliary agent, the piperazinyl aniline compound, 2,4, 6-trimethyl aniline and 4,4' -dibromobiphenyl are subjected to polymerization reaction to obtain the photo-thermal stable PTAA copolymer; Wherein the piperazinylaniline compound is selected from at least one of 4- (4-methylpiperazin-1-yl) aniline or 3- (4-methylpiperazin-1-yl) aniline.
  5. 5. The method for producing a photo-thermally stable PTAA copolymer according to claim 4, wherein the sum of the amounts of the piperazinylaniline compound and the 2,4, 6-trimethylaniline is n 1 , and the amount of the 4,4' -dibromobiphenyl is n 2 ,n 1 ：n 2 in a range of 1:1 to 1.1.
  6. 6. The method for preparing a photo-thermally stable PTAA copolymer according to claim 4, wherein the ratio of the amount of the piperazinylaniline compound to the amount of the 2,4, 6-trimethylaniline compound is 0.05 to 0.25:0.75 to 0.95.
  7. 7. The method for producing a photo-thermally stable PTAA copolymer according to claim 4, wherein a ratio of an amount of the substance of the palladium catalyst to an amount of the substance of the 4,4' -dibromobiphenyl is 0.005 to 0.03:1.
  8. 8. The method for preparing a photo-thermally stable PTAA copolymer according to claim 4, wherein the auxiliary agent comprises an organic base and a solvent.
  9. 9. The method for producing a photo-thermally stable PTAA copolymer according to claim 8, wherein the organic base is selected from potassium t-butoxide, and/or a ratio of an amount of the organic base substance to an amount of the 4,4' -dibromobiphenyl substance is 2 to 4:1.
  10. 10. The method for producing a photo-thermally stable PTAA copolymer according to claim 8, wherein the solvent is selected from toluene, and/or the ratio of the solvent to the amount of 4,4' -dibromobiphenyl is 2l to 4l to 1mol.

Description

Photo-thermal stable PTAA copolymer and preparation method thereof Technical Field The invention belongs to the field of organic high molecular polymers, and particularly relates to a photo-thermal stable PTAA copolymer and a preparation method thereof. Background Poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA) is a conjugated polymer taking triarylamine units as a main chain, and is widely focused in the field of functional materials because of the advantages of good light transmittance, adjustable energy level and the like. However, PTAA suffers from significant photo and thermal stability problems in practical applications. Under the photo-thermal condition, the triarylamine structural unit in the PTAA molecular chain is easy to absorb photon energy, and oxidation reaction is carried out to generate degradation products such as free radical cations or carbonyl groups, so that the conjugated structure of the polymer is damaged, the morphology of the film is unstable, and the long-term use reliability of the material is further affected. In order to solve the stability problem, two modification strategies are mainly adopted in the prior art. The first is a physical blending or doping mode, namely adding a small molecular antioxidant, a light stabilizer or an ultraviolet absorber into a PTAA matrix to inhibit photooxidation or thermal degradation, however, the physical additive has limited compatibility with a polymer matrix, and is easy to migrate and precipitate in long-term use or thermal aging process, so that the protection effect is attenuated, and impurities can be introduced into the additive to influence the comprehensive performance of the material. And secondly, chemical structure modification is carried out, fluorine-containing, siloxane or crosslinking groups are introduced through copolymerization or side group modification, so that the thermal stability or hydrophobicity of the material is improved, but the processability and intrinsic functional characteristics of the polymer are sacrificed to a certain extent by the modification. Therefore, how to develop a PTAA modified polymer with good processability and photo-thermal stability is a key technical problem to be solved in the art. Disclosure of Invention The invention discloses a photo-thermal stable PTAA copolymer and a preparation method thereof, wherein the copolymer has a PTAA conjugated main chain and a piperazine side group, and can realize good processing characteristics such as film forming property and improve photo-thermal stability by controlling the relative amount of the piperazine side group. Specifically, the piperazine side group of the copolymer does not damage the skeleton structure and stacking property of the PTAA conjugated main chain, is favorable for forming a uniform and compact film layer, and further has the effect of protecting the PTAA conjugated main chain due to preferential oxidation of the more active piperazine side group in the light and heat environment, so that the copolymer has improved photo-thermal stability. The first object of the present invention is to provide a photo-thermal stable PTAA copolymer having a structural formula as shown in formula (I): Formula (I); wherein R is selected from Or (b)At least one of which n is 0.03 to 0.26. For example, n may be 0.04、0.05、0.06、0.07、0.08、0.09、0.10、0.11、0.12、0.13、0.14、0.15、0.16、0.17、0.18、0.19、0.20、0.21、0.22、0.23、0.24、0.25. In some embodiments of the invention, the photo-thermally stable PTAA copolymer has a number average molecular weight of 10 to 40kda and a pdi of 1.2 to 3.0. For example, the number average molecular weight thereof may be 12kDa、14kDa、16kDa、18kDa、20kDa、22kDa、24kDa、26kDa、28kDa、30kDa、32kDa、34kDa、36kDa、38kDa、30kDa、32kDa、34kDa、36kDa、38kDa. In some embodiments of the invention, the R is selected from. When R is selected from this structure, it is advantageous to obtain both better processability and photo-thermal stability. A second object of the present invention is to provide a method for preparing the photo-thermal stable PTAA copolymer, comprising the steps of: Under the action of a palladium catalyst and an auxiliary agent, the piperazinyl aniline compound, 2,4, 6-trimethyl aniline and 4,4' -dibromobiphenyl are subjected to polymerization reaction to obtain the photo-thermal stable PTAA copolymer; Wherein the piperazinylaniline compound is selected from at least one of 4- (4-methylpiperazin-1-yl) aniline or 3- (4-methylpiperazin-1-yl) aniline. In some embodiments of the present invention, the sum of the amounts of the piperazinylaniline compound and the 2,4, 6-trimethylaniline is n 1, and the amount of the 4,4' -dibromobiphenyl is n 2,n1：n2, which is 1:1 to 1.1. In some embodiments of the invention, the ratio of the amount of the piperazinylaniline compound to the amount of the 2,4, 6-trimethylaniline compound is 0.05 to 0.25:0.75 to 0.95. In some embodiments of the invention, the ratio of the amount of the substance of th