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CN-122011380-A - Poly (2-oxazoline) thermosensitive polymer with sulfoxide structure-containing side chain, and preparation method and application thereof

CN122011380ACN 122011380 ACN122011380 ACN 122011380ACN-122011380-A

Abstract

The invention relates to the technical field of functional high polymer materials, in particular to a poly (2-oxazoline) thermosensitive polymer with a sulfoxide structure in a side chain, a preparation method and application thereof, wherein sulfide with different carbon chain lengths is introduced into the side chain of the poly (2-oxazoline) through a sulfhydryl-alkene clicking reaction and is further oxidized into the sulfoxide structure to form the poly (2-oxazoline) thermosensitive polymer with the sulfoxide structure in the side chain, the sulfide has certain hydrophobicity and obviously enhanced hydrophilicity after being oxidized into sulfoxide, so that an effective path is provided for the controllable adjustment of the hydrophilic-hydrophobic balance of molecules, the poly (2-oxazoline) thermosensitive polymer with the sulfoxide structure in the side chain shows obvious LCST type thermosensitive property, the cloud point temperature of the poly (2-oxazoline) thermosensitive polymer with the sulfoxide structure gradually decreases along with the increase of the concentration, the correlation of the thermosensitive property with the structure and the concentration of the polymer is revealed, and the thermosensitive polymer with different temperature response points can be obtained through controlling the carbon chain length and the concentration of the polymer.

Inventors

  • CAO SHUAISHUAI
  • WU DALIN
  • CHEN ZHIHUI
  • LI ZEYUAN

Assignees

  • 深圳大学总医院
  • 中山大学

Dates

Publication Date
20260512
Application Date
20260318

Claims (10)

  1. 1. A poly (2-oxazoline) thermosensitive polymer with sulfoxide structure-containing side chain is characterized in that the poly (2-oxazoline) thermosensitive polymer has a structural general formula of ; Wherein the value interval of n is 50-200, and is an integer, and R is an alkyl chain of C 2 -C 6 .
  2. 2. The poly (2-oxazoline) temperature-sensitive polymer with a sulfoxide structure-containing side chain according to claim 1, wherein R is one selected from ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl.
  3. 3. A method for preparing a poly (2-oxazoline) temperature-sensitive polymer with a sulfoxide structure-containing side chain according to any one of claims 1-2, comprising the steps of: mixing 4-pentenoyl chloride, 2-chloroethylamine hydrochloride and triethylamine, and carrying out amidation reaction to obtain an intermediate product; mixing the intermediate product with anhydrous potassium hydroxide, and performing cyclization reaction to obtain a 2-oxazoline monomer with a carbon-carbon double bond; Mixing the 2-oxazoline monomer with an initiator, and carrying out polymerization reaction to obtain poly (2-oxazoline) with carbon-carbon double bonds on side chains; Mixing the poly (2-oxazoline) with carbon-carbon double bonds on the side chains, mercaptan and a free radical initiator, and carrying out mercapto-alkene click reaction to obtain poly (2-oxazoline) containing a thioether structure; and mixing the poly (2-oxazoline) containing the thioether structure with an oxidant, and carrying out oxidation reaction to obtain the poly (2-oxazoline) temperature-sensitive polymer with the sulfoxide structure on the side chain.
  4. 4. The method for preparing a poly (2-oxazoline) thermosensitive polymer with a sulfoxide structure-containing side chain according to claim 3, wherein the molar ratio of 4-pentenoyl chloride, 2-chloroethylamine hydrochloride and triethylamine is 1 (1.2-1.5): 2.5-3.0, the temperature of the amidation reaction is 25-35 ℃, and the time of the amidation reaction is 12-24 h.
  5. 5. The method for producing a poly (2-oxazoline) thermosensitive polymer having a sulfoxide structure-containing side chain according to claim 3, wherein the molar ratio of the intermediate product to the anhydrous potassium hydroxide is 1 (1.0-1.1), the temperature of the cyclization reaction is 65 ℃ to 70 ℃, and the time of the cyclization reaction is 12h to 24h.
  6. 6. The method for preparing a poly (2-oxazoline) temperature-sensitive polymer with a sulfoxide structure-containing side chain according to claim 3, wherein the initiator is methyl triflate, the molar ratio of the 2-oxazoline monomer to the initiator is (50-200): 1, the temperature of the polymerization reaction is 80-120 ℃, and the time of the polymerization reaction is 12-24 h.
  7. 7. The method for preparing a poly (2-oxazoline) temperature-sensitive polymer with a sulfoxide structure-containing side chain according to claim 3, wherein the molar ratio of the poly (2-oxazoline) with a carbon-carbon double bond on the side chain to the mercaptan is 1 (1.5-1.8), the temperature of the mercapto-alkene clicking reaction is 70-75 ℃, and the time of the mercapto-alkene clicking reaction is 12-24 h.
  8. 8. The method for preparing a poly (2-oxazoline) thermosensitive polymer with a sulfoxide structure-containing side chain according to claim 3, wherein the mercaptan is one selected from the group consisting of ethanethiol, n-propanethiol, n-butanethiol, n-pentanethiol and n-hexanethiol.
  9. 9. The method for producing a poly (2-oxazoline) temperature-sensitive polymer having a sulfoxide structure-containing side chain according to claim 3, wherein the molar ratio of the poly (2-oxazoline) having a thioether structure to the oxidizing agent is 1 (4.0 to 4.5), the temperature of the oxidation reaction is 20 to 25 ℃, and the time of the oxidation reaction is 60 to 70 minutes.
  10. 10. Use of a poly (2-oxazoline) temperature-sensitive polymer containing a sulfoxide structure in a side chain according to any one of claims 1-2, wherein the use comprises one of a drug controlled release system, cell separation and embedding, temperature-switching hydrogel, environmental sensor, biomedical material.

Description

Poly (2-oxazoline) thermosensitive polymer with sulfoxide structure-containing side chain, and preparation method and application thereof Technical Field The invention relates to the technical field of functional high polymer materials, in particular to a poly (2-oxazoline) thermosensitive polymer with a sulfoxide structure in a side chain, and a preparation method and application thereof. Background In recent years, poly (2-oxazoline) is widely focused as a polymer obtained by controllable active ring-opening polymerization, and the poly (2-oxazoline) has the advantages of structural diversity, polymerization controllability, good biocompatibility and the like and is considered as a powerful substitute of polyethylene glycol (PEG). By regulating and controlling the side chain of the 2-oxazoline monomer, a series of functional polymers with different properties, including thermosensitive polymers, can be obtained. For example, when a proportion of hydrophilic/hydrophobic monomers is introduced, poly (2-oxazoline) may exhibit phase transition behavior of the lower critical solution temperature (LCST, lower Critical Solution Temperature) or upper critical solution temperature (UCST, upper Critical Solution Temperature) type. However, the research on the temperature sensitivity of poly (2-oxazoline) still has the defects that the temperature sensitivity is realized mainly by the copolymerization of mixed monomers, the system research on the side chain refined structure-performance relationship is lacking, and meanwhile, the controllable adjustment of the temperature sensitive transition point is still a challenge on the premise of keeping the excellent water solubility of the polymer. In addition, the existing thermosensitive polymers are limited in variety, temperature transition points are difficult to flexibly regulate and control, the structure-performance relationship is not clear, a systematic method for finely researching thermosensitive through single variables (such as side chain carbon chain length) is lacking, and novel materials with good water solubility, reversible thermosensitive property and biocompatibility are lacking. Accordingly, the prior art is still in need of improvement and development. Disclosure of Invention In view of the defects of the prior art, the invention aims to provide a poly (2-oxazoline) thermosensitive polymer with a sulfoxide structure in a side chain, and a preparation method and application thereof, and aims to solve the problems of fixed temperature response point, high regulation difficulty and insufficient functionality of the conventional thermosensitive polymer. The technical scheme of the invention is as follows: poly (2-oxazoline) thermosensitive polymer with sulfoxide structure-containing side chain, wherein the poly (2-oxazoline) thermosensitive polymer has a structural general formula of ; Wherein the value interval of n is 50-200, and is an integer, and R is an alkyl chain of C 2-C6. The side chain of the poly (2-oxazoline) thermosensitive polymer containing a sulfoxide structure, wherein R is selected from one of ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl. A preparation method of a poly (2-oxazoline) thermosensitive polymer with a sulfoxide structure-containing side chain comprises the following steps: mixing 4-pentenoyl chloride, 2-chloroethylamine hydrochloride and triethylamine, and carrying out amidation reaction to obtain an intermediate product; mixing the intermediate product with anhydrous potassium hydroxide, and performing cyclization reaction to obtain a 2-oxazoline monomer with a carbon-carbon double bond; Mixing the 2-oxazoline monomer with an initiator, and carrying out polymerization reaction to obtain poly (2-oxazoline) with carbon-carbon double bonds on side chains; Mixing the poly (2-oxazoline) with carbon-carbon double bonds on the side chains, mercaptan and a free radical initiator, and carrying out mercapto-alkene click reaction to obtain poly (2-oxazoline) containing a thioether structure; and mixing the poly (2-oxazoline) containing the thioether structure with an oxidant, and carrying out oxidation reaction to obtain the poly (2-oxazoline) temperature-sensitive polymer with the sulfoxide structure on the side chain. The preparation method of the poly (2-oxazoline) thermosensitive polymer with the side chain containing a sulfoxide structure comprises the steps of (1.2-1.5) and (2.5-3.0) of the mole ratio of 4-pentenoyl chloride, 2-chloroethylamine hydrochloride to triethylamine, wherein the temperature of the amidation reaction is 25-35 ℃, and the time of the amidation reaction is 12-24 h. The preparation method of the poly (2-oxazoline) thermosensitive polymer with the side chain containing a sulfoxide structure comprises the steps of (1.0-1.1) the molar ratio of the intermediate product to anhydrous potassium hydroxide, wherein the temperature of cyclization reaction is 65-70 ℃, and the time of cyclization reaction is 12-24 hour