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CN-122011401-A - Photo-responsive brush-shaped macromolecular emulsifier and preparation method thereof

CN122011401ACN 122011401 ACN122011401 ACN 122011401ACN-122011401-A

Abstract

The invention provides a photoresponsive brush-shaped macromolecular emulsifier and a preparation method thereof, relating to the technical field of macromolecular synthesis, and the photoresponsive brush-shaped macromolecular emulsifier comprises the following steps of (a) adding a dehydrating agent and a catalyst into a mixture of 5-norbornene-2-exomethanol and a carboxyl-terminated modified hydrophilic polymer, and reacting to obtain a hydrophilic monomer; (b) reacting a chain transfer agent containing norbornene units, a methyl acrylate monomer containing spiropyran units and a free radical polymerization initiator to obtain a hydrophobic monomer, and (c) reacting the hydrophilic monomer with the hydrophobic monomer to obtain the light-responsive brush-like macromolecular emulsifier. The photoresponsive brush-shaped macromolecular emulsifier and the preparation method thereof provided by the invention avoid using a pH regulator or inorganic salt, and introduce no impurities into a system, and the obtained emulsifier can be reversibly assembled and disassembled at a water/oil interface, so that the repeated cyclic formation and controllable damage of emulsion are realized.

Inventors

  • ZHA HAO
  • WU GUIGEN
  • WANG TAIHAI
  • CHEN LIANGYIN
  • Guo Mufei

Assignees

  • 奇瑞汽车股份有限公司

Dates

Publication Date
20260512
Application Date
20260306

Claims (10)

  1. 1. The preparation method of the light-responsive brush-shaped macromolecular emulsifier is characterized by comprising the following steps of: (a) Adding a dehydrating agent and a catalyst into a mixture of 5-norbornene-2-exomethanol and a hydrophilic polymer modified by carboxyl end groups, and reacting to obtain a hydrophilic monomer; (b) Reacting a chain transfer agent containing norbornene units, a methyl acrylate monomer containing spiropyran units and a free radical polymerization initiator to obtain a hydrophobic monomer; (c) And the hydrophilic monomer and the hydrophobic monomer react to obtain the light-responsive brush-shaped macromolecular emulsifier.
  2. 2. The method of claim 1, wherein the molar ratio of the 5-norbornene-2-exomethanol to the carboxyl-terminated hydrophilic polymer is 10:0.5-1; preferably, the carboxyl-terminated hydrophilic polymer comprises at least one of carboxyl-modified polyethylene glycol and carboxyl-modified polyacrylamide; preferably, the number average molecular weight of the carboxyl-terminated hydrophilic polymer is 1000 to 5000; Preferably, the dehydrating agent comprises at least one of dicyclohexylcarbodiimide and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride; preferably, the catalyst comprises at least one of 4-dimethylaminopyridine and 4-pyrrolidinylpyridine; Preferably, the molar ratio of the dehydrating agent, the catalyst, the 5-norbornene-2-exo-methanol, and the carboxyl-terminated hydrophilic polymer is 1.5-2:0.5-0.6:10:0.5-1; preferably, the reaction of step (a) is carried out in a first solvent; preferably, the first solvent includes at least one of dichloromethane, tetrahydrofuran and chloroform.
  3. 3. The process of claim 1, wherein the reaction temperature in step (a) is-10 to 0 ℃ and the reaction time is 8 to 28 hours.
  4. 4. The production method according to claim 1, wherein a molar ratio of the norbornene unit-containing chain transfer agent, the spiropyran unit-containing methyl acrylate monomer, and the radical polymerization initiator is 1:10 to 50:0.1; Preferably, the norbornene unit-containing chain transfer agent comprises at least one of NB-DTPA and NB-CDTPA; Preferably, the spiropyran unit-containing methyl acrylate monomer comprises at least one of SPMA and SPA; preferably, the radical polymerization initiator includes at least one of azobisisobutyronitrile and dibenzoyl peroxide; Preferably, the reaction of step (b) is carried out in a second solvent; preferably, the second solvent includes at least one of toluene and chloroform.
  5. 5. The process of claim 1, wherein the reaction temperature in step (b) is 60-80 ℃ and the reaction time is 2-3 hours.
  6. 6. The process of claim 1, wherein a third bragg catalyst is added to the reaction of step (c); Preferably, the molar ratio of the hydrophilic monomer, the hydrophobic monomer and the third bragg catalyst is 10-100:10-100:1.
  7. 7. The process according to claim 1, wherein the reaction temperature in step (C) is 0-25 ℃ and the reaction time is 0.5-2.5h.
  8. 8. The method according to claim 1, further comprising the step of (d) dispersing the light-responsive brush-like macromolecular emulsifier obtained in the step (c) in a third solvent, and mechanically dispersing to obtain an oil-in-water emulsion; The oil-in-water emulsion is obtained by irradiating the oil-in-water emulsion with ultraviolet light, removing the ultraviolet light irradiation, and mechanically dispersing.
  9. 9. The method of claim 8, wherein in step (d), the dispersion concentration of the light-responsive brush-like macromolecular emulsifier in the third solvent is 0.05-0.2 wt%; preferably, the third solvent is toluene and water mixture.
  10. 10. The photoresponsive brush-like macromolecular emulsifier according to any one of claims 1 to 9.

Description

Photo-responsive brush-shaped macromolecular emulsifier and preparation method thereof Technical Field The invention relates to the technical field of polymer synthesis, in particular to a light-responsive brush-shaped macromolecular emulsifier and a preparation method thereof. Background Amphiphilic compounds are widely used as emulsifiers because of their hydrophilic and hydrophobic structures. Compared with small-molecule emulsifiers such as sodium dodecyl sulfate, the large-molecule emulsifier is more flexible in control in terms of topological structure, molecular weight, chemical composition and the like, has stronger interfacial adsorption capacity, and can remarkably improve emulsion stability. The brush polymer has the densely grafted amphiphilic side chains, so that the brush polymer has larger contact area with an oil-water interface and stronger interaction, and can provide higher stability than the linear block copolymer. The responsive emulsifier can realize reversible destruction and reconstruction of emulsion through external stimulus, and is suitable for separation scenes of scarce resources such as crude oil recovery. It has been reported that pH-responsive brush emulsifiers, but achieving break and reconstitution of emulsions by repeated pH adjustment introduces large amounts of inorganic salts which severely affect the stability of the emulsion. Disclosure of Invention One of the objectives of the present invention is to provide a light-responsive brush-shaped macromolecular emulsifier, which at least solves one of the technical problems existing in the prior art. The second purpose of the invention is to provide a preparation method of the light-responsive brush-shaped macromolecular emulsifier. In order to achieve the above object of the present invention, the following technical solutions are specifically adopted: In a first aspect, the present invention provides a method for preparing a light-responsive brush-like macromolecular emulsifier, comprising: (a) Adding a dehydrating agent and a catalyst into a mixture of 5-norbornene-2-exomethanol and a hydrophilic polymer modified by carboxyl end groups, and reacting to obtain a hydrophilic monomer; (b) Reacting a chain transfer agent containing norbornene units, a methyl acrylate monomer containing spiropyran units and a free radical polymerization initiator to obtain a hydrophobic monomer; (c) And the hydrophilic monomer and the hydrophobic monomer react to obtain the light-responsive brush-shaped macromolecular emulsifier. Further, the molar ratio of the 5-norbornene-2-exomethanol to the carboxyl-terminated hydrophilic polymer is 10:0.5-1; preferably, the carboxyl-terminated hydrophilic polymer comprises at least one of carboxyl-modified polyethylene glycol and carboxyl-modified polyacrylamide; preferably, the number average molecular weight of the carboxyl-terminated hydrophilic polymer is 1000 to 5000; Preferably, the dehydrating agent comprises at least one of dicyclohexylcarbodiimide and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride; preferably, the catalyst comprises at least one of 4-dimethylaminopyridine and 4-pyrrolidinylpyridine; Preferably, the molar ratio of the dehydrating agent, the catalyst, the 5-norbornene-2-exo-methanol, and the carboxyl-terminated hydrophilic polymer is 1.5-2:0.5-0.6:10:0.5-1; preferably, the reaction of step (a) is carried out in a first solvent; preferably, the first solvent includes at least one of dichloromethane, tetrahydrofuran and chloroform. Further, the reaction temperature in the step (a) is-10-0 ℃ and the reaction time is 8-28h. Further, the mole ratio of the norbornene unit-containing chain transfer agent, the spiropyran unit-containing methyl acrylate monomer, and the radical polymerization initiator is 1:10 to 50:0.1; Preferably, the norbornene unit-containing chain transfer agent comprises at least one of NB-DTPA and NB-CDTPA; Preferably, the spiropyran unit-containing methyl acrylate monomer comprises at least one of SPMA and SPA; preferably, the radical polymerization initiator includes at least one of azobisisobutyronitrile and dibenzoyl peroxide; Preferably, the reaction of step (b) is carried out in a second solvent; preferably, the second solvent includes at least one of toluene and chloroform. Further, the reaction temperature in the step (b) is 60-80 ℃ and the reaction time is 2-3h. Further, a third-generation granny catalyst is added in the reaction of the step (c); Preferably, the molar ratio of the hydrophilic monomer, the hydrophobic monomer and the third bragg catalyst is 10-100:10-100:1. Further, the reaction temperature in the step (C) is 0-25 ℃ and the reaction time is 0.5-2.5h. Further, the method further comprises a step (d) of dispersing the photoresponsive brush-like macromolecular emulsifier obtained in the step (c) in a third solvent, and mechanically dispersing to obtain an oil-in-water emulsion; The oil-in-water emulsion is obtained by irradiating