US-20260125505-A1 - METHOD FOR REALIZING LIVING/CONTROLLED FREE RADICAL POLYMERIZATION OF HYDROPHILIC AND/OR HYDROPHOBIC MONOMERS UNDER AIR CONDITIONS

Abstract

A method for realizing living/controlled free radical polymerization of hydrophilic and/or hydrophobic monomers under air conditions is provided. The functional monomer including hydrophobic monomer, halide, copper bromide, ligand and non-ionic surfactant-GOx is used to initiate the polymerization of monomer in a solvent through initiator azodiisobutyric imidazoline hydrochloride (VA-044) to form polymer with narrow target molecular weight and molecular weight distribution.

Inventors

• Chunna LYU
• Mengyao DU
• Xiangcheng Pan
• Guowei Wang
• Zhiguo HU
• Congcong CUI

Assignees

• HENAN NORMAL UNIVERSITY

Dates

Publication Date

20260507

Application Date

20250115

Priority Date

20241104

Claims (8)

1. 1 . A method for realizing living/controlled free radical polymerization of hydrophilic and/or hydrophobic monomers under air conditions, comprising following steps: step 1, dissolving functional monomer, initiator, metal halide, ligand and glucose oxidase modified by non-ionic surfactant in a solvent; wherein the functional monomer is at least one among water-soluble monomer and hydrophobic monomer; and step 2, carrying out a polymerization reaction by continuous stirring under closed and heating conditions, wherein a reaction equation is as follows:
2. 2 . The method according to claim 1 , wherein the functional monomer comprises acrylic acid, methyl acrylate, ethyl acrylate, tert-butyl acrylate, n-butyl acrylate, glycidyl methacrylate ether, methyl methacrylate and polyethylene glycol monomethyl ether methacrylate.
3. 3 . The method according to claim 1 , wherein in the ligand is one or more among tris [2-(dimethylamino)ethyl]amine, tris (2-pyridinemethyl) amine, 2,2′-bipyridine and N, N, N′N′-tetramethylethylenediamine.
4. 4 . The method to claim 1 , wherein a preparation method of glucose oxidase modified by non-ionic surfactant is as follows: firstly, higher alcohol reacts with L-glutamic acid to obtain an intermediate product, then the intermediate product reacts with glucose to obtain glucosyl-1-glutamic acid diester and derivative of glucosyl-1-glutamic acid diester, and then the glucose oxidase is modified by using the derivative of glucosyl-1-glutamic acid diester; and a reaction equation is as follows: wherein the higher alcohol is n-decanol, tetradecanol or octadecanol.
5. 5 . The method according to claim 1 , wherein the initiator comprises a first initiator and a second initiator, and the first initiator is one or more among 2-bromoethyl isobutyrate and its halide; and the second initiator is azodiisobutyric imidazoline hydrochloride.
6. 6 . The method for realizing living/controlled free radical polymerization of hydrophilic and/or hydrophobic monomers under air condition according to claim 5 , wherein a molar ratio of the functional monomer, the first initiator, the metal halide, the ligand, the glucose oxidase modified with non-ionic surfactant and the second initiator is x/1/0.6/2.4/0.6/2.0; and the value of x is 50-600 determined by a degree of the polymerization.
7. 7 . The method according to claim 1 , wherein the metal halide is copper bromide.
8. 8 . The method according to claim 1 , wherein in the step 2, a mixture is stirred smoothly at 45° C. for 12-24 h.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to Chinese Patent Application No. 202411560341.4, filed on Nov. 4, 2024, the contents of which are hereby incorporated by reference. TECHNICAL FIELD The disclosure belongs to the technical field of living/controlled free radical polymerization, in particular to a method for realizing living/controlled free radical polymerization of hydrophilic and/or hydrophobic monomers under air conditions. BACKGROUND Glucose oxidase (GOx) oxidizes glucose into D-gluconic acid-δ-lactone by consuming O2 and produces hydrogen peroxide at the same time, and realize the deoxidation of living/controlled free radical polymerization. However, in GOx-assisted living/controlled free radical polymerization, the range of applicable monomers is limited to water-soluble monomer only. Therefore, it is urgent to expand a wide range of monomers. SUMMARY The technical problem solved by the disclosure is to overcome the existing defects and provide a living/controlled free radical polymerization method to realize the selection of a wide range of monomer including hydrophobic monomer under air conditions. The atom transfers radical polymerization (ATRP) of hydrophobic monomer is carried out by deoxidation of living/controlled free radical polymerization with non-ionic surfactant-GOx, which can not only realize the polymerization of hydrophobic monomer, but also improve the conversion rate of hydrophobic monomer, greatly broaden the application scope of monomer, and find a new polymerization method for living/controlled free radical polymerization of hydrophobic monomer. The technical problem to be solved by the disclosure is to overcome the existing defects and provide a method for realizing living/controlled free radical polymerization of hydrophilic and/or hydrophobic monomers under air condition, and can effectively solve the problems in the background technology. In order to achieve the above objectives, the disclosure provides a method for realizing living/controlled free radical polymerization of hydrophilic and/or hydrophobic monomers under air conditions, which adopts the technical scheme including following steps: step 1, dissolving functional monomer, initiator, metal halide, ligand and glucose oxidase modified by non-ionic surfactant in a solvent; the functional monomer is at least one of water-soluble monomer and hydrophobic monomer; andstep 2, carrying out a polymerization reaction by continuous stirring at 45° C. for 12-24 h under closed conditions, and a reaction equation is as follows: As an optional technical scheme of the disclosure, the functional monomer includes acrylic acid, methyl acrylate (MA), ethyl acrylate (EA), tert-butyl acrylate ((BA), n-butyl acrylate (nBA), glycidyl methacrylate ether, methyl methacrylate (MMA) and polyethylene glycol monomethyl ether methacrylate (OEOMA500). A structural formula of some monomers is as follows: A) hydrophobic monomer B) water-soluble monomer As an optional technical scheme of the disclosure, the ligand is one or more among tri [2-(dimethylamino)ethyl]amine (Me6TREN), tri (2-pyridinemethyl) amine (TPMA), 2,2′-bipyridine (bpy), N, N,N′N′ nn-tetramethylethylenediamine (PMDTEA). Among them, Me6TREN and TPMA are high-activity ligands, while bpy and PMDTEA are low-activity ligands, and their structural formulas are as follows: High-activity Me6TREN TPMALow-activity bpy PMDTEA As an optional technical scheme of the disclosure, a preparation method of glucose oxidase modified by non-ionic surfactant is as follows: firstly, higher alcohol reacts with L-glutamic acid to obtain an intermediate product, then the intermediate product reacts with glucose to obtain glucosyl-1-glutamic acid diester and its derivative, and then the glucose oxidase (GOx) is modified with the derivative(S) of glucosyl-1-glutamic acid diester to obtain the target product of glucose oxidase (S-GOx) modified with non-ionic surfactant; and a reaction equation is as follows: where the higher alcohol is n-decanol, tetradecanol or octadecanol. S-GOx may not only deoxygenate hydrophobic monomer, but also control the hydrophobic monomer to react with copper bromide, ligand and initiator within a certain range, so as to realize precise control of polymerization conditions, fine regulation of polymer molecular weight, molecular weight distribution, microstructure and macro-property. The precise control not only meets the strict requirements for material properties in specific applications, but also improves the consistency and reliability of products. As an optional technical scheme of the disclosure, the initiator includes a first initiator and a second initiator, where the first initiator is one or more among 2-bromoethyl isobutyrate and its halide; the second initiator is azodiisobutyl imidazoline hydrochloride (VA-044). As an optional technical scheme of the disclosure, the molar ratio of the functional monomer, the metal halide, the first init