A method for aerobic active / controlled free radical polymerization of hydrophobic monomers driven by alternating field

Abstract

This invention discloses a method for aerobic "active" / controlled free radical polymerization of hydrophobic monomers driven by an alternating field. Under the conditions of an external magnetic field and air, the method involves initiating a hydrophobic monomer polymerization reaction in an aqueous solvent with a main initiator, a copper salt catalyst, a ligand, a nonionic surfactant, glucose oxidase supported on iron oxide (Fe3O4), and a co-initiator to obtain a target polymer with a narrow molecular weight and molecular weight distribution. The external magnetic field stimulates the activity of the glucose oxidase supported on iron oxide (Fe3O4) to oxidize glucose to D-glucono-δ-lactone by consuming O2, while simultaneously generating hydrogen peroxide. The hydrogen peroxide generates hydroxyl radicals under Fenton reaction conditions, which initiate the "active" / controlled free radical polymerization reaction. This method achieves deoxygenation treatment of the free radical polymerization reaction while efficiently synthesizing the target polymer through the "active" / controlled free radical polymerization reaction of hydrophobic monomers under air and mild conditions.

Description

Technical Field

[0002] This invention belongs to the field of aerobic "active" / controlled free radical polymerization technology, specifically relating to a method for aerobic "active" / controlled free radical polymerization of hydrophobic monomers driven by an alternating field. Background Technology

[0004] In field-assisted "living" / controlled radical polymerization, currently reported methods are limited, such as acoustic, optical, electrical, and thermal methods. These polymerization methods are simple to operate and do not require strict reaction conditions. Therefore, exploring more field-assisted methods is an effective way to develop novel polymerization reactions.

[0005] The prior art patent document CN202411560341.4 discloses a method for realizing "living" / controlled free radical polymerization of hydrophilic and / or hydrophobic monomers under air conditions. The method involves polymerizing hydrophobic monomers, halides, copper bromide, ligands, and nonionic surfactants -GOx in a solvent using azobisisobutyrazoline hydrochloride as an initiator to form polymers with target molecular weights and narrow molecular weight distributions. This method introduces glucose oxidase modified with nonionic surfactants into the "living" / controlled free radical polymerization reaction, providing an effective way to rapidly and efficiently synthesize target polymers from hydrophobic monomers under air and mild conditions. Patent document CN201610179959.5 discloses a method for preparing water-soluble graft polymers based on living / controlled free radical polymerization. This method can be used for the controlled free radical polymerization of various water-soluble monomers such as (meth)acrylamide monomers, (meth)acrylic acid, and (meth)acrylates to prepare water-soluble graft polymers with different molecular weights. First, a water-soluble multifunctional macromolecular initiator is prepared by chemical modification. Second, the macromolecular initiator initiates the living / controlled free radical polymerization of water-soluble monomers under heating or visible / ultraviolet light irradiation to prepare water-soluble graft polymers with controllable molecular weight and chemical composition. The prepared macromolecular initiator dissolves quickly in the aqueous phase and has high initiation activity, thus preparing water-soluble graft polymers with controllable chemical structure and molecular weight. Patent document CN201810581790.5 describes a method for achieving "living" / controlled free radical polymerization under air conditions. It describes a polymerization reaction in a solvent using a monomer and a reversible addition-chain transfer agent initiated by triethylboron as an initiator, forming a polymer with a target molecular weight and narrow molecular weight distribution. The introduction of alkylboron into the "living" / controlled free radical polymerization reaction provides an effective route for the rapid and efficient synthesis of the target polymer under air and room temperature conditions. None of the above three patent documents contain any description of aerobic "living" / controlled free radical polymerization of hydrophobic monomers driven by an alternating field, nor do they provide any technical inspiration regarding the use of iron oxide-supported glucose oxidase as an oxygen scavenger in the polymerization system and the efficient polymerization of hydrophobic monomers driven by an external magnetic field. Therefore, this invention, based on achieving "living" / controlled free radical polymerization while simultaneously deoxygenating the free radical polymerization reaction, pioneers a new method for achieving "living" / controlled free radical polymerization of hydrophobic monomers under air conditions using a magnetic field as an alternating field stimulus, expanding its large-scale application. Currently, there are no related reports in this area. Summary of the Invention

[0007] The technical problem solved by this invention is to provide a method for aerobic "living" / controllable free radical polymerization of hydrophobic monomers driven by an alternating field. This method uses glucose oxidase supported on iron oxide as an oxygen scavenger in the polymerization system to carry out "living" / controllable free radical polymerization under alternating field driving, thereby realizing the efficient synthesis of target polymers by "living" / controllable free radical polymerization of hydrophobic monomers under air and mild conditions.

[0008] To solve the above-mentioned technical problems, this invention adopts the following technical solution: a method for aerobic "active" / controllable free radical polymerization of hydrophobic monomers driven by an alternating field. The specific reaction process is as follows: under an external magnetic field and air conditions, hydrophobic monomers, a main initiator, a copper salt catalyst, a ligand, a nonionic surfactant, glucose oxidase supported on iron oxide (Fe3O4-GOx), and a co-initiator are used to initiate a hydrophobic monomer polymerization reaction in an aqueous solvent to obtain a target polymer with a narrow molecular weight and molecular weight distribution. The external magnetic field stimulates the glucose oxidase supported on iron oxide to activate its activity, oxidizing glucose to D-gluconic acid-δ-lactone by consuming O2, while simultaneously generating hydrogen peroxide. Hydrogen peroxide generates hydroxyl radicals under Fenton reaction conditions. These hydroxyl radicals initiate an "active" / controllable free radical polymerization reaction, achieving deoxygenation treatment of the free radical polymerization reaction while efficiently synthesizing the target polymer through the "active" / controllable free radical polymerization reaction of hydrophobic monomers under air and mild conditions.

[0009] Further specified, the external magnetic field is achieved by placing it in a magnetic field generator, the center field strength of which is 200~300Oe, preferably 250Oe.

[0010] Further specifying, the hydrophobic monomer is acrylic acid, methyl acrylate, ethyl acrylate, tert-butyl acrylate, n-butyl acrylate, glycidyl methacrylate, or methyl methacrylate, and the structural formulas of some of the hydrophobic monomers are as follows:

[0011] .

[0012] Further specifying, the main initiator is an ethyl α-bromophenylacetate halide.

[0013] Further specifying, the co-initiator is azobisisobutyrazoline hydrochloride (VA-044). This co-initiator VA-044 is inexpensive and readily available, and its decomposition temperature is around 45°C. The mild reaction conditions make the polymerization reaction fast and efficient, and the monomer conversion rate can reach 100% within 4 hours.

[0014] Further specifying, the copper salt catalyst is copper bromide (CuBr2).

[0015] Further specifying, the ligand is one or more of tris[2-(dimethylamino)ethyl]amine (Me6TREN), tris(2-pyridinemethyl)amine (TPMA), 2,2'-bipyridine (bpy), or N,N,N'N'-tetramethylethylenediamine (PMDTEA), with the corresponding structural formulas as follows:

[0016] .

[0017] Further specified, the nonionic surfactant is glucosyl-1-glutamic acid dioleate or a derivative of glucosyl-1-glutamic acid dioleate;

[0018] The specific preparation process of the glucosyl-1-glutamic acid dioleate is as follows: A mixture of L-glutamic acid, octadecyl alcohol and p-toluenesulfonic acid is refluxed in toluene solution at 120°C for 4 hours. After cooling to room temperature, toluene is removed under reduced pressure, and the reaction mixture is neutralized with sodium bicarbonate solution. The aqueous phase is then extracted with ethyl acetate, and the organic phase is extracted with sodium bicarbonate solution and saturated sodium chloride solution. After extraction, anhydrous magnesium sulfate is added for drying. The white solid is removed by filtration using a Buchner funnel. The mixture is concentrated under reduced pressure and then purified by silica gel column chromatography. The raw material n-decyl alcohol is first eluted with DCM, and then the column is flushed twice with a mixture of DCM:MeOH = 60:1 (v / v). Finally, the product is eluted with a mixture of DCM:MeOH = 30:1 (v / v). The product is concentrated under vacuum to obtain a pale yellow liquid, namely glucosyl-1-glutamic acid dioleate.

[0019] The specific preparation process of the nonionic surfactant glucosyl-1-glutamic acid dioleate derivative is as follows: hydrochloric acid is added to the pale yellow liquid obtained above to form a salt, and then the salt is recrystallized in acetone to obtain a white solid salt. Then, the mixture of solid salt, gluconolactone and triethylamine is refluxed in ethanol for 2 hours, the solvent is removed under reduced pressure, and then the crude product is recrystallized in acetone to obtain the nonionic surfactant glucosyl-1-glutamic acid dioleate derivative.

[0020] The corresponding synthesis route is:

[0021] .

[0022] Further specifying, the specific preparation steps of the iron tetroxide-loaded glucose oxidase are as follows:

[0023] Step S1, Preparation of oleic acid-coated iron oxide nanorods: Commercially available iron oxide nanosphere powder, oleic acid and trioctylamine are mixed, and after being fully dispersed by ultrasound, the mixture is stirred and reacted under argon protection at 280°C to obtain oleic acid-coated iron oxide nanospheres.

[0024] Step S2, Carboxylation modification of iron oxide nanospheres: Oleic acid-coated iron oxide nanospheres and dihydrocaffeic acid (DHCA) are added to tetrahydrofuran (THF), mixed evenly, and then the reaction is carried out at 60°C with shaking to complete the carboxylation modification of iron oxide nanospheres.

[0025] Step S3: Covalently modifying and immobilizing glucose oxidase (GOx) on iron oxide nanospheres based on the EDC / NHS method: Carboxyl-modified iron oxide nanospheres and N-hydroxysuccinimide (NHS) were dispersed in phosphate buffer and shaken to disperse evenly. Then, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and glucose oxidase (GOx) were added to the dispersion and shaken to react at room temperature. After the reaction was completed, the product was centrifuged and washed with ultrapure water to remove unreacted excess glucose oxidase, EDC and NHS, finally obtaining glucose oxidase covalently modified iron oxide nanospheres.

[0026] The corresponding synthesis route is:

[0027] .

[0028] Further specifying, the aqueous solvent is a pure aqueous solution, a potassium phosphate buffer solution, or a PBS buffer solution.

[0029] Further specified, the molar ratio of the hydrophobic monomer, main initiator, copper salt catalyst, ligand and co-initiator is x:1:0.6:2.4:3.0, where the value of x ranges from 50 to 600 and is determined by the degree of polymerization, and the feeding ratio of the hydrophobic monomer to the glucose oxidase supported on iron oxide is 10 mmol: 7.5~10 mg.

[0030] Further specifying, the synthetic route in the method of alternating field-driven aerobic "living" / controlled free radical polymerization of hydrophobic monomers is as follows:

[0031]

[0032] Where R is an ethyl isobutyrate group.

[0033] The application of the alternating field-driven aerobic "active" / controlled free radical polymerization method of hydrophobic monomers described in this invention in the preparation of waterborne coatings.

[0034] The application of the alternating field-driven aerobic "active" / controlled free radical polymerization method of hydrophobic monomers described in this invention in the preparation of hydrogels.

[0035] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0036] (1) Glucose oxidase is inexpensive and environmentally friendly. It can consume oxygen in the system to oxidize glucose into D-gluconic acid-δ-lactone and generate hydrogen peroxide. Hydrogen peroxide generates hydroxyl radicals under Fenton reaction conditions. These hydroxyl radicals initiate "active" / controllable free radical polymerization reactions, thereby achieving deoxygenation treatment of free radical polymerization reactions while enabling "active" / controllable free radical polymerization of hydrophobic monomers under air and mild conditions.

[0037] (2) The reaction conditions are mild (room temperature) and the alternating field is simple;

[0038] (3) The reaction operation is simple and does not require complicated deoxygenation operations;

[0039] (4) The polymerization reaction is fast and efficient, and can realize the polymerization of hydrophobic monomers. Its conversion rate can reach more than 99% within 4 hours.

[0040] (5) The molecular weight of the target polymer is controllable and the polydispersity is narrow. Attached Figure Description

[0042] Figure 1 The infrared spectrum of glucose oxidase loaded with magnetic iron oxide in Example 4 is shown.

[0043] Figure 2 The image shows the 1H NMR spectrum of polymethyl acrylate in Example 5.

[0044] Figure 3 This is the gel permeation chromatography spectrum of polymethyl acrylate in Example 5.

[0045] Figure 4 This is a diagram of the apparatus for the polymerization reaction of the present invention. Detailed Implementation

[0047] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments, but this should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the following embodiments are conventional means well known to those skilled in the art, and the materials, reagents, etc. used in the following embodiments are commercially available unless otherwise specified.

[0048] Example 1

[0049] Preparation of the ligand tripropylene glycol methyl ether acetate (TPMA):

[0050] In a 250 mL round-bottom flask, 2-(chloromethyl)pyridine hydrochloride (30.6 mmol, 5.02 g), anhydrous sodium carbonate (300.2 mmol, 31.83 g), and anhydrous acetonitrile (100 mL) were added and the flask was sealed with a rubber stopper. Then, 2-(aminomethyl)pyridine was dissolved in 50 mL of anhydrous acetonitrile and added dropwise to the reaction flask under an Ar atmosphere. The reaction mixture was stirred for 30 min under an Ar atmosphere and then refluxed at 90 °C under an Ar atmosphere for 12 h. After the reaction was complete, the white precipitate was removed by filtration, and the acetonitrile was removed by rotary evaporation. The obtained solid was extracted with dichloromethane (3 × 60 mL) to obtain the organic phase. After removing the dichloromethane from the organic phase, it was recrystallized in hot acetone to obtain a yellow solid. 1 The structure was characterized by H NMR.

[0051] Example 2

[0052] Synthesis of the nonionic surfactant glucosyl-1-glutamic acid dioleate:

[0053] A mixture of L-glutamic acid, stearyl alcohol, and p-toluenesulfonic acid (molar ratio 1:2:1) was refluxed in toluene solution at 120°C for 4 hours. After cooling to room temperature, the toluene was removed under reduced pressure. The reaction mixture was then neutralized with 10 wt% sodium bicarbonate solution. The aqueous phase was extracted with ethyl acetate, and the organic phase (which was heavily emulsified) was extracted with 10 wt% sodium bicarbonate solution and saturated sodium chloride solution. After extraction, a large amount of anhydrous magnesium sulfate was added for drying. The white solid was removed by filtration through a Buchner funnel. The mixture was concentrated under reduced pressure and then purified by silica gel column chromatography. The starting material, n-decyl alcohol, was first passed through DCM, then the column was flushed twice with a DCM:MeOH mixture of 60:1 (v / v), and finally the product was passed through a DCM:MeOH mixture of 30:1 (v / v). The product was concentrated under vacuum to obtain a pale yellow liquid, namely glucosyl-1-glutamic acid dioleate.

[0054] Example 3

[0055] Synthesis of the nonionic surfactant glucosyl-1-glutamic acid dioleate derivative (S):

[0056] Hydrochloric acid was added to the pale yellow liquid obtained in Example 2 to form a salt (white viscous solid). The salt was then recrystallized in acetone to obtain a white solid salt. The mixture of solid salt, gluconolactone and triethylamine (molar ratio of 1:1:1) was refluxed in ethanol for 2 hours. After removing the solvent under reduced pressure, the crude product was recrystallized in acetone to obtain a glucosyl-1-glutamic acid dioleate derivative.

[0057] Example 4

[0058] Preparation of glucose oxidase supported on iron oxide:

[0059] 30 mg of commercially available iron oxide nanospheres (50 nm) powder, 0.4 mL of oleic acid and 10 g of trioctylamine were mixed and fully dispersed by ultrasound. The mixture was then stirred and reacted at 280 °C for 45 min under argon protection to obtain oleic acid-coated iron oxide nanospheres.

[0060] 2 mg of oleic acid-coated iron oxide nanospheres and 100 mg of DHCA were added to 2 mL of tetrahydrofuran. After mixing evenly, the mixture was shaken at 60 °C for 4 h to complete the carboxylation modification of the nanospheres.

[0061] 1 mg of carboxyl-modified iron oxide nanospheres and 5 mg of N-hydroxysuccinimide (NHS) were dispersed in 1 mL of phosphate buffer (0.1 M, pH 7.4) and shaken for 10 min. Then, 5 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and 3 mg of glucose oxidase (GOx) were added to the dispersion and the mixture was shaken at room temperature for 1 h. After the reaction, the product was centrifuged and washed three times with ultrapure water to remove unreacted excess glucose oxidase, EDC and NHS, finally obtaining glucose oxidase covalently modified iron oxide nanospheres.

[0062] Example 5

[0063] Atom transfer radical polymerization of hydrophobic monomer methyl acrylate in air:

[0064] The hydrophobic monomer methyl acrylate (0.86 g, 10 mmol), the main initiator ethyl α-bromophenylacetate (5.8 mg, 0.03 mmol), the copper salt catalyst copper bromide (4.6 mg, 0.02 mmol), the co-initiator VA-044 (0.032 g, 0.1 mmol), the ligand TPMA (0.023 g, 0.08 mmol), the nonionic surfactant glucosyl-1-glutamic acid dioleate derivative (0.032 g), and the iron oxide-supported glucose oxidase Fe3O4-GOx (7.5 mg) were placed in a 5 mL round-bottom flask. Potassium phosphate buffer solution (2.5 g) was used as the aqueous solvent. The flask was sealed with a glass stopper and wrapped with sealing film to place the entire polymerization system in a magnetic field with a strength of 250 Oe. The reaction mixture was stirred and polymerized at room temperature for 4 h. After the reaction, a small sample was taken to calculate the monomer conversion rate, polymer molecular weight, and molecular weight distribution. 1 (H NMR and GPC), the conversion rate of the hydrophobic monomer methyl acrylate reached over 99% within 4 hours of polymerization.

[0065] The foregoing has shown and described the basic principles, main features and advantages of the present invention. Various changes and modifications can be made to the present invention without departing from the spirit and scope thereof, and all such changes and modifications fall within the scope of the present invention as claimed.

Claims

1. A method for aerobic "living" / controlled free radical polymerization of hydrophobic monomers driven by an alternating field, characterized in that... The specific reaction process is as follows: Under the conditions of an external magnetic field and air, hydrophobic monomers, main initiators, copper salt catalysts, ligands, nonionic surfactants, glucose oxidase supported on iron oxide, and co-initiators are used to initiate the polymerization reaction of hydrophobic monomers in an aqueous solvent to obtain the target polymer with a narrow molecular weight and molecular weight distribution. The external magnetic field stimulates the activity of glucose oxidase supported on iron oxide, which oxidizes glucose to D-gluconic acid-δ-lactone by consuming O2, and at the same time generates hydrogen peroxide. Hydrogen peroxide generates hydroxyl radicals under Fenton reaction conditions. These hydroxyl radicals initiate "active" / controlled free radical polymerization, achieving deoxygenation treatment of the free radical polymerization reaction while efficiently synthesizing the target polymer through the "active" / controlled free radical polymerization reaction of hydrophobic monomers under air and mild conditions.

2. The method for aerobic "living" / controlled free radical polymerization of hydrophobic monomers driven by alternating field according to claim 1, characterized in that: The external magnetic field is achieved by placing it in a magnetic field generator, the center field strength of which is 200~300 Oe; the aqueous solvent is a pure aqueous solution, potassium phosphate buffer solution or PBS buffer solution.

3. The method for aerobic "living" / controlled free radical polymerization of hydrophobic monomers driven by alternating field according to claim 1, characterized in that: The hydrophobic monomers are acrylic acid, methyl acrylate, ethyl acrylate, tert-butyl acrylate, n-butyl acrylate, glycidyl methacrylate, or methyl methacrylate. The structural formulas of some of these hydrophobic monomers are as follows: 。 4. The method for aerobic "living" / controlled free radical polymerization of hydrophobic monomers driven by alternating field according to claim 1, characterized in that: The primary initiator is ethyl α-bromophenylacetate halide; the co-initiator is azobisisobutyrazoline hydrochloride; and the copper salt catalyst is copper bromide.

5. The method for aerobic "living" / controlled free radical polymerization of hydrophobic monomers driven by alternating field according to claim 1, characterized in that: The ligand is one or more of tris[2-(dimethylamino)ethyl]amine (Me6TREN), tris(2-pyridinemethyl)amine (TPMA), 2,2'-bipyridine (bpy), or N,N,N'N'-tetramethylethylenediamine (PMDTEA), with the corresponding structural formulas as follows: 。 6. The method for aerobic "living" / controlled free radical polymerization of hydrophobic monomers driven by alternating field according to claim 1, characterized in that: The nonionic surfactant is glucosyl-1-glutamic acid dioleate or a glucosyl-1-glutamic acid dioleate derivative; The specific preparation process of the glucosyl-1-glutamic acid dioleate is as follows: A mixture of L-glutamic acid, octadecyl alcohol and p-toluenesulfonic acid is refluxed in toluene solution at 120°C for 4 hours. After cooling to room temperature, toluene is removed under reduced pressure, and the reaction mixture is neutralized with sodium bicarbonate solution. The aqueous phase is then extracted with ethyl acetate, and the organic phase is extracted with sodium bicarbonate solution and saturated sodium chloride solution. After extraction, anhydrous magnesium sulfate is added for drying. The white solid is removed by filtration using a Buchner funnel. The mixture is concentrated under reduced pressure and then purified by silica gel column chromatography. The raw material n-decyl alcohol is first eluted with DCM, and then the column is flushed twice with a mixture of DCM:MeOH = 60:1 (v / v). Finally, the product is eluted with a mixture of DCM:MeOH = 30:1 (v / v). The product is concentrated under vacuum to obtain a pale yellow liquid, namely glucosyl-1-glutamic acid dioleate. The specific preparation process of the nonionic surfactant glucosyl-1-glutamic acid dioleate derivative is as follows: hydrochloric acid is added to the pale yellow liquid obtained above to form a salt, and then the salt is recrystallized in acetone to obtain a white solid salt. Then, the mixture of solid salt, gluconolactone and triethylamine is refluxed in ethanol for 2 hours, the solvent is removed under reduced pressure, and then the crude product is recrystallized in acetone to obtain the nonionic surfactant glucosyl-1-glutamic acid dioleate derivative. The corresponding synthesis route is: 。 7. The method for aerobic "living" / controlled free radical polymerization of hydrophobic monomers driven by alternating field according to claim 1, characterized in that... The specific preparation steps for the iron tetroxide-loaded glucose oxidase are as follows: Step S1, Preparation of oleic acid-coated iron oxide nanorods: Commercially available iron oxide nanosphere powder, oleic acid and trioctylamine are mixed, and after being fully dispersed by ultrasound, the mixture is stirred and reacted under argon protection at 280°C to obtain oleic acid-coated iron oxide nanospheres. Step S2, Carboxylation modification of iron oxide nanospheres: Oleic acid-coated iron oxide nanospheres and dihydrocaffeic acid are added to tetrahydrofuran, mixed evenly, and then the reaction is carried out at 60°C with shaking to complete the carboxylation modification of iron oxide nanospheres. Step S3: Covalently modifying and immobilizing glucose oxidase on iron oxide nanospheres based on EDC / NHS method: Carboxyl-modified iron oxide nanospheres and N-hydroxysuccinimide are dispersed in phosphate buffer and shaken to disperse evenly. Then, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and glucose oxidase are added to the dispersion and shaken to react at room temperature. After the reaction is completed, the product is centrifuged and washed with ultrapure water to remove unreacted excess glucose oxidase, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, finally obtaining iron oxide nanospheres covalently modified with glucose oxidase. The corresponding synthesis route is: 。 8. The method for aerobic "living" / controlled free radical polymerization of hydrophobic monomers driven by alternating field according to claim 1, characterized in that: The molar ratio of the hydrophobic monomer, main initiator, copper salt catalyst, ligand and co-initiator is x:1:0.6:2.4:3.0, where x ranges from 50 to 600 and is determined by the degree of polymerization; the feeding ratio of the hydrophobic monomer to the glucose oxidase supported on iron oxide is 10 mmol: 7.5~10 mg.

9. The method for aerobic "living" / controlled free radical polymerization of hydrophobic monomers driven by alternating field according to claim 1, characterized in that... The specific synthetic route is as follows: Where R is an ethyl isobutyrate group.

10. The application of the alternating field-driven aerobic "living" / controlled free radical polymerization method of hydrophobic monomers according to any one of claims 1 to 9 in the preparation of waterborne coatings or hydrogels.

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