CN112300342B - Method for synthesizing hydrophilic comb-shaped macromolecules by photoinitiation - Google Patents
Method for synthesizing hydrophilic comb-shaped macromolecules by photoinitiation Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention provides a method for synthesizing hydrophilic comb-shaped macromolecules by photo-initiation, which comprises the steps of firstly, synthesizing a linear macromolecular photoinitiator, introducing a certain proportion of hydrophilic monomer polyethylene glycol monomethyl ether methacrylate PEGMA and photoinitiator monomer 2-methyl-2-methacryloxypropylenone dimethyl methacrylate, and randomly copolymerizing DMPMA to obtain macromolecular photoinitiators PDMP-PEGMA with different initiation densities, and simultaneously, introducing the polyethylene glycol monomethyl ether methacrylate PEGMA to increase the hydrophilicity of the macromolecular photoinitiators to a certain degree; and then under the irradiation of a high-pressure mercury lamp, initiating sites of different macromolecule photoinitiator side chains are used for initiating the active polymerization of the hydrophilic monomer PEGMA, and simultaneously, the photocuring is successfully realized in non-toxic green solvent water, so that an effective method is provided for the synthesis of photoinitiated comb-shaped macromolecules and a green photocuring system.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a method for synthesizing hydrophilic comb-shaped macromolecules by photo-initiation, and in addition, relates to a method for synthesizing a novel macromolecular photoinitiator and polymerizing a photo-initiated hydrophilic monomer.
Background
The photo-initiated polymerization method is one of radical polymerization, and is a chain polymerization in which monomer molecules are initiated and activated into radicals by means of a photoinitiator or a photosensitizer. For the traditional chemical initiation system, although the processes are all relatively formed, the obtained product has poor quality and higher production cost. The photo-initiated polymerization reaction requires lower activation energy, can initiate polymerization in a large temperature range, and has the characteristics of simple and convenient operation, low investment, high product purity, environmental protection, energy conservation and the like. Photopolymerization has the following advantages over thermal polymerization: (1) the reaction rate is high, the conversion rate of the photopolymerization reaction of some acrylate monomers can reach more than ninety percent within dozens of seconds, and the reaction time is greatly shortened; (2) the reaction process is controllable, and the reaction rate and the reaction degree can be controlled by adjusting the intensity of the light source; (3) the reaction is not affected by temperature. The introduction of photoinitiators plays an important role. In 1968, environmental-friendly and energy-saving ultraviolet curing materials were developed by Bayer in Germany, which is also the first proposal of the concept of the violet photoinitiator. Currently, the photoinitiation method generally adopts a high-pressure mercury lamp. In addition to these, there are "gamma-ray initiated polymerization", "plasma system initiated polymerization", and "fluorescence initiated polymerization", and the like.
The photoinitiator is a compound which plays a role of accelerating initiation in photoinitiated polymerization. Its general mechanism of action is: the photoinitiator is excited to an excited state by absorption of light energy of appropriate wavelength and intensity, and when the energy of the excited state is greater than the energy required to break a bond, a primary reactive center, also called a primary radical, can be generated. The photoinitiators can be classified into two major classes, namely radical photoinitiators and cationic photoinitiators, due to the difference of the generated reactive intermediates. The radical photoinitiator can be classified into a cleavage type photoinitiator and a hydrogen abstraction type photoinitiator according to the difference of the reactive intermediates generated by the radical photoinitiator. Hydrogen abstraction photoinitiators are commonly coumarin, phenylacridine, benzophenone, thioxanthone and the like. The hydrogen abstraction type photoinitiator forms an exciplex with hydrogen donor molecules (especially tertiary amine molecules) through initiator molecules, generates active amine free radicals through electron transfer reaction, and generates another free radical through the reaction of the generated amine free radicals and system oxygen, so that the initiator of the type is usually matched with the tertiary amine for use, and the oxygen inhibition effect can be eliminated. The cleavage type photoinitiators usually contain phenylacetyl groups, generate free radicals mainly through an alpha bond breaking mode, and are commonly benzoin (benzoin) ethers, benzil ketals, acetophenones and the like.
The macromolecular photoinitiator with the main chain or the side chain containing the photosensitive active functional group is prepared by introducing the micromolecular photoinitiator onto the macromolecular chain in a covalent bond mode, and the macromolecular photoinitiator can effectively avoid the defects of easy yellowing, easy migration, easy volatilization, low initiation efficiency, odor and the like caused by the micromolecular photoinitiator. The introduction means is mainly through homopolymerization, copolymerization, polycondensation and the like after connecting unsaturated groups, or through post-modification of photoinitiation groups on polymer molecular chains. The macromolecular photoinitiator generates free radicals under the condition of illumination, so that a monofunctional group or polyfunctional group monomer is further initiated to polymerize, and the macromolecular photoinitiator has good performances of miscibility, low mobility, low volatility, high activity and the like.
Graft copolymers are polymers formed by linking two macromolecular backbones and side chains through chemical bonds, and the structure of the graft copolymer depends on various molecular parameters, such as the types of the backbones and the side chains, the degree of polymerization, the grafting density, the length of the side chains and the like. The graft polymers can be generally classified into two groups according to their structural characteristics, one is a graft copolymer having a relatively low graft density, and the other is a graft copolymer having a relatively high graft density, and the graft polymers can be referred to as comb copolymers or polymer molecular brushes.
To date, there are three main methods for synthesizing comb polymers: (1) the coupling method of grafting one, in this method main chain and side chain are prepared separately, will synthesize the backbone skeleton of the centre and side chain and need the grafted polymer, then through the high-efficient chemical reaction, such as "click", etc., graft the polymer to the backbone skeleton, form the comb polymer; (2) in the comb-shaped polymer obtained by the method, a side chain is the macromonomer, and a main chain is a polymer chain formed by the polymerization reaction of the polymerizable end group on the monomolecular monomer; (3) the initiation method "grafting from" is to synthesize a central skeleton having a plurality of active sites capable of initiating polymerization, and then to grow a plurality of side chains from the central skeleton through polymerization reactions such as "living"/controlled radical polymerization, ring-opening polymerization, etc., thereby finally forming the comb-shaped polymer. Compared with the former two methods, the preparation of the polymer molecular brush by the "grafting from" can well control the molecular weight and the molecular weight distribution of the main chain, and the monomer selectivity of the route is large, the structure is easy to regulate and change, and the method is widely adopted due to the characteristic that the polymerization method is realized.
In recent years, due to the structural particularity of the amphiphilic comb-shaped polymer, the amphiphilic comb-shaped polymer plays an important role in scientific research and industrial production. As a class of macromolecules with special chain structures, the comb polymers show unique physical properties different from linear congeners of the comb polymers in a solution state and a melt state and can be used as thermoplastic elastomers, stabilizers, hydrogels, drug carriers and the like, so that the molecular chain structures of the amphiphilic comb polymers and unique synthetic methods thereof are attracting more and more attention.
Disclosure of Invention
Aiming at the situation, 2-hydroxy-2-methyl propiophenone groups with different contents are introduced into the side chain of the linear polymer to serve as photoinitiation active sites, polyethylene glycol monomethyl ether methacrylate PEGMA with a certain proportion is introduced at the same time, so that the hydrophilicity of the initiator is improved, then the irradiation of the synthesized macromolecular photoinitiator in a high-pressure mercury lamp is utilized to successfully initiate the active free radical polymerization of hydrophilic monomer polyethylene glycol monomethyl ether methacrylate PEGMA, and the synthesis of photoinitiation amphiphilic comb-shaped macromolecules is realized in a 'grafting from' mode.
In order to achieve the purpose, the invention provides a synthesis method of different macromolecular photoinitiators and a synthesis method of a photoinitiated polymer molecular brush. The specific technical scheme is as follows:
step1, synthesis of photoinitiator monomer DMPMA:
adding raw materials of 2-hydroxy-2-methyl propiophenone, a small amount of triethylamine and a solvent dichloromethane into a reaction container, controlling the reaction temperature to be 0-5 ℃, and stirring for 0.5-1 hour; then diluting methacryloyl chloride with a small amount of dichloromethane, slowly dropwise adding the diluted methacryloyl chloride into the reaction container to continue reaction, and simultaneously tracking the reaction process by using thin-plate chromatography; after completion, the reaction mixture was filtered to remove solids, washed with a large amount of water, washed with saturated sodium hydrogencarbonate and then with saturated brine, dried and concentrated; and (3) carrying out column chromatography purification after spin-drying the solvent, drying, completely dissolving the crude product by using petroleum ether, and cooling and recrystallizing to obtain a pure product, namely the photoinitiator monomer DMPMA.
Step2 general procedure for random copolymerization of synthetic photoinitiator monomer DMPMA and polyethylene glycol monomethyl ether methacrylate PEGMA
Adding a synthetic photoinitiator monomer DMPMA obtained in Step1, polyethylene glycol monomethyl ether methacrylate PEGMA, RAFT reagent isobutyronitrile dithiobenzoate CPDB, an initiator azobisisobutyronitrile AIBN and a solvent anisole into a reaction vessel, deoxidizing with inert gas, and carrying out polymerization reaction under heating for 1-8 h; stopping the reaction to obtain a macromolecular photoinitiator PDM-PEGMMA; the total molar amount of two monomers including a synthetic photoinitiator monomer DMPMA and polyethylene glycol monomethyl ether methacrylate PEGMA, and the molar ratio of a RAFT reagent to the initiator is 100-1500: 3: 1.
step3 general procedure for initiating polymerization of polyethylene glycol monomethyl ether methacrylate PEGMA in solvent with macromolecular photoinitiator PDM-PEGMMA
Adding a macromolecular photoinitiator PDM-PEGMMA obtained in Step2, a hydrophilic monomer polyethylene glycol monomethyl ether methacrylate PEGMA and solvent anhydrous oxygen-free tetrahydrofuran THF into a reaction vessel, deoxidizing with inert gas, and polymerizing under the illumination condition for 1-12 h; the molar ratio of the hydrophilic monomer polyethylene glycol monomethyl ether methacrylate PEGMA to the macromolecular photoinitiator PDM-PEGMMA is 100-1000: 1.
step4 general procedure for Photocuring of a Macro photoinitiator PDM-PEGMMA in aqueous solution
Dissolving the macromolecular photoinitiator PDM-PEGMMA obtained in Step2 in water, adding PEGMA in a certain proportion, deoxidizing with inert gas, and polymerizing under the illumination condition for 1-12 h; the molar ratio of the monomer to the initiator is 100-1000: 1.
further, in Step2, the molar ratio of the synthetic photoinitiator monomer DMPMA to the monomer PEGMA is 1: 2. 1: 3 or 1: 4.
further, the inert gas in Step2 and Step3 is selected from any one of argon, nitrogen, helium and neon, and preferably argon.
Further, the molar ratio of the monomer polyethylene glycol monomethyl ether methacrylate PEGMA to the macromolecular photoinitiator PDM-PEGMMA in Step3 is selected to be 300: 1; the reaction time is 3h and 4h respectively.
Further, the molar ratio of the synthesized photoinitiator monomer DMPMA to the monomer polyethylene glycol monomethyl ether methacrylate PEGMA in Step4 is 1: 3 or 1: 4, monomer to initiator molar ratio of 300: 1, the solvent is selected to be water.
Further, the light source for initiating polymerization in Step3 or Step4 is selected from any one of a low-pressure mercury lamp, a medium-pressure mercury lamp, and a high-pressure mercury lamp is preferable.
Further, after each reaction step in the above method is completed, a purification step including, but not limited to, chromatography, dissolution/precipitation separation, filtration, may be performed to obtain a product with higher purity.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the invention tries to synthesize the macromolecular photoinitiator PDM-PEGMMA for the first time, and uses the macromolecular photoinitiator PDM-PEGMMA to initiate the living radical polymerization of the hydrophilic monomer polyethylene glycol monomethyl ether methacrylate PEGMA,
(2) the grafting mode combining photoinitiation and 'grafting from' realizes the high-efficiency synthesis of the amphiphilic comb-shaped macromolecules.
Drawings
FIG. 1 is a scheme showing the synthesis of the photoinitiator monomer DMPMA of example 1.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the photoinitiator monomer DMPMA of example 1.
FIG. 3 is a synthetic scheme of the macromolecular photoinitiator PDM-PEGMMA.
FIG. 4 shows the NMR spectrum and GPC outflow curve of PDM-PEGMMA, a macromolecular photoinitiator.
FIG. 5 is the NMR spectrum and GPC outflow curve of the macromolecular photoinitiator PDM-PEGMMA at different charge ratios.
FIG. 6 is a GPC outflow curve of polymerization of polyethylene glycol monomethyl ether methacrylate PEGMA monomer initiated by a macromolecular photoinitiator PDM-PEGMMA at different reaction times.
FIG. 7 is a schematic diagram of a photo-initiated polymerization process of a photo-curing system and a system without an initiator in an aqueous solution. (a) Adding a photoinitiator and irradiating by light. (b) Without adding photoinitiator, light irradiation. (c) Photoinitiator was added, without light.
Detailed Description
The invention will be further described with reference to specific embodiments and drawings.
The chemical reagents adopted by the invention are as follows:
97% of 2-hydroxy-2-methyl propiophenone, Macklin;
tetrahydrofuran, 99.5%, Nanjing chemical reagents, Inc.;
99.5% of methylene chloride, Jiangsu Qiangsheng functional chemistry GmbH;
anisole, 99.5%, Shanghai chemical Agents Corp;
methacryloyl chloride, 95%, aladin;
triethylamine, analytically pure, Jiangsu Qiangsheng functional chemistry GmbH;
anhydrous sodium sulfate, 98%, national drug group chemical reagents ltd;
azobisisobutyronitrile (AIBN), chemically pure, Shanghai reagent four works, recrystallized twice before use;
isobutyronitrile dithionaphthoate CPDB, 99 percent, carbofuran;
ethyl acetate, 99.5%, Jiangsu Qiangsheng functional chemistry GmbH;
petroleum ether, analytically pure, Jiangsu Qiangsheng functional chemistry GmbH;
polyethylene glycol monomethyl ether methacrylate PEGMA, Aldrich, Mn = 300, 97%, over-basic alumina short column before use.
The test instrument and conditions used in the invention are as follows:
gel permeation chromatography, GPC: molecular weight and molecular weight distribution the molecular weight of the polymer was calculated using a gel permeation chromatograph with TOSOH TSKgel SuperHM-M, in an auto-advancing format using polymethyl methacrylate as a standard, N, N-dimethylformamide DMF as the mobile phase at a flow rate of 0.65 mL/min and a temperature of 40 ℃.
Hydrogen nuclear magnetic resonance spectrum 1H-NMR: measuring at room temperature by using a Bruker 300MHz nuclear magnetic instrument, using CDCl3 as a solvent and TMS as an internal standard;
example 1: synthesizing a monomer 2-methyl-2-methacryloxypropiophenone DMPMA.
2-hydroxy-2-methyl propiophenone (10 g, 0.06 mol), dichloromethane (300 mL) and triethylamine (50 mL) were placed in a 500 mL three-necked flask, stirred while cooling in an ice salt bath, the reaction temperature was controlled to 0 ℃ to 5 ℃, after half an hour of reaction, methacryloyl chloride (10 mL, 0.104 mol) was dissolved in 40 mL dichloromethane, and slowly added dropwise to the above solution. After the completion of the dropwise addition, the reaction was carried out at room temperature.
And (3) carrying out spot plate tracking reaction, stopping the reaction until the raw material spot reaction is completed, carrying out suction filtration to remove solids, washing the obtained filtrate for a plurality of times by using a saturated sodium bicarbonate aqueous solution, and removing redundant methacryloyl chloride. The combined organic layers were dried over anhydrous sodium sulfate. After removing the solvent by rotary evaporation, purifying the crude product by silica gel column chromatography, wherein the eluent is petroleum ether: ethyl acetate = 6: 1. And (3) carrying out spin drying on the solvent to obtain a solid, recrystallizing the solid with petroleum ether, and carrying out suction filtration to obtain a white crystal, namely the photoinitiator monomer 2-methyl-2-methacryloxypropiophenone DMPMA.
Example 2: and (3) synthesizing a macromolecular photoinitiator PDM-PEGMMA.
The 2-methyl-2-methacryloxypropylphenyl ketone DMPMA, the isobutyronitrile ester of dithionaphthoic acid CPDB, the azobisisobutyronitrile AIBN and the anisole solvent which are obtained in the example 1 are added into a 5 mL ampoule bottle, after the sample addition is finished, a double-row pipe is used for carrying out freezing-air suction-inflation-unfreezing circulation for three times to remove oxygen, after the oxygen removal is finished, the bottle opening is sealed, and the mixture is heated and stirred for reaction for 5 hours at the temperature of 70 ℃. Stopping the reaction to obtain the macromolecular photoinitiator PDM-PEGMMA. Wherein the molar ratio of the two monomers, the RAFT reagent and the initiator is 100: 200: 3: 1,100: 300: 3: 1,100: 400: 3: 1. the amount of solvent used was 1 mL.
After the reaction, the polymerization tube was cooled with ice water, opened, and the reaction mixture was diluted with 2 mL of THF and settled twice in 100 mL of n-hexane. And drying the obtained solid in a vacuum oven at 30 ℃ for 12 h to obtain the macromolecular photoinitiator PDM-PEGMMA. The whole operation process should be protected from light as much as possible. The polymerization procedure for the resulting photoinitiator was similar to that described above with respect to the remaining different monomer charge ratios. The proportion of two monomers in the macromolecular photoinitiator can be calculated by calculating the hydrogen nuclear magnetic resonance spectrum: 1: 2.75,1: 5.69,1: 6.18.
example 3: photoinitiating the synthesis of amphiphilic comb-like macromolecular PPEGMA.
Adding the macromolecular photoinitiator PDM-PEGMMA obtained in the example 2 into a 5 mL ampoule bottle, adding monomer polyethylene glycol monomethyl ether methacrylate PEGMA and solvent anhydrous oxygen-free tetrahydrofuran THF, performing freeze-air extraction-inflation-unfreezing circulation three times for deoxygenation by using a double-row pipe after the sample addition is finished, sealing the bottle mouth after the completion of the oxygen removal, and placing the bottle mouth under the illumination of a high-pressure mercury lamp for polymerization. Wherein the mass of the monomer is 1 g, the molar mass ratio of the monomer to the initiating unit of the initiator is 300: 1, the using amount of the solvent is 1 mL, and the reaction time is 3h and 4h respectively.
After the reaction, the polymerization tube was opened, and 4 mL of THF was added to dilute the reaction solution, followed by precipitation twice in 100 mL of n-hexane. And drying the obtained product in a vacuum oven at 30 ℃ for 12 h to obtain the white polymer solid photo-initiated amphiphilic comb-shaped macromolecule PPEGMA. The synthesis of the resulting polymerization of the different reactants is similar to that described above.
Example 4: general procedure for the Photocuring of the Macro photoinitiator PDM-PEGMMA in aqueous solution.
The macromolecular photoinitiator PDM-PEGMMA (1: 3 and 1: 4) obtained in example 2 is respectively added into a 5 mL ampoule bottle, monomer polyethylene glycol monomethyl ether methacrylate PEGMA and solvent water are added, after the sample addition is finished, a double-row pipe is used for carrying out freezing-air suction-inflation-unfreezing circulation for three times to remove oxygen, after the oxygen removal is finished, the bottle mouth is sealed, and the bottle is placed under the illumination of a high-pressure mercury lamp for polymerization. Wherein the mass of the monomer is 1 g, the molar mass ratio of the monomer to the initiating unit of the initiator is 300: 1, the using amount of the solvent is 1 mL, and the reaction time is 3h and 4h respectively.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. A method for synthesizing hydrophilic comb-shaped macromolecules by photoinitiation comprises the following steps:
step1, synthesis of photoinitiator monomer DMPMA: adding raw materials of 2-hydroxy-2-methyl propiophenone, a small amount of triethylamine and a solvent dichloromethane into a reaction container, controlling the reaction temperature to be 0-5 ℃, and stirring for 0.5-1 hour; then diluting methacryloyl chloride with a small amount of dichloromethane, slowly dropwise adding the diluted methacryloyl chloride into the reaction container to continue reaction, and simultaneously tracking the reaction process by using thin-plate chromatography; filtering to remove solid, washing the reaction solution with a large amount of water, saturated sodium bicarbonate and saturated saline in sequence, drying and concentrating; performing rotary evaporation to remove the solvent, performing column chromatography purification, drying, completely dissolving the crude product with petroleum ether, and cooling and recrystallizing to obtain a pure product, namely the photoinitiator monomer DMPMA;
step2, general procedure for random copolymerization of the synthetic photoinitiator monomer DMPMA with polyethylene glycol monomethyl ether methacrylate PEGMA: adding a synthetic photoinitiator monomer DMPMA obtained in Step1, polyethylene glycol monomethyl ether methacrylate PEGMA, RAFT reagent isobutyronitrile dithiobenzoate CPDB, an initiator azobisisobutyronitrile AIBN and a solvent anisole into a reaction vessel, deoxidizing with inert gas, and carrying out polymerization reaction under heating for 1-8 h; stopping the reaction to obtain a macromolecular photoinitiator PDM-PEGMMA; the total molar amount of two monomers including a synthetic photoinitiator monomer DMPMA and polyethylene glycol monomethyl ether methacrylate PEGMA, and the molar ratio of a RAFT reagent to the initiator is 100-1500: 3: 1;
step3, general procedure for initiating polymerization of polyethylene glycol monomethyl ether methacrylate PEGMA by a macromolecular photoinitiator PDM-PEGMMA in a solvent: adding a macromolecular photoinitiator PDM-PEGMMA obtained in Step2, a hydrophilic monomer polyethylene glycol monomethyl ether methacrylate PEGMA and solvent anhydrous oxygen-free tetrahydrofuran THF into a reaction vessel, deoxidizing with inert gas, and polymerizing under the illumination condition for 1-12 h; the molar ratio of the hydrophilic monomer polyethylene glycol monomethyl ether methacrylate PEGMA to the macromolecular photoinitiator PDM-PEGMMA is 100-1000: 1;
step4, general procedure for photocuring of the macrophotoinitiator PDM-PEGMMA in aqueous solution: dissolving the macromolecular photoinitiator PDM-PEGMMA obtained in Step2 in water, adding PEGMA in a certain proportion, deoxidizing with inert gas, and polymerizing under the illumination condition for 1-12 h; the molar ratio of the monomer to the initiator is 100-1000: 1.
2. the method of photoinitiated synthesis of a hydrophilic comb-like macromolecule of claim 1, wherein: in Step2, the molar ratio of the synthetic photoinitiator monomer DMPMA to the monomer polyethylene glycol monomethyl ether methacrylate PEGMA is 1: 2. 1: 3 or 1: 4.
3. the method of photoinitiated synthesis of a hydrophilic comb-like macromolecule of claim 1, wherein: the inert gas in Step2 and Step3 is selected from any one of argon, nitrogen, helium and neon.
4. The method of photoinitiated synthesis of a hydrophilic comb-like macromolecule of claim 1, wherein: the molar ratio of the monomer polyethylene glycol monomethyl ether methacrylate PEGMA to the macromolecular photoinitiator PDM-PEGMMA in Step3 is selected to be 300: 1; the reaction time is 3h or 4 h.
5. The method of photoinitiated synthesis of a hydrophilic comb-like macromolecule of claim 1, wherein: in Step4, the molar ratio of the synthetic photoinitiator monomer DMPMA to the monomer PEGMA is 1: 3 or 1: 4, monomer to initiator molar ratio of 300: 1.
6. the method of photoinitiated synthesis of a hydrophilic comb-like macromolecule of claim 1, wherein: the light source for initiating polymerization in Step3 or Step4 is any one selected from a low-pressure mercury lamp, a medium-pressure mercury lamp, and a high-pressure mercury lamp.
7. The method of photoinitiated synthesis of a hydrophilic comb-like macromolecule of claim 1, wherein: after completion of each of the above processes, purification steps including, but not limited to, chromatography, dissolution/precipitation separation, filtration, are performed to obtain a product of higher purity.
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