CN108752510B - Iron-catalyzed AGET ATRP system in biomass-based solvent under ligand-free condition and polymerization method - Google Patents

Iron-catalyzed AGET ATRP system in biomass-based solvent under ligand-free condition and polymerization method Download PDF

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CN108752510B
CN108752510B CN201810474922.4A CN201810474922A CN108752510B CN 108752510 B CN108752510 B CN 108752510B CN 201810474922 A CN201810474922 A CN 201810474922A CN 108752510 B CN108752510 B CN 108752510B
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CN108752510A (en
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沈显荣
高建纲
相益信
孙道萍
李素平
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Anhui Polytechnic University
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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
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
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    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP

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Abstract

The invention relates to an iron-catalyzed AGET ATRP system and a polymerization method under the condition of no ligand in a biomass-based solvent, wherein the AGET ATRP system is composed of a polymerization monomer, an initiator, a high-valence iron halide catalyst, a reducing agent and a biomass-based solvent, and the biomass-based solvent is ethyl lactate or r-valerolactone; the invention takes a biomass-based solvent as a green solvent, takes high-valence iron halide as a catalyst and carries out atom transfer radical polymerization without additional ligands, and the polymerization process is as follows: monomers, an initiator, a catalyst, a reducing agent and a solvent form a polymerization reaction system according to a certain molar ratio, and ATRP polymerization is carried out under the anaerobic or aerobic condition. The polymer prepared by the invention has controllable molecular weight and narrow dispersity, and a biomass-based green solvent is applied in the polymerization process without adding a ligand, so that the components of a polymerization reaction substance are reduced, the influence on the environment is reduced, and a green active polymerization technology with low cost is provided.

Description

Iron-catalyzed AGET ATRP system in biomass-based solvent under ligand-free condition and polymerization method
Technical Field
The invention belongs to the technical field of high molecular compounds, and particularly relates to an iron-catalyzed AGET ATRP system in a biomass-based solvent under the condition of no ligand and a polymerization method.
Background
Since Atom Transfer Radical Polymerization (ATRP) was invented for more than two decades, the monomers polymerized by traditional free radical polymerization can be basically polymerized by ATRP method due to easy operation of reaction, and various topological structure polymers which are difficult to synthesize by traditional free radical polymerization can be synthesized, thus a revolution is developed in the field of polymer synthesis. With the development of green chemistry, scientific research workers always explore a green reaction system with low catalyst usage and environment-friendly reaction medium.
Iron catalytic systems have been of interest to researchers because of their safety and low cost. In a classical iron catalytic system, the selection of a ligand is particularly important, so that the solubility of the catalyst in a reaction system can be promoted, the oxidation-reduction potential of the catalyst can be adjusted, and the reaction activity of the catalytic system can be regulated. The ligand which can be used for catalyzing ATRP by iron is the triphenylphosphine and the derivative thereof, but the ligand has high toxicity and high price. Therefore, on the basis, a class of organic acid ligands is used in iron-catalyzed ATRP reactions. More interestingly, when the polymerization medium is a polar solvent, the iron catalytic system can be used to successfully carry out the polymerization of olefin monomers without ligand. It has been discovered that compounds such as N, N-Dimethylformamide (DMF), acetonitrile, dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), polyethylene glycol (PEG), crown ethers, etc. can be used as both a reaction medium and a ligand to successfully promote iron-mediated ATRP polymerization. The polymerization system avoids the use of ligand, reduces the reaction composition, reduces the reaction cost and has visible industrialization prospect. However, such solvents generally come from non-renewable resources such as traditional coal, petroleum and natural gas, the limited nature of fossil resources and the negative effects on the ecological environment during the use process are also serious, and the solvents do not meet the current trend of green chemical development, and the use of the solvents is limited. Therefore, it is necessary to find a green solvent with wider sources and more environment-friendly, so as to replace the application of the traditional polar solvent at present.
Disclosure of Invention
In order to overcome the problems in the prior art and solve the technical problems of high price of a controllable polymerization ligand used for catalyzing AGET ATRP by iron, environmental pollution of a used solvent and the like, the invention provides an iron-catalyzed AGET ATRP system and a polymerization method under the condition of no ligand in a biomass-based solvent.
An AGET ATRP system catalyzed by iron under the condition of no ligand in a biomass-based solvent is composed of a polymerization monomer, an initiator, a high-valence iron halide catalyst, a reducing agent and a biomass-based solvent, wherein the biomass-based solvent is ethyl lactate or gamma-valerolactone.
The invention adopts biomass-based green solvents of ethyl lactate and gamma-valerolactone as green reaction media, and high-valence iron halide (ferric bromide or ferric chloride) as a catalyst to initiate ATRP polymerization under the condition of no ligand, thereby providing a new way and a method for carrying out polymerization reaction which are milder, greener and energy-saving.
Preferably, the polymerized monomer is a methacrylate monomer or a methacrylic acid polyethylene glycol monomer; the high-valence iron halide catalyst is one of ferric bromide, ferric chloride and ferric chloride hexahydrate; the reducing agent is one of vitamin C, sodium ascorbate, sodium hydrosulfite, sodium bisulfite and sodium pyrosulfite.
the methacrylate monomer is one of methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate and β -hydroxyethyl methacrylate.
preferably, the initiator is one of ethyl 2-bromo-2-phenylacetate, ethyl α -bromoisobutyrate, ethyl 2-bromo-2-phenylpropionate and ethyl 2-bromo-2-p-methylphenylacetate.
Preferably, the initiator is a high molecular compound with Cl or Br at the end group prepared by the system or other ATRP systems.
Preferably, the molar ratio of the initiator, the polymerization monomer, the catalyst and the reducing agent is 1: 100-800: 0.1-1: 0.2-2, wherein the molar ratio of the polymerized monomer to the solvent is 1: 0.1 to 2.
The invention also provides a controllable free radical polymerization technology which takes biomass-based green solvent ethyl lactate or gamma-valerolactone as a reaction medium and ferric chloride or ferric bromide as a catalyst under the condition without ligand: the method comprises the following steps of (1) forming a polymerization reaction system by using a monomer, an initiator, a catalyst, a reducing agent and a solvent according to a certain molar ratio, and carrying out ATRP polymerization under an anaerobic or aerobic condition; specifically, the method comprises the following steps:
a polymerization process of an AGET ATRP system comprising the steps of:
(1) dissolving the catalyst in ethyl lactate or gamma-valerolactone according to the proportion;
(2) adding a weighed reducing agent;
(3) adding monomer without deoxidization, and keeping constant temperature; or adding monomer for introducing nitrogen and removing oxygen, sealing, and injecting initiator; putting the mixture into an oil bath with a set temperature, and reacting at a constant temperature;
(4) after the reaction is finished, treating the polymerization solution with methanol or a mixed precipitator of methanol and water to obtain a high molecular compound;
(5) drying the polymer to be heavy, and measuring the molecular weight and the molecular weight distribution of the obtained sample by using GPC;
the molar ratio of the initiator to the polymerization monomer to the catalyst to the reducing agent is 1: 100-800: 0.1-1: 0.2-2, wherein the molar ratio of the polymerized monomer to the solvent is 1: 0.1 to 2.
The invention uses a biomass-based green solvent which has wide sources, is completely biodegradable and nontoxic, has no ligand, and can carry out controllable polymerization reaction under anaerobic and aerobic conditions.
preferably, the polymerization monomer is a methacrylate monomer or a methacrylic acid polyethylene glycol monomer, the high-valence iron halide catalyst is one of ferric bromide, ferric chloride and ferric chloride hexahydrate, the reducing agent is one of vitamin C, sodium ascorbate, sodium hydrosulfite, sodium bisulfite and sodium metabisulfite, and the initiator is one of ethyl 2-bromo-2-phenylacetate, ethyl α -bromoisobutyrate, ethyl 2-bromo-2-phenylpropionate and ethyl 2-bromo-2-p-methylphenylacetate.
The polymer to be polymerized for the free radical polymerization reaction can be oil-soluble monomer methacrylate monomer or water-soluble monomer methacrylic acid polyethylene glycol monomer.
Preferably, the polymerization method of the AGET ATRP system comprises the following steps:
(1) weighing 1 part of ferric bromide, dissolving in 80 parts of gamma-valerolactone,
(2) weighing 2 parts of sodium ascorbate, and adding the sodium ascorbate into the catalyst solution;
(3) weighing 200 parts of methyl methacrylate monomer, introducing nitrogen to remove oxygen, injecting 1 part of 2-bromo-2-phenylacetic acid ethyl ester initiator, and sealing; putting the mixture into an oil bath, and reacting at a constant temperature of 75 ℃;
(4) after the reaction is finished, treating the polymerization solution with methanol to obtain polymethyl methacrylate with a terminal group containing bromine;
(5) filtering, and drying in a vacuum drying oven at 60 deg.C to constant weight; 20 mg of the dried product were dissolved in 2.0 ml of tetrahydrofuran, and the molecular weight and molecular weight distribution were measured by GPC.
The invention also provides an application of the AGET ATRP system in preparing a high molecular compound, which realizes the chain extension reaction:
a polymerization process of said age ATRP system comprising the steps of:
(1) weighing ferric bromide according to a proportion, and dissolving the ferric bromide in ethyl lactate;
(2) adding a weighed reducing agent to obtain a catalyst solution;
(3) weighing a macromolecular compound with a terminal base band Cl or Br as a macromolecular initiator, adding the macromolecular initiator into a monomer for dissolving, introducing nitrogen for removing oxygen, pouring the monomer into the catalyst solution, and sealing; putting the mixture into an oil bath for constant-temperature reaction;
(4) after the reaction is finished, treating the polymerization solution with methanol to obtain a chain-extended high molecular compound;
(5) drying the polymer to be heavy, and measuring the molecular weight and the molecular weight distribution of the obtained sample by using GPC;
the molar ratio of the initiator to the polymerization monomer to the catalyst to the reducing agent is 1: 100-800: 0.1-1: 0.2-2, wherein the molar ratio of the polymerized monomer to the solvent is 1: 0.1 to 2.
Preferably, the polymerized monomer is a methacrylate monomer or a methacrylic acid polyethylene glycol monomer; the high-valence iron halide catalyst is one of ferric bromide, ferric chloride and ferric chloride hexahydrate; the reducing agent is one of vitamin C, sodium ascorbate, sodium hydrosulfite, sodium bisulfite and sodium pyrosulfite; the initiator is a high molecular compound with Cl or Br at the end group, which is prepared by the system or other ATRP systems.
The invention provides a green and low-cost green active polymerization technology, which has the following beneficial effects:
(1) the used biomass-based solvent has the advantages of wide source, safety, no toxicity, complete degradation and the like;
(2) a ligand is not needed, so that the components of a polymerization reaction substance are reduced, and the influence on the environment is reduced;
(3) the used solvent has good solubility to oil-soluble polymers and water-soluble polymers, and the application range is wide;
(4) the prepared polymer has controllable molecular weight and narrow dispersity;
(5) compared with the traditional active polymerization technology, the method has the advantages of reaction system component reduction, mild condition and simple process.
Drawings
FIG. 1 shows the molecular weight and molecular weight distribution curves of polymethyl methacrylate (PMMA) synthesized in gamma-valerolactone measured by GPC;
FIG. 2 is a graph showing the molecular weight and molecular weight distribution of polymethyl methacrylate (PMMA) synthesized in ethyl lactate by GPC;
FIG. 3 is a graph of the molecular weight and molecular weight distribution of synthesized polyethyl methacrylate (PEMA) in gamma valerolactone measured by GPC;
FIG. 4 shows molecular weights and molecular weight distribution curves of poly (benzyl methacrylate) (PBMA) synthesized in ethyl lactate by GPC;
FIG. 5 is a kinetic diagram of the synthesis of Polymethylmethacrylate (PMMA) in ethyl lactate;
FIG. 6 is a graph showing the relationship between the conversion rate of synthesized Polymethylmethacrylate (PMMA) in ethyl lactate and the molecular weight and molecular weight distribution;
FIG. 7 is a kinetic diagram of the synthesis of Polymethylmethacrylate (PMMA) in gamma valerolactone;
FIG. 8 is a graph of the conversion of synthetic Polymethylmethacrylate (PMMA) in gamma valerolactone versus molecular weight and molecular weight distribution;
FIG. 9 is a graph showing the molecular weight and molecular weight distribution of chain extension reaction initiated by a polymethyl methacrylate (PMMA) macroinitiator in ethyl lactate.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
The fractions of substances referred to in the examples below are in each case molar fractions.
Example 1
AGET ATRP reaction of Methyl Methacrylate (MMA) in gamma-valerolactone
Weighing ferric bromide (FeBr)3)1 part, dissolving in 80 parts of gamma-valerolactone, weighing 2 parts of sodium ascorbate, adding into the catalyst solution, weighing 200 parts of methyl methacrylate monomer, introducing nitrogen to remove oxygen, injecting 1 part of 2-bromo-2-ethyl phenylacetate (EBPA) initiator, and sealing. Putting the mixture into an oil bath, and reacting at a constant temperature of 75 ℃. After 6 hours, treating the polymerization solution with methanol to obtain PMMA (polymethyl methacrylate) with bromine at the end group, filtering, and drying in a vacuum drying oven at 60 ℃ to constant weight.
20 mg of the dried product was dissolved in 2.0 ml of tetrahydrofuran, and the molecular weight distribution were measured by GPC as shown in FIG. 1, where Mn was 17500 and PDI was 1.36.
Example 2
AGET ATRP reaction of Methyl Methacrylate (MMA) in ethyl lactate
Weighing ferric bromide (FeBr)3)1 part, dissolving in 80 parts of ethyl lactate, weighing 2 parts of sodium hydrosulfite, adding into the catalyst solution, weighing 200 parts of methyl methacrylate monomer, introducing nitrogen to remove oxygen, injecting 1 part of 2-ethyl bromoisobutyrate initiator, and sealing. Putting the mixture into an oil bath, and reacting at a constant temperature of 75 ℃. After 6 hours, treating the polymerization solution with methanol to obtain PMMA (polymethyl methacrylate) with bromine at the end group, filtering, and drying in a vacuum drying oven at 60 ℃ to constant weight.
20 mg of the dried product was dissolved in 2.0 ml of tetrahydrofuran, and the molecular weight distribution were measured by GPC as shown in FIG. 2, where Mn is 12100 and PDI is 1.46.
Example 3
AGET ATRP reaction of Ethyl Methacrylate (EMA) in gamma-valerolactone
Weighing ferric bromide (FeBr)3)1 part of the catalyst is dissolved in 80 parts of gamma-valerolactone, 2 parts of sodium hydrosulfite is weighed and added into the catalyst solution, 200 parts of ethyl methacrylate monomer is weighed, nitrogen is introduced to remove oxygen, 1 part of 2-bromo-2-phenylacetic acid ethyl Ester (EBPA) initiator is injected, and sealing is carried out. Putting the mixture into an oil bath, and reacting at a constant temperature of 60 ℃. After 10 hours, the polymerization solution is treated with methanol to obtain PEMA (polyethylmethacrylate) with bromine at the end group, filtered and dried in a vacuum drying oven at 60 ℃ to constant weight.
20 mg of the dried product was dissolved in 2.0 ml of tetrahydrofuran, and the molecular weight distribution were measured by GPC as shown in FIG. 3, where Mn was 16500 and PDI was 1.49.
Example 4
AGET ATRP reaction of Benzyl Methacrylate (BMA) in ethyl lactate
Weighing ferric bromide (FeCl)3)1 part, dissolving in 80 parts of ethyl lactate, weighing 2 parts of sodium ascorbate, adding into the catalyst solution, weighing 200 parts of Benzyl Methacrylate (BMA) monomer, introducing nitrogen to remove oxygen, injecting 1 part of ethyl 2-bromoisobutyrate initiator, and sealing. Putting the mixture into an oil bath, and reacting at a constant temperature of 75 ℃. After 12 hours, the polymerization solution is treated by methanol to obtain PBMA (poly benzyl methacrylate) with bromine at the end group, filtered and put into a vacuum drying oven to be dried to constant weight at 60 ℃.
20 mg of the dried product was dissolved in 2.0 ml of tetrahydrofuran, and the molecular weight distribution were measured by GPC as shown in FIG. 4, where Mn was 18900 and PDI was 1.38.
Example 5
Kinetic reaction of Methyl Methacrylate (MMA) in ethyl lactate.
Weighing ferric bromide (FeBr)3)1 part, dissolving in 80 parts of ethyl lactate, weighing 2 parts of sodium hydrosulfite, adding into the catalyst solution, weighing 200 parts of methyl methacrylate monomer, introducing nitrogen to remove oxygen, injecting 1 part of 2-ethyl bromoisobutyrate initiator, and sealing. Putting the mixture into an oil bath, and putting the mixture into the oil bath,reacting at constant temperature of 75 ℃. And (3) treating the polymerization solution with methanol after the set reaction time is reached to obtain PMMA (polymethyl methacrylate) with bromine at the end group, filtering, and drying in a vacuum drying oven at 60 ℃ to constant weight.
20 mg of the dried product were dissolved in 2.0 ml of tetrahydrofuran, and the molecular weight distribution were measured by GPC.
FIG. 5 is a kinetic curve of the polymerization reaction, and it can be seen from FIG. 5 that the reaction is in a first order kinetic relationship, which indicates that the catalytic system in ethyl lactate conforms to the characteristics of active polymerization and conforms to the ATRP polymerization mechanism, and ethyl lactate can act as a ligand; meanwhile, the conversion rate and the molecular weight of the monomer can be adjusted by controlling the polymerization reaction time.
FIG. 6 is a graph showing the relationship between the monomer conversion and the molecular weight and molecular weight distribution of a polymer, and it can be seen from FIG. 6 that the molecular weight (M) of PMMA, a polymer measured by GPCn,GPC) Increases linearly with increasing monomer conversion and approaches the theoretical molecular weight of the polymer; while the molecular weight distribution (M) of the polymerw/Mn) Always kept below 1.5. The above results fully show FeBr in ethyl lactate3AGET ATRP which catalyzes MMA conforms to the polymerization characteristics of "activity"/controlled free radical.
Example 6
Kinetic reaction of Methyl Methacrylate (MMA) in gamma-valerolactone
Weighing ferric bromide (FeBr)3)1 part of the raw materials are dissolved in 80 parts of gamma-valerolactone, 2 parts of sodium erythorbate are weighed and added into a catalyst solution, 200 parts of methyl methacrylate monomer is weighed, nitrogen is introduced to remove oxygen, 1 part of 2-bromo-2-ethyl phenylacetate (EBPA) initiator is injected, and sealing is carried out. Putting the mixture into an oil bath, and reacting at a constant temperature of 60 ℃. And (3) after the set reaction time is reached, treating the polymerization solution with methanol, filtering, and drying the obtained polymer in a vacuum drying oven at 60 ℃ to constant weight.
20 mg of the dried product were dissolved in 2.0 ml of tetrahydrofuran, and the molecular weight distribution were measured by GPC.
FIG. 7 is a kinetic curve of the polymerization reaction, and it can be seen from FIG. 7 that the reaction shows a first order kinetic relationship, which indicates that the catalytic system in gamma-valerolactone conforms to the characteristics of living polymerization and conforms to the ATRP polymerization mechanism, and gamma-valerolactone not only has good dissolving capacity for both monomers and polymers, but also can function as a ligand; meanwhile, the conversion rate and the molecular weight of the monomer can be adjusted by controlling the polymerization reaction time.
FIG. 8 is a graph showing the relationship between the monomer conversion and the molecular weight and molecular weight distribution of a polymer, from which the molecular weight (M) of PMMA, a polymer measured by GPC, is shownn,GPC) Increases linearly with increasing monomer conversion and approaches the theoretical molecular weight of the polymer; while the molecular weight distribution (M) of the polymerw/Mn) Always kept below 1.2. The above results fully show FeBr in gamma-valerolactone3AGET ATRP which catalyzes MMA conforms to the polymerization characteristics of "activity"/controlled free radical.
Example 7
Chain extension reaction of methyl methacrylate macroinitiator in ethyl lactate
Weighing ferric bromide (FeBr)3)1 part, dissolving in 40 parts of ethyl lactate, and weighing 2 parts of sodium ascorbate to add into the catalyst solution. Weighing a part of PMMA macroinitiator (M)n,GPC＝5900，Mw/Mn1.20) was added to 200 parts of methyl methacrylate monomer and dissolved, nitrogen was introduced to remove oxygen, and the resulting solution was poured into the above catalyst solution and sealed. Putting the mixture into an oil bath, and reacting at a constant temperature of 75 ℃. After 10 hours, treating the polymerization solution with methanol to obtain chain-extended PMMA, filtering, and drying in a vacuum drying oven at 60 ℃ to constant weight.
20 mg of the dried product was dissolved in 2.0 ml of tetrahydrofuran, and molecular weights before and after chain extension and distribution of molecular weights in terms of molecular weight distribution were measured by GPC as shown in FIG. 9, Mn,GPC＝20100，Mw/Mn＝1.43。

Claims (10)

1. An iron-catalyzed AGET ATRP system in a biomass-based solvent without a ligand is characterized in that: the AGETATRP system is composed of a polymerization monomer, an initiator, a high-valence iron halide catalyst, a reducing agent and a biomass-based solvent, wherein the biomass-based solvent is ethyl lactate or gamma-valerolactone.
2. The system of claim 1, wherein the system is characterized by iron-catalyzed AGET ATRP in the absence of a ligand in a biomass-based solvent: the polymerization monomer is a methacrylate monomer or a methacrylic acid polyethylene glycol monomer; the high-valence iron halide catalyst is one of ferric bromide, ferric chloride and ferric chloride hexahydrate; the reducing agent is one of vitamin C, sodium ascorbate, sodium hydrosulfite, sodium bisulfite and sodium pyrosulfite.
3. the system of claim 2, wherein the initiator is one of ethyl 2-bromo-2-phenylacetate, ethyl α -bromoisobutyrate, ethyl 2-bromo-2-phenylpropionate, and ethyl 2-bromo-2-p-methylphenylacetate.
4. The system of claim 2, wherein the system is characterized by iron-catalyzed AGET ATRP in the absence of a ligand in a biomass-based solvent: the initiator is a high molecular compound with Cl or Br at the end group, which is prepared by the system or other ATRP systems.
5. The system of claim 1, wherein the system is characterized by iron-catalyzed AGET ATRP in the absence of a ligand in a biomass-based solvent: the molar ratio of the initiator to the polymerization monomer to the catalyst to the reducing agent is 1: 100-800: 0.1-1: 0.2-2, wherein the molar ratio of the polymerized monomer to the solvent is 1: 0.1 to 2.
6. A process for polymerizing an AGET ATRP system according to claim 1, characterized in that it comprises the following steps:
(1) dissolving the catalyst in ethyl lactate or gamma-valerolactone according to the proportion;
(2) adding a weighed reducing agent;
(3) adding monomer without deoxidization, and keeping constant temperature; or adding monomer for introducing nitrogen and removing oxygen, sealing, and injecting initiator; putting the mixture into an oil bath with a set temperature, and reacting at a constant temperature;
(4) after the reaction is finished, treating the polymerization solution with methanol or a mixed precipitator of methanol and water to obtain a high molecular compound;
(5) drying the polymer to be heavy, and measuring the molecular weight and the molecular weight distribution of the obtained sample by using GPC;
the molar ratio of the initiator to the polymerization monomer to the catalyst to the reducing agent is 1: 100-800: 0.1-1: 0.2-2, wherein the molar ratio of the polymerized monomer to the solvent is 1: 0.1 to 2.
7. the polymerization method of the AGET ATRP system according to claim 6, characterized in that the polymerization monomer is methacrylate monomer or methacrylic acid polyethylene glycol monomer, the high valence state iron halide catalyst is one of ferric bromide, ferric chloride and ferric chloride hexahydrate, the reducing agent is one of vitamin C, sodium ascorbate, sodium dithionite, sodium bisulfite and sodium metabisulfite, and the initiator is one of ethyl 2-bromo-2-phenylacetate, ethyl α -bromoisobutyrate, ethyl 2-bromo-2-phenylpropionate and ethyl 2-bromo-2-p-methylphenylacetate.
8. The process for polymerizing an AGET ATRP system according to claim 6, characterized in that it comprises the following steps:
(1) weighing 1 part of ferric bromide, dissolving in 80 parts of gamma-valerolactone,
(2) weighing 2 parts of sodium ascorbate, and adding the sodium ascorbate into the catalyst solution;
(3) weighing 200 parts of methyl methacrylate monomer, introducing nitrogen to remove oxygen, injecting 1 part of 2-bromo-2-phenylacetic acid ethyl ester initiator, and sealing; putting the mixture into an oil bath, and reacting at a constant temperature of 75 ℃;
(4) after the reaction is finished, treating the polymerization solution with methanol to obtain polymethyl methacrylate with a terminal group containing bromine;
(5) filtering, and drying in a vacuum drying oven at 60 deg.C to constant weight; 20 mg of the dried product were dissolved in 2.0 ml of tetrahydrofuran, and the molecular weight and molecular weight distribution were measured by GPC.
9. A process for polymerizing an AGET ATRP system according to claim 1, characterized in that it comprises the following steps:
(1) weighing ferric bromide according to a proportion, and dissolving the ferric bromide in ethyl lactate;
(2) adding a weighed reducing agent to obtain a catalyst solution;
(3) weighing a macromolecular compound with a terminal base band Cl or Br as a macromolecular initiator, adding the macromolecular initiator into a monomer for dissolving, introducing nitrogen for removing oxygen, pouring the monomer into the catalyst solution, and sealing; putting the mixture into an oil bath for constant-temperature reaction;
(4) after the reaction is finished, treating the polymerization solution with methanol to obtain a chain-extended high molecular compound;
(5) drying the polymer to be heavy, and measuring the molecular weight and the molecular weight distribution of the obtained sample by using GPC;
the molar ratio of the initiator to the polymerization monomer to the catalyst to the reducing agent is 1: 100-800: 0.1-1: 0.2-2, wherein the molar ratio of the polymerized monomer to the solvent is 1: 0.1 to 2.
10. The process for polymerizing an AGET ATRP system according to claim 9, wherein: the polymerization monomer is a methacrylate monomer or a methacrylic acid polyethylene glycol monomer; the high-valence iron halide catalyst is one of ferric bromide, ferric chloride and ferric chloride hexahydrate; the reducing agent is one of vitamin C, sodium ascorbate, sodium hydrosulfite, sodium bisulfite and sodium pyrosulfite; the initiator is a high molecular compound with Cl or Br at the end group, which is prepared by the system or other ATRP systems.
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