A Ligand-Free Atom Transfer Radical Polymerization Method Based on Elemental Metal Interaction

Abstract

The invention provides a ligand-free atom transfer radical polymerization method under the effect of metal elementary substances. Organic ligands are omitted in the ligand-free atom transfer radical polymerization method. Polymerization systems comprise vinyl monomers, halogenated hydrocarbon, the metal elementary substances and transition metal catalysts. The ligand-free atom transfer radical polymerization method has the advantages that atom transfer radical polymerization reaction can be carried out on the monomers under halogenated hydrocarbon activation effects of the metal elementary substances, and accordingly polymers with narrow molecular weight distribution can be generated; the halogenated hydrocarbon is activated by the aid of the metal elementary substances, accordingly, the reaction activity of the polymerization systems can be improved, polymerization after-treatment procedures can be simplified, and the cost can be reduced; the organic ligands are omitted in the ligand-free atom transfer radical polymerization method, and accordingly the shortcomings of high cost and toxicity, volatility and the like due to organic compounds or polar solvents which are used as ligands in existing atom transfer radical polymerization systems can be overcome.

Description

technical field

[0001] The invention belongs to the field of macromolecule synthesis, and more specifically relates to a ligand-free atom transfer radical polymerization method under the action of a metal element, which is a new implementation method of the atom transfer radical polymerization method. Background technique

[0002] The atom transfer radical polymerization method is the most important "living" / controllable polymerization method to achieve efficient design of macromolecular topology and terminal functional groups. The traditional atom transfer radical polymerization method usually uses organic ligands (such as P, N-containing compounds, organic acids, ionic liquids, etc.) Redox potential is used to improve the reactivity of the polymerization system. However, these organic compound components are expensive and highly toxic, which cannot meet the requirements of green development and wide application of polymerization methods.

[0003] Elemental metals are ofte...

Examples

Embodiment 1

[0048] After purification of methyl methacrylate monomer, ethyl 2-bromoisobutyrate halogenated hydrocarbon and micron iron powder, the polymerization reaction components are prepared, methyl methacrylate, ethyl 2-bromoisobutyrate, bromine The molar ratio of ferrous oxide (low-valence state transition metal catalyst) to metal iron powder is 200:1:1:0.5. The preparation process is as follows: weigh 0.061 grams of ferrous bromide and 0.0079 grams of iron powder in the glove box and put them into an eggplant-shaped bottle, add 6 milliliters of methyl methacrylate monomer into the eggplant-shaped bottle, and stir magnetically for 20 minutes. , and then added 37.7 microliters of ethyl 2-bromoisobutyrate, and continued to stir for 2 minutes to obtain a pre-reaction mixture.

[0049] Transfer the pre-reaction mixture in the eggplant-shaped bottle to the heating device, and control the reaction temperature to 60°C; after the polymerization reaction reaches the predetermined reaction ti...

Embodiment 2

[0051] After purification of methyl methacrylate monomer, ethyl 2-bromophenylacetate, halogenated hydrocarbons, and silver nanowires, the polymerization reaction components were prepared, methyl methacrylate, ethyl 2-bromophenylacetate, bromine The molar ratio of ferrous oxide (low-valence state transition metal catalyst) to nano-silver wire is 200:1:1:0.25. The preparation process is as follows: Weigh 0.061 g of ferrous bromide and 0.0075 g of nano-silver wire into an eggplant-shaped bottle in a glove box, add 6 ml of methyl methacrylate monomer into the eggplant-shaped bottle, and stir magnetically for 20 minutes Then, 49.5 microliters of ethyl 2-bromophenylacetate was added, and the stirring was continued for 2 minutes to obtain a pre-reaction mixture.

[0052] Transfer the pre-reaction mixture in the eggplant-shaped bottle to the heating device, and control the reaction temperature to 60°C; after the polymerization reaction reaches the predetermined reaction time interval,...

Embodiment 3

[0055] After purification of methyl methacrylate monomer, ethyl 2-bromophenylacetate halogenated hydrocarbons and silver nanowires, the polymerization reaction components were prepared, methyl methacrylate, ethyl 2-bromophenylacetate, bromine The molar ratio of ferrous oxide (low-valence state transition metal catalyst) to nano-silver wire is 200:1:1:0.1. The preparation process is as follows: Weigh 0.061 grams of ferric bromide and 0.003 grams of nano-silver wires into an eggplant-shaped bottle in a glove box, add 6 milliliters of methyl methacrylate monomer into the eggplant-shaped bottle, and stir magnetically for 20 minutes. , and then added 49.5 microliters of ethyl 2-bromophenylacetate, and continued to stir for 2 minutes to obtain a pre-reaction mixture.

[0056] Transfer the pre-reaction mixture in the eggplant-shaped bottle to the heating device, and control the reaction temperature to 60°C. After the polymerization reaction reaches the predetermined reaction time int...

technical field

[0001] The invention belongs to the field of macromolecule synthesis, and more specifically relates to a ligand-free atom transfer radical polymerization method under the action of a metal element, which is a new implementation method of the atom transfer radical polymerization method. Background technique

[0002] The atom transfer radical polymerization method is the most important "living" / controllable polymerization method to achieve efficient design of macromolecular topology and terminal functional groups. The traditional atom transfer radical polymerization method usually uses organic ligands (such as P, N-containing compounds, organic acids, ionic liquids, etc.) Redox potential is used to improve the reactivity of the polymerization system. However, these organic compound components are expensive and highly toxic, which cannot meet the requirements of green development and wide application of polymerization methods.

[0003] Elemental metals are ofte...

Examples

Embodiment 1

[0048] After purification of methyl methacrylate monomer, ethyl 2-bromoisobutyrate halogenated hydrocarbon and micron iron powder, the polymerization reaction components are prepared, methyl methacrylate, ethyl 2-bromoisobutyrate, bromine The molar ratio of ferrous oxide (low-valence state transition metal catalyst) to metal iron powder is 200:1:1:0.5. The preparation process is as follows: weigh 0.061 grams of ferrous bromide and 0.0079 grams of iron powder in the glove box and put them into an eggplant-shaped bottle, add 6 milliliters of methyl methacrylate monomer into the eggplant-shaped bottle, and stir magnetically for 20 minutes. , and then added 37.7 microliters of ethyl 2-bromoisobutyrate, and continued to stir for 2 minutes to obtain a pre-reaction mixture.

[0049] Transfer the pre-reaction mixture in the eggplant-shaped bottle to the heating device, and control the reaction temperature to 60°C; after the polymerization reaction reaches the predetermined reaction ti...

Embodiment 2

[0051] After purification of methyl methacrylate monomer, ethyl 2-bromophenylacetate, halogenated hydrocarbons, and silver nanowires, the polymerization reaction components were prepared, methyl methacrylate, ethyl 2-bromophenylacetate, bromine The molar ratio of ferrous oxide (low-valence state transition metal catalyst) to nano-silver wire is 200:1:1:0.25. The preparation process is as follows: Weigh 0.061 g of ferrous bromide and 0.0075 g of nano-silver wire into an eggplant-shaped bottle in a glove box, add 6 ml of methyl methacrylate monomer into the eggplant-shaped bottle, and stir magnetically for 20 minutes Then, 49.5 microliters of ethyl 2-bromophenylacetate was added, and the stirring was continued for 2 minutes to obtain a pre-reaction mixture.

[0052] Transfer the pre-reaction mixture in the eggplant-shaped bottle to the heating device, and control the reaction temperature to 60°C; after the polymerization reaction reaches the predetermined reaction time interval,...

Embodiment 3

[0055] After purification of methyl methacrylate monomer, ethyl 2-bromophenylacetate halogenated hydrocarbons and silver nanowires, the polymerization reaction components were prepared, methyl methacrylate, ethyl 2-bromophenylacetate, bromine The molar ratio of ferrous oxide (low-valence state transition metal catalyst) to nano-silver wire is 200:1:1:0.1. The preparation process is as follows: Weigh 0.061 grams of ferric bromide and 0.003 grams of nano-silver wires into an eggplant-shaped bottle in a glove box, add 6 milliliters of methyl methacrylate monomer into the eggplant-shaped bottle, and stir magnetically for 20 minutes. , and then added 49.5 microliters of ethyl 2-bromophenylacetate, and continued to stir for 2 minutes to obtain a pre-reaction mixture.

[0056] Transfer the pre-reaction mixture in the eggplant-shaped bottle to the heating device, and control the reaction temperature to 60°C. After the polymerization reaction reaches the predetermined reaction time int...

Images