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Method for polymerizing reverse atom transfer radicals under activation action of alkali on halohydrocarbon

A technology of atom transfer and polymerization method, which is applied in the field of new controllable free radical polymerization, can solve the problems of high price and environmental pollution, and achieve the effect of reducing reaction cost, reducing raw material cost, and solving expensive raw material cost

Active Publication Date: 2017-08-18
HUAZHONG UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] In view of the above defects or improvement needs of the prior art, the object of the present invention is to provide a new method of reverse atom transfer radical polymerization in which alkali activates the action of halogenated hydrocarbons, which promotes the breaking of carbon-halogen bonds through the activation of halogenated hydrocarbons by alkalis, Without the use of free radical initiators and low-valence state transition metal catalysts sensitive to water and oxygen, the controllable polymerization of reverse atom transfer radicals of polymerized monomers is realized, and at the same time, it overcomes the toxic and easy to use of existing atom transfer radical polymerization methods. Volatile organic compounds (such as P, N-containing compounds, organic acids, ionic liquids, and raw materials containing amide groups, etc.) as ligands are expensive and environmentally polluting

Method used

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  • Method for polymerizing reverse atom transfer radicals under activation action of alkali on halohydrocarbon
  • Method for polymerizing reverse atom transfer radicals under activation action of alkali on halohydrocarbon
  • Method for polymerizing reverse atom transfer radicals under activation action of alkali on halohydrocarbon

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Embodiment 1

[0047] After the purification of methyl methacrylate monomer, ethyl 2-bromoisobutyrate halogenated hydrocarbon and sodium phosphate, the preparation of polymerization reaction components, methyl methacrylate, ethyl 2-bromoisobutyrate, bromide The molar ratio of iron (high valence transition metal catalyst) to sodium phosphate is 200:1:1:2. The preparation process is as follows: 0.0836 grams of ferric bromide and 0.0928 grams of sodium phosphate are weighed in the glove box and put into an eggplant-shaped bottle, and 6 milliliters of methyl methacrylate monomer is added into the eggplant-shaped bottle, and after magnetic stirring for 20 minutes, Then 37.7 microliters of ethyl 2-bromoisobutyrate was added, and stirring was continued for 2 minutes to obtain a pre-reaction mixture.

[0048] 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 ...

Embodiment 2

[0050] After purification of methyl methacrylate monomer, ethyl 2-bromophenylacetate, halogenated hydrocarbon, and sodium hydroxide, the polymerization reaction components are prepared, methyl methacrylate, ethyl 2-bromophenylacetate, bromine The molar ratio of ferric oxide (high valence state transition metal catalyst) to sodium hydroxide is 200:1:1:2. The preparation process is: weigh 0.0836 grams of ferric bromide and 0.032 grams of sodium hydroxide 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 49.5 microliters of ethyl 2-bromophenylacetate, and continued to stir for 2 minutes to obtain a pre-reaction mixture.

[0051] Transfer the pre-reaction mixture in the eggplant-shaped bottle to the heating device, and control the reaction temperature to 60°C and 90°C respectively; after the polymerization reaction reaches the predete...

Embodiment 3

[0054] After purification of methyl methacrylate monomer, ethyl 2-bromophenylacetate halogenated hydrocarbon and sodium carbonate, the preparation of polymerization reaction components, methyl methacrylate, ethyl 2-bromophenylacetate, bromide The molar ratio of iron (high valence transition metal catalyst) to sodium carbonate is 200:1:1:4. The preparation process is as follows: in the glove box, 0.0836 grams of ferric bromide and 0.120 grams of sodium carbonate are weighed and put into an eggplant-shaped bottle, and 6 milliliters of methyl methacrylate monomer is added into the eggplant-shaped bottle, and after magnetic stirring for 20 minutes, Then 49.5 microliters of ethyl 2-bromophenylacetate was added, and stirring was continued for 2 minutes to obtain a pre-reaction mixture.

[0055] 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 predetermine...

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Abstract

The invention provides a method for polymerizing reverse atom transfer radicals under activation action of alkali on halohydrocarbon. According to the polymerization method, no organic ligand or radical initiator is used, a polymerization system comprises vinyl monomers, halohydrocarbon, alkali and a high-valence transition metal catalyst, and monomers are subjected to a reverse atom transfer radical polymerization reaction under the activation action of alkali on halohydrocarbon to produce a polymer with narrow molecular weight distribution. With the adoption of the polymerization method, no radical initiator or a low-valence transition metal catalyst sensitive to water and oxygen is used, and meanwhile, the defects of high price and environmental pollution due to the fact that toxic and volatile organic compounds are used as ligands in existing atom transfer radical polymerization methods are overcome.

Description

technical field [0001] The invention belongs to the field of macromolecule synthesis, and in particular relates to a reverse atom transfer radical polymerization method in which alkali activates halogenated hydrocarbons, and is a new controllable radical polymerization method. Background technique [0002] Atom transfer radical polymerization (ATRP) has become the most important "living" / controllable radical polymerization method because of its advantages such as a wide variety of applicable monomers, strong molecular design, and narrow product molecular weight distribution. The traditional atom transfer radical polymerization method uses low-valence transition metal catalysts to interact with organic ligands (such as compounds containing P and N, organic acids, ionic liquids, etc.) to endow the system with higher activity. However, low-valence transition metals are easily oxidized and sensitive to moisture and air; organic ligand components are expensive and highly toxic; c...

Claims

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Application Information

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IPC IPC(8): C08F120/14C08F120/18C08F4/10C08F4/26
CPCC08F4/10C08F4/26C08F120/14C08F120/18C08F2438/01
Inventor 薛志刚王计嵘王瑞周兴平解孝林
Owner HUAZHONG UNIV OF SCI & TECH
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