Methyl methacrylate block copolymer and preparation method thereof

Abstract

The invention discloses a methyl methacrylate block copolymer and a preparation method thereof. The copolymer is polymethylmethacrylate-b-polyacrylic acid-2-ethyl ester serving as an AB block copolymer. The polymethylmethacrylate-b-polyacrylic acid-2-ethyl ester is synthesized by a fractional step method which comprises the following steps of: obtaining end group chlorine-containing polymethylmethacrylate by adopting azodiisobutyronitrile as an initiator and ferric trichloride / triphenylphosphine as a catalytic system through the reverse atom transfer radical polymerization of methyl methacrylate; and obtaining the two-block polymer polymethylmethacrylate-b-polyacrylic acid-2-ethyl ester by adopting the end group chlorine-containing polymethylmethacrylate as the macromolecular initiator and the ferric trichloride / triphenylphosphine as the catalytic system through the atom transfer radical polymerization. The block copolymer has the structure shown as the description.

Description

technical field

[0001] The present invention relates to a kind of methyl methacrylate block copolymer and preparation method thereof Background technique

[0002] Atom transfer radical polymerization, as a free radical living polymerization method, has attracted widespread attention of polymer workers at home and abroad in recent years. The synthesis of block copolymers with regular structures by atom transfer radical polymerization is the most meaningful and challenging work in the field of polymer research. Block copolymers exhibit a series of excellent properties, not only in the theory of polymer solutions , and are of great significance in practical applications.

[0003] 2-Hydroxyethyl acrylate belongs to acrylates, and has the properties of alcohol monomers. Its polymer chain contains hydroxyl groups on the side groups of each structural unit, and has good hydrophilicity and physiological compatibility. Polymethyl methacrylate has excellent light transmittance, chem...

Examples

Embodiment 1 to 3

[0023] In a three-necked flask equipped with a stirrer, add azobisisobutyronitrile, ferric chloride, triphenylphosphine, and methyl methacrylate in sequence at a molar ratio of 1:1:3:200, and then Add xylene solvent at a concentration of 1g / ml, start stirring, and pass nitrogen gas to make it completely dissolved. The reaction process still needs to continue to pass nitrogen protection. React at 80°C for 3 hours and 4.5 hours, stop the reaction after 6 hours, cool naturally, add tetrahydrofuran until the polymer is completely dissolved, pass through a neutral alumina chromatography column, precipitate the filtrate with an appropriate amount of methanol, and filter with suction to obtain the precipitate . Then the precipitate was washed three times with deionized water, and vacuum-dried at 80° C. to constant weight to obtain polymethyl methacrylate containing terminal chlorine.

Embodiment 4 to 6

[0025] In a three-necked flask equipped with a stirrer, azobisisobutyronitrile, ferric chloride, triphenylphosphine, and methyl methacrylate were sequentially added in a molar ratio of 1:1:3:500, and then Add xylene solvent at a concentration of 1g / ml, start stirring, and pass nitrogen gas to make it completely dissolved. The reaction process still needs to continue to pass nitrogen protection. React at 70°C, 80°C, and 90°C for 5 hours to stop the reaction, cool naturally, add tetrahydrofuran until the polymer is completely dissolved, and pass through a neutral alumina chromatography column. The filtrate is precipitated with an appropriate amount of methanol, and the precipitate is obtained by suction filtration. Then the precipitate was washed three times with deionized water, and dried in a vacuum oven at 80° C. to constant weight to obtain polymethyl methacrylate containing terminal chlorine.

Embodiment 7 to 9

[0027] In a three-necked flask equipped with magnetic stirring and an inert gas conduit, polymethyl methacrylate containing terminal chlorine, ferrous chloride, triphenylphosphine, acrylic acid- 2-Hydroxyethyl ester, polymethyl methacrylate containing terminal chlorine is synthesized according to the above-mentioned Example 3, the stirring is started, and nitrogen gas is passed through to make it completely dissolved, and the reaction process still needs to continue to pass nitrogen gas for protection. React at 80°C for 3 hours and 4.5 hours, stop the reaction after 6 hours, cool naturally, add tetrahydrofuran to dissolve the polymer completely, and pass through the neutral alumina chromatography column, the filtrate is precipitated with an appropriate amount of methanol, filtered with suction, A precipitate was obtained. Then the precipitate was rinsed three times with deionized water, and vacuum-dried at 80° C. to constant weight to obtain a block copolymer polymethyl methac...

technical field

[0001] The present invention relates to a kind of methyl methacrylate block copolymer and preparation method thereof Background technique

[0002] Atom transfer radical polymerization, as a free radical living polymerization method, has attracted widespread attention of polymer workers at home and abroad in recent years. The synthesis of block copolymers with regular structures by atom transfer radical polymerization is the most meaningful and challenging work in the field of polymer research. Block copolymers exhibit a series of excellent properties, not only in the theory of polymer solutions , and are of great significance in practical applications.

[0003] 2-Hydroxyethyl acrylate belongs to acrylates, and has the properties of alcohol monomers. Its polymer chain contains hydroxyl groups on the side groups of each structural unit, and has good hydrophilicity and physiological compatibility. Polymethyl methacrylate has excellent light transmittance, chem...

Examples

Embodiment 1 to 3

[0023] In a three-necked flask equipped with a stirrer, add azobisisobutyronitrile, ferric chloride, triphenylphosphine, and methyl methacrylate in sequence at a molar ratio of 1:1:3:200, and then Add xylene solvent at a concentration of 1g / ml, start stirring, and pass nitrogen gas to make it completely dissolved. The reaction process still needs to continue to pass nitrogen protection. React at 80°C for 3 hours and 4.5 hours, stop the reaction after 6 hours, cool naturally, add tetrahydrofuran until the polymer is completely dissolved, pass through a neutral alumina chromatography column, precipitate the filtrate with an appropriate amount of methanol, and filter with suction to obtain the precipitate . Then the precipitate was washed three times with deionized water, and vacuum-dried at 80° C. to constant weight to obtain polymethyl methacrylate containing terminal chlorine.

Embodiment 4 to 6

[0025] In a three-necked flask equipped with a stirrer, azobisisobutyronitrile, ferric chloride, triphenylphosphine, and methyl methacrylate were sequentially added in a molar ratio of 1:1:3:500, and then Add xylene solvent at a concentration of 1g / ml, start stirring, and pass nitrogen gas to make it completely dissolved. The reaction process still needs to continue to pass nitrogen protection. React at 70°C, 80°C, and 90°C for 5 hours to stop the reaction, cool naturally, add tetrahydrofuran until the polymer is completely dissolved, and pass through a neutral alumina chromatography column. The filtrate is precipitated with an appropriate amount of methanol, and the precipitate is obtained by suction filtration. Then the precipitate was washed three times with deionized water, and dried in a vacuum oven at 80° C. to constant weight to obtain polymethyl methacrylate containing terminal chlorine.

Embodiment 7 to 9

[0027] In a three-necked flask equipped with magnetic stirring and an inert gas conduit, polymethyl methacrylate containing terminal chlorine, ferrous chloride, triphenylphosphine, acrylic acid- 2-Hydroxyethyl ester, polymethyl methacrylate containing terminal chlorine is synthesized according to the above-mentioned Example 3, the stirring is started, and nitrogen gas is passed through to make it completely dissolved, and the reaction process still needs to continue to pass nitrogen gas for protection. React at 80°C for 3 hours and 4.5 hours, stop the reaction after 6 hours, cool naturally, add tetrahydrofuran to dissolve the polymer completely, and pass through the neutral alumina chromatography column, the filtrate is precipitated with an appropriate amount of methanol, filtered with suction, A precipitate was obtained. Then the precipitate was rinsed three times with deionized water, and vacuum-dried at 80° C. to constant weight to obtain a block copolymer polymethyl methac...

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