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Polymerization method of in-situ catalyzing atom transfer free radical by metal-guanidine complex

A technology of atom transfer and polymerization, applied in the field of polymer chemistry, can solve problems such as inability to completely remove and unsafe polymer materials

Inactive Publication Date: 2008-06-11
NANKAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The ATRP method uses low-valent transition metal salts (such as: CuCl, FeCl 2 etc.) and electron-donating ligand organic compounds in the catalytic system, currently widely used catalyst ligands such as: 2,2'-bipyridine, triphenylphosphine and other compounds have greater toxicity, ATRP method usually uses a larger amount The catalyst ligand contained in the synthesized polymer cannot be completely removed by the polymerization reaction, so the synthesized polymer is very unsafe for human medical polymer materials

Method used

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  • Polymerization method of in-situ catalyzing atom transfer free radical by metal-guanidine complex
  • Polymerization method of in-situ catalyzing atom transfer free radical by metal-guanidine complex
  • Polymerization method of in-situ catalyzing atom transfer free radical by metal-guanidine complex

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Experimental program
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Effect test

Embodiment 1

[0021] Add cuprous chloride (0.015g, 0.15mmol) and 2-guanidino benzimidazole (0.027g, 0.15mmol) in the Schlenk type reactor, after the reactor is sealed, vacuumize, then charge into argon, repeat the pumping After three vacuum-argon operations, the mixture was stirred at room temperature for 30 minutes. Under stirring, methyl methacrylate monomer (5.0ml, 46.4mmol) was added into the reaction kettle, and finally ethyl 2-bromoisobutyrate (0.022ml, 0.15mmol) was added. Put the reaction kettle into a constant temperature oil bath, and control the bath temperature to (80±1)°C for 4 hours of constant temperature reaction. The reaction kettle was cooled with ice water. Tetrahydrofuran (20.0ml) was added to dissolve the product in the kettle, and then added dropwise to methanol to precipitate the polymer. After filtering, the precipitate was vacuum-dried at 40° C. for 24 hours to obtain a white solid, which was polymethyl methacrylate product. Yield 99.0%, polymer molecular weight:...

Embodiment 2

[0023] Add ferrous chloride (0.019g, 0.15mmol) in the Schlenk type reactor, and 2-guanidinobenzimidazole (0.081g, 0.45mmol), after the reactor is sealed, vacuumize, then charge into argon, repeat After three times of vacuum-filling with argon, the mixture was stirred at room temperature for 30 minutes. With stirring, methyl methacrylate monomer (5.0ml, 46.4mmol) was added and finally 1,1-dichloroacetone (0.015ml, 0.15mmol) was added. Put the reactor into a constant temperature oil bath, control the bath temperature to (100±1)°C, and react at constant temperature for 70 hours. The reaction kettle was cooled with ice water to stop the reaction. The product in the kettle was dissolved with tetrahydrofuran (30 ml), and then added dropwise to methanol to precipitate a polymer. After filtering, the precipitate was vacuum-dried at 40° C. for 36 hours to obtain a white solid, which was polymethyl methacrylate product. Yield 90.0%, polymer molecular weight: Mn=3.2×10 4 .

Embodiment 3

[0025] Add cuprous chloride (0.015g, 0.15mmol) and 2-amino-6-hydroxypurine (0.023g, 0.15mmol) in the Schlenk type reactor, after the reactor is sealed, vacuumize, then charge into argon, repeat After three times of vacuum-filling with argon, the mixture was stirred at room temperature for 30 minutes. Under stirring, methyl methacrylate monomer (5.0ml, 46.4mmol) was added into the reaction kettle, and finally ethyl 2-bromoisobutyrate (0.022ml, 0.15mmol) was added. Put the reaction kettle into a constant temperature oil bath, and control the bath temperature to (90±1)°C for 10 hours of constant temperature reaction. The reaction kettle was cooled with ice water. Tetrahydrofuran (25.0ml) was added to dissolve the product in the kettle, and then added dropwise to methanol to precipitate the polymer. After filtering, the precipitate was vacuum-dried at 40° C. for 48 hours to obtain a white solid, which was polymethyl methacrylate product. Yield 99.2%, polymer molecular weight: M...

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Abstract

The invention discloses the method of metal - guanidine complex compound in-situ catalyzing atom transfer free radical polyreaction (ATRP), belonging to high polymer chemistry technology field. Adopt new-style nontoxic 2-guanidine benziminazole (GBIM) or 2-amidogen-6-hydroxy purine (AHP) as ligand, have ATPR with the catalyzing system in-situ produced by cuprous chloride or ferric chloride, to synthesize human medical material - poly(methyl methacrylate) (PMMA). The craft method avoids using present widely used organic compounds as dipyridyl and triphenylphosphine as the catalyst ligand of ATRP. The PMMA synthesized by this new craft as human medical material has high biology security, and can be used as reactivity functional macromolecular material with carboxylic ester group. The craft adopts the noumenon style polymerization way, and has no pollution of waste water, gas and residue. It has simple operation.

Description

Technical field: [0001] The present invention relates to the technical field of macromolecule chemistry, specifically, adopt novel nontoxic 2-guanidinobenzimidazole (GBIM) or 2-amino-6-hydroxypurine (AHP) as ligand and cuprous chloride or chloride A method for synthesizing polymethyl methacrylate, a medical material for human body, by atom transfer radical polymerization (ATRP) using a catalytic system generated in situ with ferrous iron. Background technique: [0002] Designing and synthesizing functional polymer materials with specific structures and molecular weights by using living and controlled polymerization reactions is a frontier scientific research field that the international polymer science community has paid attention to in recent years. Compared with other living polymerization methods, Atom Transfer Radical Polymerization (ATRP) has the advantages of more types of applicable monomers, milder polymerization reaction conditions, and simple synthesis and operatio...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F4/42C08F20/14
Inventor 李弘仝浩宋立明
Owner NANKAI UNIV