Preparation and application of TEMPO-containing (4-oxo-2,2,6,6-tetramethylpiperidinooxy containing) block polymer

A technology of block polymers and materials, applied in the field of preparation of TEMPO-containing block polymers, can solve the problems of difficulty in achieving catalytic activity of supported catalysts, poor hydrophilicity of carriers, etc., achieve large load capacity, realize recycling and save energy The effect of production costs

Active Publication Date: 2016-09-21
HEBEI UNIVERSITY OF SCIENCE AND TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

When inorganic carrier or general polymer carrier is selected, the carrier has poor hydrophilicity. When sodium hypochlorite NaClO is used as the oxidant, since the reaction system is a water-oil two-phase system, the catalytic activity of the supported catalyst is difficult to reach the level of small molecule TEMPO

Method used

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  • Preparation and application of TEMPO-containing (4-oxo-2,2,6,6-tetramethylpiperidinooxy containing) block polymer

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] 1. Preparation of Block Polymer PEG-PTMA Containing TEMPO

[0027] (1) Dissolve 20g of PEG (molecular weight 20000, denoted as PEG20000) in 40mL CH 2 Cl 2 Add it into a 100mL three-neck flask equipped with a thermometer, magnetic stirring rotor, and constant pressure separatory funnel, then add 4.065mmol TEA, and put it in an ice bath; when the temperature of the reaction system drops to 0°C, 4.185mmol BiB and 20mL CH 2 Cl 2 The formed mixed solution was slowly added dropwise into the reaction kettle through a constant pressure separatory funnel, and the dropping time was 40 minutes; after the dropwise addition was completed, it was reacted at room temperature for 24 hours; 1mol / L hydrochloric acid and saturated sodium bicarbonate solution were added to the reaction solution , saturated sodium chloride solution, stirred and washed, separated after standing, added anhydrous magnesium sulfate to the organic phase to absorb excess water, precipitated with ether, filtere...

Embodiment 2

[0034] 1. Preparation of Block Polymer PEG-PTMA Containing TEMPO

[0035] (1) Dissolve 24g of PEG (molecular weight 6000, denoted as PEG6000) in 40mL CH 2 Cl 2 Add it into a 100mL three-neck flask equipped with a thermometer, magnetic stirring rotor, and constant pressure separatory funnel, then add 16.3mmol TEA, and put it in an ice bath; when the temperature of the reaction system drops to 0°C, 16.74mmol BiB and 20mL CH 2 Cl 2 The formed mixed solution was slowly added dropwise into the reaction kettle through a constant pressure separatory funnel, and the dropping time was 45 minutes; after the dropwise addition was completed, it was reacted at room temperature for 24 hours; , saturated sodium chloride solution, stirred and washed, separated after standing, added anhydrous magnesium sulfate to the organic phase to absorb excess water, precipitated with ether, filtered, and vacuum-dried the precipitate at 40°C for 12 hours to obtain a macromolecular trigger Agent PEG6000...

Embodiment 3

[0042] 1. Preparation of Block Polymer PEG-PTMA Containing TEMPO

[0043] (1) Dissolve 20g of PEG (molecular weight 4000, denoted as PEG4000) in 40mL CH 2 Cl 2 Add it into a 100mL three-neck flask equipped with a thermometer, magnetic stirring rotor, and constant pressure separatory funnel, then add 20.3mmol TEA, and put it in an ice bath; when the temperature of the reaction system drops to 0°C, 20.9mmol BiB and 20mL CH 2 Cl 2 The formed mixed solution was slowly added dropwise into the reaction kettle through a constant pressure separatory funnel, and the dropping time was 50 minutes; after the dropwise addition was completed, it was reacted at room temperature for 24 hours; , saturated sodium chloride solution, stirred and washed, separated after standing, added anhydrous magnesium sulfate to the organic phase to absorb excess water, precipitated with ether, filtered, and vacuum-dried the precipitate at 40°C for 12 hours to obtain a macromolecular trigger Agent PEG4000-...

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Abstract

The invention relates to a preparation method of TEMPO-containing (4-oxo-2,2,6,6-tetramethylpiperidinooxy containing) block polymer, comprising the specific steps: preparing macromolecular initiator PEG-Br by bromination of polyethylene glycol PEG, using 2,2,6,6-tetramethylpiperidide-4-methylacrylate TMPM as a monomer, acquiring block polymer PEG-PTMPM by means of ARGET ATRP (activator regenerated by electron transfer and atom transfer radical polymerization), and oxidizing via 3-chloroperoxybenzoic acid to obtain TEMPO-containing block polymer PEG-PTMA. In a NaClO water-oil oxidation system, benzyl alcohol is selectively catalytically oxidized by PEG-PTMA, good selective catalytic oxidation is presented, and catalytic performance still remains good after 5 times of recycling is available. The TEMPO-containing block polymer is high in TEMPO supporting capacity, simple in synthetic process and good in catalytic performance.

Description

technical field [0001] The invention belongs to the technical field of 2,2,6,6-tetramethylpiperidine-1-oxyl free radical TEMPO catalysts, in particular to a preparation method of a TEMPO-containing block polymer and its application in the field of selective catalytic oxidation of alcohols in the application. Background technique [0002] Nitroxide radicals, as mild oxidation catalysts, have been paid more and more attention in recent years in oxidation reactions. Among the many nitroxide free radicals, TEMPO is the most commonly used. TEMPO can catalyze a variety of oxidants to oxidize alcohols to corresponding aldehydes or ketones. The catalytic oxidation system has the advantages of mild reaction conditions, easy operation, good selectivity and high activity. However, TEMPO is expensive, its molecular weight is relatively small, and it is not easy to recycle. In order to realize the recycling and reuse of TEMPO, it is generally immobilized. When inorganic carrier or ge...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F293/00C08F220/34C08F8/00C08G65/48B01J31/06C07C45/30C07C47/54
CPCB01J31/006B01J31/06C07C45/30C08F8/00C08F220/34C08F293/005C08G65/48C07C47/54
Inventor 刘少杰王华丽杜慧丽崔笑菲邢玉彬赵风清
Owner HEBEI UNIVERSITY OF SCIENCE AND TECHNOLOGY
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