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Preparation method of a silver-loaded polymer catalyst with switchable selectivity

A catalyst and polymer technology, which is applied in the preparation of organic compounds, aminohydroxyl compounds, organic compound/hydride/coordination complex catalysts, etc., can solve the problems of the inability to realize the preparation of selective switchable polymer catalysts, etc. Achieve the effects of large-scale industrial production, easy large-scale industrial production, and easy preparation

Active Publication Date: 2019-05-31
JIANGSU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, based on the existing preparation methods of polymer catalysts represented by PNIPAm supported by metal nanoparticles, people can only realize the control of catalytic activity, but cannot realize the preparation of selectively switchable polymer catalysts, and domestic and foreign literature and patents There are no relevant technical reports, thus forcing people to develop new technologies and new methods for the preparation of polymer catalysts

Method used

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  • Preparation method of a silver-loaded polymer catalyst with switchable selectivity
  • Preparation method of a silver-loaded polymer catalyst with switchable selectivity
  • Preparation method of a silver-loaded polymer catalyst with switchable selectivity

Examples

Experimental program
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Embodiment 1

[0034] For the technical principle of polymer catalyst preparation, see figure 1 The binary functional monomer system used to construct two different functions of the polymer, namely the molecular recognition framework and the side chain structure of the movable functional group, is 10-hydroxy-2-decenoic acid and acrylic acid in a molar ratio of 1:4. The substrate p-nitrobenzyl alcohol (4mmol) and the silver precursor silver nitrate (2mmol) were first dissolved in 20mL dimethyl sulfoxide for complexation to form a template molecule, and the functional monomer 10-hydroxyl-2-decenoic acid ( 6mmol) and acrylic acid (24mmol), cross-linking agent N, N methylenebisacrylamide (3mmol) and initiator azobisisobutyronitrile (0.1g), then nitrogen deoxygenation (8 minutes) in the solution, sealed Afterwards, it was placed under an ultraviolet lamp to irradiate to initiate polymerization (24 hours) to form a catalyst precursor. The Ag ions in the catalyst precursor are reduced by an excess...

Embodiment 2

[0041] The operation was the same as in Example 1, except that the long-chain functional monomer was changed to 2-nonenoic acid (6 mmol), and the other operations were completely the same as in Example 1 to obtain a silver-loaded polymer catalyst AgPR-ST with a transition point of about 38°C. Under the same catalytic test conditions as in Example 1, 30°C and 45°C above and below the transition point were selected for comparative measurement, and the results are shown in Figure 8 . At 30°C, AgPR-ST, similar to AgPR-T, exhibited a highly selective catalytic effect on the specific substrate p-nitrobenzyl alcohol; in contrast, at 45°C, AgPR-ST became similar to AgPR-T. AgPR-S is similar in that it exhibits no selectivity for p-nitrobenzyl alcohol and its analog o-nitrobenzyl alcohol. The as-prepared AgPR-ST catalyst also exhibits the characteristics of selectively tunable catalysis.

Embodiment 3

[0043] The operation was the same as in Example 1, except that the long-chain functional monomer was changed to octadecenoic acid (3 mmol), and the other operations were completely the same as in Example 1 to obtain a silver-loaded polymer catalyst AgPR-ST with a transition point of about 34°C. Under the same catalytic test conditions as in Example 1, 28°C and 40°C above and below the transition point were selected for comparison and measurement, the results are shown in Figure 9 . At 28°C, AgPR-ST, similar to AgPR-T, exhibited a highly selective catalytic effect on the specific substrate p-nitrobenzyl alcohol; in contrast, at 40°C, AgPR-ST became similar to AgPR-T. AgPR-S is similar in that it exhibits no selectivity for p-nitrobenzyl alcohol and its analog o-nitrobenzyl alcohol. The as-prepared AgPR-ST catalyst also exhibits the characteristics of selectively tunable catalysis.

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Abstract

The invention provides a preparation method of a silver-loaded selectivity-changeable polymer catalyst. According to the preparation method, functional monomers involved in the method are a binary copolymerization functional monomer system for constructing a polymer molecule recognition framework and a movable functional group side chain structure. A substrate and an active component silver precursor are first dissolved in dimethyl sulfoxide for complexing, then the functional monomers, a crosslinking agent and an initiator are added, nitrogen is injected into the solution for deoxidation, the mixture is sealed and put under an ultraviolet lamp to be irradiated for polymerization initiation, and then a catalyst precursor is formed; Ag ions in the catalyst precursor are subjected to sodium borohydride reaction, an obtained product is washed repeatedly with water and ethylene alcohol to remove blotted substrate molecules, and the silver-loaded selectivity-changeable polymer catalyst is obtained after vacuum drying. The silver-loaded selectivity-changeable polymer catalyst can be used for direct preparation of aminobenzyl alcohol from an isomer mixture of nitrobenzyl alcohol and other industrial raw materials. The preparation method has the advantages of being simple in technical principle, making raw materials obtained easily, convenient to operate and making preparation easy.

Description

technical field [0001] The invention belongs to the technical field of polymer materials, and in particular relates to a preparation method of a silver-supported polymer catalyst with switchable selectivity. Background technique [0002] Catalysis is the cornerstone of the modern chemical industry, and realizing controllable and adjustable catalysis is a major scientific and technological problem that needs to be solved urgently in today's industry. The development of polymer catalyst preparation methods represented by metal nanoparticle-supported poly-N-isopropylacrylamide (PNIPAm) has created conditions for the realization of this goal. The reason is that the structure characteristics of the hydrophilic amide group-hydrophobic isopropyl group of PNIPAm in the polymer catalyst make it form a unique critical solution temperature (~32°C) in the aqueous medium. When the temperature is lower than the critical temperature, the hydrogen bond interaction between the amide group i...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/06C07C213/02C07C215/70
CPCB01J31/063B01J31/067B01J2231/64C07C213/02C07C215/70
Inventor 李松军郑晓春袁新华朱脉勇吴述平申小娟张侃
Owner JIANGSU UNIV
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