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Polymer molecule brush supported catalyst as well as synthesis method and application of catalyst

A technology of supported catalyst and synthesis method, applied in the field of polymer supported catalyst and polymer synthesis, can solve the problems of waste of environment, pollution, cumbersome separation and purification process, etc.

Inactive Publication Date: 2015-02-11
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] The synthesis of many complex molecules sometimes requires multi-step reactions to complete, involving tedious separation and purification processes
From an economic and environmental point of view, this will inevitably cause huge waste and environmental pollution.

Method used

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  • Polymer molecule brush supported catalyst as well as synthesis method and application of catalyst
  • Polymer molecule brush supported catalyst as well as synthesis method and application of catalyst
  • Polymer molecule brush supported catalyst as well as synthesis method and application of catalyst

Examples

Experimental program
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Effect test

preparation example Construction

[0032] The synthetic method of the polymer molecular brush of the present invention comprises the following steps:

[0033] (1) Using glycidyl methacrylate (GM) as a monomer, the main chain of polyglycidyl methacrylate (PGM) was synthesized by reversible addition-fragmentation chain transfer polymerization (RAFT), and the main chain of polyglycidyl methacrylate (PGM) was hydrolyzed. The epoxy group is converted into a hydroxyl group; then a RAFT chain transfer agent is installed at the end of the hydroxyl group; then the catalytic functional monomer and 4-butenyl styrene are randomly copolymerized and grafted to the molecular backbone; in order to increase its solubility and increase steric hindrance, and then a layer of N-isopropylacrylamide (NIPAAm) was added to the outside; the precursor of the polymer molecular brush was obtained;

[0034] (2) the molecular brush precursor obtained above is catalyzed and cross-linked with the first-generation Grubbs catalyst; after the cro...

Embodiment 1

[0051] Example 1: RAFT modification of the main chain

[0052] Add 4.55g RAFT reagent to a dry 100ml round bottom flask This was dissolved by adding 10 ml of dry dichloromethane. With the bubbler connected, slowly add 10 ml of oxalyl chloride (C 2 O 2 Cl 2 ), and reacted for 2h after the addition. After the reaction was completed, the oil was pumped for 6 hours, and the dry dichloromethane and the remaining oxalyl chloride were removed. The hydrolyzed backbone (500 mg) (PGM-OH) was dissolved in dry 40 ml DMF and slowly added to the reaction vial. Reaction for 24h. After the reaction was completed, a yellow precipitate was formed. is the target synthesis product. The DMF was removed by pouring, and the remaining solid was dissolved in dichloromethane and precipitated in methanol to remove impurities such as unreacted RAFT reagent. Repeat three times to ensure that impurities are removed. Finally dried under vacuum for 24h. Obtain the precursor yellow viscous solid 7...

Embodiment 2

[0053] Example 2: Catalytic application of cross-linked organic acid polymer molecular brushes and cross-linked organic base polymer molecular brushes

[0054] M1 (5mg) and M2 (14mg) were dissolved in 0.5ml DMSO, benzaldehyde acetal (4.6mg) and ethyl cyanoacetate (13.5mg) were added to the reaction solution in turn, and 10ulH was added while stirring. 2 O. After heating to 70° C. and reacting for 48 hours, the conversion rate of benzaldehyde acetal was 100%, and the yield of the final product was 87%.

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Abstract

The invention discloses a polymer molecule brush supported catalyst described in a formula (I) and a synthesis method thereof. The synthesis method comprises the following steps: firstly synthesizing a polymer molecule brush precursor, crossing-linking the polymer molecule brush precursor by use of a Grubbs catalyst, then hydrolyzing and acidizing to obtain the polymer molecule brush supported catalyst. The invention also provides application of the polymer molecule brush supported catalyst in catalyzing cascade reaction. The polymer molecule brush supported catalyst has the advantages that molecule brushes act independently without influence with one another by virtue of the cross-linking within the molecule brushes and outer-layer high-density N-isopropyl acrylamide grafting, so that the catalytic efficiency is greatly improved.

Description

technical field [0001] The invention belongs to the technical field of polymer synthesis, relates to the technical field of polymer-supported catalysts, and in particular relates to a polymer molecular brush-supported catalyst for catalyzing a series reaction and a synthesis method and application thereof. Background technique [0002] In recent years, polymer nanocatalytic materials developed based on the "space limiting valve effect" have received a lot of attention and have become a research hotspot in recent years. In particular, the research on nanocatalysts developed with dendrimers, hyperbranched and star polymers as supports has attracted much attention, thus promoting the wide application of polymer-supported organic catalysts in organic synthesis. [0003] VanKoten et al. reported the first case of dendrimer metal complex catalysts, which opened a precedent for the study of dendrimer supported catalysis. However, dendrimers have complicated steps in the synthesis ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/06C07C255/41C07C253/30C07C45/42C07C47/54C08F293/00C08F212/32C08F212/14C08F212/34C08F220/54C08F2/38C08F120/32C08F8/12
Inventor 黄琨熊林峰张慧何紫东钟爱青
Owner EAST CHINA NORMAL UNIV
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