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Modified polymer complex, complex monomer, polymer complex, and redox catalyst

A complex and polymer technology, applied in the direction of organic compound/hydride/coordination complex catalyst, physical/chemical process catalyst, copper organic compound, etc., can solve the problem of poor storage stability, poor manufacturing reproducibility, expensive catalyst, etc. problem, to achieve the effect of high reactivity and excellent thermal stability

Inactive Publication Date: 2010-07-07
SUMITOMO CHEM CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, when the above-mentioned conventional manganese dinuclear complex is used as a hydrogen peroxide decomposition catalyst, the stability, especially the thermal stability, is insufficient, and there are problems when it is used in a heating reaction. catalyst
In addition, catalysts obtained by heat-treating metal-containing proteins are not only expensive, but also have poor storage stability because they are biological substances, and the production reproducibility of catalysts using them as raw materials is poor.

Method used

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  • Modified polymer complex, complex monomer, polymer complex, and redox catalyst
  • Modified polymer complex, complex monomer, polymer complex, and redox catalyst
  • Modified polymer complex, complex monomer, polymer complex, and redox catalyst

Examples

Experimental program
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Effect test

manufacture example 1

[0250] (Production Example 1) [Synthesis of Ligand]

[0251] According to the synthesis of the HL-Et ligand described in J.Am.Chem.SOC.1984,106,pp4765-4772., 2-hydroxyl-1,3-diaminopropanetetraacetic acid and o-diaminobenzene were reacted, and then 4-Chloromethylstyrene was reacted to obtain bbpr-CH represented by the following chemical formula (5) with a yield of 85%. 2 St ligand. To measure the ligand's 1 H-NMR (0.05% (v / v) TMSCDCl 3 solution), the introduction of -CH was confirmed from the peak at 5-8ppm 2 St base. 1 The H-NMR diagram is shown in figure 1 .

[0252]

manufacture example 2

[0253] (Production Example 2) [Synthesis of Complex Monomer Precursor]

[0254] Measure p-vinylbenzoic acid (10.1g, 67.5mmol) and NaOH aqueous solution (10.2g, 64.1mmol) in a flask, add 140ml of water therein and stir to dissolve it, filter out insoluble components, and prepare sodium p-vinylbenzoate aqueous solution. Measure Mn(SO 4 )·5H 2 O (7.74g, 32.1mmol) and 50ml of water were stirred to dissolve. The above aqueous sodium p-vinylbenzoate solution was added thereto, followed by stirring at room temperature for 2 hours. The generated precipitate was collected by filtration, washed with water and ether, and then dried under reduced pressure to obtain a white powder of manganese p-vinylbenzoate·tetrahydrate (complex monomer precursor). The yield was 5.87 g (13.9 mmol), a 43% yield. Elemental Analysis Calcd for C 18 h 22 MnO 8 =C, 51.32; H, 5.26. Found: C, 51.63; H, 5.16.

manufacture example 3

[0255] (Manufacture example 3) [Manufacture of complex monomer]

[0256] Measure bbpr-CH in the flask 2 St (400mg, 0.372mmol), NEt (i-Pr) 2 (43.2mg, 0.335mmol), THF 54ml was added thereto and stirred to dissolve. Manganese p-vinylbenzoate·4 hydrate (313 mg, 0.744 mmol) was added thereto, followed by stirring at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure, and the precipitate generated by adding MeOH was collected by filtration, washed with water and ether, and then dried under reduced pressure to obtain Mn -vb-(bbpr-CH 2 St)-vb (complex monomer) light brown powder. Yield was 122 mg. ESI MS, m / Z 1477.4 ([M-(p-vinylbenzoic acid anion)] + ).

[0257]

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Abstract

Disclosed is a modified polymer complex produced by the intermolecular and / or intramolecular crosslinking of a polymer complex via its side chains, wherein the polymer complex is a copolymer of a complex monomer meeting the requirements (i) to (iii) and a comonomer represented by the general formula (1): R02R03=R01E [wherein the definitions for R01, R02, R03 and E are omitted]. (i) The complex monomer has two or more transition metal atoms. (ii) The complex monomer has a polydentate ligand having three or more coordinating atoms that coordinately bind to the transition metal atoms. (iii) The polydentate ligand has one or more polymerizable functional groups.

Description

technical field [0001] The invention relates to a modified polymer complex, a complex monomer, a polymer complex and a redox catalyst. Background technique [0002] A polynuclear complex is a complex containing two or more metal atoms as central atoms in one complex (Chemical Dictionary, 1st edition, 1994, Tokyo Chemical Doujin). Such a multinuclear complex exhibits specific and various reactivity based on the interaction between multiple metal sites, so it can be used as a reaction catalyst, for example, it is useful as a catalyst for a chemical reaction involving electron transfer such as a redox catalyst. (For example, refer to Kenichi Koyanagitsu, Makoto Yuasa, Surface 2003, 41(3), 22). [0003] As a polynuclear complex, as a catalyst (hydrogen peroxide decomposition catalyst) that suppresses the generation of free radicals (hydroxyl radicals, hydrogen peroxide radicals, etc.) and decomposes hydrogen peroxide into water and oxygen, manganese dinuclear Complexes (see, f...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D233/64B01J31/22C07D235/14C08F212/34C07F1/08C07F13/00C07F15/02C07F15/04C07F15/06
CPCC07F15/065B01J2531/0238C07D233/54C07F1/08B01J2531/16B01J31/2208B01J31/183C07D235/04B01J31/1805B01J2531/847C07F15/025C07D235/14B01J2531/845C07F13/005C07F15/045B01J2531/842C08F212/34C08F212/32C08F212/26C08F212/30C08F220/06C08F220/44C07D233/64C07F3/00C07F15/02C07F15/04C07F15/06C08F12/32C08F12/34C08F12/26
Inventor 石山武东村秀之金坂将
Owner SUMITOMO CHEM CO LTD
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