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Process for preparing composite catalyst containing ferrous chloride

A composite catalyst, ferrous chloride technology, applied in the application of controllable atom transfer radical polymerization, the field of composite catalyst preparation, can solve the problems of low catalyst residue and separation difficulties, achieve good industrialization prospects, and avoid separation Effects of Difficulty, High Economic and Social Benefits

Inactive Publication Date: 2005-09-21
SHANGHAI JIAO TONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The purpose of the present invention is to solve the problem that existing ATRP catalysts are difficult to separate, and propose a composite catalyst composed of a ferrous chloride supported catalyst and a small molecule passivator, and its specific surface area is greater than 1000m 2 / g, the use of this catalyst can control the polymerization, and prepare homopolymers and copolymers with specified molecular weight and narrow distribution. The molecular weight distribution (PDI) is 1.2 to 1.3. All of them can be separated by simple filtration, the catalyst residue is low, below 40ppm, and the residual small molecule passivation agent has little effect on the product

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] (1) Pretreatment of carrier: high specific surface polyacrylic acid ion exchange resin (specific surface area>=1000m 2 / g) washed with 1-5 wt% sodium hydroxide solution, then washed with deionized water to pH = 9, and vacuum-dried at 80°C to obtain a pretreated polyacrylic acid ion-exchange resin carrier (PAA);

[0020] (2) preparation of ferrous chloride loaded catalyst: get 13 mg of anhydrous ferrous chloride (FeCl 2 ) was dissolved in 4 ml of deoxygenated methanol, and 0.45 g of pretreated resin carrier was added according to a molar ratio of 1:50, and the system was subjected to liquid nitrogen freezing-vacuum degassing-nitrogen filling-thawing-liquid nitrogen freezing, and cycled 5 times Afterwards, after stirring and refluxing at 70° C. for 1 hour, methanol was evaporated under reduced pressure under nitrogen protection to obtain a ferrous chloride supported catalyst (PAA / FeCl 2 );

[0021] (3) Preparation of small molecule passivation agent CuCl 2 / Me 6 TREN:...

Embodiment 2

[0025] (1) Pretreatment of carrier: high specific surface polyacrylic acid ion exchange resin (specific surface area>=1000m 2 / g) washed with 1-5 wt% sodium hydroxide solution, then washed with deionized water to pH = 9, and vacuum-dried at 80°C to obtain a pretreated polyacrylic acid ion-exchange resin carrier (PAA);

[0026] (2) preparation of ferrous chloride loaded catalyst: get 13 mg of anhydrous ferrous chloride (FeCl 2 ) was dissolved in 4 ml of deoxygenated methanol, and 0.45 g of pretreated resin carrier was added according to a molar ratio of 1:50, and the system was subjected to liquid nitrogen freezing-vacuum degassing-nitrogen filling-thawing-liquid nitrogen freezing, and cycled 5 times Afterwards, after stirring and refluxing at 70° C. for 1 hour, methanol was evaporated under reduced pressure under nitrogen protection to obtain a ferrous chloride supported catalyst (PAA / FeCl 2 );

[0027] (3) Preparation of small molecule passivation agent CuCl 2 / Me 6 TREN: ...

Embodiment 3

[0031] (1) Pretreatment of carrier: high specific surface polyacrylic acid ion exchange resin (specific surface area>=1000m 2 / g) washed with 1-5 wt% sodium hydroxide solution, then washed with deionized water to pH = 9, and vacuum-dried at 80°C to obtain a pretreated polyacrylic acid ion-exchange resin carrier (PAA);

[0032] (2) preparation of ferrous chloride loaded catalyst: get 13 mg of anhydrous ferrous chloride (FeCl 2 ) was dissolved in 4 milliliters of deoxygenated methanol, and 1.5 grams of pretreatment resin carrier was added according to the molar ratio of 1:150, and the system was subjected to liquid nitrogen freezing-vacuum degassing-nitrogen filling-thawing-liquid nitrogen freezing, and cycled 5 times Afterwards, after stirring and refluxing at 70° C. for 1 hour, methanol was evaporated under reduced pressure under nitrogen protection to obtain a ferrous chloride supported catalyst (PAA / FeCl 2 );

[0033] (3) Preparation of small molecule passivation agent CuC...

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Abstract

The invention discloses a process for preparing composite catalyst containing ferrous chloride wherein the ferrous chloride-containing composite catalyst comprises ferrous chloride supported catalyst and micromolecular deactivator, which is prepared by using high specific surface ion exchange resin powder as the loading carrier of the catalyst, forming ferrous chloride supported catalyst through coordination complexing with waterless ferrous chloride, and appending a small amount of micromolecular deactivator simultaneously. The composite catalyst can form solid-liquid reaction system along with initiating agent, monomer and dissolvent, and carry out controlled atom shift free radical aggregation. After the reaction finishes, the outcome yields can be separated in a simple manner, and the catalyst can be circulated for later use after being activated. The ferrous chloride-containing composite catalyst can be employed for preparing designated molecular weight, designated chain structure, narrowly distributed homopolymer and copolymer, and has the advantages of easy isolation of supported catalyst after reaction and low residual.

Description

Technical field: [0001] The invention relates to a preparation method of a catalyst, in particular to a preparation method of a composite catalyst composed of a ferrous chloride supported catalyst and a small molecule deactivator and its application in controllable atom transfer radical polymerization. Background technique: [0002] Controllable polymerization has attracted much attention due to its mild reaction conditions, wide adaptability to monomers, narrow molecular weight distribution (close to monodisperse), specified molecular weight polymers, and well-defined block copolymers. Compared with the traditional living anion (cation) polymerization in the controllable polymerization, the monomer of the newly developed atom transfer radical polymerization (ATRP) does not need harsh pretreatment, and the operation is convenient and easy. U.S. Patent No. 5,763,548 has adopted cuprous halide / bipyridine as catalyzer in atom transfer radical polymerization, and its biggest sho...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F2/38C08F4/02C08F4/26
Inventor 张永明李忠辉薛敏钊刘燕刚
Owner SHANGHAI JIAO TONG UNIV