Unlock instant, AI-driven research and patent intelligence for your innovation.

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, difficult separation, etc., achieve good industrialization prospects, avoid separation Difficulty, high economic and social benefits

Inactive Publication Date: 2007-05-09
SHANGHAI JIAO TONG UNIV
View PDF3 Cites 0 Cited by
  • 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

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

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

[0020] (2) Preparation of ferrous chloride supported catalyst: take 13 mg of anhydrous ferrous chloride (FeCl 2 ) After dissolving in 4 ml of deoxygenated methanol, add 0.45 g of the pretreated resin carrier according to the molar ratio of 1:50, and perform liquid nitrogen freezing-vacuum degassing-nitrogen filling-thawing-liquid nitrogen freezing for the system, cycle 5 times After stirring and refluxing at 70°C for 1 hour, the 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: Take 0.54...

Embodiment 2

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

[0026] (2) Preparation of ferrous chloride supported catalyst: take 13 mg of anhydrous ferrous chloride (FeCl 2 ) After dissolving in 4 ml of deoxygenated methanol, add 0.45 g of the pretreated resin carrier according to the molar ratio of 1:50, and perform liquid nitrogen freezing-vacuum degassing-nitrogen filling-thawing-liquid nitrogen freezing for the system, cycle 5 times After stirring and refluxing at 70°C for 1 hour, the 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 / Me6 TREN: Take 0.135...

Embodiment 3

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

[0032] (2) Preparation of ferrous chloride supported catalyst: take 13 mg of anhydrous ferrous chloride (FeCl 2 ) After dissolving in 4 ml of deoxygenated methanol, add 1.5 g of the pretreated resin carrier according to the molar ratio of 1:150, and perform liquid nitrogen freezing-vacuum degassing-nitrogen filling-thawing-liquid nitrogen freezing for the system, cycle 5 times After stirring and refluxing at 70°C for 1 hour, the 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 CuCl 2 / Me 6 TREN: Take 0.84mg ...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

PropertyMeasurementUnit
specific surface areaaaaaaaaaaa
molecular weight distributionaaaaaaaaaa
molecular weight distributionaaaaaaaaaa
Login to View More

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 method for preparing a catalyst, in particular to a method for preparing a composite catalyst composed of a ferrous chloride supported catalyst and a small molecule passivator and its application in the aspect of controllable atom transfer radical polymerization. Background technique: [0002] Controllable polymerization has attracted much attention due to its mild reaction conditions and a wide range of monomers. It can produce polymers with narrow molecular weight distribution (close to monodisperse) and specified molecular weights, and block copolymers with clear structures. Compared with the traditional active anion (cation) polymerization in controllable polymerization, the newly developed atom transfer radical polymerization (ATRP) monomer does not require harsh pretreatment, and the operation is convenient and easy. U.S. Patent No. 5,763,548 uses cuprous halide / bipyridine as a catalyst in atom transfer radical polymerizati...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
IPC IPC(8): C08F4/26C08F4/02C08F2/38
Inventor 张永明李忠辉薛敏钊刘燕刚
Owner SHANGHAI JIAO TONG UNIV