Method for producing H12MDA through hydrogenation reaction

A technology of diaminodicyclohexyl and diaminodiphenylmethane, which is applied in the field of preparing 4,4'-diaminodicyclohexylmethane through hydrogenation reaction, can solve the problem that sol catalysts are not easy to separate and reuse products, and achieve Ease of regeneration, high activity and durability

Active Publication Date: 2009-09-02
WANHUA CHEMICAL (NINGBO) CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0015] The polymer-protected noble metal sol is loaded on the inorganic carrier to realize the immobilization of the metal sol catalyst, which not only solves the problem that the sol catalyst is not easy to separate from the product and reuses, but also maintains the particle size distribution and particle size similar to the sol catalyst. size, with excellent catalytic activity and better selectivity

Method used

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  • Method for producing H12MDA through hydrogenation reaction
  • Method for producing H12MDA through hydrogenation reaction
  • Method for producing H12MDA through hydrogenation reaction

Examples

Experimental program
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Effect test

Embodiment 1

[0059] Preparation of Catalyst 1

[0060] 0.1g Ru(NO 3 ) 3 Dissolve in 50mL water, add 3.9mL of 5g / L Tween20 (manufactured by DuPont) solution into Ru(NO 3 ) 3 In the aqueous solution, stir for 1h, add 4.5g / L NaBH dropwise 4 40mL of aqueous solution, after the reduction is completed, the metal ruthenium colloid protected by Tween20 is obtained. Then 2 g of activated carbon was added, stirred for 2 h, filtered and washed with water to obtain a 3% Ru / C catalyst. The average particle diameter of metal ruthenium colloidal particles measured by the HRTEM method (dispersion in ethanol, copper grid measurement) is 3 nm. The loading rate of metal ruthenium on the carrier reaches 99.8%.

Embodiment 2

[0062] Preparation of Catalyst 2

[0063] 0.1gRuCl 3 3H 2 O was dissolved in 50mL water, and 5mL of 5g / L Span20 (manufactured by DuPont) solution was added to RuCl 3 In the aqueous solution, stir for 1h, add 4.5g / L NaBH dropwise 4 Aqueous solution 40mL, after the reduction is completed, Span20-protected metal ruthenium colloid is obtained. Then 2 g of activated carbon was added, stirred for 2 h, filtered and washed with water to obtain a 3% Ru / C catalyst. The average particle diameter of metal ruthenium colloidal particles measured by the HRTEM method (dispersion in ethanol, copper grid measurement) is 3.2 nm. The loading rate of metal ruthenium on the carrier reaches 100%.

Embodiment 3

[0065] Preparation of Catalyst 3

[0066] Add 0.2589g of ruthenium acetate into 0.2732g of Span20 and 0.1943g of Tween20 and dissolve in 400mL of water. Add 0.1374g NaBH dropwise under vigorous stirring 4 200mL aqueous solution of Span20 and Tween20 protected metal ruthenium colloids were obtained after the reduction was completed. Add 2 g of activated carbon to the colloidal solution, stir for 1.5 h, filter, wash with water, rinse with THF, and prepare a 5% Ru / C catalyst. The average particle diameter of metal ruthenium colloidal particles measured by the HRTEM method (dispersion in ethanol, copper mesh) is 2.8 nm. The loading rate of metal ruthenium on the carrier reaches 100%.

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Abstract

The invention discloses a method for preparing 4,4'-diaminodicyclohexylmethane (H12MDA) by catalyzing 4,4'-diaminodiphenylmethane (MDA) through a hydrogenation reaction with a supported nanometer ruthenium catalyst. Hydrogen involves stereoselective hydrogenation. In this process, a batch-type high-pressure reactor is used, and a highly active supported nano-ruthenium catalyst is used at a temperature of 100-180 ° C and a pressure of 4-10 MPa. After 1 to 9 hours of reaction , can make the conversion rate of raw material MDA close to 100%, the mass yield of H12MDA close to 100%, wherein the content of trans H12MDA is lower than 25%. Under the premise of not adding catalyst, the supported nano-catalyst can be applied continuously for more than 30 times, and still maintain a conversion rate of 100%. After applying mechanically for many times in a row, the content of the trans isomer in the product is still lower than 27%.

Description

technical field [0001] The present invention relates to a kind of preparation 4,4'-diaminodicyclohexylmethane (H from 4,4'-diaminodiphenylmethane (MDA) by hydrogenation reaction 12 MDA) method, hydrogenation reaction uses a kind of supported nanometer ruthenium catalyst. Background technique [0002] 4,4'-Diaminodicyclohexylmethane (H 12 MDA) is an important raw material for preparing a new generation of anti-aging polyurethane "dicyclohexylmethane diisocyanate (HMDI)" with superior performance. It usually uses 4,4'-diaminodiphenylmethane (MDA) as a raw material. Under the action of high temperature and high pressure hydrogenation, H is first produced 12 MDA, then H 12 HMDI can be obtained by phosgenation of MDA. This type of isocyanate has the characteristics of stable performance and strong oxidation resistance. It is widely used in the preparation of light polyurethane coatings, paints, foam plastics, various elastomers, adhesives, fibers, synthetic leather and paving...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C209/72C07C211/36
Inventor 吕连海马德强齐旺顺杜文强荣泽明罗务习胡爽郭方王越华卫琦丁建生
Owner WANHUA CHEMICAL (NINGBO) CO LTD
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