Method of preparing polymethylene-polyphenyl-polyamine
View Patent ↗The present invention provides a method of preparing polymethylene-polyphenyl-polyamine (briefly referred to as polyamine, DAM), in which a high gravity rotating bed is used as the mixing reactor of formaldehyde and aniline hydrochloride, the mixing solution of aniline hydrochloride and circulation solution and the formaldehyde are fed into the high gravity rotating bed reactor proportionally to carry out mixing and condensation reaction under a condition of a very high gravity; the materials leaving the high gravity rotating bed reactor is introduced into a stirred vessel to proceed with the pre-condensation reaction and obtain a condensation solution; and the process steps of heating, molecular rearrangement, neutralization, water washing and purification, etc. are completed to obtain the refined DAM. With the method according to the present invention, the main by-products is obviously reduced in the condensation process, the phenomenon of deposit attaching to the inner walls of circulation pipes and heat exchanger and blockage are prevented in the condensation process, the impurity content is low in the refined DAM, and the subsequent product MDI has a lighter color, the product quality is stable and may be improved to a certain extent.
1. A method of preparing polymethylene-polyphenyl-polyamine, comprising the following steps:
a) mixing aniline with hydrochloric acid in a venturi jet mixer and conducting a reaction to produce aniline hydrochloride;
b) introducing the aniline hydrochloride stream into circulation pipes and mixing with a circulation solution coming from a condensation stirred vessel, then cooling the obtained mixed solution with a heat exchanger;
c) introducing the cooled mixed solution and formaldehyde solution into a high gravity rotating bed reactor for mixing and conducting a pre-condensation reaction;
d) introducing the materials discharged from the high gravity rotating bed reactor into the condensation stirred vessel to proceed with pre-condensation reaction and molecular rearrangement reaction; introducing a part of the reaction mixture discharged from the condensation stirred vessel into the circulation pipes as circulation solution and discharging the other part as product, and wherein the volume flow ratio of the part as circulation solution to the part as product is 3:1-50:1.
2. The method according to claim 1 , characterized in that, the high gravity rotating bed reactor used in step c) is selected from the high gravity rotating devices of rotating packed bed type, zigzag type, helix channel type, rotor-stator type or ring disks type.
3. The method according to claim 2 , characterized in that, the rotating speed of the rotor in the high gravity rotating bed reactor used in step c) is 100-3000 rpm, the molar ratio of formaldehyde to aniline is 0.1:1-0.8:1, the temperature of reaction solution is controlled at 20-70° C., and the reaction time is 0.5-10 sec.
4. The method according to claim 3 , characterized in that, in step a), the molar ratio of hydrochloric acid to aniline is 0.05:1-0.9:1; in step b), the mixed solution is cooled to 15-60° C., in step c), the rotating speed of the rotor in the high gravity rotating bed reactor is 300-2000 rpm; and in step d), the reaction temperature of pre-condensation reaction is 15-80° C., the average residence time is 10-60 min.
5. The method according to claim 4 , characterized in that, in step a), the molar ratio of hydrochloric acid to aniline is 0.2:1-0.6:1; in step b), the mixed solution is cooled to 20-50° C., in step c), the molar ratio of formaldehyde to aniline is 0.2:1-0.65:1, the temperature of reaction solution is controlled at 30-65° C., the reaction time is 0.5-5 sec, and the rotating speed of the rotor in the high gravity rotating bed reactor is 450-1500 rpm; and in step d), the reaction temperature of pre-condensation reaction is 20-70° C., the average residence time is 15-45 min, and the volume flow ratio of the part as circulation solution to the part as product is 5:1-30:1.
6. The method according to claim 5 , characterized in that, in step a), the molar ratio of hydrochloric acid to aniline is 0.25:1-0.5:1; in step b), the mixed solution is cooled to 30-45° C., in step c), the molar ratio of formaldehyde to aniline is 0.3:1-0.55:1, and the temperature of reaction solution is controlled at 30-50° C.; and in step d), the reaction temperature of pre-condensation reaction is 30-60° C., the average residence time is 20-35 min, and the volume flow ratio of the part as circulation solution to the part as products is 8:1-20:1.
7. The method according to claim 6 , characterized in that the heat exchanger used in step b) is a wing-plate heat exchanger or a tubular heat exchanger.