DD214620A1 - PROCESS FOR PREPARING AMINOL POLYETHERAL COCOOLS - Google Patents

Abstract

The invention relates to a process for the preparation of aminopolyether alcohols, which are mainly suitable for the preparation of rigid polyurethane foams and dispersion polyols. The invention has for its object to develop a process for the preparation of Aminpolyetheralkoholen by reaction of special starter substance mixtures with alkylene oxides while avoiding sanst usual high viscosities before and during the alkoxylation and the exploitation of special catalytic effects. According to the invention, the object is achieved by using as start substance a mixture of mainly aromatic and cycloaliphatic amines and cycloaliphatic and aliphatic alcohols such as aniline and derivatives thereof mixed with cyclohexylamine and cyclohexanol in the form of a water-saturated mixture, optionally mixed with other coinitiators and added in one stage, if appropriate with the addition of a catalyst or in two stages, optionally with the gradual addition of catalysts is reacted.

Description

Title of the invention

Process for the preparation of aminopolyether alcohols

Applicatio n dun of the invention gsgebiet

The invention relates to a process for the preparation of aminopolyether alcohols, which are mainly suitable for the production of polyurethane materials.

C characteristic of the known technical solutions

The preparation of polyether alcohols by reacting aliphatic and aromatic amines with alkylene oxides has been known for a long time. Since the processing properties of polyether alcohols having isocyanates or the physico-mechanical properties of the polyurethane foams depend essentially on the structure of the polyether alcohols, u. a, certain aromatic amines are also used as starting substances * Particularly suitable here are aniline, ethylenediamine, tolylenediamine and polyamines formed by acid aniline-formaldehyde condensation or "polyamine mixtures" used singly or in admixture and with alkylene oxides, in particular propylene and / or or ethylene oxide are reacted · According to the viscosity or the state of matter of the amine starting substance certain additional operations or · process steps are necessary and there are a number of known technical solutions · To produce homogeneous or stirrable or pumpable starting mixtures the amines certain inert or * functional parts Solvent added and reacted with

't \ κ η η α (λ ύ η j. Cl il 4 A. ί \

:; ·: .-. , '.. ^: -2 -'. ;. , · ^;

In order to control certain properties, such as functionality or molecular weight distribution of the polyether alcohols, OH and / or NH- or MHg-functional coinitiators are introduced and the mixture is reacted with alkylene oxides. Co-initiators are, in particular, higher alcohols or sugar alcohols, such as glycerol, trimethylolpropane, sorbitol or saccharides, such as sucrose and glucose and / or aliphatic amines or amino alcohols, such as the propoxylation products of NH. The reaction with alkylene oxides is carried out in the presence of basic catalysts, such as KOH, HaOH or certain amin shear compounds such as triethylamine at temperatures from 80 ⁰ C to 120 ⁰ C and pressures of 0 ₉ 1 MPa to 1.0 MPa and carried out in conventional stirred or stirred * For varying the properties, it is possible certain aromatic amines with each other · Often the necessarily incurred polyamine mixtures are used. In this case, control of the polyether alcohol properties is only possible to a limited extent.

Object of the invention

The aim of the invention is to develop an economical process for the preparation of aminopolyether alcohols.

Explanation of the essence of the invention

The invention has for its object to provide a process for the preparation of Aminpolyetheralkoholen by reaction of special starting substance mixtures with alkylene oxides while avoiding otherwise common high viscosities before and during or after the alkoxylation and the exploitation of special catalytic effects to develop

According to the invention the object is achieved in that the starting substance used is a mixture of aromatic and cycloaliphatic amines and cycloaliphatic and aliphatic alcohols such as aniline and derivatives thereof, preferably N-methyl and H-ethylamines in admixture with cyclohexylamine and cyclohexanol in the form of finer water-saturated mixture · The starter substance mixture consists of

- ''. , '. - 3 · »

    , , - 3 * '

5 parts »to 95 parts aniline,

0.1 parts to 55 parts of cyclohexylamine,

0.5 parts to 35 parts of cyclohexanol, 0.05 parts to 10 parts of aliphatic! Alcohol like

Methanol and / or ethanol

0.1 parts to 5 parts of aniline derivatives such as K'-methylaniline,

K-ethyl, aniline and / or toluidine,

0.01 parts to 1 part of nitro compounds and other cycloaliphatic compounds such as cyclohexanone and

0.1 parts to 50 parts of further aromatic amines, such as

Amines of the diphenylmethane series and to1uylenediamines

and is used in the form of a water-saturated mixture. The starter substance mixture according to the invention can optionally be reacted with ethylene oxide in a single stage with the addition of a catalyst. It is also possible to use the starting substance mixture in two stages, if appropriate with gradual addition of catalysts with alkylene oxides, preferably To implement ethylene and / or propylene oxide and the unreacted water, cyclohexanol and other cycloaliphatic or the nitro compounds before the 2 × reaction stage by vacuum distillation or stripping with inert gas to remove «The one- or two-stage reaction is at temperatures of 60 ⁰ C to 150 ⁰ C and pressures of 0.1 MFa to 1.0 MFa carried out in conventional circulation or stirred reactors and the respective alkylene oxide pumped by metering pump in the starting or * reaction mixture · The single-stage alkoxylation in particular ethoxylation can due to the eutokatalytischen effect of amines However, only polyether alcohols with low molecular weights can be prepared. For the preparation of relatively high molecular weight polyether alcohols, the starting mixtures according to the invention are mixed with basic catalysts, in particular KOH, NaOH or certain amines, and reacted with alkylene oxides Polyethersikohol can remain for influencing the functionality and the molecular weight distribution, the water in the polyether alcohol or after addition of a certain amount of alkylene oxide by distillation under vacuum or stripping with

 · 4 **

  ..: -.4 *. , '. ·:

Inert gas can be removed. The entry of the catalyst in the 1 * and / or 2 "stage can be carried out in this way. * The starting mixture according to the invention is liquid at room temperature, no additional solvent is required for the reaction mixture. However, further coinitiators can be mixed into the starting mixture for the purpose of property tagging Taking advantage of the low viscosity, the good solubility and the special catalytic activity are used as co-initiators, especially solid and / or higher functional alcohols, amines, Aminalkohole, sugar alcohols and saccharides «

Hach addition of the total amount of alkylene oxide, the reaction "is further stirred mixture to stabilize the amount of alkylene oxide for a certain time at temperatures from 80 ⁰ G to Igo ⁰ C in the reactor or pumped. At the end of this post-reaction, the crude polyether alcohol is separated by distillation from excess alkylene oxide or purified by neutralization with acid, distillation to remove the water and filtration of the salts. The process according to the invention has the advantage that the alkoxylation of the starting mixture without additional Operation and without the addition of solvents in conventional stirred and circulating reactors is possible. The disadvantages associated with the removal of these substances or the influence on the polyether alcohol quality are thus eliminated The use of polyether alcohols of the necessary qualities is possible over a wide range. The usual disadvantages in the reaction of aromatic amines, such as the high viscosity before, during or after the alkoxylation, which the Reaktlonsführung and Einsetzba severity of the polyether alcohols can be completely avoided by the mixture according to the invention. Due to the balanced mixture combination of the aromatic amines with the catalytically very selective cycloaliphatic amines in addition to the autocatalytic alkylene oxide addition to the functional mixture components and a catalytic activity of the polyether alcohols according to the invention in the further processing to

By influencing the amount of mixture components, the catalysis in the alkoxylation and the polyurethane reactions can be varied in selectivity and effectiveness.

The invention will be explained in more detail below on 5 exemplary embodiments:

Ausführungsbeisp iel 1

500 ml of a mixture of 76 % aniline, 3.2% cyclohexylamine, 11.5 % cyclohexanol, 8 % ethanol, 0. Are placed in a 1.5 1 autoclave with thermostat heating, stirrer, temperature and pressure measurement and a metering pump with appropriate storage vessel , 2 % H-ethylaniline, 0.5 % toluidine, 0.2 % N-methylaniline and 0.4 % Diaminodipheny! Methane filled as an aqueous mixture, rendered inert with nitrogen and then heated to a temperature of 90 ⁰ C. 500 ml of ethylene oxide are metered in at this temperature over a period of 1.5 hours, and the mixture is stirred vigorously with the reaction mixture. Wake up the dosing a Uachreaktionszeit is connected and after distilling off unreacted starting mixture constituents, a polyether alcohol with the following characteristics:

Hydroxyl number 580 mg KOH / g pH * 10.6 Viscosity ₂ c0 _c 451 m Pas

Embodiment 2

200 g of a mixture of 70% aniline, 26 % cyclohexylamine, 3 % cyclohexanol, 0.1 % ethanol, 0.4 % H-ethylaniline, 0.1 % toluidine, 0.1 % are placed in a 1.5 liter autoclave. Cyclohexanone and 0.3 % amines of the diphenylmethane series filled as a water-saturated mixture, inertized with N ₂ , heated to 110 ⁰ C and within 3 h 500 ml of propylene oxide are metered in, the pressure rises to 0.4 MPa and the temperature to values of 100 ⁰ C to. 115 ⁰ C is held · After a one-hour post-reaction and distilling off the unreacted loading

'. - - 6 - .. ·. ; , · ..

components, a PAA is created with the following key figures:

Hydroxyl number * 440 mg KOH / g pH = 98 viscosity gc O ₀ * 570 m Pas

Embodiment 3

In a 1.5 1 - autoclave "100 g aqueous mixture of ground 35" 5% aniline, 45% of cyclohexylamine, 15% cyclohexanol, 3% various aniline derivatives, 0.5% cyclohexanone, 0.5% methanol and 0 5% _t diaminodiphenylmethane filled · after inertization with nitrogen, 500 ml of propylene oxide are metered in after the heating up to a temperature of 115 ⁰ C and reacted · Thereafter, the unreacted Beetandteile will be from the reaction mixture by vacuum distillation separated · Subsequently, after adding 3 g of KOH another 800 ml Propylene oxide metered in · After a postreaction, a catalyst removal by acid neutralization, a renewed distillation to remove excess propylene oxide and a salt filtration, a polyether alcohol is obtained with the following characteristics:

Hydroxyl number 220 mg KOH / g

pH = 8.8

Viscosity ₂₅ o ₀ · '395 m Pas

Water content = 0.1%

Embodiment 4

In a 1.5 1 - autoclave 200 g of aqueous mixture of Example 1 and 400 g of urea are filled, rendered inert with N _g and heated to a temperature of 100 ⁰ C. At this temperature, 600 ml of propylene oxide are metered in continuously and stirred with the mixture. After an after-reaction and the distillation of the unreacted constituents, a PAA is formed with the following characteristics:

Hydroxyl number «550 mg KOH / g pH = 10.2 Viscosity ^ O ₀ - 870 m Pas

 Example 5

In a 1.5 1 - autoclave 200 g of aqueous mixture after .Execution Example 2 and 200 g of sucrose filled, rendered inert and after heating to a temperature of 110 ⁰ C 400 ml of propylene oxide are metered · Thereafter, by vacuum distillation unreacted components are removed and after Addition of 3 g of KOH «further 400 ml of propylene oxide metered in · _η After an after-reaction and the customary cleaning and catalyst removal, a polyether alcohol is formed with the following parameters:

Hydroxyl value 500 mg KOH / g pH. »9,3 Viscosity ₂₅ o _c * 7800 m Pas

Water content * 0.1 %

Claims (1)

' _T - «, 8 ....... Erfindunffsansprüohe 1 »process for the preparation of Aminpolyetheralkoholen at temperatures of 80 ⁰ C to 120 ⁰ C and pressures of 0.1 MPa to 1.0 MPa with alkylene oxides, in particular propylene« and / or ethylene oxide, characterized in that the starting substance is a mixture of mainly aromatic and cycloaliphatic amines and cycloaliphatic and aliphatic alcohols such as aniline and derivatives thereof preferably N'-methyl- or N-ethylaniline in admixture with cyclohexylamine and cyclohexanol and used in a minor amount of nitro compounds and other CjeLoaliphaten in the form of a water-saturated mixture optionally ₀ is reacted with other OH or NH, NHg-i-functional initiators and is reacted in one step, if appropriate with stepwise addition of catalysts, and the unreacted water, cyclohexanol and other cycloaliphates or the nitro compounds before the 2 reaction step is removed by vacuum distillation or stripping with inert gas, 2 · Method according to item 1, characterized in that the starting mixture 5 parts to 95 parts aniline
0.1 parts to 55 parts of cyclohexylamine 0.5 parts to 35 parts of cyclohexanol 0.05 parts to 10 parts of aliphatic alcohol, especially methanol and / or ethanol 0.1 parts to 5 parts of aniline derivatives, in particular N-methylaniline, N-ethylaniline and / or toluidine 0.01 part to 1 part of nitro compounds and other cyclohexanone , aliphates, such as cyclohexanone
0.1 parts to 50 parts of other aromatic amines such as Amines of the diphenylmethane series and toluenediamines and is used in the form of a water-saturated mixture.