DD212524A5 - PROCESS FOR PREPARING POLYARYLAMINES HAVING METHYLENE BRUSHES - Google Patents

Abstract

The invention relates to methods of preparation of mixtures of methylene dianiline and polymethylene polyphenylene polyamines, which can be further processed to isocyanates. The aim of the invention is to produce in a plant polyamine mixtures that can be adapted to the needs. It is an object of the invention to be able to produce by means of a new process both products with a higher content and those with a lower content of 2,4'-isomers MDA on the one hand and of monomeric MDA in the total polyamine product on the other hand and / or reduced acidity. According to the invention, the preparation from aniline and formaldehyde in the presence of acid catalysts with controllable content of isomers in the binuclear and methylenedianiline in the total mixture and / or reduced Saeurekatalysatorenmenge by splitting the reaction into at least two Stroeme: one catalytically, the other non-catalytic, then, optionally after intermediate transfer and, if appropriate, after further addition of formaldehyde, be rearranged together in one or more stages to desired products.

Description

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Process for the preparation of methylarylene-containing polyarylainines

Field of application of the invention

The invention relates to manufacturing methods of mixtures of methylenedianiline and polymethylene polyphenylene polyamines by condensation of aniline and formaldehyde in the presence of an acid catalyst "The methylene bridges having polyamines are used in the production of isocyanates, the isocyanates in turn become the Lord · set different polyurethanes * polyisocyanates and other cellular and non-cellular polymers derivable from polyisocyanates.

Characteristic of the known technical solutions

The preparation of polyamines of the diamino-diarylmethane series by condensation of aromatic amines with formaldehyde in the presence of acidic catalysts is known and provides, depending on the procedure, a differently composite product »Thus obtained in the condensation in the presence of weakly acidic or traces of strongly acidic Catalysts Polyamine mixture with high proportion of 2,4'-Oiamino-diarylmethanen * while polyamines with high content of 4 * 4 ^f -0iaroino-diaryImethanen and simultaneously low content of 2 * 4 * isomers prepared only in the presence of larger amounts of strongly acidic catalysts can be. Strong mineral acids * especially hydrochloric acid (OE-OS 1 518 406, OE-OS 2 045 834, US-PS 3 357 969) are most suitable for the last case.

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However, the advantage of the high selectivity of the strongly acidic mineral acids for the formation of 4,4'-isomers must be paid for by the known methods of the prior art with the loss of the catalyst, as this after completion of the reaction by complex neutralization with bases must be removed from the reaction mixture «Since a sensible utilization of the neutralization salts is not possible * they cause considerable environmental problems»

The properties of isocyanates prepared from methylene bridges containing polyamines are dependent on the total composition of the isomers in monomeric * methylene dianiline (MOA) and oligomeric polymethylene polyphenylene polyamines (PMPPA) in aniline-free polyamine mixture.

Object of the invention

It is the object of the invention to produce polyamine-gens in an installation which can be adapted to the needs.

Explanation of the essence of the invention

The invention is based on the object of developing a process for the preparation of methylarylene-containing polyarylamines which comprises both products having a higher content and those having a lower content of 2'-isomer MDA on the one hand and monomeric MDA in total. Polyarain product on the other hand and / or reduced acid catalyst can produce »

The subject matter of the present invention is therefore an

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for the preparation of mixtures of NDA and PMPPA with controllable content of 2,4'-MDA in binuclear and controllable content of MDA in the total mixture and / or reduced amount of acid catalyst * which is characterized * that the reaction of the starting materials in various ways performs * by

a * converts one part of formaldehyde and aniline in the presence of optionally total acid catalyst to acid condensate, essentially consisting of aminobenzylaniline and / or methylenedianiline and oligomeric polymethylene polyphenylene polyamines *

b * the remaining aniline and part or all of the remaining formaldehyde either non-catalytically converts to so-called precondensate, optionally the formaldehyde and water of reaction separated and optionally rearranged with the rest of the acid catalyst * a part or the gesarate acid condensate to the intermediate condensate or catalytically directly to the intermediate condensate in Presence of weak acids, carbonic acids * acidic ion exchangers ,, solid catalysts »salts, strong acids with short residence times and

times * thermally reacted at temperatures above 100 C.

c _#, the acidic condensate and precondensate or the intermediate condensate optionally mixed together and, optionally after the addition of residual formaldehyde, optionally rearranges a plurality of stages to methylene dianiline and oligomeric polymethylene polyphenylene polyamines, and worked up according to the prior art *

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The reaction of aniline and formaldehyde in the presence of strong acids has already been extensively studied * This is done in three stages, in the presence of strong acids resulting in the first stage compounds of Methylendianilin * or ** Anhydroformaldehydanilinart (also called precondensates) immediately in so-called N-phenylaminobenzylamines (ABA) rearrange.

At the end of the reaction, the above aminobenzylanilines are incorporated into the corresponding M3A and PMPPA compounds * and it is important for further reaction with phosgene * that this is complete: the alkylene groups must be linked virtually exclusively to the carbon atoms of the aromatic rings »

Technically, all of the formaldehyde is reacted with aniline and acid catalysts in several temperature stages, the first being generally at below about 60 ° C. due to high exothermicity, there are various methods for avoiding local overheating (DP 16 43 363).

Methods are also known * which are to promote the formation of MDA by adding one part of aniline to the more or less formed ABA / MDA / PMPPA (US Pat. No. 3,367,969).

Furthermore, processes are known * in which the entire aniline and formaldehyde without acid catalysts (non-catalytic) to form so-called precondensates and optionally after separation of formaldehyde and water of reaction with acids, acid salts and similar * or solid catalysts

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is

(Cation exchangers ,, clays u * ä _a m ») rearranges ABA directly or indirectly to MDA / PMPPA-Gemischan" The products thus obtained differ from products of the reaction in the presence of strong acids with respect to the isomer distribution of the MDA and the ratio of MDA to PMPPA considerably; In addition, it is difficult »by this process to obtain products which are free from polymeric * '" secondary amines (NMR analysis) _#

It has now been found; that it is possible to control the composition of the reaction products of the condensation of aniline with formaldehyde, if the reaction is divided into at least two streams:

One part of aniline and formaldehyde is reacted with optionally total amount of acid catalyst, in one or more stages according to the state of the art, to give the acidic condensate which consists essentially of ABA and / or 1-DA / PMPPA.

Acid catalyst is understood as meaning water-soluble acids having a pKA value below 2 * 5, such as, for example, * hydrochloric acid, sulfuric acid * methanesulfonic acid * trifluoroacetic acid, bromine * hydrogens, hydroxyethane sulfonic acid and the like. ä »

When working with neutralization of the catalyst (ζ * Β »with hydrochloric acid) it is used in aqueous solution directly or as an aqueous solution of aniline hydrochloride»

When working up the reaction mixtures by exchange with aniline (DOS 25 48 982) or extraction with hydrophobic Lö-

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Means (DAS 22 38 920) gives the acid catalyst as an aqueous amine salt solution,

The remaining aniline and formaldehyde can not be catalytically at temperatures of 5 to 100 ⁰ C, preferably 20 to 80 ° C _i; This is after separation of water of reaction and / or formaldehyde, depending on the molar ratio of aniline / formaldehyde, a more or less viscous liquid , which tends to crystallize at temperatures below 40 ⁰ C. The precondensate can be processed as an emulsion (without water separation) or after simple decantation of the water,

This precondensate is stored in a variety of ways to give intermediate condensate:

When working with concentrated acid catalysts * such as hydrochloric »can be the precondensate at temperatures below 60 C with the rest of the acid catalyst * a part or the total acidic condensate in virtually any ratio mix», with no or only finely dispersed solids form. This is important for the product quality.

Working at low temperature provides products with minimal (below 1 %) N * methyl content ♦

When working with dilute salt solutions homogeneous mixtures are obtained only at higher temperatures (above 60 ⁰ C), under these conditions, however, form higher amounts

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Ν-methyl compounds * This can be avoided * if the precondensate at temperatures below 60 C with relatively small amounts of residual catalyst or acid condensate rearranged to substantially ABA and only at temperatures above 60 ⁰ C with the rest of the acidic condensate mixed: Homogeneous solutions are obtained after final transfer of products without excessive amounts of N-methyl compounds forming *

The remaining aniline and formaldehyde can also be converted directly to intermediate condensate. * This can be done in various ways. * Z _t 3. Aniline and formaldehyde can be removed in the presence of weak acids * acidic ion exchangers * basic salts or with strong acids and short residence times.

times »thermis-ch at temperatures above 100 ⁰ C or heterogeneously reacted with aqueous acids.

The isomer ratio in binuclear (MDA) and the ratio of MDA to PMPPA can be regulated or adjusted in various ways *

a) By quantitative adjustment of the streams;

b) by different aniline / formaldehyde molar ratios in the streams;

c) by the amount of acid catalyst in the acidic condensate (degree of protonation);

d) by the amount of catalyst and temperature conditions in the production of intermediate condensate;

e) by working with more than two streams and

f) conditions under which the flows before the final transfer

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treated or under which the mixture of different streams takes place.

It has surprisingly been found that the precondensate produced by the noncatalytic reaction of aniline and formaldehyde behaves quite differently when mixed with acid condensate than in the formaldehyde addition according to the prior art to aniline salt solutions which have similar protonation degrees.

After erfindungsgeraäßen method is obtained upon mixing of acid condensate having precondensate and a Endprotonierungsgrad below 0 _A 2 moles of acid / mole of aniline per solu- tions without appreciable solids formation at temperatures below 55 ⁰ C.

Of importance is the concentration of water in the acidic condensate. The higher the amount of water is * * the higher the temperature at which the intermediate condensate dissolves homogeneously "virtually solids-free with acidic condensate.

The fact that polyamines from the reaction in the presence of large amounts of strong acids products with over 95 % 4,4'-MDA in binuclei and the polyamines from the rearrangement of the precondensates depending on Sajrekatalysetoren according to their nature and amount (eg. 8, DOS 23 01 554) provide polyamines with a high content of 2, 4 * -Ή3Α, * allows the process according to the invention to control the composition of the product and to considerably reduce the amount of catalyst required in comparison with the prior art.

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When producing methylene-bridged polyarylamines "which contain considerable amounts of Trl * tetra- and higher polyarylamines (PMPPA), these can be obtained" in particular low aniline / formaldehyde molar ratios, such as z * B _# to less than 1 * Mole aniline / per mole of formaldehyde.

The production of acidic condensates with the above aniline / formaldehyde molar ratio presents difficulties * since, under the necessary reaction conditions (temperature below 70 ° C.), the condensation leads to the formation of solids or "precipitates" which, apart from adversely affecting quality, also cause operational difficulties ( z * B "Clogging of pipes * Fittings u * ä *) ·

Also, the preparation of so-called precondensate by non-catalytic reaction of aniline with formaldehyde goes smoothly in the range of up to 2 moles of aniline / per 1 mole of formaldehyde, if one carries out reactions of less than 2 moles of aniline / per 1 mole of formaldehyde * so you get solids and difficulties in deposition of water,

It has now been found that it is possible and advantageous to add a portion of the formaldehyde to the intermediate condensate. The addition may also take place during the production of intermediate condensate. The intermediate condensate thus treated is then rearranged, optionally in multiple stages, at higher temperatures to triand higher polyarylamines having methylene dianiline and methylene bridges.

This way of working makes it possible *. Produce products with an extremely high proportion of PMPPA (about 50 %) «

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It is of course possible _r, the addition of formaldehyde in several steps to make ,, by preparing the intermediate condensate multistage and alternately and formaldehyde precondensate is added to acid condensate ·

The total molar ratio of aniline and formaldehyde is generally in the range of 1.3: 1 to 15: 1 _t, preferably 1 * 4: 1 to 10: 1 moles of aniline per mole of formaldehyde *

The distribution of the Gesaratformaldehyds on the production of acidic condensate, precondensate and addition to intermediate * - condensate (residual addition of formaldehyde) can also be varied widely:

Acid condensate: 0.05: 0 * 7 preferred 0.2; 0 ^, 5 mol formaldehyde

wise hyd pro

Mole of aniline

Precondensate: OiIO: 0 _ft 50 - "- 0 * 15: 0,49 -" - Remaining Addition: 0 ^ 01: 0 _e 40 ~ ^η - 0 * 05 ί O ^: »30 - = -

The rest of the addition should be at temperatures below 70 ⁰ C ₈ under 60 ⁰ Cj, preferably take place "

The reaction times and temperatures of the residual addition or subsequent adjustment are directly dependent on the amount of formaldehyde and the temperature: Higher temperatures are responsible for the formation of undesired by-products (N-methyl compounds) "

The total molar ratio of aniline and formaldehyde is generally 1, S: 1 to 15: 1 *, preferably 2: 1 to 10: 1 _Φ

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The distribution of the currents can be from 1:20 to 20: 1 *

The aniline / formaldehyde molar ratio may be the same or different in the streams as in the entire process. This can also influence the composition of the desired products »

The volume ratio of aniline / formaldehyde / acid to water in the production of acidic condensate is generally 5: 1 to 1:10. This parameter also has an influence on the product quality ",

Working Example

An explanation of the implementation of the erf indungsgetnäßen method show the following figures:

The plant consists of two strands: one strand for the conversion of aniline and formaldehyde non-catalytic to precondensate and the second to react aniline with formaldehyde with acid catalyst to acidic condensate and reaction of the precondensate to intermediate condensate and subsequent mixing of the streams and / or Endumlagerung to MDA / PMPPA * The system also includes a line for the addition of residual formaldehyde to the intermediate condensate _#

Fig. I

The mode of operation in the strands takes place in the following way: Strand 1

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Measured currents in aniline and formaldehyde are non-catalytically converted into VR and then passed to the separator S where they separate into organic and aqueous phases *

Strand 2

A measured flow of aqueous aniline ^ salt solution * prepared from aniline and acid in the case of working with neutralization or "as a solution obtained from the processing of the products according to the method of replacement with aniline or _# extraction with hydrophobic solvents» ~ so as formaldehyde are reacted in the reaction zone R 1 to the acidic condensate and then in the reaction zone R 2 roit the precondensate from the separator S to intermediate condensate ♦ Then the solution in the reaction zone R 3 and / or reaction zone R 4 to one or more stages rearrangement to the desired products

When working with the addition of residual formaldehyde, this is metered into Z.B * reaction zone R 3 and then rearranged in this and other reaction zones to the desired products _#

From the reaction zone R 4, the rearranged product solution for further processing according to the prior art,

Fig. 2

Here, the precondensate is reacted with a part of the acid catalyst in the reaction zone R 2 to form intermediate condensate and only then in the reaction zone R 3 with the acidic

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Condensate from the reaction zone R Γ mixed. Subsequently, this solution is rearranged in the reaction zone R 4 to MDA / PMPPA and worked up as usual,

Fig. 3

In contrast to the work shown in FIG. 2, the reaction of the precondensate to intermediate condensate takes place with the partial stream of the acidic condensate from R 1, and only then is this product mixed with the remainder of the acidic condensate from R 1 in the reaction zone R 3 or reacted and optionally rearranged in the reaction zone R 4 to the desired products.

Fig. 4

Here we work with neutralization of the catalyst * d »h ** that free acid is used as starting material * A large part of this acid is used in the form of aniline salt solutions for the production of acidic condensate in the reaction zone R 1» The remainder of the acid (or the Aniline salt) is used to convert precondensate in the reaction zone R 2 to intermediate condensate * The products from the reaction zones R 1 and R 2 are then mixed together in the reaction zone R 3 and rearranged in this or, reaction zone R 4 to MDA / PMPPA.

The temperatures in the reaction zones or separators are preferably set as follows:

η ο>

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Reaction zone VR 20 to 80 ^° C. * separator S 50 b "is 80 ^° C.,

Reaction zone R 1 20 to SO ⁰ C *

Reaction zone R 2 30 to 100 ⁰ C ₁

Reaction zone R 3 30 to 80 ° C _a

Reaction zone R 4 80 to 150 ^° C. *

The reaction zones can be carried out as stirred tank »stirred cascade, flow tubes * columns * packed columns and the like *

The design of the devices can, of course, be discontinuous, semi-continuous and similar irrespective of the drawings.

Examples 1 to 4

Four parallel experiments of the process according to the invention with hydrochloric acid catalyst are carried out *

Acid condensate production

By weight to a solution of 300 g of hydrochloric acid 31 * -% (2 ^ 58 mol) and 279 g of aniline (3 moles) with vigorous stirring and about 40 ⁰ C 109 g _Λ 5 mass% formaldehyde (1.35 moles) within about 20 min * added »is then kept for 30 min * at 50 C and then distributed according to Table I in four mixing vessels» The approach corresponds to a molar ratio of aniline / formaldehyde / Saiz3äure of 1: 0.45: 0.88.

Precondensate production;

558 g of aniline (6 mol) are placed in a stirred vessel.

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This is added at about 40 ⁰ C 219 g 37% by mass of formaldehyde (2.7 mol) within about 40 min "j without the temperature exceeds 50 ⁰ C * is then maintained with stirring for one hour at 50 C and then turned off * After about 10 minutes, an organic and aqueous phase is formed »The lower phase is the precondensate, and this is added to the acidic condensate according to Table I *

The homogeneous product formed after the addition is then followed by one hour. 50 ⁰ C, one hour at 80 ⁰ C, held for two hours at 103 ⁰ C. »

The analysis is carried out using GLC and SE ~ 30 as the stationary phase on chromosorb and 4 ^ 4'-methylene-bis-Ν, Ν-diroethylaniline as an internal standard for the determination of the diamine content *

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Examples 5 to 8

Four parallel experiments with methanesulfonic acid as catalyst are carried out.

Acid condensate production

708 * 75 g of 40% aniline-methanesulfonate solution in water * containing 5 moles of aniline and 1 * 5 moles of methanesulfonic acid are reacted with 54 »7 g of 37% by weight formaldehyde (0.675 mol) at about 45 ° C. and then for one hour held at 50 ⁰ C. The formulation corresponds to an aniline / formaldehyde / methanesulfonic acid ratio of 1: _t 45: l »0 _#

The acidic condensate is then distributed in four heated stirred vessels according to Table II and heated to 90 ⁰ C * After reaching the temperature of the Zvsischenkondensat is added according to the table to the acidic condensates * 'which dissolve immediately homogeneous. Then it is held at 90 ^° C. for one hour and at 103 ^° C. for two hours,

Pre-condensate production

The preparation of the precondensate is carried out as in Example 1 to 4 »

Between condensate production.

The precondensate is added at about 40 to 45 ⁰ C with 0.015 mol of 40% aniline-methanesulfonate in water (acid catalyst) per mole of precondensate and for one hour at

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about 50 ° C "Then, as already mentioned above, the intermediate condensate is added to the acidic condensate at 90 ° C. according to the table"

The product is tested as described in Examples 1 to 4. The results are shown in Table II *

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Examples 9 to 12

Four parallel runs of the process according to the invention with hydrochloric acid catalyst are carried out.

Acid condensate production

To a solution of 309 g of hydrochloric acid 28% by mass (2 * 41 Hol) and 256 g of aniline (2 * 76 mol) of sodium with vigorous stirring and about 40 ⁰ C. 118.0 g 31 * 5% by weight formaldehyde (1 * 24 mol) within about 20 min »added» Then 30 min * maintained at 50 ⁰ C and then distributed according to Table I in four mixing vessels * The approach corresponds to a molar ratio of aniline / formaldehyde / hydrochloric acid of 1: 0.45: 0 ^ .88 *

Precondensate production,

409 * 2 g of aniline (4.4 mol) are placed in a stirred vessel 189 g of 31.5% by mass of formaldehyde (1.98 mol) are added at about 40 ^° C. within about 40 minutes without the temperature exceeds 50 ⁰ C * is then kept under stirring for 30 min * at 40 ⁰ C * then heated to 60 ⁰ C and after about 10 min, turned off. It forms an organic and an aqueous phase "The lower phase is the precondensate" This is added according to Table III to the acidic condensate and about 15. * At 50 ⁰ C held · Then according to Table I residual formaldehyde at 50 ⁰ C for about 10 * admitted *

The product formed after the addition is then kept at 60 ^° C. for one hour at 80 ^° C. for one hour at 103 ^° C. for one hour.

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The analysis is carried out with GLC and SE.-30 as a stationary phase on Chromosorb and 4,4. ^ Methylen to Ν, Νί-dimethylaniline as an internal standard for the determination of the diamine content,

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Examples 13 to 16

Four parallel experiments of the process according to the invention with hydrochloric acid catalyst are carried out.

Acid condensate production

To a solution of 103 g of hydrochloric acid 31.5% by weight (0.9 mol) and 93 g of aniline (1 mol) with vigorous stirring and about 40 ⁰ C 43 g of 31.5% by weight of formaldehyde (0 * 45 Mol) within about 20 min *, followed by 30 min, held at 50 ⁰ C and then distributed according to Table II in four mixing vessels. The batch corresponds to a molar ratio of aniline / formaldehyde / hydrochloric acid of 1: 0 * 45: 0.9) _β

Precondensate production

409 * 2 g of aniline (4 * 4 mol) are placed in a stirred vessel. To this is added at about 40 ⁰ C 189 g of 31 "5 mass of formaldehyde (1 * 98 mol) within about 40 min *» without the temperature exceeds 50 ⁰ C * is then kept under stirring for 30 min * at 40 ⁰ C. * then heated to 50 ⁰ C and turned off after about 10 min * It forms an organic and an aqueous phase * The lower phase is the precondensate, and this is added according to Table IV to the acidic condensate and about 15 ^r at 50 C. * Subsequently II residual formaldehyde at 50 ⁰ C is for about 10 * * added according to the table

The product formed after addition of one hour at 80 ⁰ C ₁ for two hours at 103 ° C is then maintained for one hour at 60 ⁰ CV.

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The analysis is carried out with GLC and SE-30 as a stationary phase on chromosorb and 4, 4 '"- methylene to N * N-dimethylaniline as an internal standard for the determination of the dianion content *

Try N

Acid condensate mol A / F / S precondensate mol A / F

Total end product

Mol A / F / S mol A / F / S

2.2 "MDA mass"% not corrected

2.4 "MDA 4,4-MDA N-methyl _# MDA

Diamine mass% not corrected

Mole acid / mole FMA

TABLE I 1 2 " 88 1 23,2,1984 AP C 08 G / 255 913/4 63 026/12 3 0.88 4 0 , 88 > < 1 2 : 0.45: 3 $ 0.45: " 1: 0.45: » 1: 0.45: 0 , 88 3 : 0.9 O, 88 4 11 * 35 0 ^ 88 4: 1.80 0 , 88 1: 0.45 1 : 1V35: 30 1 : L, 80: 0.22 5: 2.25: 0 , 18 2: 0.90: 0 , 88 : 0.45: : 0.45: 1: 0.45: 1: 0.45: 0 , 44 0.12 0.24 0.35 O ₁ OS 6 | 48 6.74 7.8 4.1 93.0 92.6 91.5 95.5 0.40 0.42 0.35 0.35 71 70 69 72

0.66: 1

0.49: 1

0.40: 1

Try N

Acid condensate mol A / F / S Intermediate condensate "A / F / S

Total end product

Mol A / F / S mol A / F / S

2.2 · «MDA Mass% not corrected 2 * 4 · -« MDA ~ "« 4 * 4.V MDA «" «N-Methyl MDA **% m Diamine MDA« ""

Mole acid / mole FMA

TABLE II

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3: 1.35: 3 2: 0.98: 2 1: 0.45: 1 1: 0.45: 1

l! 0 _t 45i0 _# 0B 1: 0.45: 0.015 1: 0.45: 0.015 2: 0.9: 0.03

4: 1.80: 3 _# 015 3: 1.35ϊ2 _# 015 2 j 0.9: 1.015 1: 0.45: 0.75 l: 0.45i0 ₄ 67 1: 0.45: 0.50

0.15

4.95 94 _# 5

0 * 4 66 ^ 0

1.11: 1

0 A 0 A 2 , 0 3 i: -75 97 * 3 95  J " 0 * 6 0 ^ 55 71 .0 68 iO 1 66: 1 1 , 49 il

3: 1.35: 3 L, 03 L? 0.45 :( 3.34 0.30 5 ^ 95 93.5 0.25 63, 0

0,75sl

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Mole A / F / S TABLE III ! 3; 7 10 0.88 11 2.4 12 Try no * Mole A / F 9 ! -96V3 1: 0.45: 1: 0.45: 0.88 97.6 1: 0.45: 0.88 Acid condensate Mole A / F / S 1, 0.45: 0.88   0.5 1: 0.45 0.88 1: 0.45 0.5 1: 0.45 precondensate Mole A / F / S 1: 0.45 - 69.0 l: 0 _# 90: 0.44 1: 0.90: 0.88 57.8 1: 0.90: 0.88 total mol 2: 0.90: 0.88 31.0 Ii0,45: 1: 0.45: 0.44 42.2 1: 0.45: 0.44 Zwischenkonden eat Mole A / F / S 1: 0.45: 0.44 0.05 0.44 0.10 Final addition FMA 1: 0.50; 1: 0.55: 0.44 1: 0 ^ 60: 0.44; end product 1: 0.45: 0.44 mm 2,2-MDA mass% <» 3.1 2.2 2.4 "MDA 96.9 98.1 4.4 "MDA 0.5 0.5 N-methyl _# MDA (3-grain and above) 65.2 50.0 Diatnin mass **% 34.8 50.0 Polyamine Mas8e «%

Try Hr \

Acidic condensate moles A / F / S VorkondenSiit Mol A / F

Total moles A / F / S

Zwischenkondansät Mol A / F / S residual addition FMA Mol

end product

Mole A / F / S

2.2 ~ MDA Maase% not corrected

Diamin Massa ->% not corrected Polyamine Maeae «% (3-core and higher)

TABLE IV 1 14 ο " ο * 90 1 23, AP 63 2,1984 C 08 G / 255 026/12 1 913/4 13 5 : 0.45: 5 15 5 16 1: 0.45: 0 90 6 ί2-25 2 / 70i0, 0 90 6 : 0.45: 0.90 6 : 0/45: 0.90 5: 2.25 - 1 : 0.45: 15 1 : 2.25 1 : 2.25 - 6ί2 / 70ι0 »90 0 * 05 ί2,70: 0.90 : 2, 70 ^ 90 1: 0.45: 0 15 1 0.50: 15 1 : 0.45: 0/15 1 : 0/45: 0.15 0.5 0/10 0.15 1: 0.45: 0 15 6.1 : 0/55: 0.15 : 0 »60: 0; 15 ι 0.5 91/9 0.5 0/5 8.6 0.5 7.3 7.1 91.4 62/7 92.7 92.8 0 "5 37.3 0/5 0/5 68.3 56/1 52,: ο 7.31 43.9 48

Claims (9)

Process for the preparation of geraniums from methylenedianiline and polyethylenethene-polyphenylenepolyamines by condensation of aniline and formaldehyde in the presence of an acid catalyst having a controllable content of 2,4-.mu.-methylenedianiline in the binuclear and controllable content of methylenedianiline in the total mixture and / or reduced amount of acid catalyst characterized in that one carries out the conversion of at least two streams: a, a part of formaldehyde and aniline in the presence of optionally total acid catalyst to acid condensate * consisting essentially of aminobenzylamine and / or methylene dianiline and oligomeric polymethylene polyphenylene polyamines » b "the remaining aniline and a part or all of the remaining formaldehyde either non-catalytically converts to so-called precondensate % optionally the formaldehyde and water of reaction and optionally rearranges with the rest of the acid catalyst, some or all of the acidic condensate to the intermediate condensate or catalytically directly to the intermediate condensate in the presence of weak acids, carbonic acid, acidic ion exchangers, solid catalysts * salts * strong acids with short residence time err thermally at temperatures of over 100 C u. # # converts and 02/23/1934 AP C 08 G / 255 913/4 - 23 - 63 026/12 c * the acid condensate and precondensate or the intermediate condensate optionally mixed together and, if appropriate, after the addition of residual formaldehyde, if appropriate, converted in several stages to methylenedianiline and oligomeric polymethylene-polyphenylene polyamines and worked up according to the prior art * 2 "Process according to item 1, characterized in that the different molar ratios of aniline to formaldehyde are used in the streams, 3 * Procedure according to one of items 1 and 2:,; characterized by the fact that the molar ratio between acid condensate and precondensate is from 0.001: 25 to 10: 0.1. 4 * Method according to one of the items 1 and 2> characterized in that the molar ratio between acidic condensate and intermediate condensate O ₁₅ OOl: 25 to 10: 0.1 » 5 # Method according to one of the items 1, 2 and 4> characterized in that the precondensate is rearranged to intermediate condensate with O ₁₁ OOl to 0 * 3 mol of acid catalyst or * salt solution * Method according to one of the items 1 to 4, characterized in that the rearrangement of the precondensate to the intermediate condensate is carried out with Oj ₁ OOl to 0 * 5 »preferably 0.01 to 0.1 mol of acidic condensate * 7, method according to one of the items 1 to 6, characterized 23 * 2.1984 AP C 08 G / 255 913/4 -? _ / - / - 63 026/12 in that the addition of residual formaldehyde is alternately added with precondensate in several parts * 8 "Process according to one of the items 1 to 7> characterized in that the residual aldehyde addition is carried out at temperatures below 60 ° C.» 9 * Procedure according to one of the items 1 to 8>. characterized in that the reaction is carried out in total up to four stages »wherein the Reaktionstetnperatur in the first stage 20 to 60 ⁰ C, in the second stage 50 to 70 ⁰ C ,. in the third stage 60 to 90 ⁰ C and in the fourth stage 90 to 125 ⁰ C and the residence time in each stage of O ₁ ,! up to 2 hours,