DD258615A5 - METHOD FOR PRODUCING POLYAMINES - Google Patents

Abstract

The invention relates to a simplified one-step process for the preparation of polyamines having aromatic and / or aliphatic, primary amino groups, by hydrolysis of terminal isocyanate-containing compounds having an NCO content of 0.5 to 40 wt .-% with 0.75 to 50 moles of water per equivalent of NCO groups, in the presence of only very small amounts of basic and / or metal catalysts and presence of carboxylic acid amide solvant, preferably dimethylformamide, in preferably homogeneous solution at room temperature or elevated temperatures. As isocyanate-containing compounds, modified (preferred urethane-modified) polyisocyanates or, in particular, prepolymers are used. The hydrolysis results in elimination of carbon dioxide directly to the polyamines, which can be separated or isolated by conventional methods, wherein preferably can be dispensed with the separation of the small amounts of catalyst.

Description

hydrolyzed at temperatures of 35 to 165 ⁰ C.

7. The method according to claim 1, characterized in that the NCO component a) without catalyst c)

at a water / NCO ratio of 1 to 25 moles water / equivalent NCO and a carboxylic acid dialkylamide / water (preferably dimethylformamide / water) weight ratio of> 10 to 75, preferably> 25 to 50, at temperatures of 35 to 165 ⁰ C. , optionally under pressure, hydrolyzed.

8. Process according to Claims 1 to 7, characterized in that as NCO component a) NCO prepolymers having an NCO content of 1.5 to 10 wt .-% or urethane-modified polyisocyanates having an NCO content of 1.5 to 20.5% by weight, preferably 5 to 20.5% by weight.

Field of application of the invention.

The invention relates to a process for the preparation of polyamines having primary amino groups by hydrolysis of NCO-containing compounds in water-containing media, optionally with the addition of basic and / or metal catalysts.

The invention also relates to the use of the polyamines according to the invention for the preparation of polyurethane (urea) s.

The polyurethane (urea) s can be used for the production of elastomers, coatings, threads. They can also be used as a coupling component for diazo dyes and as a curing agent for epoxy and phenolic resins.

Characteristic of the known state of the art

It is known that aromatic isocyanates can be converted by acid hydrolysis into primary aromatic amines. However, the reaction is only very incomplete, since the amine formed in the hydrolysis reacts with unreacted isocyanate to the corresponding urea. This subsequent reaction can not be suppressed by using excess strong mineral acid. An example of this procedure can be found in JP-PS 55007829. Likewise, it is known that isocyanates can be converted by acidic or basic catalysis in amines, such as. In NV Sidgwick, The Organic Chemistry of Nitrogen, Clarendon Press, Oxford, p. 326 (1966) and in J. March, Advanced Organic Chemistry: Reactions, Mechanism and Structure, McGraw-Hill Book Co., New York, p 658 (1968). Here, Sidgwick gives an indication of the alkaline hydrolyzability of NCO groups, which, however, is completely unspecific and general. J. March speaks generally that the hydrolysis of isocyanates and isothiocyanantes can be catalyzed to amines with acids and bases. The skilled person is also the intermediary occurrence of isocyanates, ζ. Β. the so-called Curtius degradation or Lossen degradation of acid azides and hydroxamic acids and their decomposition with aqueous acid to amine salts known. Such a preparative procedure is e.g. in Organic Synthesis, Coil. Full. IV, 819 (1963) using the example of the preparation of putrescine hydrochloride.

E.Mohr, J. prakt. Chem., 71, 133 (1905), reports the observation that phenyl isocyanate is attacked more quickly by dilute sodium hydroxide than by water. C. Naegeli et al., HeIv. Chim. Acta, 21,1100 (1938) reported that from phenyl acceptors substituted by electron acceptors such as nitro groups, halogen atoms or acyl groups by hydrolysis in wet ether or acetone containing 1% water, ie in the absence of acids or bases, in a few minutes to 1 hour during the reaction receives the corresponding monoamines. From 2,4-dinitrophenyl isocyanate, the corresponding amine is also obtained without solvent in hot water in virtually 100% yield and without side reaction by urea formation.

DE-B 1270046 describes a process for the preparation of defined, primary aromatic amines containing polyalkylene glycol ether segments, in which reaction products of aromatic di- or triisocyanates with polyalkylene glycol ethers and / or polyalkylene glycol thioethers, preferably those with molecular weights between 400 and 4000, with secondary or tertiary carbinols and then subjected (optionally in the presence of acidic catalysts) in an inert solvent to a thermal decomposition at high temperatures. The disadvantage is that in addition to the high gap temperature in the course of thermal cleavage of the urethanes flammable, volatile alkenes are formed, which are explosive when mixed with air, so that appropriate precautions must be taken. The subject of DE-B 1 694152 (US Pat. No. 3,525,871) is the preparation of prepolymers containing at least 2 terminal amino groups by reacting hydrazine, aminophenylethylamine or other diamines with an NCO prepolymer of a polyether polyol and polyisocyanate (NCO: NH ratio = 1: 1) , 5 to 1: 5). Unreacted amine must be carefully removed in a further step, as it strongly catalyzes the reaction with polyisocyanates, so leads to short processing times and even occurs as a reactant. A similar process is described in US Pat. No. 3,931,116.

Another synthetic option for urethanes containing polyamines is described in FR-PS 1415317.

Urethane group-containing NCO prepolymers are converted with formic acid into the N-formyl derivatives, which are saponified to form terminal aromatic amines. The reaction of NCO prepolymers with sulfamic acid according to DE-PS 1155907 leads to compounds having terminal amino groups. Furthermore, higher molecular weight, aliphatic, secondary and primary amino groups having Voradukkte according to DE-B 1215373 obtained by reacting higher molecular weight hydroxyl compounds with ammonia in the presence of catalysts under pressure at high temperatures or are according to US Patent 3044989 by reacting higher molecular weight polyhydroxy compounds with aryl nitrile followed by catalytic Hydrogenation accessible. Also by reaction of NCO prepolymers with hydroxyl-containing enamines, aldimines or ketimines and subsequent hydrolysis obtained in accordance with DE-A 2546536 or US-PS 3865791 higher molecular weight, terminal amino groups and urethane-containing compounds. Another possibility for synthesizing urethane and ether-containing aromatic polyamines lies in the ring opening occurring in the reaction of isatoic anhydride and diols. Such polyamines are e.g. described in US-PS 4180644 and DE-A 2019432,2619840,2648774 and 2648825. A disadvantage for many purposes is the low reactivity of the thus obtained, aromatic ester amines.

Low reactivity are also the amino and ester group-containing compounds which are obtainable according to US Patent 4504648 by reacting polyether polyols with p-aminobenzoic acid and EP 32547 by reacting Poiyolen with nitrobenzoic and subsequent reaction of the nitro groups to amino groups.

The reaction of nitroaryl isocyanates with polyols and subsequent reduction of the nitro group to aromatic amine groups is also known (US Pat. No. 2,888,439).

The disadvantage here is mainly the high cost of the reduction step.

It is also known that certain heteroaromatic isocyanic acid esters can be converted to heteroaromatic amines by basic hydrolysis. The H.John, J. Prakt. Chemistry 130, 314ff. or 332ff. (1931) for two very specific, heteroaromatic Monoisocyansäureester said hydrolysis but are not only completely unsuitable for the conversion of poly-NCO compounds in aliphatic and / or aromatic amines, but beyond dangerous.

The subject of further proposals according to DE-A 2948419 and 3039600 are multistep processes for the preparation of polyamines by hydrolysis of NCO pre-adducts, wherein the NCO groups of the pre-adducts react in the presence of an excess of bases (alkali hydroxides) at low temperatures to carbamates obtained by acidification with equivalent or excess Decomposed amounts of mineral acids or acidic ion exchange resins and optionally after neutralization of excess amounts of acid by means of bases the polyamines are isolated.

In DE-OS 3131 252 it has been proposed to decompose the carbamates produced in a first stage by hydrolysis with alkali metal hydroxides by subsequent thermal treatment so as to obtain polyamines.

One-stage processes are described in DE-OS 3223400 / EP-97299, DE-OS 3223398 / EP-97,298 and DE-OS 3223397 / EP-97290.

According to this one-step hydrolysis process, (in DE-OS 3223400) "ether solvents" are combined as intermediates amines (in DE-OS 3223398) polar solvents such as dimethylformamide together with tertiary amines or larger amounts of alkali metal hydroxides, alkali metal silicates, alkali metal cyanides as catalysts in certain Or (in DE-OS 3223397) carbonates or carboxylates in certain amounts as catalysts in polar solvents such as DMF used.

The processes described herein for the preparation of polyamines are all more or less expensive. Even with the last-mentioned one-step process, further important simplifications are desirable in order to obtain the polyamines in an even more economical manner, in even better conversion rates of NCO / NH ₂ (ie higher NH ₂ numbers) and in an even smoother reaction. Compared to conventional methods, the following advantageous method features should be achieved, such as

no filtration is necessary

that no distillative separation of a tertiary amine catalyst is necessary,

that a drastic reduction of the necessary amount of catalyst is achieved, so that the catalyst can remain in the polyamine. This concerns both the reduction of the amount of tertiary amines (according to DE-OS 3223398) as well as the inorganic, alkaline compounds such as KOH, which are used as catalysts.

In addition, it should be achieved that the most quantitative possible conversion of NCO.in NH ₂ groups (high conversion rate NCO / NH ₂ , ie as high as possible, the theoretical value coming close amine number), that no by-products incurred, which must be disposed of, and

that a simple workup of the polyamines or auxiliaries is possible.

Object of the invention

The aim of the invention is to provide an improved, in particular simple and economical one-step process for the preparation of polyamines.

Explanation of the essence of the invention

The invention has for its object to find suitable reaction conditions and in particular to carry out the hydrolysis under mild conditions.

According to the present invention, there is provided a one-step process for the preparation of polyamines having primary amino groups, preferably aromatic amino groups, by hydrolysis of terminal isocyanate-containing compounds having an NCO content of from 5 to 40% by weight with from 0.75 to 50 moles of water per equivalent of NCO groups optionally in the presence of at most 1 wt .-% of a non-incorporable basic and / or metal catalysts in carboxylic acid amides as organic solvents, preferably in dimethylformamide, at certain weight ratios of water to carboxylic acid amides, water to NCO content and carboxylic acid amides to NCO compound , in preferably

homogeneous solution at least 20 ° C. As compounds having isocyanate groups, modified (preferably urethane-modified) polyisocyanates or, in particular, NCO prepolymers are used. The hydrolysis according to the invention leads, with elimination of carbon dioxide, directly to the polyamines, which can be isolated by customary methods, it preferably being possible to dispense with the separation of the small quantities of catalyst.

Quite surprisingly, it has been found that these and other advantages can be achieved when the one-step hydrolysis of polyisocyanates to polyamines

while maintaining certain water / NCO ratios

and certain solvent / water weight ratio,

is carried out using water-soluble carboxylic acid amides or lactams as solvent, or using at most minimal (<1 wt .-%) amounts of catalyst and while maintaining homogeneous solution conditions. Under these conditions, it is even possible to carry out the hydrolysis at low temperatures.

According to the method of the invention, water-soluble, organic solvents such as carboxylic acid amides are preferably used Carbonsäuredialkylamide or lactams to achieve a homogeneous solution of all reactants and the catalyst. Particularly suitable solvents are dimethylformamide and dimethylacetamide, particularly preferably dimethylformamide is used.

It is known from DE-AS 1235499, solutions of NCO prepolymers in dimethylformamide with about equivalent amounts of water (80 to 120% derTheorie, where 100% of theory here corresponds to V2 moles of water per NCO, ie, water acts here with 2 hydroxyl Equivalents) with chain extension via urea groups in highly viscous solutions which are suitable for the spinning of spandex threads or for coatings. The unsubstantiated reaction of the NCO compounds with excess amounts of water to form low molecular weight amines in high yields was surprising, in particular because the hydrolysis also takes place in the presence of NCO reactions with the catalysts which accelerate the forming reaction products.

It is also known that isocyanates react with dialkylformamides to formamidines (H. Ulrich et al., J. Org. Chem. 33, 3928-3930 [1968] and literature cited therein). Also, this reaction does not interfere with the smooth hydrolysis reaction to the polyamines by the process of the present invention.

A significant advantage of the process according to the invention is seen in the fact that, when using a catalyst, the amount is so low that catalyst or reaction products of the CO _{2 formed} with the catalysts (such as, for example, KHCO ₃ and K ₂ CO ₃ ) do not have to be filtered off ,

Since all usable catalysts are readily soluble in the reaction medium, there are no distribution imbalances as in the use of rapidly sedimenting alkali metal carbonates or bicarbonates, which may be present according to DE-OS 3223297. Since they remain in solution or are fully miscible, they also do not have to be filtered off.

The remaining catalysts in the final product usually interfere because of the very small amounts, as they are preferably used, not. Since no salts or catalyst residues have to be removed after workup, this method is also particularly suitable for the preparation of highly viscous or solid amino-containing compounds from which previously undissolved, residual salt or catalyst material could be removed only with great difficulty.

The hydrolysis according to the invention is also particularly suitable for the hydrolysis of NCO prepolymers based on polyesters, since the gentle reaction conditions hardly lead to cleavage of the ester groups.

Of all hitherto known hydrolysis processes in which aminopolyesters are obtained by basic hydrolysis of the corresponding NCO precursors, the process according to the invention therefore represents the gentlest method.

The invention relates to a one-step process for the preparation of polyamines having primary amino groups by hydrolysis of NCO-containing compounds in water-containing media, optionally with the addition of basic and / or metal catalysts, which is characterized in that

a) NCO groups, preferably aroamtisch bound NCO groups, having compounds having an NCO content of 0.5 to 40 wt .-%, preferably NCO prepolymers to an NCO content of 1.2 to 25 wt .-% , or modified polyisocyanates having an NCO content of 1.5 to 20.5% by weight,

b) from 0.75 to 50, preferably from 1 to 35, especially from 1.25 to 12, and particularly preferably from 1.5 to 7.5, moles of water per equivalent of NCO of component a),

c) in the presence of 0 to 1 wt .-%, preferably 0.00005 to 1 wt .-% of non-incorporable basic and / or metal catalysts, based on 100 wt .-% of component a), particularly preferably 0.0001 bis 0.099% by weight of unincorporatable basic catalysts,

d) and in the presence of> 10% by weight, based on 100% by weight of component a) of carboxamides, preferably of carboxylic acid dialkylamides as solvent, particularly preferably dimethylformamide or dimethylacetamide,

e) and optionally in the presence of from 0.1 to 5% by weight, based on 100% by weight of component a), of a compound having at least one hydroxyl and / or amino and / or amino radical bound to aliphatic, cycloaliphatic or aromatic radicals and / or or thiol group,

f) a solvent (d) / water weight ratio of 3 to 200, preferably 5 to 150, particularly preferably> 10 to 100 and in particular> 25 to 75,

g) and a homogeneous reaction phase are maintained,

at a temperature of 20 and 21O ⁰ C, preferably 35-165 ⁰ C, in particular 40 to 150 ⁰ C, particularly preferably 80 to 130 ⁰ C, hydrolyzed.

In a preferred embodiment of the process according to the invention, component a) is reacted in the presence of non-incorporable, d. H. have no reactive groups with NCO groups, catalysts such as ca) 0.0001 to 0.099, preferably 0.002 to 0.08Gew .-%, based on 100Gew .-% of component a), alkali hydroxides, alkaline earth hydroxides, tetraalkylammonium hydroxides, alkali aluminates, alkali metal phenolates, alkali thiophenolates, alkali mercaptides, alkali hydrogen sulfides, soluble alkali and alkaline earth salts of (lso) (thio) cyanic acids and alkali ß-diketone enolates and / or

css) 0.0001 to 0.099, preferably 0.002 to 0.08% by weight, based on 100% by weight of component a), of carbonates or bicarbonates of alkali metals

and or

cy) 0.0001 to 0.099, preferably 0.0001 to 0.0099, particularly preferably 0.0002 to 0.008 wt .-% of alkali and alkaline earth metal salts of organic carboxylic acids

as basic catalysts c) hydrolyzed.

A further preferred embodiment of the process according to the invention is characterized in that the NCO component a)

b) 1.25 to 12, preferably 1.5 to 7.5 moles of water per NCO equivalent

c) with the concomitant use of the basic catalysts ca), cß) and / or C7) in the amounts mentioned

d) while maintaining a carboxylic acid dialkylamide (preferably dimethylformamide) / water weight ratio of> 10 to 150, preferably 25 to 75,

at temperatures of 35 to 165 ⁰ C, preferably 80 to 130 ° C hydrolyzed.

Another embodiment of the process according to the invention is characterized in that the NCO component a) in the presence of

c5) 0.0001 to 0.99 wt .-%, preferably 0.001 to 0.099Gew .-% of a tertiary amine compounds, based on 100Gew .-% of component a), while maintaining a water / NCO ratio of 1 to 7.5 Mol of water per equivalent of NCO and a dialkylcarboxamide / water (preferably dimethylformamide / water) weight ratio of> 10 to 150, preferably> 25 to 75, hydrolyzed at a temperature of 35 to 165 ⁰ C.

In particular, the process according to the invention is carried out by reacting 0.0001 to 0.099% by weight of tertiary amine compounds while maintaining a water / NCO ratio of 1 to 24 moles of water per equivalent of NCO and of a dialkylcarboxamide / water (preferably dimethylformamide / Water) weight ratio of> 10 to 50 at a temperature of 35 to 165 ⁰ C hydrolyzed.

A further embodiment of the process according to the invention is characterized in that the NCO component a) ce) in the presence of 0.0001 to 0.0099, preferably 0.002 to 0.008% by weight, based on 100% of the component a) of metal catalysts, with preferably 1.5 to 7.5 moles of water per NCO equivalent and with simultaneous maintenance of a carboxylic acid dialkylamide / water (preferably dimethylformamide / water) weight ratio of> 10 to 50, preferably & 25 to 50, at temperatures of a 35 to 165 ⁰ C hydrolyzed.

A further embodiment of the process according to the invention is characterized in that the NCO component a) without catalyst c) at a water / NCO ratio of 1 to 25 moles of water per AquivalenrNCO and a carboxylic acid dialkylamide / water (preferably dimethylformamide / water) weight ratio from> 10 to 50, preferably 25 to 50, at temperatures of 35 to 165 ° C, optionally under pressure, hydrolyzed. It is preferred that in the various embodiments of the process as NCO component a) NCO prepolymers having an NCO content of 1.5 to 10 wt .-% or modified polyisocyanates, in particular urethane-modified polyisocyanates having an NCO content of 1.5 to 20.5 wt .-%, in particular 5 to 20.5 wt .-% is preferably used. It is also possible to use neutral salts in the hydrolysis during the hydrolysis. According to the invention, 1 to 35, in particular 1.25 to 12 equivalents of water per equivalent of NCO in the NCO component a) are furthermore preferably used.

Dimethylformamide in amounts of 100 to 1000% by weight, based on 100% by weight of NCO component a), is preferably used as component d).

The hydrolysis is preferably carried out at temperatures of 40 to 150, more preferably at 80 to 130 ⁰ C and preferably without pressure. As the solid concentration of the hydrolysis batch, a concentration of from 20 to 75% by weight, preferably from 25 to 60% by weight, in particular from 30 to 55% by weight, is generally selected. Although even lower solids concentrations are likewise possible, they are not preferred for practical reasons (reprocessing of the solvents d)). In particular, NCO prepolymers having a content of from 0.5 to 40, preferably from 1.2 to 25, particularly preferably from 1.5 to 10,% by weight of aromatically bonded NCO groups based on relatively high molecular weight, are used as component a). or polyfunctional polyether, polyester, polycaprolactone and polycarbonate polyols and diisocyanates used or with low molecular weight diols or polyols (molecular weight to 399) modified di- or polyisocyanates with 1.5 to 20.5Gew .-%, preferably 5 to 20.5Gew .-% NCO, used.

The invention also relates to the polyamines obtained by the process according to the invention, preferably those which have from 0.46 to 9.52% by weight of primary, preferably aromatically bound, NH ₂ groups.

Another object of the invention are also processes for the preparation of optionally cellular polyurethane (urea) s by reacting the inventively obtained polyamines A, with

B) polyisocyanates and optionally

C) further compounds with isocyanate-reactive groups, if appropriate

D) in the presence of known auxiliaries and additives and / or solvents.

According to the invention may optionally minor amounts of 0.1 to 5Gew .-% of a compound e), based on 100Gew .-% component a), with at least one attached to aliphatic, cycloaliphatic or aromatic radicals hydroxy and / or amino and / or Thiol groups are used. The concomitant use of these compounds containing "Η-active groups" leads to the following advantages: NCO compounds containing low molecular weight polyisocyanates, for example NCO semiprepolymers, can be prepared without treatment of the NCO compounds by thin layers or similar processes, polyamines which are practically It is thus possible in a simple manner and without further reaction step also to produce modified polyamines which additionally have urethane groups, thiourethane groups or urea groups linked polyamine segments, optionally of different types, in one molecule.

From a z. B. difunctional NCO compound can be obtained by using a trifunctional or higher functional, "H-active groups" possessing compound in the NCO hydrolysis so a tri- or higher polyamine functional The two or more, aromatic, heterocyclic and / or aliphatic, preferably aromatic, NCO-containing NCO-containing compounds which can be used in the process according to the invention a) (hereinafter also referred to as "NCO compounds" for short) are either modified polyisocyanates, as formed by partial conversion of the isocyanate groups into urethane, Urea, biuret, uretdione, isocyanurate and / or uretonimine groups are formed.

or are so-called NCO prepolymers from NCO group-reactive Η-group-carrying, polyhydric compounds of molecular weight 62 to 12,000, preferably 400 to 6000, and (excess) amounts of aromatic polyisocyanates or are optionally (less preferably) semiprepolymers of NCO prepolymers and additional low molecular weight polyisocyanates.

Suitable modified aromatic polyisocyanates are, for example:

Polyisocyanates containing urethane groups (formed by modification with low molecular weight polyols), polyisocyanates containing urea groups (for example by water modification, DE-PS 1 230778), polyisocyanates containing biuret groups (US Pat. No. 3,124,605,320,173, British Patent No. 889050), polyisocyanates containing isocyanurate groups (DE-PS '1 022789 and 1 222067) and dimeric or oligomeric polyisocyanates containing uretdione or uretonimine groups. These are known compounds or accessible by known methods. A number of such uretdione polyisocyanates are listed in Analytical Chemistry of the Polyurethanes, Volume 16/111, High Polymers-Series (Wiley 1969). Such modified polyisocyanates with urethane and / or urea and / or biuret and / or uretdione and / or isocyanurate and / or uretonimine groups, as can be used in the process according to the invention, usually have an NCO content of 1, 5 to 20.5% by weight, preferably 5 to 20.5% by weight. Particularly preferred are urethane-containing polyisocyanates, (by modifying with low molecular weight [molecular weights 62 to 399]) di- and / or polyols), with NCO contents of> 1.5 to 20.5Gew .-%, preferably 5 to 20.5 wt .-%.

However, the NCO compounds a) to be used in the process according to the invention are especially NCO prepolymers, as are known per se by reaction of low molecular weight and / or higher molecular weight hydroxy and / or amino and / or thiol groups as reactive group-containing compounds (molecular weight 62 to approx 12000) with an excess of polyisocyanates.

Suitable polyisocyanates for the preparation of the compounds having free NCO groups are in principle any, aromatic, aliphatic and heterocyclic di- and polyisocyanates in question, as z. B. von W. Siefken in Justus Liebigs Annalen der Chemie, 562, pp. 75-136, (1949), or as they are, together with suitable for these reactions, low molecular weight and / or higher molecular weight hydroxy and / or amino and / or thiol groups containing reactive group-containing compounds of the MG range 32 and 60-12000, on p 12-23 of DE ÖS 3223397, or in the prior art are known. For the process according to the invention, NCO prepolymers are preferred which are composed of relatively high molecular weight polyols (molecular weight 400-12,000), preferably polyether polyols, optionally with the use of chain extenders of the type described above (molecular weight 62-399), by reaction with aromatic diisocyanates in an equivalent ratio of 1: 1.5 to 1: 2.8, in particular about 1: 1.5 to 1: 2, have been obtained.

The NCO content of the (preferably urethane group-free) NCO prepolymers used should be 0.5% to 40% by weight, preferably 1.2 to 25% by weight, but in particular 1.5 to 10% by weight for functionalities of 2 to 8, preferably 2 to 4 and in particular 2 to 3.

In the process according to the invention, however, it is also possible to use so-called "semiprepolymers", ie mixtures of NCO prepolymers or modified polyisocyanates with further free polyisocyanates, as water, preferably in liquid form, as component b), in order to achieve adequate conversion of the NCO groups In NH ₂ groups, at least one equivalent of water per equivalent of NCO must be used (this is understood to mean 1 mol of water per equivalent of NCO for the present reaction).

If significantly less than 1 mol (in particular <0.75 mol) of water is used, preference is given to pre-extension to form urea. On the other hand, it has surprisingly been found that the use of a very large excess of water also leads to higher, unwanted Vorverlängerungsanteilen. This also applies if the reaction mixture is single-phase. It has been found that the optimum amount of water must also be oriented, inter alia, to the amount of solvent used, not only to the amount of NCO groups to be converted: relative to 1 equivalent of NCO,> 0.75 mol of water, preferably> 0, 75-50 moles of water, more preferably 1-35 moles of water, most preferably 1.25-12 moles of water, using, for example, a bifunctional NCO prepolymer with T 100 = 2,4-tolylene diisocyanate of the NCO content 3.6% by weight. This results in an NCO equivalent weight of about 1167. That is, to about 1167g of this prepolymer should> 13.5 g of water, preferably 13.5-90Og, more preferably 18-63Og, most preferably 22.5-216g Water can be used.

However, according to the invention, certain weight ratios of solvent d) to water must be maintained at the same time as the claimed water / NCO ratio. These weight ratios range from 3: 1 to 200: 1, but are preferably from 5: 1 to 150: 1, especially> 10: 1 to 100: 1, and most preferably optimally> 25: 1 to 75: 1.

That is, based on e.g. 1 000 g of solvent d) (preferably dimethylformamide) water in amounts of 5 to 333 g is used.

It has been shown that - while maintaining the other conditions according to the invention - in particular a relatively high content of solvent d) in the solvent / water mixture (in particular dimethylformamide / water mixture) leads to a particularly favorable NCO / NH 2 conversion rate and that then the amount of catalyst to be used can be minimal.

Considering the necessary, absolute amount of water and the more favorable solvent / water ratio, the solvent is such that> 10 parts by weight, preferably> 100 parts and more preferably up to 10 parts by weight of solvent d) per 10 parts by weight of the NCO Component can be used. It has been shown that the minimum amount of solvent necessary to achieve complete NCO / NH ₂ conversions depends on the reaction temperature. The higher the reaction temperature, the lower the amount of solvent d) can be maintained. The necessary amount of water (relative to NCO) remains largely unaffected.

Optionally, in order to determine the optimum ratio of NCO equivalents, water and solvent d) for a particular NCO component c), a few experiments may be carried out within the given general scope.

As component c) basic, no NCO-reactive groups-containing and / or metal catalysts can be used. As such, those compounds are considered which are capable of raising the product NH of the amines as obtained without the use of catalysts.

The catalysts used may be solid or liquid but must have sufficient, preferably complete, solubility in the reaction mixture. Based on 100% by weight of the isocyanate component, they are generally used at 0.00005-1% by weight. For the individual catalyst types, different, preferred quantitative ranges apply, as listed in the claims and in the description. The amount of catalyst required is also dependent on the solvent / water ratio. With a determined optimum solvent / water ratio, the catalyst requirement is the lowest, but still a surprisingly small amount of catalyst is needed to achieve the highest possible NCO / NH ₂ conversion rates. By an increased amount of catalyst, on the other hand, a not completely optimized water / solvent ratio can also bring good results. The amount of catalyst necessary for complete conversion of NCO to NH ₂ groups is also dependent on the reaction temperature. It was found that this amount at low temperature, z. B. 45 ⁰ C, should be chosen appropriately higher than at higher reaction temperature, for. At 100 ° C. For a given amount of catalyst and incomplete amine yield, these can be increased by increasing the reaction temperature

 As catalysts c) can be used:

1. Basic, non-NCO-reactive groups containing inorganic and organic salts and preferably hydroxides.

As such, salts of strong organic or inorganic bases with weak inorganic or organic acids which give an alkaline reaction in water are considered. In particular:

Hydroxides of alkali and alkaline earth metals and tetraalkylammonium, in particular NaOH and KOH, further soluble aluminates such. B. Na-aluminate,

Carbonates of alkali metals, in particular soda and potash,

Hydrogen carbonates of alkali metals, in particular sodium and potassium bicarbonate, alkali metal and alkaline earth metal salts of mono- and polycarboxylic acids containing no NCO-reactive groups, preferably salts of aliphatic monocarboxylic acids having up to 18C atoms, for. Sodium formate, sodium acetate, potassium octoate or potassium stearate.

Alkali salts of optionally substituted with non-NCO-reactive groups phenols and thiophenols, soluble alkali and alkaline earth salts weak, preferably inorganic acids such as cyanic acid, isocyanic acid, thiocyanic acid, isothiocyanic acid, silicic acid, phosphorus-bis-V-acids, hydrocyanic acid, hydrazoic acid, etc. , Alkali metal mercaptides and sulfides or hydrogen (poly) sulfides,

ß-diketone compounds such as the Na-, K-, Mg-acetylacetonate and acetoacetate.

2. Tertiary amines

As tertiary amines, preferably those aliphatic or cycloaliphatic structure are used, wherein mixtures of different tertiary amines can be used.

Examples are z. B. usually not completely water-soluble representatives such as the trialkylamines, z. B. trimethylamine, triethylamine, tripropylamine, triisopropylamine, dimethyl-n-propylamine, tri-n-butylamine, tri-isobutylamine, tri-iso-pentylamine, dimethylbutylamine, triamylamine, trioctylhexylamine, dodecyldimethylamine, dimethylcyclohexylamine, dibutylcyclohexylamine, dicyclohexylethylamine, tetramethyl-1, 3-butanediamine, but also tertiary amines with an araliphatic group such as dimethylbenzylamine, diethyl-benzylamine, a-methylbenzyl-dimethylamine.

Preference is given to trialkylamines having a total of 6 to 15C atoms in all alkyl radicals, for. As triethylamine to triamylamine or dimethylcyclohexylamine.

Highly suitable tertiary amines, in addition to the trialkylamines, are those amines which, in particular in the β-position to the tertiary group, have a further tertiary amino or an ether group. Examples are dialkylamino-alkyl ethers or bis-dialkylaminoalkyl ethers (US Pat. No. 3,330,782, DE-B 1030558), eg. Dimethyl (2-ethoxyethyl) amine, diethyl (2-methoxypropyl) amine, bis [2-dimethylaminoethyl] ether, bis [2-diethylaminoethyl] ether, bis [2-diethylaminoisopropyl] - ethers, 1-ethoxy-2-dimethylaminoethoxyethane, N-methylmorpholine, N-ethylmorpholine, N-butylmorpholine, furthermore permethylated polyalkylenediamines such as tetramethylethylenediamine, tetramethyl-1,2-propylenediamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine and higher permethylated homologs (DE-A 2624527 and -528), furthermore diethylaminoethylpiperidine, 1,4-diaza- (2,2,2) -bicyclooctane, N, N'-dimethylpiperazine, Ν, Ν'-diethylpiperazine, N-methyl -N'-dimethylaminoethylpiperazine, Ν, Ν'-bis-dimethylaminoethyl-piperazine, Ν, Ν'-bis-dimethylaminopropylpiperazine and other bis-dialkylaminoalkyl-piperazines cited in DE-A 2636787.

Preferred from this group are the water-soluble compounds such as tetramethylenediamine, permethylated diethylenetriamine, N-methylmorpholine, bis-2-dimethylaminoethyl ether and N-methylpiperidine.

Can also be used acylated tertiary amine derivatives, such as. B. i-dimethylamino-3-formylaminopropan, N- (2-DimethylaminoethyO-propionamide, N- (2-diethylaminoethyl) benzamide, and other amide groups (preferably formamide groups) containing tertiary amines according to DE-A 2523633 and 2732292.

Also active are tertiary amines of the pyridine type and tertiary amines having at least one aromatic radical attached to the N atom, ζ. B. dimethylaniline.

Insofar as it is not water-soluble tertiary amines, their boiling point should advantageously below 250 ⁰ C, preferably below 200 ⁰ C, are.

3. Metal catalysts

As compounds c) it is also possible to use the polyvalent metal compounds known from the literature for the catalysis of isocyanate chemistry in the process according to the invention. These are preferably compounds of tin, zinc or lead, for example dibutyltin dilaurate, tin octoate, zinc acetylacetonate or lead octoate; Overall, they are less preferred.

The catalysts to be used according to the invention are industrially readily available, inexpensive catalysts which may optionally be separated off and reused, but remain in the product in the preferred embodiment. If, for certain reasons, it is necessary to obtain a completely catalyst-free product, it is also possible to work without basic and / or metal catalyst if conditions a) to c), but especially also the optimum ratio of solvent d ) to water and at the same time the ratio of water to NCO is maintained, which can be determined in a preliminary experiment, and if at comparatively high temperatures within the below

-α- »ο σ is

said temperature ranges, ie preferably above 80-100 ⁰ C is worked. However, preference is always given to working in the presence of catalysts, preferably basic catalysts, even if extremely small amounts of catalysts are used.

As the solvent component d)

d 1) at least partially, preferably completely, water-miscible or water-soluble aromatic, aliphatic or cycloaliphatic carboxylic acid amides having 1-10C atoms in the acid moiety, such as dialkylamides or N-substituted lactams, e.g.

Dimethylformamide (DMF), formamide, diethylformamide, dimethylacetamide, dimethylpropionamide, Benzoesäuredimethylamid, N-methylpyrrolidone used. Preference is given to carboxylic acid dialkylamides, in particular dimethylformamide.

Component d) may contain up to 75% by weight of other aprotic dipolar solvents:

d2) water-soluble, tetraalkylated aliphatic ureas having 4 to 12 C atoms, ζ. Tetramethylurea or tetraethylurea,

d3) water-soluble, aliphatic or cycloaliphatic sulfones or sulfoxides of 2 to 10 carbon atoms, e.g.

Tetramethylsulfone or dimethylsulfoxide;

d4) water-soluble, aliphatic or cycloaliphatic phosphoric acid amides, e.g. Hexamethylphosphoramide.

The solvents d2) -d4) can also be used in any mixing ratios to each other. Among the solvents mentioned d2) -d 4), preferred are those which at atmospheric pressure from 56 to 250 ° C, preferably 64-165 ⁰ C, boil, since this simplifies the work-up.

Co-use of incompletely water-miscible solvents, e.g. Propionitrile, methyl ethyl ketone, ethyl acetate or hydrocarbons is possible in minor amounts, but not preferred. Preferably, solely and exclusively DMF is used as the solvent.

For the quantities (in particular the upper limits) of solvents to be used d) the following boundary conditions of the method apply:

1. Per 100% by weight of NCO compound a) should be used in the hydrolysis reaction mixture> 10, preferably 100-1000 wt .-% d).

2. It must be used as much water b) and optionally solvent d) that a substantially homogeneous (at most slightly turbid) or preferably a homogeneous, clear solution with the NCO compound is formed at the reaction temperatures; more preferably so much water that a single-phase mixture is formed at all process temperatures, but always in compliance with the above-mentioned about the ratio of solvent (DMF): water and that of water-NCO component a).

The catalytically active compounds are generally added to the solvents and water. The addition to the isocyanate group-containing compound is u. U. possible, but not preferred.

For hydrolysis of the NCO compound to polyamines having a sufficiently high amine number (holier conversion rate), it is advantageous to maintain a concentration of the NCO compound of> 75, preferably> 55 wt .-% in the reaction mixture.

A limit of the dilution results practically from the economy of both workup; In practice, it should be around 3% solution.

However, taking into account the abovementioned relationships between amounts of water, solvent and isocyanate, it is necessary to use at least as much solvent d) as possible to leave a substantially homogeneous, preferably complete, homogeneous reaction mixture.

In a further embodiment, it is also possible to admix "Η-active group-containing" compounds e) having two or more hydroxyl, amino and / or thiol groups to the reaction mixture, These compounds have already been mentioned as synthesis components of the NCO compounds which can be used in the process according to the invention. Particular preference is given to difunctional to optionally tetrafunctional compounds having a molecular weight of 62-2000, in particular those containing at least 2 primary hydroxyl groups, for example ethanediol, butanediol, propanediol, polyethylene glycols, trimethylolpropane or the like It is of course also possible to use compounds having different "Η-active groups". be used, for. B.

Aminoalkanols.

Compounds that have only one Η-active group, ζ. Β. Methanol, ethanol, cyclohexanol, cyclohexylamine, aniline, asymmetric dimethylhydrazine, can be used as monofunctional chain terminators.

As a side reaction in the process according to the invention, the pre-extension can occur, ie isocyanate and already formed amine react under chain linkage to ureas. This side reaction can be achieved by working in dilute solution, .the use of the catalysts of the invention c) and solvents d) and the maintenance of relatively high reaction temperatures, eg. B. 80 to 13O ⁰ C, largely suppress. Although the smallest possible extent of these side reactions is desired, but for economic reasons, a certain degree of Vorverlängerung can be accepted.

However, the method according to the invention allows, with sufficient attention to the process parameters, a virtually complete conversion of NCO into NH ₂ groups.

The reaction according to the invention is preferably carried out in a homogeneous phase. By slightly overdosing the amount of water or the amount of NCO compound may optionally temporarily be obtained a slight turbidity of the reaction mixture, since the starting materials are no longer completely dissolved.

However, a polyphase obtained by excess addition of water to precipitate the NCO prepolymer gives insufficient products. By means of a few preliminary experiments, the optimum mixing ratios dependent on the starting compounds can be determined in order to obtain homogeneous mixtures, taking into account the ratios between a), b), c) and d).

As already stated, the reaction can be carried out at temperatures of 20 to 210 ⁰ C. Preferably, however, at temperatures of 40 to 150 ⁰ C, in particular from 80 to 130 ⁰ C worked, since in this case the best space / time yields are achieved with high solubility and surprisingly least urea extension. In special circumstances, it may also be necessary to carry out the reaction under pressure in order to obtain sufficiently high temperatures.

The onset of the reaction can be recognized by the almost spontaneous elimination of CO ₂ , which is already at low temperatures, eg. B. 1O ⁰ C, is observable. However, it is much cheaper to work according to the invention at both higher temperatures indicated in order to suppress urea formation. It is important that a very good and rapid mixing is provided under homogeneous solution of the reactants, which must be ensured substantially by the use of solvents. In the same direction, the viscosity reduction acts when using the higher reaction temperature ranges. The reaction may be carried out batchwise or continuously.

For the continuous or discontinuous embodiment, the in DE OS 3 223 397, p. 32, Z. 20-S applies. 35, Z. 10 Revealed.

The workup can also be continuous or discontinuous. The workup of the reaction mixture is usually carried out by distillation, extractive or via a phase separation or a combination of these methods.

The extraction process, optionally after dilution with water, can be carried out with water-insoluble solvents, such as methylene chloride or chlorobenzene.

A phase separation of the reaction mixture by cooling occurs in some cases when the hydrolysis was carried out at relatively high temperatures and in the presence of relatively high water at the limit of solubility. The phase separation can be improved or even achieved by the addition of water. The aqueous, optionally solvent-containing and usually catalyst-containing phase is separated off from the polyamine phase.

The aqueous phase can then be reused mostly directly.

The polyamine phase contains in addition to the polyamine optionally residual amounts of the catalyst, optionally some water, and possibly solvent d), which are removed as completely as possible by distillation, optionally under application of a vacuum or by thin film distillation.

Contains the NCO group-containing compound - due to their production - still free, i. monomeric isocyanate, so u.U. the resulting monomeric amine in the workup by phase separation strongly accumulate in the water / solvent phase. The polyamine obtained by this simple workup is then virtually free of monomers. However, it may then be advisable to largely free the solvent phase by working up of monomeric amine before it is reused.

Preferred refurbishment:

Preferably, the work-up of the reaction mixture without phase separation is carried out so that after completion of the reaction (no more CO 2 evolution observed), the solvent or solvent / water mixture, preferably using vacuum, for. B. 1-700 torr, is distilled off, to remove volatile residues even higher vacuum, z. B. 0.001-1 torr, can be applied. A temperature range of initially about 60-100 ° C, later 80-100 ⁰ C, has proven itself here. The distilled off solvent can be reused, if necessary several times.

The polyamines obtained according to the invention after working up are generally colorless to pale-colored, medium-viscosity to highly viscous and optionally higher melting products with the amino groups already indicated. These polyamines also have according to their starting materials urethane and / or urea and / or uretdione and / or isocyanurate and / or biuret groups and / or uretonimine groups, and optionally ether and / or acetal and / or carbonate and / or ester and / or thioether and / or dialkylsiloxane groups and / or the radicals of polybutadienes, such as already existed in the NCO compounds. By side reactions, however, additional bonds can arise, for. B. urea groups from already saponified shares and remaining NCO groups during the hydrolysis reaction. The amount of the primary aromatic amino groups contained in the polyamines corresponds at most to the amount of NCO groups in the NCO compounds, that is about 0.19 to 15.23% by weight of NH ₂ (at 0.5 to 40% by weight of NCO). , preferably 0.46 to 9.52 wt .-% NH ₂ (at 1.2 to 25 wt .-% NCO) and particularly preferably 0.58 to 3.81 wt .-% NH ₂ (at 1.5 to 10Gew .-% NCO).

Because of their low vapor pressure, the preferably aromatic polyamines obtained according to the invention are preferably used as reactants for optionally blocked polyisocyanates in the preparation of polyurethanes (polyurethane ureas), optionally cell-containing polyurethane plastics or polyurethane foams, optionally also with other low molecular weight (molecular weight 32 to 399) and / or or higher molecular weight (molecular weight 400 to about 12000) compounds with isocyanate-reactive groups can be combined.

Suitable starting components for the production of polyurethane plastics known per se are described above in connection with the preparation of prepolymers or also in DE-A 2302564, DE-A 2432764 US-PS 3903679) and in DE-A 2639083.2512385,2513815,2550 796,2550797, 2550 833.2550 860 and 2550 862 called. There are also references to in the polyurethane production optionally used auxiliaries and additives.

A process for the preparation of polyurethane (ureas) using the polyamines obtained according to the invention is likewise provided by the present invention. Elastomers, coatings, threads in the application of melts, solutions, dispersions or reactive component mixtures are produced.

Further uses of the polyamines according to the invention are z. For example, coupling components for diazo dyes, curing agents for epoxies and phenolic resins, as well as all other known reactions of amines such as amide or imide formation and others.

embodiment

The following examples serve to illustrate the process according to the invention. Unless otherwise stated, quantities are to be understood as parts by weight or% by weight.

Examples

Example 1 (without basic catalyst)

In this example, an NCO prepolymer having an NCO content of 3.65% is used prepared by stirring a mixture of polypropylene glycol of OH number 56 and toluene-2,4-diisocyanate in equivalent ratio NCO: OH = 2 for 3 hours : 1 at 8O ⁰ C.

A mixture of 1750 ml of dimethylformamide (DMF) and 50 ml of water (DMF / H ₂ O = 33.2: 1) is introduced and heated to 90 ^° C. with stirring. Within 20 minutes at this temperature, 500 g of the above NCO prepolymer is added. After completion

the addition is stirred for 5 min (rapidly decaying CO ₂ evolution) and then distilled off by applying a vacuum (first 19.5mbar, then 0.13mbar at 80 to 100 ⁰ C) DMF and water

NH number (HCIO ₄ ): 31.1 mg KOH / g

Example 2 (use of a neutral electrolyte)

A mixture of 1750 ml of DMF, 50 ml of water and 1 g of sodium chloride is introduced. After carrying out the experiment and working up as in Example 1, an NH number (HCIO ₄ ) of 31.3 mg KOH / g is found.

As examples 1) and 2) show, with DMF / H ₂ O mixtures can be carried out hydrolysis with relatively good results, but the conversion rates without catalyst are considerably lower than with addition (even small) amounts of catalyst -vgl.

Example 9.

Example (Comparative Example)

(Use of an acid as a catalyst)

Is presented at 9O ⁰ C, a mixture of 1750ml DMF, 50 ml of water and 1 g of acetic acid. After carrying out the experiment and working up as in Example 1, a product having an NH number (HCIO ₄ ) of only 28.4 mg KOH / g is obtained.

Examples 4-6 (Comparative Example)

(Use of non-inventive solvents)

In these examples, an NCO prepolymer prepared identically to the prepolymer of Example 1 is used but having an NCO content of 3.3%.

At 9O ⁰ C or reflux temperature, a mixture of 1.751 acetone or 1.751 dioxane or 1.751 acetonitrile, 25 ml of water and 0.1 g of sodium hydroxide, carrying out the experiment and working up as in Example 1, is initially introduced with stirring.

NH numbers (HCIO ₄ )

when using

Acetone: 27.9 mg KOH / g

Dioxane: 6.85 mg KOH / g

Acetonitrile: 26.9 mg KOH / g

Despite the use of alkaline catalysts, only unsatisfactory conversion rates of NCO into NH _{2 are} achieved (ie low NH numbers).

Example 7 (comparative example)

(Use of a non-inventive solvent)

Is presented at 9O ⁰ C, a mixture of 1 750 ml of methyl ethyl ketone, 50 g of water and 0.2 g of sodium formate. Within 20 minutes, 500 g of the NCO prepolymer from Example 1 are added. After working up as in Example 1, a product with an NH number (HCIO ₄ ) VOn 31.5mg KOH / g is maintained. The OH number is significantly lower than when using solvents d) according to the invention.

Example 8 (Comparative Example)

Are introduced at reflux temperature 11 methyl ethyl ketone, 15.2 g of dimethylformamide, 30 ml of water and 1 g of sodium formate. 300 g of an NCO prepolymer from Example 1 are added within 20 minutes. After working up as in Example 1, a product having an NH number (HCIO ₄ ) of 23.9 mg KOH / g is obtained.

Examples 9-22

In these examples, the catalytic properties of caustic soda (NaOH) are presented.

Example 9

In this example, a prepolymer of the NCO content is 3.9%, prepared by stirring a mixture of tolylene-2,4-diisocyanate and a polyester of OH number 56 for 3 hours from adipic acid, ethylene glycol and butane-1,4-diol ( Mol ratio of ethylene glycol-butanediol = 7: 3) in NCO: OH ratio 2: 1.

A mixture of 5.51 DMF, 125 ml of water (DMF / water ratio = 41.7: 1, 2.9 moles of water per NCO equivalent) and 0.25 g of NaOH (0.01% by weight) is initially charged. , based on NCO prepolymer) and heated to 90 ⁰ C. Be within 45 min 2.5kg desauf 7O ⁰ C heated, Polyetherprepolymerszugegeben described above. Work-up as in Example 1.

NH number (HCIO ₄ ): 47.85 mg KOH / g

NH number (Ac ₂ O / Py): 47.9 mg KOH / g [Py = pyridine]

S number (Ac ₂ O / Py): 0.35 mg KOH / g [S number = acid number]

TDA content (HPLC): 0.921% [HPLC = High Pressure Liquid Chromatography]

DMF residual content (GC): 0.225% [GC = gas chromatography]

Example 10

Is submitted to a 90 ⁰ C hot mixture of 1.751 DMF, 0.08 g NaOH (0,016Gew .-%, based on NCO prepolymer), and 50 ml of water (DMF / H ₂ O ratio = 33.2: 1; 6.375 moles of water per NCO equivalent). Within 1 min, 500 g of the NCO prepolymer from Example 1 with 3.65% NCO are added. Work-up as in Example 1.

NH number (HCIO ₄ ): 44.8 mg KOH / g

NH number (Ac ₂ O / Py): 46.4 mg KOH / g

S number (Ac ₂ O / Py): 0.1 mg KOH / g

Examples 11 and 12

Is introduced at 90 ⁰ C a mixture of 1.11 of DMF, 0.05 g NaOH (0.01 wt .-%, based on NCO prepolymer) and 25g water (DMF / water ratio = 41.7: 1; 3 , 52 moles of water per NCO equivalents). Within 20 minutes, 500 g of the NCO prepolymer from Example 4 with 3.3% NCO are added. Work-up as in example

NH number (HCIO ₄ ): 47.4 mgKOH / g

NH number (Ac ₂ O / Py): 47.6 mgKOH / g S number (Ac ₂ O / Py): 0.09 mgKOH / g

TDA content (HPLC): 0.438%

If, instead of 0.05 g of NaOH, 0.1 g of NaOH (0.02% by weight, based on NCO prepolymer), under otherwise identical conditions and components is used, a product with an NH number (HCIO4) of 46.1 mg KOH / g received.

Example 13

A mixture of 1.11DMF, 0.025 g NaOH (0.005 wt.%, Based on NCO prepolymer) and 25 g of water is heated to 90.degree. C. (DMF / water ratio = 41.7: 1).

500 g of NCO prepolymer from Example 1 with 3.6% NCO (3.23 moles of water per NCO equivalent) are added within 20 minutes. Work-up as in Example 1.

NH number (HCIO4): 46.7 mg KOH / g

Example 14

A mixture of 1.751 DMF, 0.01 g of NaOH (0.002 wt .-%, based on NCO prepolymer) and 50 g of water (DMF / water ratio = 33.2: 1) and heated to 9O ⁰ C is submitted. 500 g of the NCO prepolymer from Example 1 are added within 20 minutes with 3.6% NCO (6.46 mol of water per NCO). Work-up as in example

NH number (HCIO ₄ ): 43.4 mg KOH / g

NH number (Ac ₂ O / Py): 49.15 mg KOH / g

S number (Ac ₂ O / Py): 0.1 mg KOH / g

Example 15

A mixture of 1.11 DMF, 0.025 g NaOH and 25 g water is placed and heated to 90 ° C. 500 g of the NCO preplymer from Example 4 are added with 3.3% NCO within 1 minute, stirring is continued for 20 minutes. Other work-up as in example

NH number (HCIO ₄ ): 42.6 mg KOH / g

Example 16

In this example, an NCO prepolymer is used from a polyester of OH number 50 and toluene-2,4-diisocyanate in the NCO: OH ratio 2: 1 of the NCO content 3.19%. The polyester used consists of adipic acid and 1,6-hexanediol and was prepared at a molar ratio of = 1: 1.

Vorgelegtund is heated with stirring to 90 ⁰ C a mixture aus4,4l DMF, 100g WasserundO, 2g NaOH. While stirring, 2 kg of the above NCO prepolymer (6O ⁰ C warm) are added within 45 min. Work-up as in example

NH number (HCIO4): 43.5 mg KOH / g

NH number (Ac ₂ O / Py): 43.85 mg KOH / g S number (Ac ₂ O / Py): 0.4 mg KOH / g

TDA content (HPLC): 0.81%

Example 17

In this example, an NCO prepolymer of NCO content 2.34% of a polyester and toluene-2,4-diisocyanate in the NCO: OH ratio 2: 1 is used. The polyester consists of adipic acid and diethylene glycol and has an OH number of 9O ⁰ C is a hot mixture of 1.751 DMF, 0.05 g of NaOH and 50 ml of water. Within 30 minutes, 500 g of the above prepolymer are added while stirring. Work-up as in example

NH number (HCIO ₄ ): 28.05 mg KOH / g

TDA content (HPLC): 0.206%

Example 18

In this example, a thinned-NCO prepolymer of NCO content 3.4% of a polyether mixture and toluylene-2,4-diisocyanate is used. The blend has an OH number of 50 and a functionality of 2.5 and consists of a 1: 1 mixture of a PO / EO polyether started on trimethylol propane and a propylene glycol started. Is presented a 90 ° C hot mixture of 3.51 DMF, 0.1 g of NaOH and 100 ml of water. Within 40 minutes, 1000 g of the above prepolymer are added with stirring. Work-up as in example

NH number (HCIO ₄ ): 44.3 mg KOH / g

NH number (Ac ₂ O / fy): 43.5 mg KOH / g

S number (Ac ₂ O / Py): 0.3 mg KOH / g

TDA content (HPLC): 0.087%

Example 19

In this example, a prepolymer of NCO content obtained by stirring at 80 ° C for 3 hours is used 3.1% of polytetramethylene glycol of OH number 56 and toluene-2,4-diisocyanate with NCO: OH ratio 2: 1. A 90 ° C. hot mixture of 1.751 DMF, 0.05 g of NaOH and 50 ml of water is introduced. Within 20 minutes were added 500 g of the above prepolymer. Work-up as in example

NH number (HCIO ₄ ): 39.5 mgKOH / g

TDA content (HPLC): 0.281%

Example 20

In this example, a obtained by stirring for 4 hours at 80 ⁰ C prepolymer of the NCO content is 2.8% (from an ester of OH number 56 [as Example 9] and diphenylmethane-M'-diisocyanate in the NCO: OH ratio of 2 : 1) used. A 9O ⁰ C hot mixture of 1.751 DMF, 0.05 g NaOH and 50 g water is introduced. Within 35 minutes, a freshly prepared mixture of 500 g of the above prepolymer and 200 g of DMF is added. Work-up as in example

NH number (HCIO ₄ ): 31.4 mg KOH / g

NH number (Ac ₂ O / Py): 29.25 mg KOH / g

S number (Ac ₂ O / Py): 0.2 mg KOH / g

MDA 4,4'-content (HPLC): 1.48%

Example 21

In this example, a 1.88% NCO content prepolymer obtained by stirring at 80 ^° C. for 4 h is obtained from a polyether diol of OH number 28 (obtained by bl.ockwise addition of 80% propylene oxide and then 20% by weight). Ethylene oxide on propylene glycol), and tolylene-2,4-diisocyanate in the NCO: OH ratio of 2: 1.

A 9O ⁰ C hot mixture of 1.751 DMF, 0.05 g of NaOH and 50 ml of water is introduced. 500 g of the above prepolymer are added in 30 minutes. Work-up as in example

NH number (HCIO ₄ ): 23.7 mg KOH / g

Example 22

In this example, an NCO: OH-2: 1 prepolymer obtained by stirring at 8 ° C. for 3 hours is obtained from a polyether triol of OH number 28 obtained by addition of first 87% by weight of propylene oxide and then 13% by weight of ethylene oxide Trimethylolpropane, the NCO content used 1.8%.

Is presented on a heated 9O ⁰ C mixture of 1.751 DMF, 0.05 g NaOH and 50 ml of water (12.9 moles of water per NCO equivalent; DMF / H ₂ O ratio = 33.2: 1). 500 g of the above NCO prepolymer are added in 30 minutes. Work-up as in Example 1.

NH number (HCIO ₄ ): 25.15 mg KOH / g

NH number (Ac ₂ O / Py): 24.0 mg KOH / g

S number (Ac ₂ O / Py): 0.2 mg KOH / g

Examples 23-25

In these examples, the good effectiveness of sodium aluminate is demonstrated.

Example 23

Is introduced at 90 ⁰ C, a mixture of 1750 ml of DMF, 50 g of water and 0.1 g of sodium aluminate. With stirring, 500 g of the NCd prepolymer from Example 1 with 3.65% NCO are added (ratio H ₂ O: NCO about 6.4: 1). Implementation and work-up as in Example 1.

NH number (HCIO ₄ ): 51.6 mg KOH / g

NH number (Ac ₂ O / Py): 51.5 mg KOH / g

S number (Ac ₂ O / Py): 0.1 mg KOH / g

TDA content (HPLC): 0.81%

Example 24

A 9O ⁰ C hot mixture of 1100 g of DMF, 25 g of water and 0.01 g of sodium aluminate is presented. While stirring, 500 g of the NCO prepolymer from Example 4 with 3.3% NCO are added within 20 minutes (ratio H ₂ O: NCO = about 3.5: 1). Implementation and work-up as in Example

NH number (HCIO ₄ ): 47.15 mg KOH / g

Example 25

A 9O ⁰ C hot mixture of 1100 g of DMF, 25 g of water and 0.05 g of sodium aluminate is presented. With stirring, 500 g of an NCO prepolymer prepared in the same way as the NCO prepolymer from Example 1 but having an NCO content of 3.2% are added (ratio H ₂ O: NCO = 3.65: 1). Implementation and work-up as in Example

NH number (HCIO ₄ ): 41.7 mg KOH / g

Example 26

Is introduced at 90 ⁰ C a mixture of 1.751 DMF, 50g water and 2,5KHCO ₃ (0,5Gew .-%, based on the isocyanate prepolymer; DMF / water weight ratio = 33.2: 1, 7.05 mol of water per NCO). Within 20 minutes, 500 g of the NCO prepolymer from Example 4 with 3.3% NCO are added. Work-up as in example

NH number (HCIO ₄ ): 47.3 mg KOH / g

Examples 27-28

These examples demonstrate that the incorporation of increased amounts of water results in poorer results, ie, lower NH numbers due to lower NCO / NH ₂ conversion rates.

Example 27

A mixture of 1.51 DMF, 250 ml of water (32.32 moles of water / NCO equivalent: DMF / water ratio = 5.9: 1) and 0.05 g of KHCO ₃ (0.01% by weight) are introduced at 90 ° C. -%, based on prepolymer). Within 20 minutes, 500 g of the NCO prepolymer from Example 1 with 3.6% NCO are added. Work-up as in example

NH number (HCIO ₄ ): 37.8 mgKOH / g

NH number (Ac ₂ O / Py): 38.95 mg KOH / g

S number (Ac ₂ O / Py): 0.1 mg KOH / g

Example 28

A 90 ° C. mixture of 1.51 DMF, 250 ml of water (DMF / H ₂ O ratio = 5.9: 1) and 0.05 g of sodium formate are introduced. Within 20 minutes, 500 g of the prepolymer from Example 4 with 3.3% NCO are added. Work-up as in example

NH number (HCIO ₄ ): 33.7 mg KOH / g

Example 29

Is presented at 90 ⁰ C, a mixture of 1.751 DMF, 50g of water and 0.24 g of sodium formate (HCO ₂ Na). With stirring, 500 g of the NCO prepolymer from Example 1 are added and worked up as described in Example 1.

NH number (HCIO ₄ ): 50.5 mg KOH / g

NH number (Ac ₂ O / Py): 48.4 mg KOH / g

S number (Ac ₂ O / Py): 0.1 mg KOH / g

Examples 30-40

In these examples, NCO prepolymers are used, which are formed by stirring for 4 h at 80 ⁰ C of a mixture of tolylene-2,4-diisocyanate and a starting on trimethylolpropane polyoxypropylene glycol of OH number 32. In Examples to 33, a product having an NCO content of 2.1%, in Examples 34 to 36, 38, 39 of 2.3 and in Example 37 and 2.2% is used.

Example 30

Is introduced with stirring at 9O ⁰ C, a mixture of 1.11 DMF, 25 ml of water and 0.025 g of NaOH. While stirring, 500 g of a prepolymer of the NCO content 2.1% as described above are added at this internal temperature and worked up and worked up as in Example 1.

NH number (HCIO ₄ ): 30.8 mg KOH / g

NH number (Ac ₂ O / Py): 34.0 mg KOH / g

S number (Ac ₂ O / Py): 0.05 mg KOH / g

Example 31

Is introduced with stirring at 90 ⁰ C, a mixture of 1.11 DMF, 25 ml of water and 0.01 g of NaOH. While stirring, 500 g of the NCO prepolymer from Example 30 are added at this internal temperature and worked up and worked up as in Example 1.

NH number (HCIO ₄ ): 29.8 mg KOH / g

NH number (Ac ₂ O / Py): 33.5 mg KOH / g

S number (Ac ₂ OZPy): 0.05 mg KOH / g

Example 32

Is introduced with stirring at 9O ⁰ C, a mixture of 1.11 DMF, 25 ml of water and 0.005 g of NaOH. While stirring, 500 g of the NCO prepolymer from Example 30 are added at this internal temperature and worked up and worked up as in Example 1.

NH number (HCIO ₄ ): 31.1 mg KOH / g

NH number (Ac ₂ O / Py): 32.1 mg KOH / g

S number (Ac ₂ O / Py): 0.05 mg KOH / g

Example 33

(0.0005 .-%, based on the prepolymer) is introduced with stirring at 9O ⁰ C a mixture of 1.11 DMF, 25ml water and 0,0025g NaOH. While stirring, 500 g of the NCO prepolymer from Example 30 are added at this temperature and worked up and worked up as in Example 1.

NH number (HClO ₄ ): 29.4 mg KOH / g

NH number (Ac ₂ O / Py): "28.6 mg KOH / g

S number (Ac ₂ O / Py): 0.05 mg KOH / g

Practically the same results are obtained when using 0.0025 g KOH.

Example 34

Is introduced with stirring at 90 ⁰ C, a mixture of 1.11 DMF, 25 ml of water and 0.005 g KOH. While stirring, however, added the NCO content of 2> 3%, and continue as described in Example 1 and processed at 90 ⁰ C 500g of a prepolymer as described above.

NH number (HCIO ₄ ): 29.2 mg KOH / g

Example 35

Is introduced with stirring at 45 ⁰ C, a mixture of 1.11 DMF, 25 ml of water and 0.0025 g of NaOH. While stirring, 500 g of the NCO prepolymer from Example 34 are added at this internal temperature, but stirring is continued for 20 minutes (end of the evolution of CO 2). The procedure is as in Example 1.

NH number (HCIO ₄ ): 19.6 mgKOH / g

Example 36

A mixture of 1.11 DMF, 25 ml of water and 0.1 g of NaOH is added with stirring at 45 ° C. While stirring, 500 g of the NCO prepolymer from Example 34 are added at this internal temperature. Stirring is continued for 25 minutes, after which a sample is drawn after 5 minutes. Both samples are worked up as in Example 1.

NH number (HCIO ₄ , after 5 min): 29.4 mg KOH / g NH number (HCIO ₄ , after 25 min): 29.0 mg KOH / g

This shows that even at 45 ⁰ C, the reaction is completed at the latest 5 minutes after completion of the addition, and that prolonged stirring brings no advantages.

Example 37

Is introduced with stirring at 45 ⁰ C, a mixture of 1.11 DMF, 25 ml of water and 0.05 g KOH. With stirring, 500 g of the NCO prepolymer are added at this temperature as described above, but with 2.2% NCO. Further and working up as in Example 1.

NH number (HCIO4): 29.0 mg KOH / g

Example 38

Is introduced with stirring at 90 ⁰ C, a mixture of 1.11 DMF and 25 ml of water. While stirring, 500 g of the NCO prepolymer from Example 34 are added at this internal temperature. Work-up as in Example 1.

NH number (HCIO ₄ ): 17.5 mgKOH / g

If this reaction mixture after completion of the addition offset even with 0.2 g 1 / 1ON NaOH and stirred for 45 min at 90 ⁰ C, then after work-up as in Example 1, a product with an NH number of 17.8 mg KOH / g (HCIO ₄ method). This shows that even in the absence of a catalyst, the reaction is completed at the latest 5 minutes after completion of the addition of the NCO prepolymer.

Example 39

Is introduced at an internal temperature of 137 ⁰ C (reflux) with stirring, a mixture of 1.11 DMF and 25 ml of water.

Within 27 min the addition takes place of 500 g of the NCO prepolymer from Example 34, whereby the internal temperature is lowered to 130 ⁰ C (bath-T. 160-18O ⁰ C) and reflux was dried up.

If, after stirring for 5 minutes, worked up under reflux, a product with an NH number (HCIO ₄ ) of 20.7 mg KOH / g is obtained.

If the mixture is worked up after reflux for 30 minutes, a product having an NH number (HCIO ₄ ) of 21.3 mg KOH / g is obtained.

This shows that even without catalyst and at this temperature, the reaction is completed no later than 5 minutes after completion of the addition of the NCO prepolymer.

Examples 38 and 39 also demonstrate that, without co-use of a catalyst, a product is obtained which is superior to a product prepared without using a catalyst according to DE 3223398, but which has a high degree of pre-extension (urea formation).

Example 40 (Comparative Example to Example 38).

Is introduced and heated to 90 ⁰ C with stirring, a mixture of 1.11 DMF and 300 ml of water. While stirring, 500 g of the NCO prepolymer from Example 37 were added over the course of 20 minutes. This precipitates a gel-like polymer, which no longer dissolves in pure DMF or acetic acid. If one tries to determine an NH number of the insoluble material, one obtains (2 mg KOH / g as NH number).

This experiment shows that water / solvent (or water / DMF) ratios, as used in DE 3223398 and 3223397, give less favorable results than in the inventive method. That is, where the known

If the process resulted in a virtually no longer usable product, the process according to the invention still gives usable, liquid and soluble products with respectable NCO / NH ₂ conversion and considerable NH numbers.

Example 41

616 ml of DMF and 14 ml of H ₂ O are placed in a 1.31 autoclave and heated to 150 ° C. With stirring, 280 g of an NCO prepolymer, as used in Example 37, are then added over 5 minutes with a metering pump.

The temperature of the NCO prepolymer was 5O ⁰ C. There were 5 min then stirred at 150 ⁰ C, then cooled, vented and the solvent was distilled as in Example. 1 There will be a brown material with the following data:

NH number (HCIO ₄ ): 28.9 mg KOH / g

NH number (AC ₂ O / Py): 27.1 mgKOH / g

S number: <0.05 mg KOH / g

Molecular weight: 3825, th. 3851 (determined by steam pressure osmometry)

TDA content: 0.288% by weight

Example 42 (comparative example)

600 ml of water are heated in a 1.3-liter autoclave to 150 ⁰ C, and then within 10 minutes 300 g of the NCO prepolymer from Example 37, which was heated to 50 ⁰ C, was added. 5min was further stirred at 150 ° C, then cooled, relaxed and the water decanted from gegärmem, tough rubber, which, however, could be partially dissolved at 8O ⁰ C in a DMF / ethanol mixture.

The NH number of the still soluble part was (after distilling off the solvent) 11.1 mg KOH / g (HCIO ₄ ).

Example 43 (Comparative Example)

If the above experiment is repeated, but 0.06 g of KOH is added to the water, a swollen, totally insoluble DMF material is obtained after work-up. An NH number can not be determined.

Example 44

a) Prepolymer

1218g Toluylendiisoeyanat (7 mol) are heated to 60 ⁰ C. Within 40 minutes 90 g of 1,4-butanediol are added. Towards the end of the reaction, the reaction product precipitates. It is stirred at 60 ⁰ C for 1 hour. The mushy mixture is diluted at 23 ° C with 21% cyclohexane and filtered with suction, washed with cyclohexane and petroleum ether and dried at 40 ⁰ C in a vacuum oven. The product melted at 130 to 131 ° C and had an NCO content of 19.0% (for a 2: 1 adduct, 19.2% NCO was calculated).

b) Polyamine production

A mixture of 3256 ml of DMF, 0.15 g of KOH and 74 ml of water is introduced. With stirring, at 9O ⁰ C, a slurry of 310 g of the above NCO prepolymer in 600 ml of DMF is added within 20 min. A development of 311 CO _{2 is} observed (theoretical 31.41). The solvent is then largely distilled off and from the liquid residue the product is precipitated with a 10: 1 mixture of water and methanol. The product is filtered off with suction, washed with water and dried.

NH number (Ac ₂ O / Py): 274 mg KOH / g (Th .: 288)

Acid number (Ac ₂ O / Py): 0.4 mg KOH / g -

Molecular weight (vapor pressure osmometry): 395; 400 (Th .: 378)

TDA value (HPLC): 0.352%

NH number (HCIO ₄ ): 264 mg KOH / g; Mp .: 168-169 ° C

Example 45

A mixture of 1750 ml of dimethylformamide and 30 ml of water and 0.01 g of potassium octoate (0.002% by weight, based on the NCO prepolymer) is introduced. The mixture is warmed to 9O ⁰ C. Within 20 minutes 500 g 70 ⁰ C desauf heated NCO prepolymer from Example 9 is added and worked up as described there. The polyamine has an NH number (Ac ₂ O / Py) of 47.95 mg KOH / g.

Claims (6)

1. One-step process for the preparation of polyamines having primary amino groups by hydrolysis of NCO-containing compounds in water-containing media, optionally with the addition of basic and / or metal catalysts, characterized in that a) NCO groups, preferably aromatically bonded NCO-containing compounds having an NCO content of 0.5 to 40 wt .-%, preferably NCO prepolymers having an NCO content of 1.2 to 25 wt .-% or modified polyisocyanates with an NCO content of 1.5 to 20.5% by weight, b) from 0.75 to 50, preferably from 1 to 35, especially from 1.25 to 12 and particularly preferably from 1.5 to 7.5, moles of water per equivalent of NCO of component a), c) in the presence of 0 to 1 wt .-%, preferably 0.00005 to 1 wt .-%, basic, non-incorporable and / or metal catalysts, more preferably 0.0001 to 0.099Gew .-% based on 100Gew. % of component a), basic catalysts, d) and in the presence of> 10% by weight, based on 100% by weight of component a), of carboxamides as solvent, preferably carboxylic acid dialkylamides, more preferably dimethylformamide or dimethylacetamide, , e) and optionally in the presence of from 0.1 to 5% by weight, based on 100% by weight of component a), of a compound having at least one hydroxyl and / or amino radical bound to aliphatic, cycloaliphatic or aromatic radicals and / or thiol group, wherein , f) a solvent (d) / water weight ratio of 3 to 200, preferably 5 to 150, more preferably> 10 to 100 and in particular> 25 to 75,
g) and a homogeneous reaction phase are maintained, at a temperature of 20 to 21O ⁰ C, preferably 40 to 15O ⁰ C, hydrolyzed. 2. The method according to claim 1, characterized in that as catalysts c) ca) 0.0001 to 0.099, preferably 0.002 to 0.08Gew .-%, based on 100Gew .-% of the NCO component a), alkali metal hydroxides, alkaline earth metal hydroxides, tetraalkylammonium hydroxides, alkali aluminates, alkali phenolates, alkali thiophenolates, Alkalimercaptide, alkali hydrogen sulfides , soluble alkali and alkaline earth salts of (lso) (thio) cyanic acids and alkali-β-diketone enolates and / or css) 0.0001 to 0.099, preferably 0.002 to 0.08Gew .-%, based on 100Gew .-% of the NCO component a), carbonates or bicarbonates of alkali metals and / or cy) 0.0001 to 0.099, preferably 0.0002 to 0.008 wt .-% ^: alkali and alkaline earth metal salts of organic carboxylic acids used. 3. The method according to claim 1 or 2, characterized in that one uses the component b) in amounts of 1.25 to 12, preferably 1.5 to 7.5 moles per mole of NCO equivalent, while a Carbonsäuredialkylamid / water (preferably Dimethylformamide / water) weight ratio of> 10 to 100, preferably> 25 to 75. 4. The method according to claim 1, characterized in that the NCO component a) in the presence of c5) 0.0001 to 0.99 wt .-%, preferably 0.001 to 0.099 wt .-% tertiary amine compounds, based on 100 wt .-% NCO component a), as basic catalysts c) while maintaining a water / NCO ratio from 1 to 7.5 moles of water per equivalent of NCO and of a dialkylcarboxamide / water (preferably dimethylformamide / water) weight ratio of> 10 to 100, preferably 2:25 to 75, at a temperature of 35 to hydrolyzed. 5. The method according to claim 1, characterized in that the NCO component a) in the presence of 0.001 to 0.099 parts by weight of tertiary amino compound while maintaining a water / NCO ratio of 1 to 24 moles of water per equivalent of NCO and a Dialkylcarbonsäureamid / Water (preferably dimethylformamide / water) weight ratio of> 10 to 50, at a temperature of 35 to 165 ° C, hydrolyzed. 6. The method according to claim 1, characterized in that the NCO component a) it) in the presence of 0.0001 to 0.0099, preferably 0.002 to 0.008 wt .-%, based on 100Gew .-% of component a) , Metal catalysts, b) with 1.5 to 7.5 moles of water per NCO equivalent d) and maintaining a carboxylic acid dialkylamide / water (preferably dimethylformamide / water) weight ratio of> 10 to 50, preferably> 25 to