JPS6299349A - Polyamines and preparation - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a simplified one-step process for the preparation of polyamines containing primary amine groups.

It is known that aromatic isocyanates can be converted to primary aromatic amines by acid hydrolysis.

However, the amine obtained from this acid hydrolysis reacts with unreacted isocyanate to form the corresponding urea, thereby reducing the amount of amine product. This secondary reaction cannot be suppressed by using an excess of strong mineral acids.

A recent example of this method is JP-P (#Koaki)
No. J 007♂. It is described in No. 27.

The ability to convert isocyanates to amines by acid- or alkaline-catalyzed reactions has also been shown, for example, in N.V. Sfdgwick's ``The Organic Chemistry of Elements'' (The Organic Chemistry of Elements).
emistry of Nitrogen) J, Clareaon Press
, Oxford, p. 32 (/ri 6) and Soei, March (J, March), "Advanced Organic Chemistry: Reactions, Mechanisms and Structures".
anicChemlstry: Reaction,
Mechanism and Structures
) J. McGraw-Hill Book Co., Ltd.
It is known as described in the book), New York, page Otsuyo♂. Although Shijiuisoku shows that isocyanate groups can be hydrolyzed under alkaline conditions, details of this method are not disclosed. Jay? - also generally refers to the fact that the hydrolysis of isocyanates and inthiocyanates to amines can be catalyzed by acids or bases. The generation of isocyanates as intermediates is also known to those skilled in the art. For example, isocyanates are obtained during curtium or Rossene decomposition of acid acids and hydroxamic acids and are decomposed (by an aqueous solution of the acid) to form amine salts. This type of method is called [Organic Synthesis].
) Volume ■ of J, coil (coil), K/ri (/7
As described in Otsu 3), the preparation of citrescine hydrochloride is used here as an example.

It was first observed by E. Mohr that phenyl isocyanate is more susceptible to attack by dilute solutions of sodium hydroxide than by water at low temperatures:
Practicalization (J, Prakt, Chem) J,
7/, /33C/riOj). Help, Him, Acta (He1v, Chim, Acta)
1.2/, iioo (i73g) of a phenolic isocyanate substituted with a tro group, . Alternatively, hydrolysis in acetone has been reported to yield the corresponding monoamines during reactions lasting from a few minutes to 7 hours. This amine is 2. It is obtained in virtually 100% yield from ≠-dinitrophenyl isocyanate in hot water without solvent and without side reactions leading to the formation of urea.

In the method for preparing certain primary aromatic amines containing polyalkylene glycol ether segments described in DE-B No. 72100'A No. or polyalkylene glycol thioether (preferably molecular weight 400 to 400>
The resulting product is reacted with secondary or tertiary carpinol and then thermally decomposed (optionally in the presence of an acid catalyst) in an inert solvent at elevated temperatures. One disadvantage of this method, besides its high decomposition temperature, is that flammable and easily volatile alkenes are produced during pyrolysis, which explode when mixed with air, thus requiring appropriate safety measures. It is.

DE-B No. 1 Otsu 5;'≠/Yu λ (U.S. Patent No. 3525
♂ No. 77) is hydrazine, aminophenylethylamine mata is other amino acids, polyether polyol and polyisocyanate) (NGO/NH ratio = /: /, evening /
Regarding the preparation of prepolymers containing at least two amine end groups by reacting with the isocyanate prepolymers obtained from :j), all unreacted amines have to be carefully removed in subsequent steps of the process, since the amines are This is because it is a strong catalyst during the reaction with isocyanates, reducing processing time, and may also act as a reaction component. A similar method is described in US Pat. No. 393///O.

Another method for the synthesis of polyamines containing urethane groups is described in French Patent (FR-P) No. 1≠753/7. In this method, an isocyanate prepolymer containing urethane groups is reacted with sulfuric acid to produce an N-formyl derivative that saponifies aromatic amines containing amine end groups. German patent (DE-P) No. 1/j! The reaction of the isocyanate pre-4lima with sulfamino acid according to No. 107 also gives compounds containing amine end groups. A relatively high molecular weight prepolymer containing aliphatic secondary and primary amino groups DE-B No. 12/! No. 373, it is obtained by reacting a relatively high molecular weight hydroxyl compound with ammonia in the presence of a catalyst under pressure and at elevated temperatures. According to US Pat. No. 30≠4L, a high molecular weight amine is obtained by reacting a relatively high molecular weight polyhydroxy compound with acrylonitrile followed by catalytic hydrogenation. Relatively high molecular weight compounds containing amino terminal groups and urethane terminal groups may also be used as DE-A 26'
No. 1-6536 and U.S. Patent '1X3F! No. 777 is obtained by reacting the isocyanate grebolimer with an enamine, alnomine or ketimine containing a hydroxyl group, followed by hydrolysis. Another method for the synthesis of aromatic polyamines containing urethane or ether groups is ring opening, which occurs during the reaction of isatoic anhydride with nool. Polyamines of this type are known, for example, from US Pat. 1A3
2.2 Otsu/PI4LO1xgttv77tt OxU
It is written in the 2 otsu 4t♂ryo 2 evening issue. The aromatic ester amines obtained by this process have the disadvantage that they are not sufficiently reactive for many purposes.

Low reactivity is achieved by reacting I-ether polyols with P-aminobenzoic acid ethyl ester, US Pat.
in the compound containing amino and ester groups obtained by reacting the polyol with nitrobenzoic acid chloride and then reacting the amine groups with the nitro groups obtained by EP 325≠7. is also found.

It is also known to react nidroarylisocyanates with polyols and then reduce the nitro groups to aromatic amine groups (US Pat. Nos. 2g-39). The main drawback of this process is the high cost of the reduction stage of the process.

It is also known that certain heteroaromatic incyanate esters can be converted to heteroaromatic amines by basic hydrolysis. However, by H, Joho (H, Joho), ``J, Prakt.

Chemie) J, pp. 30.3/4 and 332 et al. (/3/), the hydrolysis conditions for two completely specific heteroaromatic monoisocyanate esters were the same. It is completely incomplete and dangerous for converting isocyanate compounds to aliphatic and/or aromatic amines.

DE-AM291. #ll/9th issue! 303?1t
Applicant's own process disclosed in No. 11C of No. 00 involves the alkaline hydrolysis of isocyanate prepolymers at low temperature with excess base (alkali metal hydroxide) to form carbamate esters, and the process of producing carbamic acid esters in equivalent or excess amounts. Multi-stage process for the preparation of polyamines by acidification with acids or with acid ion exchange resins, followed by decomposition of the carbamate esters and optionally neutralization of excess acid with a base and subsequent isolation of the polyamines. It is.

German Patent Publication (DE-O8) No. 3/3/252 discloses that the carbamate ester obtained in the first step by hydrolysis with an alkali metal hydroxide is decomposed by peeling and heat treatment to form a polyamine. A method is disclosed.

A one-step process for the production of polyamines is described in DE-O8 No. 32.
234LOO (EP No. 5772 Tata), DE-O8
No. 32.2332r (EP?!'5'7.2t1) Oj Hi DIE-O8 No. 3.2 3377 (EP
No. 972-0). Various solvent-catalyst combinations are used in these one-step hydrolysis methods.

In DE-O8 No. 32234t00 "ether solvents" are used as catalysts together with tertiary amines.

In DE-O8flE 32.2337r, a polar solvent such as dimethylformamide is used as a catalyst in a given amount together with a tertiary amine or a relatively large amount of an alkali metal hydroxide or alkali metal silicate or alkali metal cyanide. It is used. DE-O8 No. 32233
No. 77, the carbonate or carboxylate is DMF
used in certain amounts in polar solvents such as '.

All these methods for preparing polyamines are complex and expensive. The last mentioned simple method for converting polyisocyanates to polyamides also allows polyamines to react more smoothly, more economically and with better NCO/
Further simplification is desired in order to obtain conversions of NH2 (i.e. higher N1 (number of 2)).A good process should have the following advantages compared to conventional processes.

(1) No need for filtration, (2) No need to separate the tertiary amine catalyst by distillation.
(3) Catalyst (tertiary amine (DIE-O8 No. 3.223)
(4) The amount of catalyst required is significantly reduced so that both (according to No. 3'Z♂) and inorganic alkaline compounds such as KOH) can remain in the polyamine and (4) NCo
is quantitatively converted to NH2 groups (high NCO/NH conversion, i.e. large amine number close to the theoretical value), (5) no removal of by-products is necessary, and (6)
Easy purification of polyamines and auxiliaries.

SUMMARY OF THE INVENTION The above-mentioned advantages are achieved by the present invention? It has been found quite unexpectedly that polyamines can be obtained by one-step hydrolysis of polyisocyanates.

This hydrolysis is carried out at a specific ratio of water to NCO and at a specific weight ratio of water to solvent, using a water-soluble cardanamide as solvent, and in some cases very small amounts of catalyst. (Unpreferable) Use is carried out under conditions such that a homogeneous solution is maintained.

These optimal conditions make it possible to use low temperatures for hydrolysis.

In the process of the present invention, a carmenic acid amide, preferably a carboxylic acid dialkylamide or lactam-based aqueous solvent is used to obtain a substantially homogeneous solution of the reactants (i.e. isocyanate and water) and catalyst. It will be done. Particularly suitable solvents are dimethylformamide and optionally also dimethylacetamide.

By reacting a solution of the isocyanate solopolymer in dimethylformamide with approximately an equivalent amount of water (IO to 720% of theory; 100% is water/NCO//2
(i.e. water reacts with hydroxyl di-equivalents) and convert them into high viscosity solutions suitable for spinning elastane fibers or coatings.
It is known from AS 1235≠99. This reaction involves chain lengthening via the urea group. It was expected that a completely different reaction of an isocyanate compound and an excess amount of water would produce high yields of low molecular weight amines, but this was not the case. It is particularly surprising that this reaction is carried out in the presence of a catalyst according to the invention which also promotes the reaction of the isocyanate with the reaction product formed.

It is also known that isocyanates react with sialkyl-formamides to form formamidines (H, Ulrich et al.).
372r-3ri30 (/'?♂0) and the literature cited therein].

This reaction does not interfere with smooth hydrolysis to polyamines by the method of the invention.

One of the important advantages of the process of the invention is that very small amounts of catalyst are used. Therefore, there is no need to remove the catalyst or the reaction products of the catalyst (e.g. KOH yields KI (co3 or 2CO3) with the CO□ generated during the reaction).

Because the catalysts useful in this invention are readily soluble in the reaction medium, problems arise when using rapidly precipitating alkali metal carbonates or bicarbonates (Dg-O8 No. 3223.2).
(as in the case of No. P7) does not occur when practicing the present invention. The catalysts remain in the solution or are completely miscible so there is no need to remove them. Catalysts remaining in the amine product usually do not present any difficulties since they are preferably used in small amounts. Since there is no need to remove salt or catalyst residues after purifying the product, the process of the present invention does not require removal of salt or catalyst residues from highly viscous or solid materials containing amino groups from which it is very difficult to remove salts or insoluble residues of catalyst material. Particularly suitable for the preparation of compounds.

The catalysts of the present invention are also particularly suitable during the hydrolysis of polyester to isocyanate polymers, since the ester groups are not separated to any significant degree under the mild reaction conditions used during the hydrolysis reaction.

Compared to alkaline hydrolysis methods for obtaining aminopolyesters from isocyanates, the process of the invention represents a significant improvement.

The catalyst of the present invention is inexpensive and easily commercially available. They can also be separated from the product and used again or preferably left in the product in some embodiments. When it is necessary to produce a product completely free of catalyst, isocyanate, water and solvent are mixed in the proportions required according to the invention (in particular the optimum ratio of solvent to water,
The process can also be carried out without non-incorporable alkali and/or metal catalysts if used in such amounts that the optimal ratio of water to NCO and relatively high temperatures are used. 0 This optimal ratio can be determined by preliminary experiments.

Relatively high temperatures are used, preferably temperatures in the range of 0°C to 100°C. The conversion obtained from such a non-catalyzed process is approximately 2 times that obtained using a catalyst.
/3, but still DE-O8 No. 3.2.2337
This is extremely large (advantageous) when compared to that obtained by the method according to No. ♂ that does not use a catalyst. When carrying out the invention, it is always preferable to carry out the present invention in the presence of a catalyst, even in very small quantities.

The present invention comprises primary amine groups by hydrolyzing compounds containing isocyanate groups (preferably aromatic isocyanate groups) in a water-containing medium, optionally with the addition of non-inclusive alkaline and/or metal catalysts. This invention relates to a one-step process for the preparation of polyamines. More specifically, in the case of isocyanate prepolymers, 0. 740% by weight, preferably from /1.2 to 2 J-weight and in the case of modified polyisocyanates from 20.5% by weight, preferably /! to 10% by weight
The isocyanate groups of an organic compound containing isocyanate groups, preferably aromatic-bonded isocyanate groups, based on isocyanate prepolymers or modified polyisocyanates having an isocyanate content of , preferably from / to 3J, more preferably from 4.25 to /2 and most preferably from / to 7J moles of water. This hydrolysis produces 100% by weight of isocyanate.
0 to 7% by weight, preferably o, ooo
It is carried out in the presence of from os to 7% by weight of a non-inclusive alkali and/or metal catalyst, preferably from 0.000 to 7% by weight of an alkali catalyst. At least 10% by weight, based on 100% by weight of isocyanate, of cargenic acid amide, preferably carpic acid noalkylamide or lactam, most preferably trimethylformamide or dimethylacetamide, is used as solvent in the hydrolysis mixture.

optionally containing 7 or more hydroxyl and/or amino and/or thiol groups attached to aliphatic, cycloaliphatic or aromatic groups, based on 100 g/m of isocyanate compound; and 5% by weight of the compound.

The weight ratio of solvent/water should be in the range from 3 to 200, preferably from 1 to 0, more preferably from 10 to 100 and most preferably from 2 to 7. The hydrolysis mixture is maintained in a homogeneous reaction phase. The hydrolysis is carried out at a temperature of 20 to 210°C, preferably 35 to 165°C, more preferably 40 to 130°C and most preferably ♂0 to 730°C.

A preferred embodiment of the present invention is based on 100% by weight of isocyanate as alkaline catalyst.
fZ is 0, O? Weight% of alkali metal hydroxides, alkaline earth metal hydroxides, tetraalkylammonium hydroxides, alkali metal aluminates, alkyl metal ferrates, alkali metal thioferrates, alkali metal mercagutides, alkali metal hydrogen sulfides, (iso )-Soluble alkaline earth metal salts and alkali metal β-nogatone salts of (thio)cyanic acid; and/or isocyanates o, oo based on 100N-#
oi to 0.0001 to 0.099, preferably 0.
002 to 0.0 g% by weight of alkali metal carbonate or bicarbonate; and/or 0,000/to 0
．． 0ri7, preferably 0.000/day, ooy
A process having the above-mentioned characteristics in which isocyanates are hydrolyzed in the presence of alkali metal and alkaline earth metal salts of organic cardanic acids, more preferably o, ooox or 0.00 g% by weight of formic acid salts.

In a further preferred embodiment of the invention, the weight ratio of cargenic acid amide (preferably dimethylformamide/
water) from 10 to /jO, preferably from 25 to 7
isocyanate equivalent υ while maintaining the range up to ta.
The isocyanate is hydrolyzed with 2 to 2, preferably 75 mol of one of the abovementioned non-containing catalysts at a temperature of 35 to 730°C, preferably 0 to 730°C.

In another embodiment of the method of the invention, the NGO equivalent equivalent water/water/to 7! r mol water/NCO ratio and 10 to/! tertiary amino compound at a temperature of 35 to 165° C. using a noalkyl cargenic acid amide (preferably dimethylformamide/water) weight ratio in the range of 0.0, preferably 2 to 7. Tata weight %, preferably 0.007 to 0.0001 to 0.0
The isocyanate is hydrolyzed in the presence of 99% by weight (based on 100% by weight of isocyanate compound). This method uses NGO equivalent equivalent water/ to 2≠mol water/N
3 to 165 in the presence of 0.0007 to 0,000% by weight of a tertiary amine compound using a CO ratio and a dialkylcargenamide/water (preferably dimethylformamide/water) weight ratio of 10 to 0. Particular preference is given to carrying out the reaction at .degree.

In another less preferred embodiment of the invention, the weight ratio of cargenic acid sialkylamide/water (preferably dimethylformamide/water) of IO to 1 to 2 to in the presence of 0.0007 to 75 mol of water, preferably 0.0007 to 0.05;ly, preferably o, oo, z to o, oog% by weight of a metal catalyst, from 2 to 1
Hydrolyze the isocyanate at a temperature of 65°C.

In the process of the present invention, the isocyanate has a water/isocyanate ratio of from 1 to 2 moles of water per equivalent of isocyanate and a caldenic acid dialkylamide/water (preferably dimethylformamide/water) of from 10 to 1, preferably from 12.3 to 0,00 mol of Ir. The isocyanate may be hydrolyzed without the use of a solvent at temperatures from 35 to 165°C, optionally under pressure.

The catalysts used in the process of the invention must be non-containing, meaning that they do not contain groups capable of reacting with NCO groups.

In various embodiments of the present invention, the isocyanate compound is preferably O! Isocyanate polymers having an isocyanate content of from 10% to 10% by weight or/and from 20% to 20% by weight. Evening weight%, especially evening weight%, 20.5 weight%
Modified polyisocyanates, especially urethane-modified polyisocyanates, having an isocyanate content of . Neutral salts may also be included in the hydrolysis mixture. Preference is given to using from 35 to 35 mol of water, especially from 2 to 72 mol of water per equivalent of isocyanate.

The solvent is preferably dimethylformamide used in an amount of 100 to 1000 parts by weight based on 100% by weight of the isocyanate compound.

The hydrolysis is preferably carried out at a temperature of from 4L0 to 150°C, more preferably from go to 730°C and most preferably without using excessive pressure. The solids concentration of the reaction mixture to be hydrolyzed is generally from 20 to 75% by weight, preferably from 2 to 60% by weight, and most preferably from 30 to 60% by weight. Even lower solids concentrations may be used, but this is less advantageous for practical reasons (e.g. solvent recovery).
%, preferably from 7.2 to 2% by weight, more preferably from 1 to 10% by weight, of aromatically bonded isocyanate groups and relatively high molecular weight difunctional or higher order functionality. based on polycarnate polyols and diisocyanates modified with polyethers, polyesters, polycabrolactones and/or low molecular weight soles or polyols (molecular weight up to 3 Tata) and with NCO of /, j to 20.5 weight%,
Preferably not in the evening, 20. The isocyanate polymer contains 1% NCO by weight.

The invention also provides f IJ amines obtained by the process according to the invention,
In particular, it relates to polyamines containing 2 to 2% by weight of primary, preferably aromatically bonded, groups.

Furthermore, the present invention provides a method of combining polyisocyanates and optionally other compounds containing isocyanate-active groups, optionally with known auxiliaries and additives and/or additives.
It also concerns the use of the polyamides obtained by the process of the invention for the preparation of optionally cellular /IJ urethanes (ureas) by reaction in the presence of solvents.

According to the invention, a small amount of a compound containing an aliphatic, cycloaliphatic or aromatic group (bonded/, two or more hydroxyl and/or amino and/or thiol groups) (i.e. each 100 About O
9! 5%) may be added. The addition of these compounds containing "H-active groups" allows polyamines containing almost no monomeric polyamines to be converted into low molecular weight polyisocyanates (e.g. isocyanate semibreed polymers) by methods such as thin film evaporation without processing the isocyanate compounds. It is advantageous because it is obtained from isocyanate compounds containing. In this way modified polyamines containing various segments linked via urethane, thiourethane or urea groups can be obtained very simply and without additional reaction steps.

Therefore, trifunctional or higher functionality polyamines can be converted from difunctional isocyanates using trifunctional or higher functionality compounds containing "H-active groups" during the isocyanate hydrolysis step. Obtainable.

The isocyanate compounds used in the process of the invention contain two or more aromatic, heterocyclic and/or aliphatic (preferably aromatic) isocyanate groups. These isocyanates include modified polyisocyanates of the type obtained by partial conversion of isocyanate groups into urethane, urea, biuret, uretdione, incyanurate and/or uretonimine groups, and those with molecular weights containing isocyanate-reactive H groups. 62 years old,
/2.000 (goodt L < [lAo 0 naiL
Isocyanate brepolymers obtained by reaction of polyhydric compounds in the range of 1,000) with (excess) aromatic polyisocyanates and K (to a lesser extent) isocyanate brepolymers and additional low molecular weight polymers. There are semi-bleed polymers made of isocyanates. .

Examples of modified aromatic polyisocyanates useful in the present invention include: polyisocyanates containing urethane groups (obtained by modification with low molecular weight preols); polyisocyanates containing urea groups (e.g. by modification with water:
DE-PK123077♂); polyisocyanate containing biuret groups (U.S. Pat. No. 3/21/-Oj,
3207372 and British Patent No. ♂♂ri 050);
Polyisocyanate containing isocyanurate groups (DE-
PS 10227 and 752.2067) and daif and oligomeric polyisocyanates containing uretdione or uretonimine groups. These are known compounds and can be obtained by known methods ◇ Some of these uretdione preisocyanates are described in "Polyurethane Analytical Chemistry J.
alChemlatry of the Po1
yurethane), Volume 1/I [Volume 1, “
Bipolymer Series J (High-Polymer
-8eries) (Wiley Co., Ltd.
Wiley), /7 Otori).

The polyisocyanates thus modified containing urethane and/or urea and/or biuret and/or uretdione and/or incyanurate and/or uretonimine groups suitable for the process of the invention are generally/ Weight: Iil, preferably 10
It has an isocyanate content of from 20% to 20% by weight. Contains urethane groups (low molecular weight (molecular weight
(by modification with diols and/or polyols), and A! or 20. Weight%, preferably! Particular preference is given to polyisocyanates having an isocyanate content of from 1 to 20% by weight.

Among the essential isocyanate compounds useful in the process according to the invention are compounds containing hydroxyl and/or amino and/or thiol groups as reactive groups of low and/or relatively high molecular weight (molecular weight from about 0 to about 72 .000) with an excess of polyisocyanate in a known manner.

The polyisocyanates used for the preparation of compounds containing free isocyanate groups can in principle be used, for example, in the Justus Libieg Yearbook of Chemistry.
s Annalan der Chemie) J,
jA, 2.7j ~ /3 Otsu (/5't1tri) Dapru Siefken (W.

5iefksn) K may be any aromatic, aliphatic or heterocyclic no- or polyisocyanate of the type described by DE-O8 No. 322337
No. 7/,! These are known in the technical field as described on pages 1-23. Suitable for the preparation of prepolymers and modified isocyanates containing hydroxyl and/or amino and/or thiol groups as reactive groups with a molecular weight of 3
2 and Otsu Q~/2.000 low and/or relatively high molecular weight compounds are also described in these disclosures.

Relatively high molecular weight polyol (molecular weight 400 to 72
．． 000), preferably from polyether polyols,
Possibly with chain extenders of the aforementioned type (molecules 162 to 39) in the equivalent ratio /:/! Not/:, 2.
Isocyanate prepolymers obtained by reaction of aromatic diisocyanates at a temperature of about 100 ml (in particular from about 2 to 2) are preferred for the process of the invention.

The isocyanate content of the isocyanate prepolymer used in this method is 0. J' to 30% by weight, preferably A2 to 2% by weight, especially /, 10% by weight, with a functionality of from 1 to 3, preferably from 1 to 3, and also preferably from 1 to 3. It is.

So-called "semipolymers", ie isocyanate prepolymers or mixtures of modified polyisocyanates and other polyisocyanates with a higher isocyanate content, for example up to ≠0% by weight, may be used in the process of the invention. However, for practical soil and economic reasons, the use of these semi-limas is not preferred in most cases. The monomeric amine content produced from the monomeric 4-lysocyanate component tends to be a hindrance in many applications.

Compounds containing free isocyanate groups are O0! in the form of their modified isocyanates (often free of urethane groups) or in the form of their "semi-prepolymers" or isocyanate prepolymers (containing urethane groups). to l/LO wt%, preferably /1.2
to 2% by weight, and most preferably A! It has a total isocyanate group content of from 10% to 10% by weight.

Water is preferably used in liquid form as a reaction component. In order to substantially convert isocyanate groups to NF2 groups, N
It is necessary to use at least 1 mol of water per equivalent of CO.

Substantially less than 1 mole (especially 0.7 tamol or less)
With water, a preliminary chain elongation occurs selectively with the formation of urea. On the other hand, it has surprisingly been found that even when very large excesses of water are used, relatively large proportions of undesired pre-chain extension products are formed. This also occurs when the reaction mixture is single-phase. It has been found that the optimum amount of water depends not only on the amount of isocyanate groups converted but also on the amount of solvent used.

This means that the amount of water used per equivalent of isocyanate is 0.75 mol or more, preferably 0.7 mol or more.
mol, preferably 72 moles of water. For example, when using a bifunctional isocyanate prepolymer of T/00 (=,2-)rylene isocyanate) with an isocyanate content of 3.4%, the equivalent weight of isocyanate groups is approximately
It is. For this prepolymer of iit'yi/3. yo or more, preferably /3. ．． 3--FOO9, more preferably /f~309 and even more preferably 22j~, 2/g water is used. The lower limit of water in this process is 0.7 j mol of water, often 1 mol of water, and can be combined with the upper limit in any desired manner.

However, according to the present invention, the water/
The NCO ratio must be used in conjunction with a specific weight ratio of solvent to water. The weight ratio of these ranges from 3:/ to 200:/, preferably from 1:/ to 1:/, especially from 10:/ to 100:/, with the optimum range often being 2! :/ or 7ta:
/ is.

This means, for example, that the amount of water used on the basis of solvent (preferably dimethylformamide >ioog) is
It means that it is in the range of g.

Particularly favorable NCO/NH2 conversions are obtained when the other conditions according to the invention are observed, especially when a relatively large proportion of solvent in the solvent/water mixture (in particular the dimethylformamide/water mixture) is used. It was also found that the amount of catalyst used was minimal.

If the absolute t of required water is used and the more preferred solvent/water ratio is followed, the amount of solvent should be greater than or equal to 10% by weight, preferably 100% by weight for 100% by weight of the isocyanate component, and most preferably is 1000
The amount is such that up to % by weight of solvent is used. It has been found that the minimum amount of solvent required to achieve complete NCO/NH2 conversion depends on the reaction temperature. The higher the reaction temperature, the lower the amount of solvent used. Amount of water required (NCO standard)
is not significantly affected by these factors.

If necessary, the NCOC for the particular isocyanate component in the general formulation indicated by experimentation.
The optimum ratio of O2 amount and solvent may be determined.

In the present invention, alkaline and/or metal catalysts that do not contain N00 reactive groups may be used.

These compounds can increase the NH number of the amine in the product over that obtained without catalyst.

The catalyst used may be solid or liquid, but must be sufficiently soluble, preferably completely soluble, in the reaction mixture. Based on 10% by weight of the isocyanate component, the catalyst is generally used in an amount of 0 to 100% by weight. Different types of catalysts have different preferred amount ranges. The amount of catalyst required also depends on the solvent/water ratio.

The required amount of catalyst is minimized when an optimal solvent/water ratio is used, but even in this case the highest possible NCO/NH2
Surprisingly small amounts of K are required as a catalyst to achieve conversion. Even when the water/solvent ratio is not completely optimal, good results can be obtained by increasing the amount of catalyst. The amount of catalyst required to completely convert NCO groups to orchid groups depends on the reaction temperature.

It has been found that this amount should be higher at a lower temperature, eg, TLT, than at a higher reaction temperature, eg, 100°C. If the yield of amine is insufficient with a given amount of catalyst, the yield can be increased by increasing the reaction temperature.

Basic inorganic or organic salts and especially hydroxides (particularly preferred) may be used as catalysts.

These include salts of inorganic or organic weak acids and organic or inorganic strong bases which produce alkaline reactions in water.Special examples of such catalysts include alkali metal and alkaline earth metal hydroxides and Tetraalkylammonium hydroxides (especially NaOH and KOH) and soluble aluminates (such as sodium aluminate); carbonates of alkali metals, especially sodium and potassium carbonates; bicarbonates of alkali metals, especially sodium bicarbonate and Potassium bicarbonate; alkali metal and alkaline earth metal salts (preferably /alkali metal salts of phenols or thiophenols, optionally substituted with groups that do not react with NCO; cyanic acid, isocyanic acid, thiocyanic acid, isothiocyanic acid, silicic acid Soluble salts of alkali metals and alkaline earth metals of weak acids such as phosphorous acid, hydrocyanic acid, hydrazonic acid, etc.; mercaptides and sulfides of alkali metals and (poly) hydrogen sulfide; and sodium, Included are more β-nogatone compounds such as potassium or magnesium acetylacetonate and acetoacetate. Tertiary amines are also used as catalysts, but are less preferred. The tertiary amines preferably used have an aliphatic or cycloaliphatic structure, and mixtures of various tertiary amines are used. Examples that include compounds that are not completely water-soluble include trimethylamine, triethylamine,
Tripropylamine, triisopropylamine, zomethyl-n-globylamine, tri-n-butylamine, triisobutyl-amine, triiso-pentylamine, trimethylbutylamine, triamylamine, trioctylamine, dodecyltumethylamino, dimethylcyclohexylamine, dibutyl Trialkylamines such as cyclohexylamine, nocyclohexylethylamine, tetramethyl-to-3-butannoamine and trimethylbernoramine, diethylbenzylamine and α-
Examples include tertiary amines containing an araliphatic group such as methylpencil and trimethylamino. Trialkylamines having a total of from to/from carbon atoms in all alkyl groups (eg triethyl- to triamyl-amine and dimethylcyclohexylamine) are preferred.

Suitable tertiary amines other than trialkylamines also include those having an additional tertiary amino group or ether group in the β-position relative to the tertiary group. Examples include sialkylaminoalkyl ethers and bis-
Sialkylaminoalkyl ether (U.S. Pat. No. 333)
07g2 and DE-B No. 1030! dimethyl-(a!-nitoxyethyl)-amine, diethyl-(2-methoxypropyl)-amine, bis-(
2-dimethylaminoethyl)-ether, bis-(2-
diethylaminoethyl)-ether, bis-C2-zoethylaminoisogropyl)-ether, /-ethoxy-
2-dimethyl-aminoethoxyethane, N-methylmorpholine, N-ethyl-morpholine and N-butylmorpholine; tetramethylethylenesoamine, tetramethyl-/, 2-f lobilenenoamine, pentamethyldiethylenetriamine, hexamethyl-triethylenetriamine and Higher hypermethylated congeners (DE-A No. 2 Otsu 2)
41! λ7 and 2 Otsu 2≠! permethylated I-realkylenecyamines such as
cyclooctane, N, N'-nomethylpiperazone, N,
N'-noethylbiperazine, N-methyl-y-dimethylaminoethylpylazine, N,N'-bisinomethylaminoethylpyrazine, N,N'-bis-dimethylaminoglopyrubiperazine, and others. bis-sialkylaminoalkylbiveracine (for example, as described in DE-A No. 2 Otsu 3 Otsu 7g7).

Preferred representatives of these groups include tetramethylenecyamine, permethylated diethylenetriamine, N
-Methyl-morpholine, bis-2-dimethylaminoethyl ether and N-methyl bi4 lysine.

/-trimethylamino-3-formylaminoglono-4,
Acylated tertiary amine derivatives of N-(,2-methyl-aminoethyl)-propionamide, N-(a!-zomethylaminoethyl)-penzuabad and DE-
Other tertiary amines containing amide groups (preferably formamide) according to A2J23O33 and 27322 Octopus are also used.

Also useful are tertiary amines of the pyridine type and tertiary amines of the nomethylani IJy type containing at least seven aromatic groups attached to the nitrogen atom.

If tertiary amines are not soluble in water, their boiling point is 2
! It should be below rO<0>C, preferably below 200<0>C.

Metal catalysts are also used in the present invention, but these are less preferred.

Polyvalent metal compounds, which are described in the literature as catalysts for isocyanate chemistry, are used in the process according to the invention. These are preferably tin, zinc or lead compounds such as dibutyltin dilaurate, tin octoate, zinc acetylacetonate and lead octoate. These are generally less preferred.

The solvent component is at least partially, preferably completely, water-based.
Aromatic, aliphatic or cycloaliphatic cargenic acid amides which are miscible/water-soluble and have/~10 carbon atoms in the acid moiety, such as trimethylformamide (DMF)
, formamide, diethylformamide, dimethylacetamide, dimethylnoropionic acid amide, benzoic acid trimethylamide and N-methylpyrrolidone. Preferred are carboxylic acid sialkylamides, especially trimethylformamide.

The solvent is a water-soluble tetraalkylated aliphatic urea having ≠ to 72 carbon atoms, such as tetramethylurea or tetraethyleneurea; a water-soluble aliphatic or cycloaliphatic urea having 2 to 10 carbon atoms; 7j% by weight of a sulfone or sulfoxide, such as tetramethyl sulfone or dimethyl sulfoxide; and other neutral dipolar solvents such as water-soluble aliphatic or cycloaliphatic phosphoamides, such as hexamethyl phosphorylamide, etc. It may include up to

These optional solvents may be mixed in any proportion. Among these optional solvents are
Preferably, it is preferable to use one that boils at a temperature of 4 L to 4 L/l and at 70° C., since this simplifies the purification process.

Small amounts of solvents that are not completely miscible with water, such as gropionitrile, methyl ethyl ketone, ethyl acetate or hydrocarbons, may be used, but the addition of such solvents is not preferred. Preferably, only the image is used as a solvent.

The following restrictive conditions of this method apply to the amount of solvent used (in particular the upper limit).

/, more than b10, preferably 100 to 100% by weight of solvent should be used per 100% by weight of the isocyanate compound in the reaction mixture for hydrolysis.

Sufficient water and optional solvent should be used to produce a substantially homogeneous (very slightly cloudy) or preferably completely homogeneous clear solution of the isocyanate compound at the reaction temperature. Sufficient water is used at all temperatures of the process to produce a single-phase mixture, but to ensure that the ratios of solvent (DMF):water and water:NCO components are always within the ranges mentioned above. Particularly preferred.

Catalytically active compounds are generally added to the solvent and water. These may optionally be added to compounds containing isocyanate groups, but this is less preferred.

In order to hydrolyze the NGO compound to polyamines with a sufficiently large amine number (high conversion), the concentration of the NCO compound in the reaction mixture is preferably below 7% by weight!
It is advantageous to maintain less than or equal to j weight.

The degree of dilution is limited by the economics of the purification process, and in practice is within the range of three solutions.

However, in order to ensure that the reaction mixture remains substantially homogeneous, preferably completely homogeneous, at least sufficient solvent within the above ratios for the amounts of water, solvent and isocyanate may be used. is necessary.

According to a less preferred embodiment of the method, “H
Compounds having two or more hydroxyl, amino and/or thiol groups may be added to the reaction mixture.

Such compounds are those already mentioned as starting components for the isocyanate compounds used in the process according to the invention, and most preferably have a molecular weight of 62
It is a difunctional, or in some cases tetrafunctional, compound ranging from 5ooo to 5ooo. Compounds of this type containing at least two primary hydroxyl groups are preferred, such as ethanediol, butanediol, gulonocundiol, polyethylene glycol, trimethylol gulonone, and the like. Compounds containing different "H-reactive groups" can also be used, such as aminoalkanols.

Compounds containing only one H-reactive group may be used as monofunctional chain terminators. methanol, ethanol,
Cyclohexanol, cyclohexylamine, aniline or asymmetric dimethylhydrazone are examples of such stoppers.

Preliminary chain extension reactions, ie the reaction of the isocyanate with the already formed amine resulting in chain linkage and the formation of urea, can occur as a side reaction of the process according to the invention. This side reaction can be suppressed to a large extent by carrying out the process in dilute solution using the catalyst and solvent according to the invention and by maintaining a relatively high reaction temperature, for example IO to 730°C. Although it is preferable to reduce these side reactions as much as possible, some degree of preliminary chain extension is acceptable from an economic point of view.

However, if the process parameters are observed with sufficient precision, the process according to the invention makes it possible to virtually completely convert the isocyanate groups into NF2 groups.

The reaction according to the invention is preferably carried out in a homogeneous phase. When the starting material is incompletely dissolved due to the presence of a slight excess of water or excess isocyanate groups, a slight turbidity may temporarily occur in the reaction mixture.

However, the presence of multiphasic mixtures and precipitation of isocyanate brepolymers due to the addition of excessive amounts of water results in undesirable products. The optimal proportions in which the starting components should be mixed so that a homogeneous mixture is obtained in the required proportions is determined by a few preliminary tests.

As already mentioned, the reaction is carried out at a temperature of 20 to 210°C. However, using temperatures in the range 35 to 730°C, especially ♂O to 730°C, this gives the best volume/time yields with great solubility and surprisingly minimizes chain extension by urea. Therefore, it is preferable. In special circumstances it may be necessary to carry out the reaction under pressure in order to obtain sufficiently high temperatures.

The initiation of the reaction is confirmed by the almost spontaneous evolution of CO□, which is observed to occur even at low temperatures, for example 10°C. However, it is highly advantageous for the purposes of the present invention to use higher temperatures to suppress the formation of urea. It is important to ensure thorough and rapid mixing of the reactants to form a homogeneous solution.

This is primarily achieved by using solvents. The reduction in viscosity obtained when using elevated reaction temperatures occurs in the same direction. This reaction may be carried out patchwise or continuously.

3 of DE-O8 No. 3223327. ! Page, lines 20-3
The information disclosed on page 5, line 10 applies to both continuous and patch embodiments.

Purification of the final product is also carried out continuously or in patches. The reaction mixture is usually purified by distillation, extraction or phase separation or a combination of these methods. Extraction methods are carried out with solvents such as methylene chloride or chlorobenzene which are not soluble in water, optionally after dilution with water, but these methods are less preferred.

Phase separation of the reaction mixture upon cooling occurs when the hydrolysis is carried out at relatively high temperatures and in the presence of relatively large amounts of water at the limit of solubility. Phase separation is improved or actually carried out by the addition of water. The aqueous phase, which optionally contains the solvent and in most cases also the catalyst, is separated from the je lyamino.

This aqueous phase is then reused in most cases.

The polyamine phase contains other catalyst residues of the polyamine; some water and possibly a solvent.

These substances are removed as completely as possible by distillation or thin film distillation, using a vacuum if necessary.

When a compound containing isocyanate groups still contains free (i.e. monomeric) isocyanate due to the method used for its preparation, the polyamine produced from this monomeric isocyanate can be used to purify the product by phase separation. However, large amounts can accumulate in the water/solvent phase. The polyamines obtained by this simple purification method contain almost no monomers. However, it is desirable to purify the solvent phase to be as free from monomeric amines as possible before using it again.

The reaction mixture is preferably purified after the end of the reaction (no more cO2 evolution is observed) by distillation of the solvent or solvent/water mixture without phase separation. Distillation is preferably carried out under vacuum (eg, 100 Torr), although a higher vacuum (eg 0.00 Torr) may be applied to remove volatile residues.

It has been found preferable to start from a temperature in the range of about 10-100°C and then increase the temperature to ♂O-100°C. The distilled solvent is used in several iterations.

The preamines obtained by the process of the invention after the purification step are generally colorless or slightly colored, have a medium to high viscosity, and in some cases have a viscosity of 0. /Rinaishi/3. ．． It is a relatively high melting point product with an amino group content of 23% by weight. These polyamines were also already present in the starting materials from which they were prepared. These include urethanes and/or ureas and/or uretdiones and/or incyanurates and/or biuret groups and/or uretonimine groups and optionally ethers and/or acetals and/or car&nates and/or esters and/or thioethers. and/
or containing groups such as dialkylsiloxane groups and/l or polybutadiene groups. Additional bonds are generated by side reactions. For example, urea groups are generated during hydrolysis from previously saponified moieties or from residual isocyanate groups. The amount of primary aromatic amino groups present in the polyamine is at most the same as the amount of isocyanate groups present in the isocyanate compound, ie about 0. /23% by weight of NH2 (if the isocyanate content is from 0.! to 40% by weight), preferably 0.5% to 40% by weight. lIL Otsunaishi Z! , 2% by weight NH2
(NCO content 7.2 to 2% by weight) and preferably o,! r, r to 3, ♂wt% NH
2 (NCO content/10% by weight).

In view of their low vapor pressure, the polyamines of the invention, which are preferably aromatic, can be blocked or free during the production of polyurethanes (polyurethaneureas), cellular or non-cellular I-urethane plastics or polyurethane foams. It is preferably used as a reactant for the lysocyanate stock. These amines may also have relatively low molecular weight (molecular weight 3.2 to 377) and/or relatively high molecular weight (molecular weight 1It00 to about i2.ooo).
may be combined with other compounds containing isocyanate-reactive groups. Suitable starting components for the production of polyurethanes by known methods are also DE-A No. 230.2! Otsu≠, 2≠3.274≠ (U.S. Patent No. 3103 Otsu No. 7)
, 2 otsu 390f3.2 j / 23 f t1.2 to 731/! , 25 pm 07 ri otsu, 2 tata 07 ri 7.2! j
O♂33.2! ! It is described in i-0 dootsu 0 and 2 tata o dootsu 2.

! Already described in connection with the preparation of repolymers, these disclosures also teach auxiliaries and additives used in the production of polyurethanes.

The invention also provides polyurethanes of polyamines according to the invention (
It also relates to uses for the production of urea).

These are used for example for the production of elastomers, coatings and textured yarns and are solvent-free melts,
Applied as a solution, dispersion or mixture of reactive components.

The polyamines of the present invention can also be used in the reaction of all other known amines, such as coupling components of diazo dyes, curing agents of epoxy or phenolic resins, and the formation of amides or imides and the like.

The following examples are intended to illustrate the invention. Amounts given herein are in excess of parts or percentages by weight unless otherwise specified.
It should be understood as indicating the

(Left below) Example / The isocyanate compound used in this example is OI (the number is I).
2 polypropylene glycol tolylene-, l! ,l
, L-) iso'/1. +-to and no NCO: 0H=2:
The isocyanate content was prepared by stirring a mixture with an equivalent ratio of / for 3 hours at ♂Q°C. It was Otachi's isocyanate prepolymer.

/7 ml of dimethylformamide (Dη) som
Mixture of i with water (DMF/H20= J 3., :z
: / ) was introduced into the reactor and heated to 10° C. with stirring.

5ooi of the isocyanate prepolymer was added at this temperature during 2Q minutes. After adding all the prepolymers,
As stirring continued throughout the evening, the CO2 generation rapidly decreased)
, then DMF and water under vacuum (♂0~100℃ initially/
0.0 millibars, then 0. / 3 Mi IJ Pearl)
It was removed by distillation.

Number of books (HCl04): 3/, /da KOH/g example! /7 j-0111 DMF, j Q ml water and 7 g sodium chloride mixture was introduced into the reactor.

Experiments were then carried out using the same amounts of the same isocyanate prepolymer as described in Example/, and the products were purified in the same way. Number of books (HCl04) is 37.3m9KOV
It turned out to be g.

As shown in Examples/and 2, the hydrolysis could be carried out relatively favorably with the mixture of DMl/H20, but the conversion rate was better with the addition of a catalyst (even a small amount) than with the addition of a catalyst (even a small amount). Relatively low (see examples).

Example 3 (comparative example) /7! A mixture of 1000 DMF, 100% water and 100% acetic acid was introduced into the reactor at 20° C., and the same amount of the same isocyanate prepolymer as in Example 1 was then used and the product was purified in the same way, I conducted an experiment. Number of books (HC
A product with lO4) of only 2 and ≠~KOH/,9 was obtained.

Examples Hiroshi-Otsu (Comparative Examples) The isocyanate compound used in these examples was an isocyanate prepolymer that was identical to the prepolymer from Example/, except that the isocyanate content was only 3.3%.

2! d of water and/, 7jl of acetone or/, 7
j l's nooxane or/, 7! A mixture of RL of acetonitrile and 0.7g of hydroxide was introduced into the reactor with stirring at 90°C or the reflux temperature of each of acetone, acetonitrile, and 5ooy of the above prepolymer was used for example/and Similar experiments were conducted to purify the product.

Number of volumes (HClO4) When acetone is used: 2Z m9KOH/g When dioxane is used - B, f m9KOH/g When acetonitrile is used: 2 B, 7m9 KOVgThe conversion rate of NCO to NH2 is when an alkaline catalyst is used. Nevertheless, it was insufficient (i.e., low NI(number)).

Example 7 (comparative example) /7! rOrnl's Methyl Ethyl Ketone,! 0.9% water and 0.29% sodium formate were introduced into the reactor at 20°C. The isocyanate prepolymer from zoog example/was added within 20 minutes. After purification of the reaction mixture as in Example/, 3/, j my KoH,/, p
A product was obtained having an NH number (HClO4) of . O
The H number was clearly lower than that obtained when using the solvent according to the invention.

Example ♂ (comparative example) /l of methyl ethyl ketone, /! 2 g of dimethyl formaldehyde, 3.0 rnl of water and 7 g of sodium formate were introduced into the reactor at reflux temperature.

The isocyanate prepolymer from Example 30011 was added within 20 minutes. After purification of the reaction mixture as in Example/, the NH number (H
A product with ClO4) was obtained.

example? -2,2 These examples are hydroxide solution (NaOH)
) is a catalytic property.

example? In this example, tolylene-2,4L-diisocyanate and adipic acid, ethylene glycol and butane-hemogudiol (ethylene glycol: ftanediol, molar ratio = 7:J) OH number! Otsu de NCO10H
A prepolymer with an isocyanate content of 3.7% was used, which was prepared by stirring a mixture with a ratio of 2:/ for 3 hours.

Yoll's DMF', /2 water (D/water ratio ≧ 4'/
, 7:/: water per isocyanate equivalent, 2.7 mol) and 0.2jfi of NaOH (0.07% by weight based on the isocyanate brepolymer) were introduced into the reactor and heated to 10°C. Heat to 10°C, 2. Yuyu's polyether! Added lima within ≠j minutes. The product was purified as in Example/.

Number of books (HClO4): 4t7.1 free KOI (/, 9NH number (AczO/Py)
: 11t75' 9 KOH/1(Py
= pyricin) S number (Ac20/Py): 0
．． 3Img KoH7g (S number = acid value) TDA content (HPLC): 0.92
/ % (HPLC = high pressure liquid chromatography) y residue content (GC); o, mpi% (c
c=gas chromatography) Example/Q/, 7 j l ODMF, 0.0? ,! 9
0 NaOH ((oit wt% based on 7'y7ate prepolymer) and somt water (DMF/H2
0 ratio = 33.2: /: Iacyanate equivalent water, 37! mol) was heated to 2°C,
was introduced into the reactor. Isocyanate content is 3. Otsuj%
5ooi of isocyanate pre-4lima from example 1 of 7
Added within minutes. The product was purified as in Example/.

Number of NH (HClO4): 4tIIL, Img
KOH/gNH number (Ac20/Py)'
≠Otsu, 4'9 KOH/gS number (Ac20/Py)
: 0. Img KoH7g example // and /2 /, /ll DMF, o, OJ-y NaOH (
0. based on isocyanate bleed polymer. O/weight f%
) and a mixture of 25I water (DMF/water ratio: 4t
/,7:/:Isocyanate equivalent water3. J″22
The mol was introduced into the reactor at 20°C. 3.34 00g of the isocyanate pre-4lima from Example 4tb containing NCO was added in 2° portions. The product was purified as in Example/.

Number of NH (HClO4): 4'7. Hiro!
KOH/, 9NH number (A e 20/Py):
4t7. OtsuIn9KoH/! yS number (AczO/P
y): 0.07~KOH/7TDAt (
? LC): 0.4t3f%0.7I NmO
H (o, o2 based on isocyanate bleed polymer
% by weight) was used in place of NaOH for o, o t , p, but using the same conditions and the same components, 4 tl
s, Img KOH/, 9 no M number (HClO4)
o product was obtained.

Example/3 /, / l (D DMF, 0.02 evening/i 0
NaOH (0.0% based on isocyanate bleed polymer)
00I weight %) and! A mixture of diluted water (DMF/water ratio = 4/, 7:/) was heated to 10° C. and introduced into the reactor. Isocyanate content is 3. Example of Otsuchi (3.23 moles of water per isocyanate equivalent) / soog isocyanate bleed polymer from,! Added within 0 minutes. The product was purified as in Example/.

Constant (HClO4): ≠6.7■KOH/
, 9 cases/Hiroshi/, 7 j l DMF, o, oig NaOH (0.002% by weight based on isocyanate bleed polymer)
) and a mixture of water (DMF''/water ratio 33.
λ:/) was introduced into the reactor and heated to 0°C. Isocyanate content is J, I, % (NCO!!l, 4
The isocyanate pre-4 Lima from Example/T6 moles of water was added within 20 minutes. The product was purified as in Example/.

Number of NH (HClO4): 4t3. Hiromy
KOH/p number (Ac 20/Py): 4'
? ! / j'li' KOH/ gS a(Ac2
0/Py): 0. / m9 KOH/F
Example / evening /, / / ODMF, o, o, zrp Na OH
and a mixture of 9 water was introduced into the reactor and heated to 5) oc. Isocyanate content is J,
5ooy of isocyanate brepolymer from example≠ of 3% NCO was added within 7 minutes and the mixture was stirred for 2θ minutes.

The product was otherwise purified as in Example/.

Number of NH (HClO4): 4t2.
l, my KOH/g Example/2 In this example, the isocyanate content is 3. /Rideashi,
Then, a preester using an isocyanate prepolymer obtained from a polyester with an OH number of 3″0 and an NC010H ratio of trilene-co,≠-zoisocyanate of 2:/, has an amount close to the equivalent of anovic acid and hexane/,
It was made from Otsu-Sool, and the OH number was ≠/.

lA! l OIIMF, / 00.9 A mixture of O water and 0.2 fl (D water) was introduced into the reactor and heated to 20 °C with stirring. 2 kl of said isocyanate prepolymer (O °C) was added within 4 tJ'' min. The product was purified as in Example/.

N'H number (HClO4): 1It3. Evening In9KOH/gNH count (Ae 20/P y)
: 4tJ, f evening m9KOI(/pS number(Ac 20
/Py): 0.4t DaKQH/gTDA content (?LC): 0. ♂/% Example/7 In this example, an isocyanate prepolymer obtained from an isocyanate content of 2.3≠H and an NC010H ratio of polyester to tolylene-2μ-diisocyanate of 2:/ was used. The polyester was prepared from /:/ adipic acid and diethylene glycol and had an OH number of 11 t/.

A mixture of 7 liters of DMF, 100 ml of NaOH and 100 ml of water was heated to 10° C. and introduced into the reactor. 30 I of the prepolymer while stirring
Added within minutes. The product was purified as in Example/.

■Number (HClO4): , 2 Otsu 0 ~ KOH
/gTDA content (HPLC): 0. ．． 20
Otsuchi example/In this example, the isocyanate content is 3.4t%,
and polyether mixture and trilene-2,4t-
An isocyanate prepolymer obtained from diisocyanate was used. This preether mixture has a 0OOH number and a functionality of Jj, and is a trimethylol glo/gun and hi PO/E starting from globylene glycol.
It was a mixture of /:/ of Oyjf riether.

3,! l DMF, 0. /i NaOH and 100 m
A mixture of water in step 1 was heated to 0° C. and introduced into the reactor.

1000 ji of the prepolymer was added within ≠θ minutes while stirring. The product was purified as in Example/.

■Number (HClO4): 4tlA3 In9
KOH/g constant (Ac20/Py): '13
．． j rn9KOH/gS number (Ac 20/Py)
'0-3g KoH/9TDA content () IPLC
): 0.0t7chi example/9 In this example, the number of OH! NC01 of Otsu's 4-tetramethylene glycol, trilenco, and Kudi isocyanate.
A prepolymer with an isocyanate content of 3.7% obtained by stirring at 0° C. for 3 hours with an 0H ratio of 2:/ was used.

A mixture of /, 7 j l DMF, o, ori NaOH and joli water was heated to 10°C and introduced into the reactor. The prepolymer 5009 was added within 20 minutes. The product was purified as in Example/.

Number of books (HClO4): 39J mgKOH/
jiTDA content (HPLC) 2 09.2♂/
In this example, the number of OH! NC of ester B (same as in Example) and diphenylmethane≠,≠'-diisocyanate
The isocyanate content obtained by stirring at fO ℃ for a long time from one with an O/OH ratio of 2:/ is 2. A horse chestnut prepolymer was used.

/, 7 J” l of DMF′, o, o t , p of NaOH and 50 g of water were heated to 10° C. and introduced into the reactor.!ooi of the above prepolymer and h,
Add a freshly prepared mixture of 200p DMF to 3j
Added within minutes. The product was purified as in Example/.

Number of NH (HClO4): 3/, G~KOH
/, 9 ■ Number (Ae 20/Py): -29
, -25m9 KOH/9S number (A c 20/P)'
) : (7,-2m9 KOH/gMDA-≠
, 4t' content (HPLC): /, 4t♂ multiple example 2
/ In this example, polyether diol (polyethylene glycol) with an OH number of 3" was added in blocks with 1096-1' propylene oxide, then 20% ethylene oxide, and using an NC010H ratio of !:/ obtained) and!, from cootolylene diisocyanate♂
Isocyanate content obtained by stirring at O℃ for a long time /,♂
A 7-chi prepolymer was used.

/, 7 j l DMF″, o, o t g Na
A mixture of OH and jQd water was heated to 5'0°C and introduced into the reactor. 5ooy of the prepolymer was added to 30
Added in minutes. The product was purified as in Example/.

Number of books (HClO4): 23.7 Da/KOH
/g Example 2.2 In this example, the polyether triol with an OH number of 2♂ obtained by adding 7% by weight of propylene oxide and then 73% by weight of ethylene oxide to trimethylolpropane and the isocyanate content are NCO obtained by stirring 2.4L-tolylene diisocyanate at gO ℃ for ≠ hours
: A prepolymer of OH=2 :/ was used.

/, 7 j l DMF, O, O, +, V NaO
H and! A mixture of 0 p of water (p per isocyanate equivalent)
/2.2 moles of water: DMF/H20 ratio = 33.2
:/) was introduced into the reactor. rooy's isocyanate prepolymer was added for 30 minutes. The product was purified as in Example/.

Number of NH (HClO4): 25/! ηKO
H/, pNH number (Ac20/P)'): -2
4', Om9KOH//! S number (Ac20/Py)
: 0.2 myKoH/g Example 23~. 25 The effective action of sodium aluminate is illustrated in these examples.

Example, 23/7JOmle Month ■ A mixture of JOg of water and 0.7g of sodium aluminate was introduced into the reactor at 10°C. Isocyanate content is 3. % (H2O: NC
O ratio; approximately 6.41. 1, 5" OOI of the isocyanate-containing portion of Example/) was added with stirring.

The product was purified as in Example/.

Number of friends (HClO4): 3/, Otsu I
n9KOH/g number of books (Ac 20/P y):
! r /, evening In9KOH/gS number (Ac20/p
y): o, /myKoH7g TDA Content (HPLC) 20, 1/% Example, 1iioog DMF, 23g water and 0.0/9
A mixture of sodium aluminate was heated to 10° C. and introduced into the reactor. While stirring, 300 fj of isocyanate prepolymer from Yukihiro with an isocyanate content of 3.3 t (H2O:NCO ratio = about 3.5:/) was added to l! Added within 0 minutes. The product was purified as in Example/.

Number of NH (HClO4): 1l-7/jm
9KOH/, 9 cases 2 nights/100.1i+ of DMF, 2 nights of water and o,
A mixture of sodium aluminate with o t and p is 0'
CK was heated and introduced into the reactor. An isocyanate prepolymer (H
2O:NCO ratio=3. tj: /) 100, 5
' was added while stirring. The product was purified as in Example/.

Number of NH (HClO4): tA/, 7 tn9
KOH/1 Example 2 B A7 tal DMF, 50/i water and λ,! KH of g
Mixture of CO3 (wt% O, S based on isocyanate prepolymer: DMF/water type ratio = 33..2:
8 NCO/97.03 moles of water) were introduced into the reactor.

The isocyanate prepolymer zoog from example≠ with an isocyanate content of 3.3 was added within 20 minutes. example/
The product was purified as follows.

Number of volumes (I (clO2): 'A7.3 m9K
OH, #Examples 27-2♂ These examples show cases where a large amount of water is used which gives unfavorable results, ie when the OH number is low due to low NCO/NH2 conversion.

Example 27 /, j l DMF, 23;0rrLt water (3,2
,3,2 moles of water/NCO/DMF/water ratio=
J:9':/) and 0.05I of KHCO, (0.0/wt% based on the 7' repolymer) at 10%
It was heated to ℃ and introduced into the reactor. Isocyanate content is 3. Example of Otsuchi/Isocyanate prepolymer from! r
Added within 20 minutes. The product was purified as in Example/.

Number of cells (T (clO2): 37gm9KOH
/9 ■ Number (Ac O/Py): 31ri 3m9
KOH/1S number (Ae 20/Py): (
:), / 'Ii' KOH/II example 2/, j J's DMF,, 2 evenings 0 go's water (DMF/H2
A mixture of sodium formate with a ratio of 0 = s, 9 : / ) and o, o ty was introduced into the reactor. A OOy prepolymer from Reihiro with an isocyanate content of 3.3 t was added within 20 minutes. The product was prepared as in Example/.

Example 2 /, 7 j J DMF, sOg water and 0.21
Af! A mixture of sodium formate (HCO2N11 ) was heated to 10° C. and introduced into the reactor. The inocyanate furopolymata OOy from Example/ was added with stirring, the reaction was continued, and the product was purified as described in Example/.

Number of NH (HCIO4): Evening OJ rru
iKOH/gNH number (Ac20/Py): t
ll, tA m9KOH/, 9S number (Ac O/Py)
: 0. /m9KOH7gExamples 30-410 In these examples, a mixture of polyoxypropylene glycol with an OH number of 32 starting from tolylene-2,41-diisocyanate and trimethylolpro-9 was stirred at 0°C for an hour. The obtained isocyanate prepolymer was used. Examples 30-33 used a product with an isocyanate content of 2.1%. Examples 3, 3, 3, and 3 used a product with an isocyanate content of 2.3%, and Examples 37 and 40 used a product with an isocyanate content of 2.2%.

Example 30 /, /l of father-in-law, Kota d of water and 0. Q2 evening NaO
The mixture of H was introduced into the reactor under heating and stirring. 100 g of the prepolymer with an isocyanate content of 2.7% are added at the reaction temperature with stirring, the reaction is then continued and the product is purified as in Example/NH number (Hclo4): 3 o , I my
KOH/gNI (number (Ac20/Py):
J IAO”9 KoH/IS number (Ac20/Py
): 0.0 t rwKou/g Example 3/ /3/l DMFl, 2jd water and 0.0/l,
9 was heated to 10° C. and introduced into the reactor with stirring, the roog inocyanate fluoropolymer from Example 3/ was added at this reaction temperature with stirring and produced as in Example/. Purified things.

Number of NH (HCIO): , 2Zf m1i
KOK/9NH number (Ac O/Py): 33
J m9KOH/gS number (A (! 20/Py)
: 0,0! '9 KOH/g Example 32 /, /A DMFS,? Evening ml water and o, oorg
of NaOH was heated to 10° C. and introduced into the reactor with stirring. 00 g of inocyanate fleopolymer from Example 30 were added at this reaction temperature and reacted and purified as in Example/.

Number of NH (HCIO4): 3/, / m9K
OH/fj ■ Number (Ac O/Py): 3.2
．． / rtu;zKoH/gS number (Ae 20/Py)
: 0.0! ηKOH/, 9 examples 33 DMF/l, 2 d water and 0.002 s N
The aOH mixture (o,ooos weight % based on prepolymer) was heated to 10° C. and introduced into the reactor with stirring. 50 g of the isocyanate prepolymer of Example 30 were added at this temperature with stirring and reacted and purified as in Example/.

Number of NH (HCIO4: ,
25'! ≠ Fly *OH/,! i'NH number (Ae 20
/Py) '-21otrn9KOH/, 9S
Number (Ac20/Py): 0. Ojmtp K
Substantially similar results were obtained using OH/10.00.2 days of KOH.

Example 3 A mixture of 1/1 DMF, 2 d water and 0,000 ml KOH was heated to 20° C. and introduced into the reactor with stirring. Isocyanate content similar to that used in Example 30,! , 3% same pre? Lima 100
g at 90℃, stirred, reacted, and Example/
It was purified as follows.

Number of NH (HClO4): , 2P, 2~KO
A mixture of H/g Example 3j/, /l DMF, 2 td water and 0,002 td9 NaOH was introduced into the reactor with stirring at 4 tJ''°C and the same as used in Example 3 was added. The same isocyanate prepolymer soog was added at this reaction temperature with stirring, but stirring was continued for 20 minutes (cO2 evolution ceased). The product was purified as in Example/.

Example 3z /, /l DMF, 2 liters of water and 0.7 g NaO
A mixture of H was introduced into the reactor at 4 tons with stirring. The same isocyanate prepolymer used in Example 3≠
oog was added at this reaction temperature with stirring. Stirring was further continued for 2t minutes, during which time one sample was removed after 5 minutes. Both samples were purified as in Example/.

Number of spaces (MCI04j diameter): 2? , <A tp
lKoH/gN) (number (after HC'1042 evening):
, 29.0 myKoH/! ? This is I/Lt℃
The reaction was also complete 5 minutes after all reactants had been added, indicating that no benefit was gained from further prolongation of stirring.

Example 37 /, /l DMFl, 23; ml water and o, or
4 t of KOH mixture of i was added to the reactor with stirring at 5''°C. Similar to Example 30 except that the isocyanate prepolymer containing 2.2% was added to the reactor with stirring.
It was added at this temperature with stirring. Subsequent processing and M preparation were similar to Example/.

Number of NH (HCl04): 2ZOmg KO
H/9 Example 3/, /J DMF' and 2. A mixture of rml water was introduced into the reactor at 90° C. with stirring. 5 ooi of isocyanate prepolymer from Example 3≠ were added at this reaction temperature with stirring. The product was purified as in Example/.

Number of NH (HClO4): /7J m9KO
H/g 0 after adding all isocyanate prepolymer
,．． 2 g of //10 N NaOH were added to the reaction mixture and the mixture was then heated at 10°C for 4t! After stirring for a minute, the product obtained after purification of the reaction mixture as in Example / had an NH number of /7♂drops KOH/g (HCl04 method). This shows that the reaction was completed within 5 minutes after adding all the isocyanate prepolymer even without catalyst.

Example 3 DMF of ri/, /l and 2! d water mixture at 737℃
was introduced into the reactor with stirring at a reaction temperature of (reflux).

The isocyanate prerif soog from Example 3≠ is 2
Added within 7 minutes. The reaction temperature was lowered to 730°C due to the addition of the isocyanate prepolymer, and the bath temperature was lowered to 730°C.
(0°C) and reflux subsided.

Even more under reflux! After stirring for minutes, the reaction mixture was purified to yield 1.20.7 my KoH/g of Nl (number (H
A product with C104) was obtained.

The reaction mixture was stirred for 3Q minutes and then purified under reflux to yield 2/3 mg KOH/7 NHs (HCl0
4) A product having the following properties was obtained.

This shows that the reaction was complete without catalyst and at this temperature within 5 minutes after adding all the isocyanate pre-4 lima.

Also, in Examples 3♂ and 3, the products obtained without catalyst are superior to those prepared without catalyst according to DE 322 339♂, but preliminary chain extension (urea formation) This indicates that the degree of

EXAMPLE 0 (COMPARATIVE EXAMPLE TO EXAMPLE 3♂) A mixture of /, /l DMF' and 300 ml of water was introduced into the reactor and heated to 0° C. without stirring.

The isocyanate prepolymer from Example 37 was added to the roog with stirring within 20 minutes. A dull polymer was then separated which did not dissolve even in pure MF or acetic acid. When we attempted to measure the number of insoluble materials, the results obtained were NH
The number was J~KOH/, p.

This experiment is based on DE 322339f and 3.223
It is shown that the water/solvent (or water/DMF) ratio used in No. 377 gave less favorable results than those obtained with the method of the present invention. This means that the process of the invention, even when carried out in a less preferred manner, has a favorable NCO/NH2 conversion and a considerably large NH number, whereas the products obtained by the prior art processes are practically unusable. It is shown to give useful liquid and solid products.

Example Hiro/Otsu/Otsugo's DMF'and/Hirogo's water were introduced into a 31 autoclave and heated to 130°C. 2♂Oy of the isocyanate prepolymer used in Example 37 was then added within 5 minutes with stirring using a metering pump. The temperature of the isocyanate pre/+77 was 50°C. Stirring was then continued for a further 5 minutes at 150° C., and the reaction mixture was cooled, the pressure was released and the solvent was distilled off as in Example 1. A brown substance was obtained with the following data:

Number of NH (HClO4): 2F, Ta r
Number of n9KOH/7NH (Ac20/Py):
, 27/rn9KOH/IS number: 0.0
3m9 KOH/, 9 molar mass = 3g2ta, the theoretical value is 3! / (measured by vapor osmotic pressure method) TDA content: O, CO f♂ wt % Example 4t2 (comparative example) 600 - of water /, in an autoclave of 31 / 0
C. and the isocyanate prepolymer 3009 from Example 37 heated to 50.degree. C. was added within 10 minutes.

Stirring at 760° C. was continued for an additional evening, then the reaction mixture was cooled, the pressure was released, and the water was decanted from the resulting product.

The product was a viscous gum but still partially dissolved in the 10,000/ethanol mixture at VCIO°C.

In addition, O of the soluble portion (after removal of solvent by distillation)
The H number was //, /■KOH/g (HClO4).

Example 413C Comparative Example Example ≠C was repeated except that 0.06 I of KOH was added to the water. The product obtained after purification is DMF
It was a swollen substance completely insoluble in.

NH number could not be measured.

Example Hiro≠ (IL) Preparation of Prepolymer/2/Toluylene diisocyanate (7 mol) of ♂I was heated to 0°C. Hiro-diol was added to 90 g of butane within 40 minutes. The reaction product precipitated as the reaction approached completion. Then t.

Stirring was continued for 7 hours at °C. Paste mixture at 23℃
It was diluted with 27 cyclohexane, filtered with suction, washed with cyclohexane and petroleum ether and dried in a vacuum drying mold at 4°C and 0°C. The product melted at 730~/3/°C and the isocyanate content was /'ZO% (2:
/ Calculated value of isocyanate content for adduct: /1
．． 2%).

(b) Preparation of polyamine A mixture of 31M DMFlo, /6&KOH and 7≠G water was introduced into the reactor. toomt's DMF
A dispersion of 310 g of the isocyanate prepolymer in the solution was added at 0° C. within 20 minutes with stirring. 3
It was found that CO□ of /l was generated (theoretical value 3 /l).
, 4tl). The solvent was then extensively distilled off and the product was precipitated from the liquid residue with a 10:1 mixture of water and methanol. The product was filtered off with suction, washed with water and dried.

M number (Ac20/Py): 27'A mgKo
H/11 (theoretical value: 2dodo) Acid value (Ac 20/P y): 0,4'
"fi' KOH/9 molar mass (vapor osmotic pressure method) = 3
7ta~Hirooo (theoretical value: 37f) TDA value (HPLC
): 0.352% positive number (HPLC):
2 Otsu 4Lm9 KOH/,! i' : m, p, :
/Otsu♂～/Otsuri℃ Example 4t! A mixture of 1/750!14 dimethylformamide, 30 ml of water and 0.0/g potassium octoate (0.00.2 g based on isocyanate prepolymer) was introduced into the reactor. The mixture was heated to 0°C, 0g of isocyanate prepolymer from an example heated to 10°C was added within 20 minutes and purified as described in the previous example. This preamine has NH number (A
c20/Py) was 4477jm9KOH/g.

Claims (17)

[Claims] (1) In a one-step method for producing a polyamine containing primary amino groups, (a) an organic isocyanate having an isocyanate content of 0.5 to 40% by weight is added (b) to each equivalent of isocyanate groups in (a) above. (c) at least 10% by weight, based on 100% by weight of (a), of a carboxylic acid amide; and (d) from 0 to 1% by weight, based on 100% by weight of (a), by 0.75 to 50 moles of water. % of a non-inclusive base and/or metal catalyst, the weight ratio of (c) to (b) is from 3 to 200 to maintain a homogeneous phase during the hydrolysis and the hydrolysis is from 20 to 200. The method for producing polyamine, characterized in that it is carried out at a temperature of 210°C. (2) Process according to claim 1, characterized in that the isocyanate (a) contains aromatically bonded isocyanate groups and is an NCO-prepolymer or a modified polyisocyanate. (3) 1.2 to 25% by weight of isocyanate (a)
2. The method according to claim 1, wherein the method has an isocyanate content of . (4) The catalyst (d) is present in an amount of 0.0001 to 0.099% by weight.
Manufacturing method described in section. (5) The catalyst (d) is an alkali metal hydroxide, alkaline earth metal hydroxide, tetraalkylammonium hydroxide, alkali metal aluminate, alkali metal phenolate, alkali metal thiophenolate, alkali metal mercaptide, alkali Metal hydrogen sulfides, cyanic acid, thiocyanic acid, isocyanic acid, soluble alkali metal salts of thiocyanic acid, cyanic acid, thiocyanic acid, isocyanic acid and alkaline earth metal salts of thiocyanic acid, alkali metal β-diketone-enolates, alkali metal 5. The manufacturing method according to claim 4, wherein the manufacturing method is selected from carbonates, alkali metal hydrogen carbonates, alkali metal salts of organic carboxylic acids, and alkaline earth metal salts of organic carboxylic acids. (6) 1.5 to 1.2 mol of water per equivalent of (a) (
b), the solvent (c) is a carboxylic acid dialkylamide, and the weight ratio of (c) to (b) is from 10 to 150, and the hydrolysis is from 35 to 165.
6. The manufacturing method according to claim 5, wherein the manufacturing method is carried out at a temperature of .degree. (7) The manufacturing method according to claim 6, wherein the weight ratio of (c) to (b) is from 25 to 75. (8) The manufacturing method according to claim 1, wherein the solvent (c) is dimethylformamide or dimethylacetamide. (9) (e) For every 100% by weight of (a), from 0.1 to 5% by weight of a compound containing at least one hydroxyl, amino and/or thiol group. The manufacturing method according to item 1. (10) The manufacturing method according to claim 1, wherein the hydrolysis is carried out at 40 to 150°C. (11) containing catalyst (d), using 0.0001 to 0.99% by weight of tertiary amine as catalyst (d), based on 100% of each of isocyanate (a); Process according to claim 1, characterized in that from 1 to 24 mol of water per equivalent is used and the weight ratio of (c) to (b) is 10 or more and 100 or less. (12) A process according to claim 11, characterized in that the solvent (c) is dimethylformamide and 1 to 7.5 mol of water is used for each equivalent of isocyanate (a). (13) 0.0002 to 0.008% by weight of metal catalyst (d) from 2 to 7 for each equivalent of isocyanate;
．． Process according to claim 1, characterized in that 5 mol of water and a weight ratio of (c) to (b) of 10 to 50 and a temperature of 35 to 165° C. are used. (14) 1 to 25 for each equivalent of isocyanate
Solvent (c) using mol of water (b) (c) (b)
dimethylformamide used in such an amount that the weight ratio to
The manufacturing method according to claim 1, characterized in that the temperature is 5 to 165°C. (15) The isocyanate (a) is an isocyanate prepolymer having an isocyanate content of 1.5 to 10% by weight or a urethane-modified polyisocyanate having an isocyanate content of 1.5 to 20.5% by weight. The manufacturing method according to claim 1. (16) A polyamine characterized by containing 0.46 to 9.52% by weight of primary NH_2 groups produced by the method described in claim 1. (17) A method for producing polyurethane, which comprises reacting the polyamine produced by the method according to claim 1 with an isocyanate, optionally in the presence of another compound containing an isocyanate-reactive group.