DE2318154C2 - Process for the preparation of compounds containing hydantoin rings - Google Patents

Description

R ⁴
Hai —C —COOR ⁷

OR ⁴ R ⁴ O

R'-OC-C-C-C-O-R '

10

15th

Shark shark

and

/ R ⁴ O

I ii

R ⁶ - C - C - O - R ⁷

Shark

25th

in which

Hai a halogen atom,

R ^{4 is} hydrogen, an alkyl, aralkyl or aryl

rest,
R ^{6 is} an aliphatic Cj — Cio radical, aliphatic-aromatic C6 — Qo radical or aromatic C ₅ —Qo radical,

R ^{7 is} an alkyl or aryl radical and y is an integer from 1 to 3,

optionally in a solvent, at temperatures from 20 to 220 ⁰ C and, after the end of the first reaction stage, the reaction product in a second stage with an aliphatic or aromatic monoisocyanate, optionally substituted by heteroatoms, or an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanate or a cleavage of these isocyanates at temperatures of 80 to 250 = C, characterized in that the crude reaction product obtained in the first stage, consisting of glycine esters with the structural units

-RS-NH-C (R ⁴ J ₂ -COOR ⁷

and amides of -halocarboxylic acids with the structural units

wherein R ^{5 represents} the remainder of the mono-, di- or polyamine, is used directly without purification in the second stage.

2. The method according to claim 1, characterized in that there is at least 2 primary Amino group-containing compound with a -halocarboxylic acid ester and at least 2 Reacts isocyanate group-containing compound.

3. Process according to Claims 1 and 2, characterized in that there is an aromatic polyamine with at least 2 primary amino groups with one -halocarboxylic acid ester and one aromatic Reacts polyisocyanate

4. Process according to Claims 1 to 3, characterized in that one per equivalent of primary Amino group between 0.9 and 1.1 equivalent of a -halocarboxylic acid ester and at least 1 Reacts equivalent of a polyisocyanate.

It is known that polyhydantoins can be simplified by the implementation of dantoins by the following

at least difunctional glycine ester derivatives with 45 and a schematic reaction equation illustrated

To produce polyisocyanates (cf. French Pa publication 14 84 694). This formation of polyhy-

R ¹

R ¹

R ¹

R ¹

flOCN - R ³ - NCO
(H)

O = C
R ³ -N

R ¹ R ¹

-CR ¹ R ¹ - C-

N Ar N

C. O

C =

N

C O

_(| Equation 1

In this reaction equation, R 'denotes, independently of one another, hydrogen or alkyl, preferably with 1 to 4 carbon atoms, R ² denotes hydroxyl, amino, alkylamino, dialkylamino, alkoxy or aroxy, the alkyl groups preferably having 1 to 4 carbon atoms and the aryl groups preferably 6 to 10 Contain carbon atoms, Ar is an aromatic radical and R ³ is the organic radical of a diisocyanate.

The response can also be multifunctional Starting materials, d. H. on glycine ester derivatives with more than 2 glycine ester functions and on polyisocyanates with more than 2 isocyanate groups are transferred. In this case, branched molecules are formed.

The invention relates to a process for the preparation of compounds containing hydantoin groups, wherein a primary mono-, di- or polyamine with a c-halocarboxylic acid ester is used in a first stage of the following general formulas

R ⁴
Hai —C —COOR ⁷

OR ⁴ R ⁴ O

₇ Il II Il

R ⁷ -OC-C-C-C-O-R ⁷
Hal Hal

R ⁴ O

R "-rC - C - O - R ⁷
Shark

in which

Hai a halogen atom,

R ^{4 is} hydrogen, an alkyl, aralkyl or aryl radical,

R ^{6 is} an aliphatic Ci-Qo radical, aliphatic-aro-

matic Ce-Cio radical or aromatic

Cs-Cio residue,

R ^{7 is} an alkyl or aryl radical and
y is an integer from 1 to 3.

IO

15th

20th

JO

optionally in a solvent, at temperatures from 20 to 220 ⁰ C and after completion of the first reaction stage the reaction product in a 2nd stage with an aliphatic or aromatic monoisocyanate, optionally substituted by heteroatoms, or an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanate or a cleavage of these isocyanates at temperatures of 80 to 250 ° C, which is characterized in that the crude reaction product obtained in the first stage, consisting of glycine esters with the structural units

-R5-NH-C {R ⁴ ) 2-COOR '

and amides of. «- Halocarboxylic acids with the Structural units

-R5-NH-CO-qR ⁴ ) ₂ -Hal,

wherein R ^{5 represents} the remainder of the mono-, di- or polyamine, is used directly without purification in the second stage.

The reactions can be illustrated as follows:

R ⁴
- R ⁵ -NH-C -COOR ⁷

- R ⁵ —NH ₂ + Hal —C-COOR ⁷
R ⁴

(D

R ⁴

R ⁵ NH-CO-C-Hal

(ii)

R ⁴ R ⁴

CO

+ —R ³ —NCO

R ⁴ R ⁴

- R ⁵ - NC = O + ^{- R 3} - NC

C N C N

y \ y \

OR ³ - OR ⁵ -

According to the known process for the preparation of products only the «-aminocarboxylic acid esters of the formula (I) Polyhydantoins (French patent specification used, i.e. one has the glycine esters after their

14 84 694 = DE-OS 15 70 552) one has as a starting pro-production by reaction of a-halo acid

esters and polyamines isolated from the corresponding reaction mixture and now these compounds used for the production of hydantoins by further reaction with isocyanates.

Accordingly, the present invention has been made clear based on the fact that these compounds do not have to be in pure form, but that crude reaction products, which contain various reaction products, such as amides of α-halogenic acid, to form polyhydantoins can be condensed.

As amines in the context of the present invention, in principle all aromatic, aliphatic, cyclic and heterocyclic primary amines, preferably those with several primary amino groups, are used, these also having substituents which do not interfere with the reaction can.

Amines of the formula are particularly suitable

R ⁵ T ₁ -NH ₂ ) *,

20th

in the χ is an integer \ ⁵ on an x-valent 1 to 4 and R aliphatic, mean aliphatic-aromatic or aromatic radical. The radical R ^{5 of} the general formula is preferably that of ethane, n-, iso-, tert-butane, hexane, eicosane, propene, diethyl ether, dipropyl sulfide, cyclopentane, cyclohexane, benzene, naphthalene, diphenyl, diphenyl methane, diphenyl sulfone, diphenyl ether, 4 , 4'-diphenoxydiphenylpropane, toluene, o-, m-, p-xylene, tristolylmethane, ethylene glycol bis-phenylcarboxylic acid ester, triaryl phosphate, N, N'-bis-phenoxyphenylhydantoin. Polyesters, polyesters, polyacetals, polyureas, polyurethanes, polyamides and can be substituted one or more times, e.g. B. by alkyl, halogen, nitro, alkoxy, aroxy, amido, imido, acyl, hydroxy, carboxy, carbalkoxy, carbaroxy, carbamido and sulfonic acid groups. Examples from this series are butylamine, aniline, 1,3- or 1,4-phenylenediamine, 2,4- or 2,6-tolylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-diphenyl ether, tris - (4-aminophenyl) thiophosphate and the technical amine mixture, which is obtained from the condensation of aniline with formaldehyde.

Preferred esters of -halocarboxylic acids correspond to the general formula

R ⁴

Hal — C-COOR ⁷
R ⁴

45

50

where Hal halogen such as F, Cl, Br, I, preferably Cl, the two radicals R ⁴ , which can be identical or different, hydrogen, an alkyl, aralkyl or aryl radical and R ⁷ an alkyl or aryl radical mean. R ⁴ and R ⁷ preferably have the meaning of alkyl or arylalkyl radicals with 1-10 carbon atoms and / or that of aromatics with 5-10 carbon atoms, e.g. B. methyl, bo ethyl, n, sec., Tert-butyl, octyl, cyclohexyl, penyl, omp-tolyl, naphthyl and benzyl groups. Suitable α-halocarboxylic acid esters are the alkyl or aryl esters of chloroacetic acid, propionic, butyric, 2-ethylhexane, stearic, μ phenylacetic, diphenylacetic, dimethyl acetic and isopropylacetic acid. Starting products which are likewise suitable for the purposes of the invention are α-halocarboxylic acid esters of the general type

OR ⁴ R ⁴ O
R ⁷ -OC-C-C-C-O-R ⁷

I I

Shark shark
and

R "

¹ R ⁴ O

-C —C —O —R ⁷

Shark

in which R ⁴ and R ^{7 have} the meaning already given, y for an integer from 1-3 and R ⁶ for an aliphatic radical with 1-10 carbon atoms, for an aliphatic-aromatic radical with 6-10 carbon atoms and stand for an aromatic radical with 5-10 carbon atoms. The dichlorosuccinic and dibromosuccinic esters obtainable from maleic and fumaric acid are preferred.

In principle, the process can also be used with all known isocyanate group-containing compounds are carried out. When using Monoisocyanates, monoamines and compounds having only one -halocarbon ester group Here, molecules with only one hydantoin ring are formed, while polyisocyanates, polyamines and / or compounds with several -halocarbon ester groups, depending on the ones used Ratios of linear or branched, oligomeric or also polymeric substances with hydantoin rings as links.

Mono- or polyisocyanates suitable for the process are compounds of the general formulas

in which R ^{3 stands} for an optionally substituted alkyl radical with 1-20 carbon atoms, an aryl radical with 5-12 carbon atoms, a cycloalkyl radical with 5-12 carbon atoms, an alkyl-aryl radical with 6-20 carbon atoms and an aryl or cycloalkyl radical containing heteroatoms such as N, O or S and having 5-12 C atoms. Alkyl radicals with 2-6 carbon atoms, phenyl, tolyl, naphthyl, diphenylmethane and diphenyl ether radicals are particularly preferred. ζ is an integer from 1 to 4, especially 2 to 3.

As monoisocyanates in the context of the invention, aliphatic and aromatic, optionally through Heteroatoms-substituted compounds with an NCO group in the molecule are used, e.g. B. alkyl isocyanates such as ethyl, methyl, butyl, dodecyl and stearyl isocyanate, aromatic, optionally substituted Monoisocyanates such as phenyl, ToIyI, isopropyl, nonyl isocyanate, nitro, alkoxy, aroxy, chlorine, dichloro, Trichloro, tetrachloro, pentachloro, benzyl, bromophenyl isocyanate or isocyanato-benzoic acid ester, -phthalic acid ester, -isophthalic acid ester, isocyanatobenzonitrile, cycloaliphatic isocyanates such as cyclohexyl isocyanate.

As starting components to be used according to the invention there are also aliphatic, cycloaliphatic, araliphatic. aromatic and heterocyclic polyisocyanates into consideration (cf. Annalen 562, p. 75 to 136), for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate,

l. ^ - dodecane diisocyanate, cyclobutane KS diisocyanate, cyclohexane l ^ - and -1,4-diisocyanate and any mixtures of these isomers, l-isocyanato-SSS-trimethyl-5-isocyanatomethyl-cyclohexane (DE-AS 12 02 785 ), 2,4- and 2,6-hexahydrotoluylene diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or -I ₁ ^ phenylene diisocyanate, perhydro-2,4'- and / or -4,4 ijiphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or 4,4'-diisocyanate, naphthylene-1 , 5-diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, polyphenyl-polymethylene polyisocyanates, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and described, for example, in British patents 8 74 430 and 8 48 671 perchlorinated aryl polyisocyanates such as are described, for example, in German Auslegeschrift 11 57 601, polyisocyanates containing carbodiimide groups, such as those described in German patent 10 92 007 are described, allophanate polyisocyanates, such as are z. B. in British patent specification 9 94 890, the Belgian patent specification 7 61 626 and the published Dutch patent application 71 02 524 are described, isocyanurate-containing polyisocyanates, as they are, for. B. in the German patents 10 22 789, 12 22 067 and 10 27 394 and in the German Offenlegungsschriften 19 29 034 and 20 04 048 are described. Polyisocyanates containing urethane groups, such as those used, for. B. in Belgian patent 7 52 261 or in US patent 33 94 164, acylated urea group-containing polyisocyanates according to German patent 12 30 778, biuret group-containing polyisocyanates, such as those. B. in German patent 11 01 394, in British patent 8 89 050 and in French patent specification 70 17 514, polyisocyanates produced by telomerization reactions, such as are described, for. B. in the Belgian patent 7 23 640 are described. Polyisocyanates containing ester groups, such as those used, for. B. in British patents 9 56 474 and 10: 2 956, in US patent 35 67 763 and in German patent 12 31 688 are mentioned, reaction products of the above isocyanates with acetals according to German patent 10 72 385.

It is also possible to use the isocyanate groups obtained in the technical production of isocyanates having distillation residues, optionally dissolved in one or more of the aforementioned Polyisocyanates to be used. It is also possible to use any mixtures of the aforementioned polyisocyanates to use.

The technically easily accessible mixtures of toluene diisocyanates are preferably used, m-phenylene diisocyanate and phosgenated condensates made of aniline and formaldehyde with a polyphenylene-methylene structure and the symmetrical compounds 4,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanatodiphenyl ether, p-phenylene diisocyanate, 4,4'-diisocyanatodiphenyl-dimethylmethane, analogous hydroaromatic diisocyanates and hexamethylene diisocyanate.

The isocyanates can also be used in free form or completely in the form of their compounds containing reactive hydrogen on reaction accessible and reacting under the reaction conditions, cleavers can be used.

The aromatic cleavers are preferably used and aliphatic mono- and polyhydroxy compounds obtained carbamic acid esters z. B. the general formulas

R ³ —NH-C —Ο —Α

- C ^{- NH - R - 1} - NH - C - O - B - O -

Il Il

ο ο

are used, where R ^{3 is} the organic radical of an isocyanate and the organic radical A is a monohydroxy compound or the organic radical B of a bis- or trisfunctional hydroxy compound is an alkyl radical with 1-10 carbon atoms, a cycloalkyl radical with 5-10 carbon atoms. Atoms, an alkyl-aryl radical with 6-12 carbon atoms and an aryl radical with 5-12 carbon atoms and each of which can also be substituted; z is an integer from 1 to 4.

Examples are the carbamic acid esters from phenol, isomeric cresols, their technical mixtures and similar aromatic hydroxyl compounds, aliphatic monoalcohols such as methanol, ethanol, Propanol, isopropanol, butanol, isobutanol, cyclohexanol, benzyl alcohol and aliphatic di- or polyols such as Ethylene glycol and trimethylol propane are listed.

The O-alkyl urethanes can be used as such or can only be generated in situ by reaction with alcohols. When using O-alkyl urethanes for Implementation used, up to 100%, of the isocyanate groups are in the O-alkyl urethane form.

To carry out the process according to the invention, the amine and the «-halocarboxylic acid ester, generally in a solvent, heated to temperatures of 20-220 ° or it becomes a the two components entered into the heated solution of the second reactant. After completion the first reaction stage, with elimination of hydrogen halide and alcohol or phenol takes place, the isocyanate is added and the reaction is brought to an end at temperatures of 80-250 °.

The reaction can also take place under an inert protective gas such as COj or nitrogen or, in particular in the case of volatile reaction components, can be carried out in an autoclave.

Solvents that can be used are those which are opposed to the reaction and opposed to the. Reaction products are inert. Examples are: higher-boiling, optionally halogenated aliphatics and aromatics such as paraffin oils, chlorinated paraffins, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, decalin, Alkylbenzenes or alkylnaphthalenes and diphenyl ethers.

However, preference is given to using such solvents, if appropriate together with the above solvents which form so-called splitting compounds or blocked isocyanates with the isocyanates, as they do are already described above. In particular, these are solvents with active hydrogen atoms with the isocyanates form thermally easily cleavable derivatives, e.g. urethanes. Are particularly preferred phenolic solvents, e.g. B. phenol, cresols or their mixtures. '

The compounds obtained according to the invention can be high molecular weight or low molecular weight. This depends essentially on the functionality of the starting products and their molar ratios, which can be varied within wide limits. ^r >

Since the reaction is usually carried out in solvents, the products are generally obtained as solutions. These solutions can be used directly as coating agents. By heating them to about 100-500 ⁰ C, temperature-resistant coatings are created which are extremely resistant chemically, thermally and physically.

With regard to the application of these systems, their miscibility with other polymer systems, the Test methods and the achievable mechanical values are based on those in the German Offenlegungsschrift 14 94 443 details listed in detail.

Particularly noteworthy is the modification described there, which is not protected here Concomitant use of reactive hydroxyl-containing polyesters with compounds according to of the present invention which still contain, optionally blocked or free, NCO groups, directly or after the capping agent has been split off, the molecules are elongated or crosslinked Effect urethane groups.

example 1

In the solution of 246 g (2 moles) of ethyl chloroacetate in 250 g of cresol, 198 g (1 mole) of 4,4'-diamino-diphenylmethane are added in part. The mixture is then heated to 160-165 ° for 4 hours and to 185 ° for 3 hours and then 250 g of cresol and 250 g (1 mol) of 4,4'-diisocyanatodiphenylmethane, the latter in proportions according to v, depending on the heat development, are added. The mixture is then stirred for a further 7 hours at 190 ° and 4 hours at 200 °. The polyhydantoin is obtained as a brown viscous solution with corresponding bands in the IR spectrum at 1710 and 1765 cm - 'and can, after further dilution of the solution with cresol, gradually form a clear film of lacquer on a metal sheet, first at 200 and then at 300 ° to be burned in.

Example 2

In the solution of 171 g (1 mol) of phenyl chloroacetate 93 g (1 mol) of aniline are added dropwise to 300 g of cresol. Then 4 hours at 60 ° and 2 Stirred at 100 ° for hours. Then 119 g (1 mol) Phenyl isocyanate added and the further reaction in 4 hours at 100 °, 4 hours at 150 ° and 7 hours carried out at 200 °. A solution of the hydantoin is created, which evaporates in a water jet vacuum will. Recrystallization from ethanol gives 160 g of 1,3-diphenylhydantoin with a melting point of 128-133 °. A sample, recrystallized again from ethanol, melts at 136-137 °.

C, 5H ₁₂ N ₂ O ₂ (252.3)

calc .: C 71.4 H 4.8 NlI ₁ I.
Found: C 71.3 H 5.0 N 11.2

Example 3

246 g (2 mol) of ethyl chloroacetate and 198 g (1 mol) of 4,4'-diamino-diphenylmethane in 250 g of cresol are heated to 160 ° for 2 hours and then to 170 ° for 10 hours. Then 238 g (2 mol) Phenyl isocyanate was added dropwise and the reaction was completed in 5 hours at 200 °. The resulting Hydantoin is characterized by bands at 1700 and 1755 cm- '.

Example 4

123 g (1 mol) of ethyl chloroacetate and 93 g (1 mol) of aniline are introduced into 250 g of cresol. then the mixture is heated to 160 °, the temperature slowly, in the course of 8 hours, further to 185 ° increased and held in this range for a further 5 hours until the end of the condensation, with Ethanol and hydrogen chloride escape. 119 g (1 mol) of phenyl isocyanate are then added dropwise and the reaction mixture is stirred for 4 hours at 200-205 ° and 7 hours at 205-210 ° Solution of the hydantoin with the bands characteristic of hydantoins at 1710 and 1760 cm- '.

Claims (1)

Patent claims: 1. A process for the preparation of compounds containing hydantoin groups, wherein one in a first stage a primary mono-, di- or polyamine with a -halocarboxylic acid ester of the following general formulas