DE2318154A1 - PROCESS FOR PRODUCING CONNECTIONS CONTAINING HYDANTOIN RINGS - Google Patents

Description

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509 Leverkusen, Bayerwerk

G / Ra

APR 10. 1973

Process for the preparation of compounds containing hydantoin rings

It is known that polyhydantoins can be produced by reacting at least difunctional glycine ester derivatives with polyisocyanates (see French patent 1,484,694). This formation of polyhydantoins can be achieved by the following greatly simplified and schematized reaction equation are illustrated

η R

O = Ci

- N ^

R.
C-NH

A ¹

η
O

Ar

- NH -

_? 1 "1

. "1" 1

N-Ar-N,

III

I ρ

C - COR ^Z

R ¹

-c-

ti 0

+ nOCN II

- NCO

, C = 0

«N-

Equation 1

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In this reaction equation, R, independently of one another, denote hydrogen or alkyl, preferably with 1-4 carbon atoms, R is hydroxyl, amino, alkylamino, dialkylamino, alkoxy or aroxy, the alkyl groups preferably being 1-4 carbon atoms and the aryl groups preferably contain 6-10 carbon atoms, Ar is an aromatic radical and R ^ is the organic residue of a diisocyanate.

The reaction can also be based on multifunctional starting materials, i.e. on glycine ester derivatives with more than two glycine ester functions and on polyisocyanates with more than two isocyanate groups be transmitted. In this case, branched molecules are formed.

The invention relates to a process for the preparation of compounds containing hydantoin groups, which is characterized in that a mono-, di- or polyamine is reacted with an oC-halocarboxylic acid ester in a first stage and the crude reaction product in a second stage with a mono- , Di- or polyisocyanate or isothiocyanate to react.
The reactions can be illustrated as follows:

? ^4th

R ^ ^ -R ⁵ - NH - C - COOR ⁷

- R ⁵ - NH ₀ + Hai -C- COOR ⁷ ^ I "

• 4 ^ V

"R Νλ R *

"■ ■ - R ^P NH - CO - C - HaI-

II

V "*

- R ³ - NCO -> - R ⁵ ^ ³ ^ ^X C = 0

ί I ^ C
O = C N- R <±

According to the known process for the production of Polyhydanto-

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inen (ζ. B. French patent specification 1 484 694) one has only the p (-aminocarboxylic acid esters of the formula I are used as starting products. The present invention is based on the knowledge based on the fact that these compounds do not have to be in pure form, but that crude reaction products that contain various reaction products can be used.

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 may have substituents which do not interfere with the reaction.

Amines of the formula are particularly suitable

R ⁵ (-

in which χ is an integer from 1-4 and R is an x-valent aliphatic, aliphatic-aromatic or aromatic radical. The radical R 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'-Diphenoxy-diphenylpropane, toluene, o-, m-, p-xylene, tristolyl-methane, ethylene glycol-bis-phenylcarboxylic acid ester, triaryl phosphate, Ν, Ν'-bis-phenoxyphenyl-hydantoin, polyethers, 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-tolylene diamine, 4,4 ^{f-diaminodiphenylmethane,} 4,4'-diamino-diphenyl ether, tris - (4-aminophenyl) -

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thiophosphate and the technical amine mixture obtained from the condensation of aniline with formaldehyde.

Preferred esters of ^ -halocarboxylic acids correspond to general formula

R ⁴

HaI-C-COOR
R ⁴

where Hal is halogen such as F, Cl, Br, I, preferably Cl, the two radicals R, which can be identical or different, are hydrogen, an alkyl, aralkyl or aryl radical and R ^{7 is} an alkyl or aryl radical .

R and R preferably have the meaning of alkyl or arylalkyl radicals with 1 - Io carbon atoms and / or that of aromatics with 5 - Io carbon atoms, e.g. B. methyl, ethyl, n, sec., Tert-butyl, octyl, cyclohexyl, phenyl, o, m, p-tolyl, naphthyl and benzyl groups. Suitable d -halocarboxylic acid esters are the alkyl or aryl esters of chloroacetic acid, propionic, butter, 2-ethylhexane, stearic, phenylacetic, diphenylacetic, dimethyl acetic and isopropylacetic acid, chlorinated in the o ^ position. Starting materials which are likewise suitable for the purposes of the invention are α-halocarboxylic acid esters of the general formulas

OR ⁴ R ⁴ O 7 tt ι t ti R'- OC-CCCOR ' ι t

Shark shark

R ^ O

and R ⁶ (-C COR ⁷ ) Hal

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

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sr

In principle, the process can also be carried out with all known iso (thio) cyanate groups containing compounds are carried out. When using monoiso (thio) cyanates, monoamines and having only one ct -halocarbon ester group In this connection, molecules are formed with only one hydantoin ring, while polyiso (thio) cyanates, polyamines and / or compounds with several o ^ -halocarbon ester groups Depending on the proportions used, linear or branched, oligomeric or polymeric substances with hydantoin rings as links.

Mono- or polyiso (thio) cyanates suitable for the process are compounds of the general formulas

R ⁵ C-NCO) or R ⁵ C-NCS)

in which R? 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 a heteroatoms such as N. , 0 or S containing aryl or cycloalkyl radical with 5-12 C atoms. Particularly preferred are alkyl radicals with 2-6 carbon atoms, phenyl, tolyl, naphthyl, diphenyl methane and diphenyl ether radicals. z. is an integer from 1-4, especially 2-3.

Aliphatic monoisocyanates for the purposes of the invention and aromatic compounds, optionally substituted by heteroatoms, with an NCO group in the molecule, z. B. alkyl isocyanates such as ethyl, methyl, butyl, dodecyl and stearyl isocyanate, aromatic, optionally substituted monoisocyanates such as phenyl, tolyl, isopropyl, nonyl isocyanate, Nitro, alkoxy, aroxy, chlorine, dichloro, trichloro, tetrachloro, pentachloro, benzyl, bromophenyl isocyanate or Isocyanato-benzoic acid ester, -phthalic acid ester, -isophthalic acid

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acid esters, isocyanatobenzonitrile, cycloaliphatic isocyanates such as cyclohexyl isocyanate and unsaturated isocyanates such as Allyl, oleyl, cyclohexenyl isocyanate.

Other suitable starting components to be used according to the invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates (cf. Annalen 562, pages 75 to I36), for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate , 1,12-dodecane diisocyanate, cyclobutane-1,3-diisoeyanate, cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, l-isocyanato-jJ ^ iS-trimethyl-S-isocyanatomethyl-cyclohexane ( DAS 1 2o2 785), 2,4- and 2,6-hexahydrotolylene diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or 1,4-phenylene diisocyanate, perhydro-2,4'- and / or -4,4'-diphenylmethane 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 ^f , 4 "-triisocyanate, polyphenyl-polymethylene polyisocyanates, as they are by Aniline-Fo rmaldehyde condensation and subsequent phosgenation obtained and z. B. in British patents 874 43o and 848 671 are described, perchlorinated ary! Polyisocyanates, as z. B. in the German Auslegeschrift 1 157 60I are described, carbodiimide-containing polyisocyanates, as they are in the German patent. 1,092,007, diisocyanates as described in US Pat. No. 3,492,330, polyisocyanates containing allophanate groups, such as. she z. B. in British patent specification 994 890, the Belgian patent specification 76I 626 and the published Dutch patent application 7 Io2 524, polyisocyanates containing isocyanurate groups, such as are described, for. B. in the German patents 1,022,789, 1,222,067 and 1,027,394 and in the German Offenlegungsschriften 1,929,034 and 2,04,048, urethane groups

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containing polyisocyanates, such as those used, for. B. in Belgian patent specification 752 261 or in US patent specification 3,394,164 are described, polyisocyanates containing acylated urea groups according to German Patent 1 23o 778, Polyisocyanates containing biuret groups, such as those used, for. B. in the German patent 1 lol 394, in the British Patent specification 889 o50 and in French patent specification 7 0I7 514 are described by telomerization reactions manufactured polyisocyanates, as they are z. B. in the Belgian patent 723 64o are described containing ester groups Polyisocyanates, such as those used, for. In British Patents 956,474 and 1,072,956 in U.S. Patent 3 567 763 and mentioned in German patent specification 1 23I 688 are, reaction products of the above-mentioned isocyanates with acetals according to German Patent 1,072,385.

It is also possible to remove the isocyanate group-containing distillation residues obtained during the technical production of isocyanates, optionally dissolved in one or more of the aforementioned polyisocyanates, to be used. Furthermore it is possible to use any mixtures of the aforementioned polyisocyanates.

The mixtures of tolylene diisocyanates, m-phenylene diisocyanate, and phosgenated condensates of aniline and formaldehyde with a polyphenylene-methylene structure and the symmetrical compounds 4,4 ^l -diisocyanato-diphenylmethane, 4,4-diisocyanatodiphenyl ether, p -Phenylene diisocyanate, 4,4'-DiXSOCyOnBtO ^ iphenyl-dimethylmethane, analogous hydroaromatic diisocyanates and hexamethylene diisocyanate.

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The isocyanates can be used in free form, and also partly or completely in the form of them, when they react with reactive hydrogen containing compounds accessible and reacting under the reaction conditions, releasers are used,

Preferred as cleavers are those from aromatic and aliphatic Carbemic acid esters obtained from mono- and polyhydroxy compounds, e.g. the general formulas

R- ⁵ C-NH-COA)., Or

Il

-C-NH-R ⁵ -NH-COBO-

11 It

0 LO 0

are used, where R ^ is the organic radical of an iso (thio) cyanate 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 C atoms, an alkyl-aryl radical with 6-12 C atoms and an aryl radical with 5-12 C atoms, and each of which can also be substituted; ζ is an integer from 1-4.

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 trimethylolpropane are listed.

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

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Instead of the (poly) isocyanates mentioned, the analogous (Poly) isothiocyanates can be used.

To carry out the process according to the invention, the amine and the o (-halocarboxylic acid ester are generally heated in a solvent to temperatures of 20-220 ° or one of the two components is added to the heated solution of the second reactant. After the first reaction stage has ended , which takes place with elimination of hydrogen halide and / or alcohol or phenol, the isocyanate is added and the reaction at temperatures of 80 - 250 ⁰ out to the end.

The reaction can also take place under an inert protective gas such as COp or nitrogen or, especially in the case of volatile Reaction components, are carried out in the autoclave.

Solvents which can be used are those which are inert to the reaction and to the reaction products are. 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, if appropriate together with the above solvents, those solvents which react with the isocyanates Form so-called splitting compounds or blocked isocyanates, as already described above. In particular these are solvents with active hydrogen atoms, which are easily thermally cleavable with the isocyanates Derivatives, e.g. B. urethanes. Particularly preferred are phenolic solvents, e.g. B. Phenol, cresols or their Mixtures.

According to the invention, the reaction can be accelerated by catalysts will. As catalysts come z. B. question: '

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1) Tertiary amines, such as triethylamine, tributylamine, N-methylmorpholine, N-ethyl-morpholine, N-cocomorpholine, Ν, Ν, Ν ', Ν ^1- tetramethyl-ethylenediamine, 1,4-diaza-bicyelo- (2 , 2,2) octane, N-methyl-N'-dimethylaminoethyl piperazine, N, N-dimethylbenzylamine, bis (N, N-diethylaminoethyl) adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine, N, N-dimethylcyclohexylamine , N, N, N ¹ , N ¹ -tetramethyl-l ^ -butanediamine, Ν, Ν-dimethyl-ß-phenylethylamine, 1,2-dimethylimidazole and 2-methylimidazole.

2) Tertiary amines containing hydrogen atoms active towards isocyanate groups, e.g. B. triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, Ν, Ν-dimethyl-ethanolamine and their reaction products with alkylene oxides such as propylene oxide and / or ethylene oxide.

3) Silaamines with carbon-silicon bonds (compare German patent specification 1 229 290) e.g. B. 2,2,4-trimethyl-2-silamorpholine, 1,3-diethylaminomethyl-tetramethyl-disiloxane.

4) Nitrogen-containing bases such as tetraalkylammonium hydroxides and hexahydrotriazines.

5) Organic metal compounds, especially of iron, lead and / or tin. Organic tin compounds are preferred Tin (ll) salts of carboxylic acids such as tin (ll) acetate, Tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate and dialkyltin (IV) salts such as dibutyltin dichloride, acetate, laurate, maleate or dioctyltin diacetate in Ber also iron salts such as iron acetylacetonate or iron chloride, lead oxide, lead carbonate or beecharboxylates.

Further catalysts to be used according to the invention are in Kunststoff-Handbuch, Volume VII, edited by Vieweg and

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Höchtlen, Carl-Hanser-Verlag, Munich 1966, on the pages 96 - 102 as well as in High Polymers, Vol. XVI, Part I, (Polyurethanes Chemistry), edited by Saunders and Frisch, Interscience Publishers, New York 1962, at pages 129-217 described.

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

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. There arise from them by heating at about 100 - 500 ⁰ C temperature-resistant coatings which are chemically, thermally and physically extremely robust.

With regard to the application of these systems, their miscibility with other polymer systems, the test methods and the achievable mechanical values should be based on the details listed in the German Offenlegungsschrift 1,494,443 pointed out.

Particularly noteworthy is the modification described there by using reactive hydroxyl-containing polyesters with compounds according to the present Invention which still contain, optionally blocked or free, NCO groups, directly or after the blocking agent has been split off cause an extension or crosslinking of the molecules via urethane groups.

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example 1

In the solution of 246 g (2 mol) of ethyl chloroacetate in 250 g of cresol, 198 g (1 mol) of 4,4 ^f- diamino-diphenylmethane are introduced in part. Then, 4 hours Ιβο - heated I65 ⁰ and 3 hours at ⁰ and then I85 25o g of cresol and 250 g (1 mol) of 4,4'-diisocyanatodiphenylmethane, the latter added in portions in accordance with the evolution of heat. Then a further 7 hours at 190 ⁰ and 4 hours is stirred at 2oo °. The polyhydantoin is obtained as a brown, viscous solution with corresponding bands in the IR spectrum at 1710 and 1765 cm ~ and, after further dilution of the solution with cresol, can be baked on a metal sheet, first at 200 ° and then at 300 °, to form a clear film of varnish .

Example 2

93 g (1 mol) of aniline are added dropwise to the solution of 17I g (1 mol) of phenyl chloroacetate in 300 g of cresol. The mixture is then stirred for 4 hours at 60 ° and 2 hours at 100 °. Then II9 g (1 mol) of phenyl isocyanate are added and the further reaction carried out in 4 hours at loo °, 4 hours at I50 ⁰ and 7 hours at 2oo °. A solution of the hydantoin is formed, which is evaporated in a water jet vacuum. 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 °.

15 12 2 2 ^ * 3)

Calcd .: C 71.4 H 4.8 N 11.1
Found: 71.3 5.0 11.2

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Example 3

246 g (2 mol) of ethyl chloroacetate and 198 g (1 mol) of 4,4-diamino-diphenylmethane ^t in 25o g cresol are heated for 2 hours on I6O ° and then Io hours I70 ^0th Then 258 g (2 mol) of phenyl isocyanate are added dropwise and the reaction is completed in 5 hours at 2oo °. The hydantoin formed is characterized by bands at 1700 and 1755 cm ".

Example 4

123 g (1 mol) of ethyl chloroacetate and 95 g (1 mol) of aniline are introduced into 250 g of cresol. Then, the mixture is heated to l6o °, the temperature slowly with ethanol and hydrogen chloride escaping during the course of 8 hours, further increased to I85 ⁰ and held for 5 hours in this area up to the end of the condensation. 119 g (1 mol) of phenyl isocyanate are then added dropwise and the reaction table is stirred for 4 hours at 200-2o5 ° and for 7 hours at 205-210 °. A solution of the hydantoin is obtained with the bands characteristic of hydantoins at 1710 and 1760 cm ".

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Claims (4)

Claims; .) Process for the preparation of hydantoin groups Compounds, characterized in that a mono-, di- or polyamine is used in a first stage with a 0 (-halogericarboxylic acid ester and the Reacts crude reaction product in a second stage with a mono-, di- or polyisocyanate or isothiocyanate. 2.) The method according to claim 1, characterized in that one containing at least 2 primary amino groups Compound with a (/ -halogenocarboxylic acid ester and a compound containing at least 2 isocyanate groups implements. 3.) Process according to claim 1, characterized in that there is an aromatic polyamine with at least 2 primary Amino groups with an ad-halocarboxylic acid ester and a converts aromatic polyisocyanate. 4.) Process according to claim 1, characterized in that between 0.9 and 1.1 % equivalent of an OC-halocarboxylic acid ester and at least one equivalent of a polyisocyanate are reacted per equivalent of primary amino groups. Le A 15 006 - 14 - 409844/0423