CA1121374A - Process for the preparation of an aryl mono-, di-, and/or polyurethane - Google Patents
Process for the preparation of an aryl mono-, di-, and/or polyurethaneInfo
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- CA1121374A CA1121374A CA000349798A CA349798A CA1121374A CA 1121374 A CA1121374 A CA 1121374A CA 000349798 A CA000349798 A CA 000349798A CA 349798 A CA349798 A CA 349798A CA 1121374 A CA1121374 A CA 1121374A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/701—Compounds forming isocyanates or isothiocyanates in situ
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
PROCESS FOR THE PREPARATION OF AN
ARYL MONO, DI-, AND/OR POLYURETHANE
Abstract of the Disclosure A process for the preparation of an aryl-mono and/or polyurethane comprising the steps of A. reacting a primary aromatic mono, di-, and/or polyamine with an O-alkyl carbamate in the presence of alcohol and catalysts, and B. separating the ammonia and other by-products from the aliphatic and/or cycloaliphatic di- and/or poly-urethane.
The reaction is preferably carried out in the presence of urea. The aryl mono-, di-, and/or polyurethanes produced are valuable end and intermediate products. They can be transferred into the corresponding isocyanates which can then be used for the preparation of polyurethanes.
ARYL MONO, DI-, AND/OR POLYURETHANE
Abstract of the Disclosure A process for the preparation of an aryl-mono and/or polyurethane comprising the steps of A. reacting a primary aromatic mono, di-, and/or polyamine with an O-alkyl carbamate in the presence of alcohol and catalysts, and B. separating the ammonia and other by-products from the aliphatic and/or cycloaliphatic di- and/or poly-urethane.
The reaction is preferably carried out in the presence of urea. The aryl mono-, di-, and/or polyurethanes produced are valuable end and intermediate products. They can be transferred into the corresponding isocyanates which can then be used for the preparation of polyurethanes.
Description
PROCESS FOR THE PREPARATION OF AN
ARYL MONO , DI-, AND/O~ POLYURETHANE
Background of the Invention 1. Field of the Invention The invention pertains to the preparation of an aryl mono-, di- and/or polyurethane by reacting a primary aromatic mono-, di- and/or polyamine with an O-alkyl car-bamate in the presence of an alcohol and catalysts. The reaction is preferably carried out in the presence of urea.
ARYL MONO , DI-, AND/O~ POLYURETHANE
Background of the Invention 1. Field of the Invention The invention pertains to the preparation of an aryl mono-, di- and/or polyurethane by reacting a primary aromatic mono-, di- and/or polyamine with an O-alkyl car-bamate in the presence of an alcohol and catalysts. The reaction is preferably carried out in the presence of urea.
2 Descri tion of the Prior Art On an industrial scale, N-aryl urethanes are normally produced by the reaction of alcohols with isocyanates or by the reaction of amines with chlorocarbonates. The isocyana~es and chlorocarbonates used in these reactions are obtained by phosgenation of the corresponding amines or the corresponding alcohols. Houben~Weyl, Methods of Organic Chemistry, Vol. 8, pages 137, 120 and 101, (Geory Thieme Publishers, Stuttgart, 1952). These processes are very expensive and phosgene must be used with care because of its potential danger to man and the environment.
N-aryl urethanes are used as intermediates and end products. For instance, German Published Application 26 35 490 and U~Sr Patent 3,919~278 disclose the use of N substituted urethanes for the manufacture of isocyanates.
Because of their utility, many attempts have been made to develop better methods for preparing N-su~stituted ure-thanes. These methods and their shortcomings will be discussed.
31~2~3~
German Published Application 21 60 111 describe~ a process for the manufacture of N-substituted urethanes by reacting an organic carbonate with a primary or secondary amine in the presence of a Lewis acid. There are several problems with this pro~ess. The conversion rates are rather low and the reaction times are long. Furthermore, N-alkyl-arylamines are always produced as by-products.
U.S. Patent 2,834,799 describes a process for making carbamic and carbonic esters by the reaction of urea with alcohols in the presence of boron trifluoride. The problem with this method is that the boron trifluoride is required in equimolar quantities so that at least one molecule of boron trifluoride is used per molecule of produced carbamic ester and at least two molecules of boron trifluoride are consumed per molecule of carbonic ester. This process is not only expensive, but it causes problems in the environment because the boron trifluoride is produced in the form of the H3N.BF3 adduct.
R. A. Franz et al, Journal of Or~anic Chemistry, Vol. 28, page 585 (1963) describe a process for making methyl N-phenyl urethane from carbon monoxide, sulfur, aniline, and methanol. Very low yields are produced by this method; the yield does not exceed 25 percent even when there is a long reaction period.
U.S. Patent 2,409,712 describes a process for making N-alkyl and N-aryl urethanes by the reaction of monoamines with urea (either N,N'-dialkyl-- or N,N'-diarylurea is used)
N-aryl urethanes are used as intermediates and end products. For instance, German Published Application 26 35 490 and U~Sr Patent 3,919~278 disclose the use of N substituted urethanes for the manufacture of isocyanates.
Because of their utility, many attempts have been made to develop better methods for preparing N-su~stituted ure-thanes. These methods and their shortcomings will be discussed.
31~2~3~
German Published Application 21 60 111 describe~ a process for the manufacture of N-substituted urethanes by reacting an organic carbonate with a primary or secondary amine in the presence of a Lewis acid. There are several problems with this pro~ess. The conversion rates are rather low and the reaction times are long. Furthermore, N-alkyl-arylamines are always produced as by-products.
U.S. Patent 2,834,799 describes a process for making carbamic and carbonic esters by the reaction of urea with alcohols in the presence of boron trifluoride. The problem with this method is that the boron trifluoride is required in equimolar quantities so that at least one molecule of boron trifluoride is used per molecule of produced carbamic ester and at least two molecules of boron trifluoride are consumed per molecule of carbonic ester. This process is not only expensive, but it causes problems in the environment because the boron trifluoride is produced in the form of the H3N.BF3 adduct.
R. A. Franz et al, Journal of Or~anic Chemistry, Vol. 28, page 585 (1963) describe a process for making methyl N-phenyl urethane from carbon monoxide, sulfur, aniline, and methanol. Very low yields are produced by this method; the yield does not exceed 25 percent even when there is a long reaction period.
U.S. Patent 2,409,712 describes a process for making N-alkyl and N-aryl urethanes by the reaction of monoamines with urea (either N,N'-dialkyl-- or N,N'-diarylurea is used)
3'7~
and alcohols at temperatures of 150C to 350C under increased pressure. It should be noted that this patent only describes the manufacture of N-alkylmonourethanes and does not mention the manufacture of N,N'-disubstituted diurethanes and poly-urethanes. U.S. Patent 2,677,698 also describes a process for the manufacture of N-substituted monourethanes. In this process, the urea is initially converted into the cor-responding N,M'-disubstituted urea with monoamines, is then cleaned, and subsequently is reacted with an alcohol. The processes described are expensive and the yields are very low. Attempts to improve the yield by improving the methods of preparing and purifying the N,N'-disubstituted ureas have been unsuccessful.
Other processes have not been successful in elimina-ting the problems described thus far. U.S. Patent 2,806l051 describes a process whereby N-substituted urethanes are produced by reacting aniline with urea and alcohol at a mole ratio of 1.0:1.2:2.0 at temperatures below 200C, prefer-ably of 120C to 160~C. Even in the preferably used tempera-ture range, this process produces only small yield~ of N-sub-stitued urethanes if the reaction time is limited to a period which i5 practical in an industrial setting. In view of the problems with this process t it is not surprising ~hat U.S.
Patent 3,076,007, which describes the manufacture o N-alkyl-and N-cycloalkyl urethanes, does not incorporate the above-referenced methods in its process. It does, however, describe the reaction of phosgene with alcohols to form chloroalkyl-formates, and it describes their subsequent reaction with amines to form urethanes. It also discloses the reaction of amines with ethylene carbonate to form urethanes. German Published Application 27 16 540 describes a more recent variation of this process wherein aromatic urethanes are prepared by reactin~ dialkyl carbonates with N-ethyl amines.
It is also known that ethyl carbamates do not react with amines in boiling dioxane lD.G. Crosby and C. Niemann, Journal of_the American Chemical Society, Vol. 76, page 4458 (1954)], and that the reaction of N-alkyl urethanes with alcoholic ammonia solutions at temperatures of 160C to 180C result in an alkali solution from which aminohydro-chloride, urea, alkylurea and alkyl urethane can be isolated by means of hydrochloric acid after neutralization [M. Brander, Rec. trav. Chim., Vol~ 37, pages 88-91 (1917);. The refer-enced publications do not contain any disclosure concerning the reaction of aromatic primary amines with carbamates although it is known that the heating of ethyl car~amate with aniline at 160C in a bomb tube will produce diphenylurea.
See Annalen, Vol. 147~ page 163 (1868).
U.S. Patent 2,409,712, discloses that the reaction of aliphatic monoamines, urea and alcohol will produce alkyl urethanes~ However, only small yields result even though excess urea is used. Since somewhat higher yields are achieved with less urea and at lower temperatures according to U.S. Pa ent 2,806,051, one has to assume that higher mole ratios of urea to amines are disadvantageous~ Diphenylurea 379~
and O-alkyl carbamate were determined as by-products of the synthesis of phenylurethane. The O-alkyl carbamate was isolated by means of distillation in addition to unreacted aniline~ The formation of O-alkyl carbamate from urea and alcohol wa3 therefore considered as an interferring secondary reaction. Since even the manuacture of N-monoalkylsubsituted urethanes from alkylamines, urea, and alcohols succeeds with moderate yields only, and since carbamates are produced as by-products, it is not surprising that the prior art does not teach the preparation of aryl mono-, di- and/or polyurethanes from arylamines and O-alkyl carbamates.
Because of th~ problems identified thus far, other ; methods of producing N-arylurethanes have been tried. Some have suggested that N-arylurethanes can be prepared by re-acting nitroaromatics with carbon monoxide, and alcohols in the presence of catalysts. German Published Application 15 68 044 (U.S. Patent 3,~67,694) teaches that urethanes may be prepared by the reaction of organic nitro compounds, carbon monoxide, and hydroxyl-containing compounds in the presence of a catalysts consisting of a noble metal and a Lewis acid under essentially anhydrous conditions in the absence of hydrogen under increased pressure and at temperatures above 1~0C.
German Published Application 23 43 826 (U.S. Patent 3,895,054) teaches that urethanes can be prepared from hydroxyl group-containing compounds, carbon monoxide, and nitro-l nitroso-, azo- and azoxy group-containing compounds in the presence of sulfur, selenium, a sulfur and/or selenium compound and at ~1~137~
least one base and/or water. German Published Application 26 23 694 (U~S. Patent 4,080,365) describes the preparation of aromatic urethanes from the above-referenced starting com-pounds in the presence of selenium-containing catalyst systems as well as speclal aromatic amino and urea compounds.
However, the use of these processes involve serious draw-backs. The toxic carbon monoxide and catalysts which are toxic or form toxic compounds during the reaction, such as hydrogen selenide and hydrogen sulfide, or catalysts which are very expensive and are difficult to recycle such as paladium, require great technical expenditure and costly safety measures.
None of the references cited discloses the prepara-tion o~ aryl mono , di and/or polyurethane by reacting an aromatic amine with an O-alkyl carbamate in the presence of an alcohol and catalysts at temperatures greater than 120C.
Moreover, the processes described all involve several dis-advantages. It is surprising that aryl mono, di and/or polyurethanes can be produced in one process stage with good yields by reacting carbamates with prîmary aromatic amines in the presence of alcohol and catalysts at temperatures greater than 120C. Prior teachings indicate that corresponding diureas are obtained from diamines and carbamates; for example, hexamethylenediurea is obtained from hexamethylenediamine and carbamates. Prior art also teaches that, although urea and alcohol may react to produce urethanes, they continue to react to form N,N'-disubstituted ureas in the presence of amines~
See Houben-Weyl, Metbcd~ ~t o~3ggD?gLrh~ y~ Vol. 8, pages llZ~L37~
152, 140, and 160, (Georg Thieme Publishers, Stuttgart, 1952).
These side reactions decrease the yield of the desired product.
Furthermore, German Patent 896 412 indicates that high molecular, spinnable condensation products may be produced from the diamides of carbonic acid such as urea and diamines. This result is likely to occur if the amino groups of the diamines are separated by a chain of more than three atoms. U.S. Patent 2,181,663 and U.S. Patent 2,568,885, for instance, disclose that high molecular poly-ureas with molecular weights of snoo to 10,000 and greater, may be produced when diurethanes are condensed with diamines at temperatures of approximately 150C to 300C. Moreover, mono- and polyurethanes can furthermore be split thermally into isocyanates, alcohols and possibly olefins, carbon dioxide, urea and carbodiimide, and these products can be split into products such as biurets, allophanates, isocy-anurates, polycarbodiimides, and others. 5ee Yh~
the American Chemical Society, Vol. 80~ page 5495 (1958) and Vol. 48, page 1946 (1956).
In view of the problems disclosed in the prior art, it was surprising that our process~ which involved very similar reaction conditions, would result in a mono-, di-and/or polyurethane with very gooa yields. It was particularly surprising because when diurethanes were prepared from the products mentioned in the previous paragraph according to the reaction conditions of our invention, good yields did not result.
37~
Summar of the Invention Y
The purpose of this invention was to produce an aryl mono-, di-p and/or polyurethane from readily available raw materials in one reaction stage under economically justifiable conditions with good yields. The use of strongly toxic raw materials such as phosgene, carbon monoxide, or catalysts which are toxic and form toxic compounds during the reaction, such as hydrogen sulfide, wa~ to be avoided.
The problem was solved by developing a process for the preparation of aryl mono-, di-, and/or polyurethanes comprising the steps of A~ reacting a primary aromatic mono-, di-, and/or polyamine with an O-alkyl carbamate in the presence of an alcohol and at least one compound containing one or more cations of metals of groups IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, V~, VIB, VIIB, and YIIIB of the periodic system as catalysts, and B. separating the ammonia and other by-products from the aryl mono-p di-, and/or polyurethane.
The reaction may be illustrated hy the following equation I:
Ar(-NH~)n + n H2N-COOR - > Ar(-NH-COOR)n ~ n N~3 (I) However, the reaction i5 preferably carried out in the presence of urea according to equation (II):
Ar(-NH2)n + a H2N-CO-NH2 + b H2N-COOR + a ROH >
(II) Ar(-NH-COOR)n + (2a+b)NE13 In equations (I) and (II), n, a, and b stand for whole numbers with n representing 1-7, preferably 1-5, and in which, according to (II), a+b equals n and a:n equals 1.5-0.
The aryl mono-, di-, and/or polyurethanes produced according to the process of this invention are valuable end and intermediate products. They are usedt for instance, as pesticides. As intermediate products, they are used as components for polycondensation and polymer systems and, in particular, they are transformed into the corresponding di-and/or polyisocyanates by removal of the alcohol. The di-and/or polyisocyanates can be used in the manufacture of polyurethanes.
Descri tion of the Preferred Embodiments In order to prepare the aryl mono-, di-, and/or polyurethane in accordance with the process of this invention, a primary aromatic mono, di, and/or polyamine is reacted with an O-alkyl carbamate in the presence of an alcohol and cata-lysts in such quantities that the ratio of amino groups of the primary aromatic amines to O-alkyl carbamates to the hydroxyl groups of the alcohol i5 1:0.5-20-0-100, preferably 1:0.8-10:0-30, and particularly for arylmonourethanes 1:1-6:0-5, and for aryl-di- and/or polyurethanes, 1:1-6:2-20. The reaction preferably is carried out in the presence of urea.
It is not necessary to separately produce O-alkyl-carbamates in a proceeding process stage. In an easily L3'7~
practiced, preferably used version, the O-alkyl carbamate is used together with urea and alcohol and after extensive to complete reaction of their aromatic mono- and/or polyamines, the O-alkyl carbamate is separated by means of distillation and i5 recycled if so required~ The process according to this invention may also be conducted in a continuous phase.
Unsubstituted or substituted primary aromatic mono-, di- and polyamines are suited or the reaction with the O-alkyl carbamate in the presence of alcohol and in the absence or presence of ureas according to this invention.
Representative amines include the following: aromatic mono-amines such as aniline, substituted anilines, such as anilines substituted in the 2, 3 and/or 4 position by a nitro-, methyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl-, secondary butyl-, tertiary butyl group or a chlorine atom; ortho-, meta- and/or parahydroxy-, methoxy-, ethoxy-, propoxy-, isopropoxy-, N-butoxy-, isobutyoxy-, secondary butoxy-, and tertiary butoxyaniline; an alkylbenzoate with l to 4 carbon atoms in the alkyl radical substituted by an amino group in the n- and/or p- position; N-alkoxycarbonylaminobenzenes and -toluenes with 1 to 4 carbon atoms in the alkyl radical substituted by an amino group in the m and/or p-position;
alpha- and beta-naphthylamine; aromatic diamines such as 1,3-and 1,4 diaminoben2ene; 1,3-diaminobenzene substituted in the 2 and/or 4 position by nitro, methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy groups or halogen atom, preferably fluorine or 7~
chlorine; or 1,4-diaminobenzene, 1,5- and 1,8-diamino-naphthalene, 4,4l-diaminodiphenyl, 2,2'-, 2,4'- and 4,4'-di-aminodiphenylmethane and the corresponding isomer mixtures thereof, all of which may be substituted in the 2 position by a nitro, methyl, ethyl, n-propyl, i~opropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxyt ethoxy, n-propoxy, isopropoxy, n-butoxy, lsobutoxy, sec-butoxy, tert~butoxy group or a halogen atom, preferably a fluorine or a chlorine atom; and polyamines such as 1,3,5-triaminobenzene, 2,4,6-triamino-benzene, and 1,3,5-triaminobenzene and polyphenylpolymethylene polyamines as well as mixtures of diaminodiphenyl methanes and polyphenylpolymethylene polyamines which are produced in accordance with familiar methods by the condensation of aniline and formaldehyde in the presence of preferably mineral acids as catalysts and which may be substituted with any of the above identified groups or atoms.
The following compounds are preferably used as aromatic monoamines: O-J m- andjor p-toluidine, o-, m- and/or p-anisidine, 3-hydroxyaniline, o-, m- and/or p-chloroanlline, 2,4-, 3,4- and 3,5-dichloroaniline, 2-nitro-4-aminotoluene,
and alcohols at temperatures of 150C to 350C under increased pressure. It should be noted that this patent only describes the manufacture of N-alkylmonourethanes and does not mention the manufacture of N,N'-disubstituted diurethanes and poly-urethanes. U.S. Patent 2,677,698 also describes a process for the manufacture of N-substituted monourethanes. In this process, the urea is initially converted into the cor-responding N,M'-disubstituted urea with monoamines, is then cleaned, and subsequently is reacted with an alcohol. The processes described are expensive and the yields are very low. Attempts to improve the yield by improving the methods of preparing and purifying the N,N'-disubstituted ureas have been unsuccessful.
Other processes have not been successful in elimina-ting the problems described thus far. U.S. Patent 2,806l051 describes a process whereby N-substituted urethanes are produced by reacting aniline with urea and alcohol at a mole ratio of 1.0:1.2:2.0 at temperatures below 200C, prefer-ably of 120C to 160~C. Even in the preferably used tempera-ture range, this process produces only small yield~ of N-sub-stitued urethanes if the reaction time is limited to a period which i5 practical in an industrial setting. In view of the problems with this process t it is not surprising ~hat U.S.
Patent 3,076,007, which describes the manufacture o N-alkyl-and N-cycloalkyl urethanes, does not incorporate the above-referenced methods in its process. It does, however, describe the reaction of phosgene with alcohols to form chloroalkyl-formates, and it describes their subsequent reaction with amines to form urethanes. It also discloses the reaction of amines with ethylene carbonate to form urethanes. German Published Application 27 16 540 describes a more recent variation of this process wherein aromatic urethanes are prepared by reactin~ dialkyl carbonates with N-ethyl amines.
It is also known that ethyl carbamates do not react with amines in boiling dioxane lD.G. Crosby and C. Niemann, Journal of_the American Chemical Society, Vol. 76, page 4458 (1954)], and that the reaction of N-alkyl urethanes with alcoholic ammonia solutions at temperatures of 160C to 180C result in an alkali solution from which aminohydro-chloride, urea, alkylurea and alkyl urethane can be isolated by means of hydrochloric acid after neutralization [M. Brander, Rec. trav. Chim., Vol~ 37, pages 88-91 (1917);. The refer-enced publications do not contain any disclosure concerning the reaction of aromatic primary amines with carbamates although it is known that the heating of ethyl car~amate with aniline at 160C in a bomb tube will produce diphenylurea.
See Annalen, Vol. 147~ page 163 (1868).
U.S. Patent 2,409,712, discloses that the reaction of aliphatic monoamines, urea and alcohol will produce alkyl urethanes~ However, only small yields result even though excess urea is used. Since somewhat higher yields are achieved with less urea and at lower temperatures according to U.S. Pa ent 2,806,051, one has to assume that higher mole ratios of urea to amines are disadvantageous~ Diphenylurea 379~
and O-alkyl carbamate were determined as by-products of the synthesis of phenylurethane. The O-alkyl carbamate was isolated by means of distillation in addition to unreacted aniline~ The formation of O-alkyl carbamate from urea and alcohol wa3 therefore considered as an interferring secondary reaction. Since even the manuacture of N-monoalkylsubsituted urethanes from alkylamines, urea, and alcohols succeeds with moderate yields only, and since carbamates are produced as by-products, it is not surprising that the prior art does not teach the preparation of aryl mono-, di- and/or polyurethanes from arylamines and O-alkyl carbamates.
Because of th~ problems identified thus far, other ; methods of producing N-arylurethanes have been tried. Some have suggested that N-arylurethanes can be prepared by re-acting nitroaromatics with carbon monoxide, and alcohols in the presence of catalysts. German Published Application 15 68 044 (U.S. Patent 3,~67,694) teaches that urethanes may be prepared by the reaction of organic nitro compounds, carbon monoxide, and hydroxyl-containing compounds in the presence of a catalysts consisting of a noble metal and a Lewis acid under essentially anhydrous conditions in the absence of hydrogen under increased pressure and at temperatures above 1~0C.
German Published Application 23 43 826 (U.S. Patent 3,895,054) teaches that urethanes can be prepared from hydroxyl group-containing compounds, carbon monoxide, and nitro-l nitroso-, azo- and azoxy group-containing compounds in the presence of sulfur, selenium, a sulfur and/or selenium compound and at ~1~137~
least one base and/or water. German Published Application 26 23 694 (U~S. Patent 4,080,365) describes the preparation of aromatic urethanes from the above-referenced starting com-pounds in the presence of selenium-containing catalyst systems as well as speclal aromatic amino and urea compounds.
However, the use of these processes involve serious draw-backs. The toxic carbon monoxide and catalysts which are toxic or form toxic compounds during the reaction, such as hydrogen selenide and hydrogen sulfide, or catalysts which are very expensive and are difficult to recycle such as paladium, require great technical expenditure and costly safety measures.
None of the references cited discloses the prepara-tion o~ aryl mono , di and/or polyurethane by reacting an aromatic amine with an O-alkyl carbamate in the presence of an alcohol and catalysts at temperatures greater than 120C.
Moreover, the processes described all involve several dis-advantages. It is surprising that aryl mono, di and/or polyurethanes can be produced in one process stage with good yields by reacting carbamates with prîmary aromatic amines in the presence of alcohol and catalysts at temperatures greater than 120C. Prior teachings indicate that corresponding diureas are obtained from diamines and carbamates; for example, hexamethylenediurea is obtained from hexamethylenediamine and carbamates. Prior art also teaches that, although urea and alcohol may react to produce urethanes, they continue to react to form N,N'-disubstituted ureas in the presence of amines~
See Houben-Weyl, Metbcd~ ~t o~3ggD?gLrh~ y~ Vol. 8, pages llZ~L37~
152, 140, and 160, (Georg Thieme Publishers, Stuttgart, 1952).
These side reactions decrease the yield of the desired product.
Furthermore, German Patent 896 412 indicates that high molecular, spinnable condensation products may be produced from the diamides of carbonic acid such as urea and diamines. This result is likely to occur if the amino groups of the diamines are separated by a chain of more than three atoms. U.S. Patent 2,181,663 and U.S. Patent 2,568,885, for instance, disclose that high molecular poly-ureas with molecular weights of snoo to 10,000 and greater, may be produced when diurethanes are condensed with diamines at temperatures of approximately 150C to 300C. Moreover, mono- and polyurethanes can furthermore be split thermally into isocyanates, alcohols and possibly olefins, carbon dioxide, urea and carbodiimide, and these products can be split into products such as biurets, allophanates, isocy-anurates, polycarbodiimides, and others. 5ee Yh~
the American Chemical Society, Vol. 80~ page 5495 (1958) and Vol. 48, page 1946 (1956).
In view of the problems disclosed in the prior art, it was surprising that our process~ which involved very similar reaction conditions, would result in a mono-, di-and/or polyurethane with very gooa yields. It was particularly surprising because when diurethanes were prepared from the products mentioned in the previous paragraph according to the reaction conditions of our invention, good yields did not result.
37~
Summar of the Invention Y
The purpose of this invention was to produce an aryl mono-, di-p and/or polyurethane from readily available raw materials in one reaction stage under economically justifiable conditions with good yields. The use of strongly toxic raw materials such as phosgene, carbon monoxide, or catalysts which are toxic and form toxic compounds during the reaction, such as hydrogen sulfide, wa~ to be avoided.
The problem was solved by developing a process for the preparation of aryl mono-, di-, and/or polyurethanes comprising the steps of A~ reacting a primary aromatic mono-, di-, and/or polyamine with an O-alkyl carbamate in the presence of an alcohol and at least one compound containing one or more cations of metals of groups IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, V~, VIB, VIIB, and YIIIB of the periodic system as catalysts, and B. separating the ammonia and other by-products from the aryl mono-p di-, and/or polyurethane.
The reaction may be illustrated hy the following equation I:
Ar(-NH~)n + n H2N-COOR - > Ar(-NH-COOR)n ~ n N~3 (I) However, the reaction i5 preferably carried out in the presence of urea according to equation (II):
Ar(-NH2)n + a H2N-CO-NH2 + b H2N-COOR + a ROH >
(II) Ar(-NH-COOR)n + (2a+b)NE13 In equations (I) and (II), n, a, and b stand for whole numbers with n representing 1-7, preferably 1-5, and in which, according to (II), a+b equals n and a:n equals 1.5-0.
The aryl mono-, di-, and/or polyurethanes produced according to the process of this invention are valuable end and intermediate products. They are usedt for instance, as pesticides. As intermediate products, they are used as components for polycondensation and polymer systems and, in particular, they are transformed into the corresponding di-and/or polyisocyanates by removal of the alcohol. The di-and/or polyisocyanates can be used in the manufacture of polyurethanes.
Descri tion of the Preferred Embodiments In order to prepare the aryl mono-, di-, and/or polyurethane in accordance with the process of this invention, a primary aromatic mono, di, and/or polyamine is reacted with an O-alkyl carbamate in the presence of an alcohol and cata-lysts in such quantities that the ratio of amino groups of the primary aromatic amines to O-alkyl carbamates to the hydroxyl groups of the alcohol i5 1:0.5-20-0-100, preferably 1:0.8-10:0-30, and particularly for arylmonourethanes 1:1-6:0-5, and for aryl-di- and/or polyurethanes, 1:1-6:2-20. The reaction preferably is carried out in the presence of urea.
It is not necessary to separately produce O-alkyl-carbamates in a proceeding process stage. In an easily L3'7~
practiced, preferably used version, the O-alkyl carbamate is used together with urea and alcohol and after extensive to complete reaction of their aromatic mono- and/or polyamines, the O-alkyl carbamate is separated by means of distillation and i5 recycled if so required~ The process according to this invention may also be conducted in a continuous phase.
Unsubstituted or substituted primary aromatic mono-, di- and polyamines are suited or the reaction with the O-alkyl carbamate in the presence of alcohol and in the absence or presence of ureas according to this invention.
Representative amines include the following: aromatic mono-amines such as aniline, substituted anilines, such as anilines substituted in the 2, 3 and/or 4 position by a nitro-, methyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl-, secondary butyl-, tertiary butyl group or a chlorine atom; ortho-, meta- and/or parahydroxy-, methoxy-, ethoxy-, propoxy-, isopropoxy-, N-butoxy-, isobutyoxy-, secondary butoxy-, and tertiary butoxyaniline; an alkylbenzoate with l to 4 carbon atoms in the alkyl radical substituted by an amino group in the n- and/or p- position; N-alkoxycarbonylaminobenzenes and -toluenes with 1 to 4 carbon atoms in the alkyl radical substituted by an amino group in the m and/or p-position;
alpha- and beta-naphthylamine; aromatic diamines such as 1,3-and 1,4 diaminoben2ene; 1,3-diaminobenzene substituted in the 2 and/or 4 position by nitro, methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy groups or halogen atom, preferably fluorine or 7~
chlorine; or 1,4-diaminobenzene, 1,5- and 1,8-diamino-naphthalene, 4,4l-diaminodiphenyl, 2,2'-, 2,4'- and 4,4'-di-aminodiphenylmethane and the corresponding isomer mixtures thereof, all of which may be substituted in the 2 position by a nitro, methyl, ethyl, n-propyl, i~opropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxyt ethoxy, n-propoxy, isopropoxy, n-butoxy, lsobutoxy, sec-butoxy, tert~butoxy group or a halogen atom, preferably a fluorine or a chlorine atom; and polyamines such as 1,3,5-triaminobenzene, 2,4,6-triamino-benzene, and 1,3,5-triaminobenzene and polyphenylpolymethylene polyamines as well as mixtures of diaminodiphenyl methanes and polyphenylpolymethylene polyamines which are produced in accordance with familiar methods by the condensation of aniline and formaldehyde in the presence of preferably mineral acids as catalysts and which may be substituted with any of the above identified groups or atoms.
The following compounds are preferably used as aromatic monoamines: O-J m- andjor p-toluidine, o-, m- and/or p-anisidine, 3-hydroxyaniline, o-, m- and/or p-chloroanlline, 2,4-, 3,4- and 3,5-dichloroaniline, 2-nitro-4-aminotoluene,
4-nitro-2-aminotoluene, 2-nitro-6-amino-toluene, and N-alkoxy-carbonylarylamines having the formula M~COOR
3~
in which R represents a methyl-, ethyl-, propyl-, isopropyl-, n-butyl-, isobutyl-, secondary butyl-, or tertiary butyl-radical and in which R' stands for a hydrogen atom or the radical R a~ well as particularly aniline, 3,3'-ditolulene-4,4'-diamine, 2j4- and 2,6-tolulenediamine as well as the corresponding isomer mixtures, 2,2'-, 2,4'- and 4,4'-diamino- :
diphenylmethane and the corresponding isomer mixtures, 1,5-and 1,8-naphthalenediamine as aromatic diamines and mixtures of diaminodiphenylmethanes and polyphenylpolymethylene poly-amines as polyaminesO During the reaction, the amino groups are transformed into alkoxycarbonylamino groups independent of whether or not the remaining substituents remained unchanged or are also converted.
Suitable O-alkylcarbamates for the reaction have the formula H2N-COOR in which R represents an unsubstituted or substituted aliphatic, cycloaliphatic or aromatic-aliphatic radical. Representative examples include O-alkyl carbamates based upon primary aliphatic monoalcohols having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms such as methyl carbamate, ethyl carbamate, propyl carbamate, n-butyl car-bamate, isobutyl carbamate7 2- and 3-methylbutyl carbamate, neopentyl carbamate, pentyl carbamate, 2-methylpentyl car-bamate, n-hexyl carbamate, 2-ethylhexyl carbamate, heptyl carbamate, n-octyl carbamate, n-nonyl carbamate, n-decyl carbamate and n-dodecyl carbamate, 2-phenylpropyl carbamate and benzyl carbamate; and O-alkyl carbamates based upon secondary aliphatic and cycloaliphatic monoalcohols having 3 to 15 carbon atoms, preferably 3 to 6 carbon atoms such as -~2-37~
isopropyl carbamate, secondary butyl carbamate, secondary isoamyl carbamate, cyclopentyl carbamate, cyclohexyl car-bamate, tertiary butylcyclohexyl carbamate, and bicyclo-(2,2,11-heptyl carbamate. Preferably used are methyl car-bamate, ethyl carbamate, propyl carbamate, butyl carbamate, isobutyl carbamate, 2- and 3-methylbutyl carbamate, pentyl carbamate, hexyl carbamate, 2-ethylhexyl carbamate, heptyl carbamate, octyl carbamate~ and cyclohexyl carbamate.
; Unsubstituted, or substituted, primary or secondary aliph~tic alcohols, as well as mixtures thereof, may be used as alcohols. Preferably used is the alcohol which has an alkyl group corresponding with the alkyl group of the O-alkyl carbamate. Representative examples include primary aliphatic alcohols having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methanol, ethanol, propanol, n-butanol, 2-methylbutanol, n-pentanol, neopentylalcohol, 2-methylpentanol, n-hexanol, n-heptanol, n-octanol, nonanol, n-decanol, and n-dodecanol; and secondary aliphatic and cycloaliphatic alcohols having 3 to 15 carbon atoms, prefer-ably 3 to 6 carbon atoms, such as isopropanol, secondarybutanol, secondary isoamylalcohol, cyclopentanol, 2-~ 3- or 4-methylcyclohexanol, cyclohexanol, and bicyclo-(2,2,1)-heptanol. Preferably u~ed as monoalcohols are methanol, ethanol, propanol, n-butanol, isobutanol, 2-ethylbutanol, 2-and 3-methylbutanol, n-pentanol, n-hexanol, 2-ethylhexanol 9 heptanol, octanol and cyclohexanol. If required, the alcohols may be mixed with other organic solvents which are inert under the reaction conditions.
As already indicated, a preferred process version uses urea in addition to the O-alkyl carbamate for the manu-facture of the aryl mono- and/or polyurethanes with the ratio of amino groups of the aromatic amines to the total of O alkyl carbamate and urea also being 1:0.5-20, preferably 1:0.8-10, and particularly ls1-6 with the mole ratio of urea to amino groups of the primary, aromatic amines being equal to or less than 1.5, preferably 1.25-0~75, and the mole ratio of urea to hydroxyl groups of the alcohol being equal to or less than 1. The urea is appropriately used in com-mercially-available form and purity.
In accordance with the invention, the reaction is carried out in the presence of one or more catalysts. Suit-able catalysts are inorganic and organic compounds containing one or more, preferably one cation of metals of the groups IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB~ VIB, VIIB and VIIIB of the periodic system defined in accordance with the Handbook of Chemistr and (14th edition, Chemical Rubber Publishing Company, 2310 Superior Avenuet N.E., Cleveland, Ohio~O These compounds include, for instance, halides such as chlorides and bromides, sulfates, phosphates, nitrates, boratesl alcoholates, phenolates, sulfonates, oxides, oxide hydrates, hydroxides, carboxylates, chelates, carbonates and thio- or dithioarbamates. The compounds should contain cations of the following metals: lithium, sodium, 7~
potassium, magnesium, calcium, aluminum, gallium, tin, lead, bismuth, antiomony, copper, silver, gold, zinc, mercury, cerium, titaniu~, vanadium, chromium, molybdenum, manganese, iron, cobalt and nickel. Preferably used are the ~ations of lithium, calcium, aluminum, tin, bismuth, antimony, copper, zinc, titanium, vanadium, chromium, molybdenum, manganese, iron and cobalt. Without recognizable marked drawbacks, the catalysts may also be used in form of their hydrates or ammoniates.
Examples of typical catalysts include the follo~
ing compounds: lithium methanolate, lithium ethanolate, lithium propanolate, lithium butanolate, sodium methanolate, potassium-tertiary butanolate, magnesium methanolate, calcium methanolate, tin-(II)-chloride, tin-(IV) chloride, lead acetate, lead phosphate, antimony-(III)-chloride, antimony-(V)-chloride, aluminum isobutylate, aluminum trichloride, bismuth-(III)-chloride, copper-(II)-acetate~ copper (II) sulfate, copper-(II)-nitrate, bis-(triphenylphosphineoxido)-copper-(II)-chloride, copper molybdate, silver acetate, gold acetate, ~inc oxideS zinc chloride, zinc acetate, zinc acetonylacetatet zinc octoate, zinc oxylate, zinc hexylate, zinc benzoate, zinc, undecylenate, cerium-(IV)-oxide, uranyl acetate, titanium tetrabutanolate, titanium tetrachloride, titanium tetraphenolate, titanium naphthenate, vanadium-(III)-chloride, vanadium acetonylacetate, chromium-(III)-chloride~
molybdenum-(VI)-oxide, molybdenum acetonylacetate, tungston-(VI)-oxide, manganese-(II)-chloride, manganese-(II)-acetate, 3~7~
manganese-(III)-acetate, iron-(II)-acetate, iron-(III)-acetate, iron phosphate, iron oxylate, iron-(III)-chloride, iron-(III)-bromide, cobalt acetate, cobalt chloride, cobalt sulfate, cobalt naphthenate; nickel chloride, nickel acetate, and nickel naphthenate as well as their mixtures~
Advantageously, the catalysts are used in quantities corresponding with 0.0001 to 0.1, preferably 0.0005 to 0.05, équivalents of the metal cation relative to the amino groups of the aromatic mono-, di~ and polyamines. The metal ions may also be used bonded to ion exchangers in the heterogenous phase.
The reactions are carried out at increased tempera-tures, ~or instance at temperatures of 100C to 250C, preferably 120C to 210C, and particularly 135C to 190C, and under pressures of 0.1 bar to 120 bars, preferably 0~5 bar to 60 bars, and particularly 1 bar to 40 bars. It has proven to be advantageous to remove the resultant ammonia from the resultant mixture~ for instance by means of distil-lation. At a given temperature, the reaction is then prefer-ably carried out under a pressure at which the result-ant ammonia can be removed selectively from the reaction mixture by means of distillation. The corresponding values are contained in tables with the physical characteristics of ammonia and alcohols. The reaction times which are appro-priate for the above-referenced temperature ranges are 0.5 hour to 100 hours, preferably 1 hour to 50 hours, and parti-cularly 2 hour to 25 hours.
7~
The aryl-mono-, -di- and/or ~polyurethanes are advantageously produced according to the process of this invention by mixing the reactants in the referenced quantity ratios and in the presence of at least one catalyst. They are then heated, with or without agitation, in a reaction vessel equipped with a device for separating the ammonia.
After completed reaction, the resultant ammonia may be separated. Preferably, however, it is removed during the reaction either continuously or by a batch-type operation and by means of distillation~ It may be advantageous, particularly during the reaction in the presence of low molecular alcohols under pressure, to separate the ammonia with the assistance of a stripping agent which is inert under the reaction conditions, such as a gas like nitrogen or part of the alcohol. Subsequently, before or after separating the catalyst, and after filtering off solid materials, the aryl-mono-, di- and/or polyurethane is isolated from the resultant reaction mixure. This can be done by removing the excess O-alkyl carbamate and/or the alcohol by distillation, by partially distilling off the exce~s O-alkyl carbamate, and/or the alcohol and crystallization, by crystal-lization, or by precipitating with or also by transcrystal-lizing from other solvents. The separated O-alkyl carbamate can be recycled if so required.
The parts referred to in the examples, which follow, are relative to parts by weight. The elementary compositions and structures were confirmed by elementary analysis, mass ~2~7~
spectroscopy, and infra-red and nuclear magnetic resonance spectra.
~Z~37~:
Example 1 In a reaction vessel, 93 parts of aniline with 257 parts of butyl carbamate, 0.9 parts of cobalt acetate, and 250 parts butanol are heated to 175C for 8 hours with a pressure of 5 bars to 15 bars being adjusted in the reactor via a pressure valve. Using 25 liters of nitrogen per liter of reaction mixture an hour, as a stripping agent, the ammonia formed during the reaction is removed continuously by means of distillation. After completed reaction, unreacted aniline, excess butanol and excess butyl carbamate are removed at ap-proximately 20 millibars. By means of distillation at 145C
to 148C and 0.1 millibar, 172 parts of phenylbutyl urethane ; (98 percent of theory relative to the reacted aniline) are obtained having a melting point of 80C to 83C. The con-version of aniline is 91 percent.
In a reaction vessel, 93 parts of aniline with 450 parts of methyl carbamate, 0~9 parts of cobalt acetate and 96 parts of methanol are heated to 175C for 6 hours with a pressure of 5 bars to 6 bars being adjusted in the reactor via a pressure valve. The ammonia formed during the reaction is removed by batch-type distillation. After completed reaction, the reaction mixture is analyzed gas chromatographically usins the internal standards method. It is determined that 140 parts of phenylmethyl urethane (98.6 percent of theory relative ~o reacted aniline) have formed. The conversion of aniline is 94 percent.
3'7~
Comparison Example Example 2 is duplicated except a catalyst is not added to the reaction mixture. The gas chromatographical analysis shows that 113 parts oE phenylmethyl urethane (88 percent of theory relative to reacted aniline) and 7 part~ of N-methylaniline (7.7 percent of theory relative to reacted aniline) were formed. Eighty-five percent of the aniline was reacted.
Example 3 In a reaction vesel, 18 parts of aniline with 36.5 parts of methyl carbamate and 0.2 part of vanadium trichloride in 75 parts of diethylene glycol dimethyl ether are heated to boiling for 3 hours. After completed reaction, the reaction mixture is analyzed gas chromatographically using the internal standards method. It is shown that 19 parts of phenylmethyl urethane were formed (73.9 percent of theory relative to reacted aniline~. Eighty-eight percent of the aniline has been reacted.
In a reaction vessel, 93 parts of aniline with 240 parts of butyl carbamate and 0.9 parts vanadium trichloride in 86 parts butanol are heated to 135~C to 140C for 16 hours.
After completed reaction~ the reaction mixture is analyzed by gas chromatography. It is shown that 176 parts of phenylbutyl urethane were formed (97 percent of theory relative to reacted aniline). Ninety-four percent of the aniline was reacted By means of fractionatal distillation, 164 parts of phenylbutyl urethane are isolated at a boiling point of 138C to 144~C at 0.03 millibars.
Comparison Ex~e~
Example 4 is duplicated except a catalyst is not added. The gas chromatographical analysis shows that 6.7 parts of phenylbutyl urethane were formed (87 percent of theory relative to reacted aniline). However, only 4 percent of the aniline was reactedO
Examples 5 to 35 Example 4 is duplicated except the vanadium tri-chloride catalyst is replaced with other compounds having metal cations as catalysts.
The catalysts used as well as the resultant yields and conversions have been compiled in the following table.
The formulas in the table denote the following:
C2H3O2 Acetate radical [(C6Hs)3po]2 Bis(triphenylphosphineoxide) C24 Oxylate radical cl1H1go2 Undecylenate radical 20 C5H72 Acetylacetaonate radical C4HgO Butylate radical CH3O Methylate radical n-C3H7O n-Propylate radical iso-C3H7O iso~Propylate radical 3~7~
Table Aniline Phenyl-Butyl-ExampleConversion Urethane Yi~ld No Ca~ st ~ %
MnCl2 31 98 6 Mn(c2H3o2)2 x H2O 31 58 7 Mn(C2H3O2)3 x H2O 37 72 8 CoCl2 67 51 g Co(c2H3o2)2 x 4H2089 99 CoSO4 x 7H2O 58 85 11 ~U(No3)2 x 3H20 33 72 10 12 CU(c2H3o2)2 x ~2 71 86 13 CU[(c6Hs~3Po]2cl2 70 84 14 Ni-naphthenate 57 87 Fe(OH~(c2H3O2)2 82 99 16 Fe(C2H3O2~2 91 99 17 FePO4 83 93 18 Fe(C2O4) x 2H2 5 19 zn(C2H3O2)2 x 2H2 72 100 ZnC12 40 90 21 Zn(C11H19O2)2 98 20 22 MoO2(csH7O2)2 85 96 24 SbC15 87 88 CrCl3 69 97 26 SnCl2 90 88 27 SnCl4 92 79 28 BiC13 47 85 29 TiCl4 50 98 Ti(C4H9O)4 64 94 31 LiC4HgO 67 83 30 32 NaCH3O 16 99 33 Ca(n-c3~7o)2 58 97 34 Al(iso-C3~7O)3 67 93 CeO2 12 97 3~
Exam~le 36 In a reaction vessel, 12.2 parts of 2,4-diamino-toluene with 22.3 parts of ethyl carbamate, 1 part of iron-(II)-acetate and 28 parts of ethanol are heated to 180C for 6 hours with a pressure of 14 bars to 17 bars being adjusted in the reaction vessel via a pressure valve. Using 30 liters of nitrogen per liter of reaction mixture an hour as a stripping agent, the ammonia formed during the reaction is continuously removed by means of distillation. After completed reaction, the reaction mixture is analyzed by means of high perssure liquid chromatography using the external standard method.
It is determined that 19 parts of 2~4-bis(ethoxycarbonyl-amino)toluene (73.6 percent of theory relative to reacted 2,4-diaminotoluene) and 3.6 parts of a mixture of 2-amino-4-(ethoxycarbonylamino)toluene and 4-amino-2-(ethoxycarbonyl-amino)toluene (19.1 percent of theory relative to reacted 2,4-diaminotoluene) have been formed. Ninety-seven percent of the 2,4-diaminotoluene has been converted.
In order to isolate the 2,4-bis(ethoxycarbonyl-amino)toluene, the excess ethanol and excess ethyl carbamateare reduced by distillation under reduced pressure at 10 millibars. The residue is dissolved in 250 parts of methylene chloride, and is washed repeatedly with water. Following this, the methylene chloride is separated~ 50 parts of ethanol are added, and the mixture is allowed to cool in an ice-sodium ~2~
chloride mixture. Eventually, 2,4-bis(ethoxycarbonylamino)-toluene will crystallize having a melting point of 108C to Example 37 In a reaction vessel, 7.9 parts of 1,5-diamino-naphthaline with 24.5 parts of ethyl carbamate, 3 parts of urea, 0.15 part of uranyl acetate, and 34 parts of ethanol are heated to 180C for 12 hours with a pressure of 16 bars to 18 bars being adjusted within the reactor via a pressure valve.
Using 20 liters of nitrogen per liter of reaction mixture an hour as a stripping agent, the ammonia formed during the reaction is continuously removed by means of distillation.
After completed reaction, the reaction mixture is analyzed by high pressure liquid chromatography using the external standard method. It is determined that 9 parts of 1,5-bis-(ethoxycarbonylamino~naphthalene (83.9 parts of theory relative to reacted 1,5-diaminonaphthalene) have been formed having a melting point of 221C to 224C. Seventy~one percent 1,5-diaminonaphthalene has been converted.
Exam~le 38 In a reaction vessel, 120 parts of 3,5-dichloro-aniline with 220 parts of methyl carbamate and 6 parts of cobalt acetate in 10~ parts of diethylene glycol dimethyl ether are heated under reflux for 10 hours. After completed reaction, excess methyl carbamate and diethylene glycol di-methyl ether are removed by means of distillation under reduced pressure at 15 millibars. The residue is dissolved in -2~-137~
500 parts of methylene chloride, is mixed with 60 parts of 10 percent sulfuric acid, and is washed 3 times with 100 parts of water. The organic phase is dried and concentrated resulting in 123 parts of 3,5-dichlorophenylmethyl urethane (90.9 percent of theory relative to converted 3,5-dichloroaniline) having a melting point of 117C to 119C. Eighty-three percent of the 3,5-dichloroaniline has been converted.
In a reaction vessel 10~0 parts of 4,4l-diamino-diphenylmethane with 143 parts of octyl carbamate, 6 parts ofurea and 0.3 part of cobalt acetate are heated to boiling in 150 parts of octanol for 6 hours. Using 10 liters of nitrogen per liter of reaction mixture an hour as a stripping agent, the ammonia formed during the reaction is continuously removed by means of distillation. After cooling, 16 parts of 4,4'-bis(octoxycarbonylamino)diphenylmethane crystallize (71.4 percent of theory relatiave to reacted 4~4'-diaminodiphenyl-methane) having a melting point of 117C to 119C. Eighty-seven percent of the 4,4'-diaminodiphenylmethane has been converted. The mother liquor still contains 4-amino-4'-(octoxycarbonylamino)diphenylmethane~
One proceeds according to the data in Example 39 without using additional urea. Obtained are 11 parts of 4,4'-bis~octoxycarbonylamino)diphenylmethane (61.9 percent of theory relative to reacted 4,4'-diaminodiphenylmethane).
Sixty-nine percent of the 4,4'-diaminodiphenylmethane was converted.
~I~Z~L37~
Exam~le 41 In a reaction vessel, 15 parts of a commercially-available mixture of 2,2'-, 2,4'- and 4,4'-diaminodiphenyl-methane and polyphenylpolymethylene polyamines with 40 parts of ethyl carbamate and 0.5 part of cobalt acetate in 70 parts of ethanol are heated to 190C to 195C for 8 hours with a pressure of 18 bars to 20 bars being adjusted in the reactor via a pressure valve. Using 25 liters of nitrogen per liter of reaction mixture an hour as a stripping a~ent, the ammonia formed during the reaction is continuously removed by means of distillation. The mixture is allowed to cool and excess ethanol and excess ethyl carbamate are removed by distillation under reduced pressure at 10 millibars. The residue is washed with water, is dried and is mixed with cyclohexane, and is agitated. This results in a powdery precipitate which is separated and analyzed by means of high pressure liquid chromatography. It is determined that a mixture of 2,4'-, 2,2'- and 4,4'-bis(ethoxycarbonylamino)diphenylmethane and polyphenylpolymethylene polyethylurethane has been formed containing the same components as a comparison product produced from a mixturP of 2,4'-, 2,2'- and 4,4'-diiso-cyanatodiphenylmethane and polyphenylpolymethylene poly-isocyanates with ethanoI~
Exam~le 42 In a reaction vessel, 22 parts of 3-aminophenol with 100 parts of ethyl carbamate, 12 parts of urea, 1 part o zinc-(II)-acetate and 45 parts of ethanol are heated to 180C
3~
to 185C for 8 hours with a pressure of 7 bars to 8 bars being adjusted in the reactor via a pressure valve. Using 20 liters of nitrogen per liter of reaction mixture an hour as a strip-ping agent, the ammonia formed during the reaction is con-tinuously removed by means of distillation. After completed reaction, the reaction mixture is analyzed by means of gas chromatography using the internal standard method. It is determined that 29 parts of 3-ethoxycarbonylaminophenol (90.2 percent of theory relative to reacted 3-aminophenol) were formed. Eighty-eight percent of the 3-aminophenol was reacted.
ExamEle 43 In a reaction vessel, 61 parts of 2,4-diaminotoluene with 432 parts of octyl carbamate and 1.5 parts of sodium methanolate in 1950 parts of octanol are heated to the boiling point (195C). After 23 hours, the mixture is allowed to cool and excess octanol and excess octyl carbamate is removQd by distillation to a sump temperature of 180~C. Using high pressure liquid chromatography, the residue is analyzed using the external standard method. It is determined that 57 percent of the 2,4-diaminotoluene reacted, resulting in 101 parts (81.7 percent of theory) of 2,4-bis(octoxycarbonyl-amino)toluene, C2sH4~O4N2 (molecular weight 434) and 10.9 parts (13.8 percent of theory) of a mixture consisting of 2-amino-4-(octoxycarbonylamino~toluene and 4-amino- -(octoxy-carbonylamino )toluene.
3l~Z~3~7~
Exam~le ~4 In a reaction vessel, 40 parts of 2,4-dimainotoluene with 240 parts of hexyl carbamate, 1.5 parts cobalt acetate, and 170 parts of hexanol are heated to 155C to 175C for 15 hour~ with the resultant ammonia being removed continuously by means of distillation. After completed reaction, the reaction solution is examined by means of high pressure liquid chroma-tography usin~ the external standards method. It is found that the 2,4~diaminotoluene is completely converted resulting in 119 parts of 2,4-bis(hexoxicarbonylamino)toluene (96 percent of theory relative to the reacted 2,4-diaminotoluene).
In a reaction vessel, 100 parts of a commercially-available crude MDA mixture, 46 percent of which consists of diaminodiphenylmethane and 54 percent of which consists of polyphenylpolymethylene polyamines with 30.3 parts of urea, 300 parts of hexyl carbamate, 1.5 parts of cobalt acetate and 260 parts of hexanol are heated to 155C to 175C for 25 hours with the resultant ammonia being removed continuously by means of distillation. After completed reaction, the reaction solution is examined by means of high pressure liquid chroma-tography which shows that a mixture of bis(hexoxycarbonyl~
amino)diphenylmethanes and poly(hexoxycarbonylamino)poly-phenylpolymethanes has been formed which is identical with a comparison product produced from a mixture of diphenylmethane-diisocyanates and polyphenylpolymethylene polyisocyanates and hexanol.
-2~-IL3~74 Example 46 In a reaction vessel, 50 parts of 4,4'-diaminodi-phenylmethane with 360 parts of hexyl carbamate, 1 part of cobalt acetate and 260 parts of hexanol are heated to 155C to 175C. The mixture is agitated at 155C to 175C for 27 hours. After cooling, the mixture is filtered off the preci-pitated catalyst and is analyzed by high pressure liquid chromatography using the external standard method. It is found that the 4,4'-diaminodiphenylmethane is completely reacted resulting in 108 parts of 4,4'-bis(hexoxycarbonyl-amino)diphenylmethane (94~2 percent of theory relative to reacted 4,4'-dimainodiphenylmethane). The reaction solution further contains some 4-amino-4'-(hexoxycarbonylamino)di-phenylmethane.
3~
in which R represents a methyl-, ethyl-, propyl-, isopropyl-, n-butyl-, isobutyl-, secondary butyl-, or tertiary butyl-radical and in which R' stands for a hydrogen atom or the radical R a~ well as particularly aniline, 3,3'-ditolulene-4,4'-diamine, 2j4- and 2,6-tolulenediamine as well as the corresponding isomer mixtures, 2,2'-, 2,4'- and 4,4'-diamino- :
diphenylmethane and the corresponding isomer mixtures, 1,5-and 1,8-naphthalenediamine as aromatic diamines and mixtures of diaminodiphenylmethanes and polyphenylpolymethylene poly-amines as polyaminesO During the reaction, the amino groups are transformed into alkoxycarbonylamino groups independent of whether or not the remaining substituents remained unchanged or are also converted.
Suitable O-alkylcarbamates for the reaction have the formula H2N-COOR in which R represents an unsubstituted or substituted aliphatic, cycloaliphatic or aromatic-aliphatic radical. Representative examples include O-alkyl carbamates based upon primary aliphatic monoalcohols having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms such as methyl carbamate, ethyl carbamate, propyl carbamate, n-butyl car-bamate, isobutyl carbamate7 2- and 3-methylbutyl carbamate, neopentyl carbamate, pentyl carbamate, 2-methylpentyl car-bamate, n-hexyl carbamate, 2-ethylhexyl carbamate, heptyl carbamate, n-octyl carbamate, n-nonyl carbamate, n-decyl carbamate and n-dodecyl carbamate, 2-phenylpropyl carbamate and benzyl carbamate; and O-alkyl carbamates based upon secondary aliphatic and cycloaliphatic monoalcohols having 3 to 15 carbon atoms, preferably 3 to 6 carbon atoms such as -~2-37~
isopropyl carbamate, secondary butyl carbamate, secondary isoamyl carbamate, cyclopentyl carbamate, cyclohexyl car-bamate, tertiary butylcyclohexyl carbamate, and bicyclo-(2,2,11-heptyl carbamate. Preferably used are methyl car-bamate, ethyl carbamate, propyl carbamate, butyl carbamate, isobutyl carbamate, 2- and 3-methylbutyl carbamate, pentyl carbamate, hexyl carbamate, 2-ethylhexyl carbamate, heptyl carbamate, octyl carbamate~ and cyclohexyl carbamate.
; Unsubstituted, or substituted, primary or secondary aliph~tic alcohols, as well as mixtures thereof, may be used as alcohols. Preferably used is the alcohol which has an alkyl group corresponding with the alkyl group of the O-alkyl carbamate. Representative examples include primary aliphatic alcohols having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methanol, ethanol, propanol, n-butanol, 2-methylbutanol, n-pentanol, neopentylalcohol, 2-methylpentanol, n-hexanol, n-heptanol, n-octanol, nonanol, n-decanol, and n-dodecanol; and secondary aliphatic and cycloaliphatic alcohols having 3 to 15 carbon atoms, prefer-ably 3 to 6 carbon atoms, such as isopropanol, secondarybutanol, secondary isoamylalcohol, cyclopentanol, 2-~ 3- or 4-methylcyclohexanol, cyclohexanol, and bicyclo-(2,2,1)-heptanol. Preferably u~ed as monoalcohols are methanol, ethanol, propanol, n-butanol, isobutanol, 2-ethylbutanol, 2-and 3-methylbutanol, n-pentanol, n-hexanol, 2-ethylhexanol 9 heptanol, octanol and cyclohexanol. If required, the alcohols may be mixed with other organic solvents which are inert under the reaction conditions.
As already indicated, a preferred process version uses urea in addition to the O-alkyl carbamate for the manu-facture of the aryl mono- and/or polyurethanes with the ratio of amino groups of the aromatic amines to the total of O alkyl carbamate and urea also being 1:0.5-20, preferably 1:0.8-10, and particularly ls1-6 with the mole ratio of urea to amino groups of the primary, aromatic amines being equal to or less than 1.5, preferably 1.25-0~75, and the mole ratio of urea to hydroxyl groups of the alcohol being equal to or less than 1. The urea is appropriately used in com-mercially-available form and purity.
In accordance with the invention, the reaction is carried out in the presence of one or more catalysts. Suit-able catalysts are inorganic and organic compounds containing one or more, preferably one cation of metals of the groups IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB~ VIB, VIIB and VIIIB of the periodic system defined in accordance with the Handbook of Chemistr and (14th edition, Chemical Rubber Publishing Company, 2310 Superior Avenuet N.E., Cleveland, Ohio~O These compounds include, for instance, halides such as chlorides and bromides, sulfates, phosphates, nitrates, boratesl alcoholates, phenolates, sulfonates, oxides, oxide hydrates, hydroxides, carboxylates, chelates, carbonates and thio- or dithioarbamates. The compounds should contain cations of the following metals: lithium, sodium, 7~
potassium, magnesium, calcium, aluminum, gallium, tin, lead, bismuth, antiomony, copper, silver, gold, zinc, mercury, cerium, titaniu~, vanadium, chromium, molybdenum, manganese, iron, cobalt and nickel. Preferably used are the ~ations of lithium, calcium, aluminum, tin, bismuth, antimony, copper, zinc, titanium, vanadium, chromium, molybdenum, manganese, iron and cobalt. Without recognizable marked drawbacks, the catalysts may also be used in form of their hydrates or ammoniates.
Examples of typical catalysts include the follo~
ing compounds: lithium methanolate, lithium ethanolate, lithium propanolate, lithium butanolate, sodium methanolate, potassium-tertiary butanolate, magnesium methanolate, calcium methanolate, tin-(II)-chloride, tin-(IV) chloride, lead acetate, lead phosphate, antimony-(III)-chloride, antimony-(V)-chloride, aluminum isobutylate, aluminum trichloride, bismuth-(III)-chloride, copper-(II)-acetate~ copper (II) sulfate, copper-(II)-nitrate, bis-(triphenylphosphineoxido)-copper-(II)-chloride, copper molybdate, silver acetate, gold acetate, ~inc oxideS zinc chloride, zinc acetate, zinc acetonylacetatet zinc octoate, zinc oxylate, zinc hexylate, zinc benzoate, zinc, undecylenate, cerium-(IV)-oxide, uranyl acetate, titanium tetrabutanolate, titanium tetrachloride, titanium tetraphenolate, titanium naphthenate, vanadium-(III)-chloride, vanadium acetonylacetate, chromium-(III)-chloride~
molybdenum-(VI)-oxide, molybdenum acetonylacetate, tungston-(VI)-oxide, manganese-(II)-chloride, manganese-(II)-acetate, 3~7~
manganese-(III)-acetate, iron-(II)-acetate, iron-(III)-acetate, iron phosphate, iron oxylate, iron-(III)-chloride, iron-(III)-bromide, cobalt acetate, cobalt chloride, cobalt sulfate, cobalt naphthenate; nickel chloride, nickel acetate, and nickel naphthenate as well as their mixtures~
Advantageously, the catalysts are used in quantities corresponding with 0.0001 to 0.1, preferably 0.0005 to 0.05, équivalents of the metal cation relative to the amino groups of the aromatic mono-, di~ and polyamines. The metal ions may also be used bonded to ion exchangers in the heterogenous phase.
The reactions are carried out at increased tempera-tures, ~or instance at temperatures of 100C to 250C, preferably 120C to 210C, and particularly 135C to 190C, and under pressures of 0.1 bar to 120 bars, preferably 0~5 bar to 60 bars, and particularly 1 bar to 40 bars. It has proven to be advantageous to remove the resultant ammonia from the resultant mixture~ for instance by means of distil-lation. At a given temperature, the reaction is then prefer-ably carried out under a pressure at which the result-ant ammonia can be removed selectively from the reaction mixture by means of distillation. The corresponding values are contained in tables with the physical characteristics of ammonia and alcohols. The reaction times which are appro-priate for the above-referenced temperature ranges are 0.5 hour to 100 hours, preferably 1 hour to 50 hours, and parti-cularly 2 hour to 25 hours.
7~
The aryl-mono-, -di- and/or ~polyurethanes are advantageously produced according to the process of this invention by mixing the reactants in the referenced quantity ratios and in the presence of at least one catalyst. They are then heated, with or without agitation, in a reaction vessel equipped with a device for separating the ammonia.
After completed reaction, the resultant ammonia may be separated. Preferably, however, it is removed during the reaction either continuously or by a batch-type operation and by means of distillation~ It may be advantageous, particularly during the reaction in the presence of low molecular alcohols under pressure, to separate the ammonia with the assistance of a stripping agent which is inert under the reaction conditions, such as a gas like nitrogen or part of the alcohol. Subsequently, before or after separating the catalyst, and after filtering off solid materials, the aryl-mono-, di- and/or polyurethane is isolated from the resultant reaction mixure. This can be done by removing the excess O-alkyl carbamate and/or the alcohol by distillation, by partially distilling off the exce~s O-alkyl carbamate, and/or the alcohol and crystallization, by crystal-lization, or by precipitating with or also by transcrystal-lizing from other solvents. The separated O-alkyl carbamate can be recycled if so required.
The parts referred to in the examples, which follow, are relative to parts by weight. The elementary compositions and structures were confirmed by elementary analysis, mass ~2~7~
spectroscopy, and infra-red and nuclear magnetic resonance spectra.
~Z~37~:
Example 1 In a reaction vessel, 93 parts of aniline with 257 parts of butyl carbamate, 0.9 parts of cobalt acetate, and 250 parts butanol are heated to 175C for 8 hours with a pressure of 5 bars to 15 bars being adjusted in the reactor via a pressure valve. Using 25 liters of nitrogen per liter of reaction mixture an hour, as a stripping agent, the ammonia formed during the reaction is removed continuously by means of distillation. After completed reaction, unreacted aniline, excess butanol and excess butyl carbamate are removed at ap-proximately 20 millibars. By means of distillation at 145C
to 148C and 0.1 millibar, 172 parts of phenylbutyl urethane ; (98 percent of theory relative to the reacted aniline) are obtained having a melting point of 80C to 83C. The con-version of aniline is 91 percent.
In a reaction vessel, 93 parts of aniline with 450 parts of methyl carbamate, 0~9 parts of cobalt acetate and 96 parts of methanol are heated to 175C for 6 hours with a pressure of 5 bars to 6 bars being adjusted in the reactor via a pressure valve. The ammonia formed during the reaction is removed by batch-type distillation. After completed reaction, the reaction mixture is analyzed gas chromatographically usins the internal standards method. It is determined that 140 parts of phenylmethyl urethane (98.6 percent of theory relative ~o reacted aniline) have formed. The conversion of aniline is 94 percent.
3'7~
Comparison Example Example 2 is duplicated except a catalyst is not added to the reaction mixture. The gas chromatographical analysis shows that 113 parts oE phenylmethyl urethane (88 percent of theory relative to reacted aniline) and 7 part~ of N-methylaniline (7.7 percent of theory relative to reacted aniline) were formed. Eighty-five percent of the aniline was reacted.
Example 3 In a reaction vesel, 18 parts of aniline with 36.5 parts of methyl carbamate and 0.2 part of vanadium trichloride in 75 parts of diethylene glycol dimethyl ether are heated to boiling for 3 hours. After completed reaction, the reaction mixture is analyzed gas chromatographically using the internal standards method. It is shown that 19 parts of phenylmethyl urethane were formed (73.9 percent of theory relative to reacted aniline~. Eighty-eight percent of the aniline has been reacted.
In a reaction vessel, 93 parts of aniline with 240 parts of butyl carbamate and 0.9 parts vanadium trichloride in 86 parts butanol are heated to 135~C to 140C for 16 hours.
After completed reaction~ the reaction mixture is analyzed by gas chromatography. It is shown that 176 parts of phenylbutyl urethane were formed (97 percent of theory relative to reacted aniline). Ninety-four percent of the aniline was reacted By means of fractionatal distillation, 164 parts of phenylbutyl urethane are isolated at a boiling point of 138C to 144~C at 0.03 millibars.
Comparison Ex~e~
Example 4 is duplicated except a catalyst is not added. The gas chromatographical analysis shows that 6.7 parts of phenylbutyl urethane were formed (87 percent of theory relative to reacted aniline). However, only 4 percent of the aniline was reactedO
Examples 5 to 35 Example 4 is duplicated except the vanadium tri-chloride catalyst is replaced with other compounds having metal cations as catalysts.
The catalysts used as well as the resultant yields and conversions have been compiled in the following table.
The formulas in the table denote the following:
C2H3O2 Acetate radical [(C6Hs)3po]2 Bis(triphenylphosphineoxide) C24 Oxylate radical cl1H1go2 Undecylenate radical 20 C5H72 Acetylacetaonate radical C4HgO Butylate radical CH3O Methylate radical n-C3H7O n-Propylate radical iso-C3H7O iso~Propylate radical 3~7~
Table Aniline Phenyl-Butyl-ExampleConversion Urethane Yi~ld No Ca~ st ~ %
MnCl2 31 98 6 Mn(c2H3o2)2 x H2O 31 58 7 Mn(C2H3O2)3 x H2O 37 72 8 CoCl2 67 51 g Co(c2H3o2)2 x 4H2089 99 CoSO4 x 7H2O 58 85 11 ~U(No3)2 x 3H20 33 72 10 12 CU(c2H3o2)2 x ~2 71 86 13 CU[(c6Hs~3Po]2cl2 70 84 14 Ni-naphthenate 57 87 Fe(OH~(c2H3O2)2 82 99 16 Fe(C2H3O2~2 91 99 17 FePO4 83 93 18 Fe(C2O4) x 2H2 5 19 zn(C2H3O2)2 x 2H2 72 100 ZnC12 40 90 21 Zn(C11H19O2)2 98 20 22 MoO2(csH7O2)2 85 96 24 SbC15 87 88 CrCl3 69 97 26 SnCl2 90 88 27 SnCl4 92 79 28 BiC13 47 85 29 TiCl4 50 98 Ti(C4H9O)4 64 94 31 LiC4HgO 67 83 30 32 NaCH3O 16 99 33 Ca(n-c3~7o)2 58 97 34 Al(iso-C3~7O)3 67 93 CeO2 12 97 3~
Exam~le 36 In a reaction vessel, 12.2 parts of 2,4-diamino-toluene with 22.3 parts of ethyl carbamate, 1 part of iron-(II)-acetate and 28 parts of ethanol are heated to 180C for 6 hours with a pressure of 14 bars to 17 bars being adjusted in the reaction vessel via a pressure valve. Using 30 liters of nitrogen per liter of reaction mixture an hour as a stripping agent, the ammonia formed during the reaction is continuously removed by means of distillation. After completed reaction, the reaction mixture is analyzed by means of high perssure liquid chromatography using the external standard method.
It is determined that 19 parts of 2~4-bis(ethoxycarbonyl-amino)toluene (73.6 percent of theory relative to reacted 2,4-diaminotoluene) and 3.6 parts of a mixture of 2-amino-4-(ethoxycarbonylamino)toluene and 4-amino-2-(ethoxycarbonyl-amino)toluene (19.1 percent of theory relative to reacted 2,4-diaminotoluene) have been formed. Ninety-seven percent of the 2,4-diaminotoluene has been converted.
In order to isolate the 2,4-bis(ethoxycarbonyl-amino)toluene, the excess ethanol and excess ethyl carbamateare reduced by distillation under reduced pressure at 10 millibars. The residue is dissolved in 250 parts of methylene chloride, and is washed repeatedly with water. Following this, the methylene chloride is separated~ 50 parts of ethanol are added, and the mixture is allowed to cool in an ice-sodium ~2~
chloride mixture. Eventually, 2,4-bis(ethoxycarbonylamino)-toluene will crystallize having a melting point of 108C to Example 37 In a reaction vessel, 7.9 parts of 1,5-diamino-naphthaline with 24.5 parts of ethyl carbamate, 3 parts of urea, 0.15 part of uranyl acetate, and 34 parts of ethanol are heated to 180C for 12 hours with a pressure of 16 bars to 18 bars being adjusted within the reactor via a pressure valve.
Using 20 liters of nitrogen per liter of reaction mixture an hour as a stripping agent, the ammonia formed during the reaction is continuously removed by means of distillation.
After completed reaction, the reaction mixture is analyzed by high pressure liquid chromatography using the external standard method. It is determined that 9 parts of 1,5-bis-(ethoxycarbonylamino~naphthalene (83.9 parts of theory relative to reacted 1,5-diaminonaphthalene) have been formed having a melting point of 221C to 224C. Seventy~one percent 1,5-diaminonaphthalene has been converted.
Exam~le 38 In a reaction vessel, 120 parts of 3,5-dichloro-aniline with 220 parts of methyl carbamate and 6 parts of cobalt acetate in 10~ parts of diethylene glycol dimethyl ether are heated under reflux for 10 hours. After completed reaction, excess methyl carbamate and diethylene glycol di-methyl ether are removed by means of distillation under reduced pressure at 15 millibars. The residue is dissolved in -2~-137~
500 parts of methylene chloride, is mixed with 60 parts of 10 percent sulfuric acid, and is washed 3 times with 100 parts of water. The organic phase is dried and concentrated resulting in 123 parts of 3,5-dichlorophenylmethyl urethane (90.9 percent of theory relative to converted 3,5-dichloroaniline) having a melting point of 117C to 119C. Eighty-three percent of the 3,5-dichloroaniline has been converted.
In a reaction vessel 10~0 parts of 4,4l-diamino-diphenylmethane with 143 parts of octyl carbamate, 6 parts ofurea and 0.3 part of cobalt acetate are heated to boiling in 150 parts of octanol for 6 hours. Using 10 liters of nitrogen per liter of reaction mixture an hour as a stripping agent, the ammonia formed during the reaction is continuously removed by means of distillation. After cooling, 16 parts of 4,4'-bis(octoxycarbonylamino)diphenylmethane crystallize (71.4 percent of theory relatiave to reacted 4~4'-diaminodiphenyl-methane) having a melting point of 117C to 119C. Eighty-seven percent of the 4,4'-diaminodiphenylmethane has been converted. The mother liquor still contains 4-amino-4'-(octoxycarbonylamino)diphenylmethane~
One proceeds according to the data in Example 39 without using additional urea. Obtained are 11 parts of 4,4'-bis~octoxycarbonylamino)diphenylmethane (61.9 percent of theory relative to reacted 4,4'-diaminodiphenylmethane).
Sixty-nine percent of the 4,4'-diaminodiphenylmethane was converted.
~I~Z~L37~
Exam~le 41 In a reaction vessel, 15 parts of a commercially-available mixture of 2,2'-, 2,4'- and 4,4'-diaminodiphenyl-methane and polyphenylpolymethylene polyamines with 40 parts of ethyl carbamate and 0.5 part of cobalt acetate in 70 parts of ethanol are heated to 190C to 195C for 8 hours with a pressure of 18 bars to 20 bars being adjusted in the reactor via a pressure valve. Using 25 liters of nitrogen per liter of reaction mixture an hour as a stripping a~ent, the ammonia formed during the reaction is continuously removed by means of distillation. The mixture is allowed to cool and excess ethanol and excess ethyl carbamate are removed by distillation under reduced pressure at 10 millibars. The residue is washed with water, is dried and is mixed with cyclohexane, and is agitated. This results in a powdery precipitate which is separated and analyzed by means of high pressure liquid chromatography. It is determined that a mixture of 2,4'-, 2,2'- and 4,4'-bis(ethoxycarbonylamino)diphenylmethane and polyphenylpolymethylene polyethylurethane has been formed containing the same components as a comparison product produced from a mixturP of 2,4'-, 2,2'- and 4,4'-diiso-cyanatodiphenylmethane and polyphenylpolymethylene poly-isocyanates with ethanoI~
Exam~le 42 In a reaction vessel, 22 parts of 3-aminophenol with 100 parts of ethyl carbamate, 12 parts of urea, 1 part o zinc-(II)-acetate and 45 parts of ethanol are heated to 180C
3~
to 185C for 8 hours with a pressure of 7 bars to 8 bars being adjusted in the reactor via a pressure valve. Using 20 liters of nitrogen per liter of reaction mixture an hour as a strip-ping agent, the ammonia formed during the reaction is con-tinuously removed by means of distillation. After completed reaction, the reaction mixture is analyzed by means of gas chromatography using the internal standard method. It is determined that 29 parts of 3-ethoxycarbonylaminophenol (90.2 percent of theory relative to reacted 3-aminophenol) were formed. Eighty-eight percent of the 3-aminophenol was reacted.
ExamEle 43 In a reaction vessel, 61 parts of 2,4-diaminotoluene with 432 parts of octyl carbamate and 1.5 parts of sodium methanolate in 1950 parts of octanol are heated to the boiling point (195C). After 23 hours, the mixture is allowed to cool and excess octanol and excess octyl carbamate is removQd by distillation to a sump temperature of 180~C. Using high pressure liquid chromatography, the residue is analyzed using the external standard method. It is determined that 57 percent of the 2,4-diaminotoluene reacted, resulting in 101 parts (81.7 percent of theory) of 2,4-bis(octoxycarbonyl-amino)toluene, C2sH4~O4N2 (molecular weight 434) and 10.9 parts (13.8 percent of theory) of a mixture consisting of 2-amino-4-(octoxycarbonylamino~toluene and 4-amino- -(octoxy-carbonylamino )toluene.
3l~Z~3~7~
Exam~le ~4 In a reaction vessel, 40 parts of 2,4-dimainotoluene with 240 parts of hexyl carbamate, 1.5 parts cobalt acetate, and 170 parts of hexanol are heated to 155C to 175C for 15 hour~ with the resultant ammonia being removed continuously by means of distillation. After completed reaction, the reaction solution is examined by means of high pressure liquid chroma-tography usin~ the external standards method. It is found that the 2,4~diaminotoluene is completely converted resulting in 119 parts of 2,4-bis(hexoxicarbonylamino)toluene (96 percent of theory relative to the reacted 2,4-diaminotoluene).
In a reaction vessel, 100 parts of a commercially-available crude MDA mixture, 46 percent of which consists of diaminodiphenylmethane and 54 percent of which consists of polyphenylpolymethylene polyamines with 30.3 parts of urea, 300 parts of hexyl carbamate, 1.5 parts of cobalt acetate and 260 parts of hexanol are heated to 155C to 175C for 25 hours with the resultant ammonia being removed continuously by means of distillation. After completed reaction, the reaction solution is examined by means of high pressure liquid chroma-tography which shows that a mixture of bis(hexoxycarbonyl~
amino)diphenylmethanes and poly(hexoxycarbonylamino)poly-phenylpolymethanes has been formed which is identical with a comparison product produced from a mixture of diphenylmethane-diisocyanates and polyphenylpolymethylene polyisocyanates and hexanol.
-2~-IL3~74 Example 46 In a reaction vessel, 50 parts of 4,4'-diaminodi-phenylmethane with 360 parts of hexyl carbamate, 1 part of cobalt acetate and 260 parts of hexanol are heated to 155C to 175C. The mixture is agitated at 155C to 175C for 27 hours. After cooling, the mixture is filtered off the preci-pitated catalyst and is analyzed by high pressure liquid chromatography using the external standard method. It is found that the 4,4'-diaminodiphenylmethane is completely reacted resulting in 108 parts of 4,4'-bis(hexoxycarbonyl-amino)diphenylmethane (94~2 percent of theory relative to reacted 4,4'-dimainodiphenylmethane). The reaction solution further contains some 4-amino-4'-(hexoxycarbonylamino)di-phenylmethane.
Claims (12)
1. A process for the manufacture of an aryl mono-, di- and/or polyurethane comprising the steps of A. reacting a primary aromatic mono-, di and/or polyamine with an O-alkylcarbamate in the presence of an alcohol and at least one compound containing one or more cations of metals of groups IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIB, VIIB, VIIIB of the periodic system as catalysts, and B. separating the ammonia and other by-products from the aryl mono, di-, and/or polyurethane.
2. The process of claim 1 wherein the raw materials are reacted in such quantities that the ratio of amino groups of the aromatic mono-, di- and polyamine to O-alkyl-carbamate to hydroxyl groups of the alcohol is 1:0.5-20:0-100.
3. The process of claim 1 carried out in the presence of urea with the mole ratio of urea to alcohol being equal to or less than 1.
4. The process of claim 3 wherein a maximum of 1.5 equivalents of urea relative to the amino groups of the mono-, di- and polyamines is used in addition to the O-alkyl carbamate.
5. The process of claim 1 or 2 wherein the mono-amine is selected from the group consisting of aniline, 3-hydroxyaniline, and 3,5-dichloroaniline.
6. The process of claim 1 or 2 wherein the diamine is selected from the group consisting of 2,4- and 2,6-diamino-toluene, the corresponding isomer mixtures thereof, 1,5-di-aminonaphthalene, 3,3'-ditolulene-4,4'-diamine, 2,2'-, 2,4'-and 4,4'-diaminodiphenylmethane and the corresponding isomer mixtures thereof.
7. The process of claim 1 or 2 wherein the aromatic polyamine is a mixture of diaminodiphenylmethanes and poly-phenylpolymethylene polyamines.
8. The process of claim 1 wherein the O-alkyl-carbamates are those of carbamic acids and aliphatic and cycloaliphatic monoalcohols having 1 to 10 carbon atoms in the alcohol radical.
9. The process of claim 1 wherein the alcohol used has an alkyl group which corresponds with the alkyl group of the O-alkylcarbamate.
10. The process of claim 1 wherein compounds con-taining cations of the metals lithium, calcium, aluminum, tin, bismuth, antimony, copper, zinc, titanium, vanadium, chromium, molybdenum, manganese, iron, and cobalt are used as catalysts.
11. The process of claim 1 wherein the reaction is carried out at temperatures above 120°C.
12. The process of claim 1 wherein the resultant ammonia is simultaneously separated.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2917568.6 | 1979-04-30 | ||
| DE19792917568 DE2917568A1 (en) | 1979-04-30 | 1979-04-30 | METHOD FOR PRODUCING AROMATIC DI- AND POLYURETHANES |
| DEP2942510.3 | 1979-10-20 | ||
| DE19792942510 DE2942510A1 (en) | 1979-10-20 | 1979-10-20 | METHOD FOR PRODUCING ARYL MONO- AND POLYURETHANES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1121374A true CA1121374A (en) | 1982-04-06 |
Family
ID=25778937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000349798A Expired CA1121374A (en) | 1979-04-30 | 1980-04-14 | Process for the preparation of an aryl mono-, di-, and/or polyurethane |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0018583B1 (en) |
| JP (1) | JPS6485958A (en) |
| BR (1) | BR8002596A (en) |
| CA (1) | CA1121374A (en) |
| DE (1) | DE3066550D1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2942542A1 (en) * | 1979-10-20 | 1981-05-07 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING MIXTURES FROM DIPHENYL-METHANE-DIISOCYANATES AND POLYPHENYL-POLYMETHYLENE-POLYISOCYANANTS |
| DE2942503A1 (en) * | 1979-10-20 | 1981-05-07 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING AROMATIC DI- AND / OR POLYISOCYANATES |
| DE2943480A1 (en) * | 1979-10-27 | 1981-05-07 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF N, O-DISUBSTITUTED URETHANES, AND THEIR USE AS STARTING MATERIAL FOR THE PRODUCTION OF ISOCYANATES |
| DE2943551A1 (en) * | 1979-10-27 | 1981-05-07 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING N, O-DISUBSTITUTED URETHANES AND THEIR USE FOR PRODUCING ISOCYANATES |
| DE3110573A1 (en) * | 1981-03-18 | 1982-10-21 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING N- AND O-SUBSTITUTED DI- AND / OR POLYURETHANES |
| DE4141402A1 (en) * | 1991-12-16 | 1993-06-17 | Bayer Ag | METHOD FOR PRODUCING HIGH-PURITY AROMATIC DI- AND / OR POLYURETHANES |
| JP5499023B2 (en) * | 2009-04-09 | 2014-05-21 | 三井化学株式会社 | Method for producing urethane compound and method for producing isocyanate |
| EP2363386A1 (en) * | 2010-02-23 | 2011-09-07 | Mig Material Innovative Gesellschaft MBH | Reduction of CR(VI) ions in cement or products containing cement |
| JP5917794B2 (en) * | 2010-07-07 | 2016-05-18 | 三井化学株式会社 | Method for producing toluene dicarbamate composition, and method for producing toluene diisocyanate |
-
1980
- 1980-04-14 CA CA000349798A patent/CA1121374A/en not_active Expired
- 1980-04-23 DE DE8080102179T patent/DE3066550D1/en not_active Expired
- 1980-04-23 EP EP80102179A patent/EP0018583B1/en not_active Expired
- 1980-04-28 BR BR8002596A patent/BR8002596A/en unknown
-
1988
- 1988-07-11 JP JP63171075A patent/JPS6485958A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| EP0018583B1 (en) | 1984-02-15 |
| BR8002596A (en) | 1980-12-09 |
| DE3066550D1 (en) | 1984-03-22 |
| JPS6485958A (en) | 1989-03-30 |
| JPH0246575B2 (en) | 1990-10-16 |
| EP0018583A1 (en) | 1980-11-12 |
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