DE1081460B - Use of acyl urethanes as acylating agents for organic hydroxy and amino compounds - Google Patents

Description

Use of acyl urethanes as acylating agents for organic Hydroxy and amino compounds It is known that compounds which comprise the group -NH-CO-N (Y) -Coz, in which Y is hydrogen or an alkyl radical and Z is hydrogen or an organic radical, in particular a hydrocarbon radical, which is associated with the Carbonyl group linked through a carbon atom when heated to higher Temperatures decompose with isocyanate formation. Such urea derivatives can accordingly be used as isocyanate releasers and acylating agents.

It has now been found that such compounds can also be used very advantageously as an isocyanate releaser or with the effect of an isocyanate releaser and thus can be used as acylating agent for organic hydroxy and amino compounds, which contain the group —CO — NH — GOXR one or more times, preferably multiple times. In this formula, R denotes an optionally substituted alkyl, cycloalkyl, Aryl or aralkyl radical, while X stands for oxygen or sulfur. Preferably should the residues "kr" correspond to alcohols or mercaptans below Boil 130 ° C. These connections are very stable, but easily reactive and leave corresponding ones when using urethanes with volatile alcohols Alkyl residues are no troublesome splits. It is expedient to choose carbonamic acid esters such alcohols) whose hydroxyl group adheres to a carbon atom that is at most 1 hydrogen atom carries.

The reaction can be carried out by catalysts such as alkali metal alcoholates or Aluminum alcoholates are accelerated, but there is usually an addition of such Means not required and sometimes because of the remaining inorganic Foreign matter undesirable.

According to the invention as acylating agents such. B.

Acyl urethanes from mono-, di- and polycarboxylic acid halides, such as isobutyric acid chloride, Oxalic acid chloride, diglycolic acid chloride, adipic acid chloride, benzoyl chloride, sebacic acid chloride, Isophthalic acid chloride, tert-butyl isophthalic acid chloride, trimesic acid chloride and urethanes such as carbamic acid methyl ester, carbamic acid 2-propyl, -2-butyl, -2-amyl ester, Ss-methoxyethyl carbamic acid, B-methoxy-propyl carbamic acid, p-methoxyethoxyethyl carbamic acid, Monothiocarbamic acid methyl ester, carbamic acid phenyl ester, carbamic acid L2-chlorophenyl ester into consideration.

According to the invention, they are particularly valuable as polyacylating agents the polymerization products of the acyl derivatives of simple carbamic acid esters, e.g. of carbamic acid methyl ester or carbamic acid ß-methoxyethyl ester with polymerizable a ß-unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, a-chloroacrylic acid, -Phenylacrylic acid, itaconic acid. This is how by polymerizing the acroyl compound of the β-methoxyethyl carbamic acid ester which can advantageously be used in accordance with the invention Polymerization product that is particularly valuable because of its water solubility.

Most of the acylated urethanes described have the advantage of in the usual organic solvents, especially those in the paint industry preferred solvents to be soluble. The two and polyvalent acyl urethanes of low molecular weight and therefore highly volatile alcohols excellent for linking or crosslinking high molecular weight substances with acyl residues replaceable hydrogen, especially for crosslinking polyhydroxyl compounds, such as polyvinyl alcohol, polyallyl alcohol, polyglycide, polyglycerols, partially saponified Cellulose esters and polyvinyl esters, partial ethers containing hydroxyl groups, polymeric Carbohydrates such as methyl cellulose, p-oxyethyl cellulose and carboxymethyl cellulose, partial acetals of polyvinyl alcohol, also containing hydroxyl end groups soluble polymers, such as. B.

Polyglycols, linear and branched polyesters, polyurethanes, Polyamides and polyester amides.

The favorable responsiveness is already evident during the implementation the usual SCellit test for isocyanate releasers (cf. Liebigs Annalen, Vol. 562, 1949, p. 2197. In most cases at 140 to 1600 C complete crosslinking occurs and insolubility of the acetyl cellulose in acetone without causing a disturbing discoloration occurs.

Even lighter than the esters of alcohols, even at 120 to 1300 C, occasionally even below that, the derivatives of low molecular weight mercaptans react and the phenols.

With water-soluble, reactive polymers, the water-soluble ones settle Acyl urethanes made from carbamic acid ether esters even at a remarkably low temperature around. rubn zrm, r ^ r «o This applies e.g. B. for the implementation of the diglykoyl-bis-carbamic acid-ß-methoxy-ethyl ester with proteins such as gelatine.

The above-mentioned polymers are particularly reactive the carbamic acid ester, which is attached to nitrogen by residues of a polymerizable α, ß-unsaturated Carboxylic acid are substituted, especially the water-soluble polyacroylcarbamic acid-B-methoxyalkyl ester. You sit down e.g. B. with polyvinyl alcohol at 100 to 110 ° C with crosslinking around. Amino compounds, especially primary amino compounds, are particularly easy acylated. So you can z. B. in the implementation of bis (acyl) urethanes of dicarboxylic acids with polymethylene diamines, such as hexamethylene diamines, decamethylene diamines, N-methyl-dipropylene-triamine, linear, film-forming substances are obtained even at low temperatures, if exactly equivalent amounts of the components necessary for the linkage is worked. With polyamines, especially polyamines with more than two primary amino groups, which are also available as salts with volatile acids, e.g. B. acetic acid, is obtained one in the heat crosslinked, more or less strongly basic resins, their properties can be largely influenced by the choice of components. Suitable basic The starting compounds are not just polyamines, like the reduction products of alkaline ones Polymerization of acrylonitrile, reduction products of polyacrolein oxime, which are practical Represent polyallylamines, polyalkylene ruins, but also obtained by condensation Plastics, e.g. B. polyamides made from oxalic esters and mixtures of diprimary diamines and primarily secondary or primarily tertiary polyamines such as di-propylene-triamine and N-methyl-di-y-amino-propyl-amine.

The process is accordingly suitable for a wide range of uses in the chemistry of paints, plastics and textile finishing. Crosslinked resins with basic and / or acidic groups can be used as ion exchangers, or produced on fibers, serve to modify their dyeing properties.

Example 1 18 g of 4-chlorobenzyl alcohol and 20 g of N, N'-adipyl-bis- (carbamic acid isopropyl ester) are heated in 200 ccm of o-dichlorobenzene to 160 to 1700 C for 1 hour. The beginning the splitting off of the isopropanol is evident after a few minutes by brisk activity Boiling the solution.

On cooling, 17.5 g of N, N'-adipyl-bis- (carbamic acid Xchlorbenzyl ester) crystallize the end. After recrystallizing from dioxane, the urethane melts at 213-2140 C with decomposition.

Example 2 6.32 g of N, N'-adipyl bis (carbamic acid isopropyl ester) and 2.08 g of neopentyl glycol are heated to 1600 ° C. for 3 hours. Intense smell after isopropanol, the reaction sets in after a short time and soon disappears So it runs off quickly. The reaction product forms a stringy melt and solidifies to a resinous mass on cooling. The resin is in dimethylformamide soluble.

Example 3 5.7 hexamethylenediamine and 18.3 g of N, N'-adipyl-bis- (2-amyl carbamic acid) are heated in 100 ccm of o-dichlorobenzene to 1600 C for 90 minutes. After just a few The minutes began to boil briskly, releasing amyl alcohol. The solution will be very viscous and soon a solid product is eliminated. After boiling out several times with acetone it melts at 190 to 2050 C with decomposition. The relative viscosity (measured on a 0.5% solution in m-cresol) is 1.38. At very fast Work can be carried out despite the thermal instability of the polymer obtained pull threads from the melt.

Example 4 A 100/0 solution of approximately 54010 bound acetic acid containing cellulose acetate in acetone are 10 percent by weight (based on the Acetyl cellulose) N, N'-oxalyl bis (carbamic acid 2-chlorophenyl ester) added, from it Films poured and these in the drying cabinet for 30 minutes at different temperatures heated. A crosslinking can be determined from 1200 C, from about 1300 C the films become completely insoluble in acetone.

Example 5 The procedure is as in Example 4, but instead of the urethane used there, the N, N'-adipyl-bis (carbamic acid-2-butyl ester). The lower temperature limit of the crosslinking, i.e. H. the temperature above which Foils are obtained, depending on the heating temperature and duration in acetone only are still partially or not at all soluble, is 140 to 1500 C.

Example 6 A corresponding to Example 5 with N, N'-adipyl bis (carbamic acid isopropyl ester) A film made of a polyvinyl butyral treated at 1400 C, which after analysis was still contains about 20 to 30,010 vinyl alcohol as a component, in dioxane is only too 1001, soluble.

Example 7 A 1001, own aqueous solution of polyvinyl alcohol from a K value of 70, 5 percent by weight (based on the polyvinyl alcohol) is achieved Heating to about 1000 C polymerized N-acryl-carbamic acid-ß-methoxy-ethyl ester added. Films are cast from the solution and then differentiated for 30 minutes Exposed to temperatures. The films crosslinked at 105 to 110 "C are in cold and cold moderately warm water of about 40 to 500 C insoluble. If the crosslinking temperature is increased up to 1400 C, films are obtained which are self-contained when heated with water for 8 hours at 90 to 1000 C only partially dissolve, while slides that work in the same way be heated, but do not contain any addition of the acyl urethane, in water completely remain soluble.

Example 8 The procedure is the same as in Example 7, with the The difference is that instead of the polymeric urethane, the monomeric acroyl compound is added. An effect similar to that described in Example 7 is obtained is because during the heating of the films, acylation of the polyvinyl alcohol takes place at the same time and vinyl polymerization occurs. Known water-soluble starting agents for the Polymerization such as sodium benzene sulphinate can be added but theirs is Presence not absolutely necessary.

Claims (4)

PATENT CLAIMS: 1. Use of acylated carbonic acid amides as Acylating agents for organic hydroxy and Amino compounds at elevated temperature, characterized in that the acylated carbonic acid amide is an acyl urethane which contains the group -CO -NH-CO -x -R, in which X is the same Oxygen or sulfur and R is an alkyl, cycloalkyl, aryl or aralkyl radical. 2. Use of acyl urethanes according to claim, characterized in that that R is the residue of a secondary alcohol or an ether alcohol. 3. Use of acyl urethanes according to Claim I and 2, characterized in that that the groups -CO-NH-COXR on a macromolecular formed by vinyl polymerization Stick chain. 4. Use of acyl urethanes according to Claim 3, characterized in that that polymerizable vinyl monomers are used which form the group -CO -NH -COXR included at least once.