CH617190A5 - Process for the preparation of 1,3-bishydroxyethylhydantoin esters - Google Patents

Description

The present invention relates to a process for the preparation of certain carboxylic acid monoesters or diesters of 1,3-bis-hydroxyethyl-hydantoins of the formula

R3 C C ~ 0

R1COCH2CH2) xiJ ^ (CHjCH ^ O ^ y-Rg

V

1y

o in which R3 and R4 individually denote hydrogen, a lower alkyl radical, cycloalkyl or alkoxy radical, where if one or both radicals R3 and R4 are alkyl, cycloalkyl or alkoxy, these together have at most 7 carbon atoms, or R3 and R4 together represent the divalent tetramethylene - or pentamethylene radical, one of the radicals Rj or R. can mean hydrogen, while the other or both radicals R, or R2 represent the benzoyl, oleoyl, linoleoyl, linolenoyl or a saturated fatty acid acyl radical having 2 to 22 carbon atoms, or a mixture of saturated fatty acid acyl groups having 8 to about 22 carbon atoms or a mixture of any of said saturated fatty acid acyl groups and the oleoyl, linoleoyl or

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Linolenoyl-palmitoleoyl or Myristoieoylrest represent, and x + y mean any sum from 3 to 100.

The closest prior art is described in U.S. Pat. Nos. 3,676,454, 3,832,098, 3,852,302, and 3,904,644 and also in Japanese Patent No. 3,819,987.

The monoesters and diesters which can be prepared according to the invention can be used in various ways as heat-resistant plasticizers and lubricants for incorporation into films and other forms of use of plastics such as polyvinylpyrrole-don; they are e.g. usable as spinning sizing for various textile fibers such as cellulose fibers, e.g. Cotton, or nylon, also as improved antistatic agents for nylon and textile fibers, and as a dispersant for various substances such as formaldehyde-dimethylhydantoin resins, and as emulsifiers, the esters for which oil, water, and / or R2 is an acyl radical with at least 10 carbon atoms and for water-in-oil emulsions esters with Rx and / or R2 in the form of an acyl radical with less than 10 carbon atoms are suitable. Preferably R means! or R2 the isostearoyl radical.

The so-called isostearic acid, which provides the above-mentioned isostearoyl radical, is the acid mixture which is obtained after separating off the dimeric acid in the dimerization of linolenic acid and subsequent hydrogenation of the dimerization product (compare US Pat. No. 3,527,705, column I, line 48 to 67).

The process according to the invention is characterized in that (a) a bis-hydroxyethyl hydantoin of the above formula, but in which R and R are hydrogen, with (b) benzoic acid or a saturated fatty acid with 2 to 22 carbon atoms or oleic acid, linoleic acid or linolenic acid, or a mixture of saturated fatty acids with 8 to 22 carbon atoms, optionally in a mixture with oleic acid, linoleic acid, linolenic acid, palmitolic acid and / or myristic acid, in the ratio of 1 mol of bis-hydroxyethyl-hydantoin to 1 to 2 mol of carboxylic acid under esterification conditions in the presence reacting a catalytically effective amount of a compatible esterification catalyst by heating the reaction mixture to the initial temperature of the esterification, separating the water of reaction, raising the temperature to 220 to 250 ° C. and continuing to heat until a sample taken indicates that the esterification has essentially ended .

According to the invention, monoesters or diesters are obtained. In order to compensate for losses of substituted hydantoin by evaporation during the esterification, it is occasionally advisable to use the hydantoin used as the starting material in a slight excess, for example in an approximately 6% molar excess.

Esterification conditions include the use of a catalytically effective amount of an esterification catalyst, e.g. hypophosphorous acid, and the heating of the reaction mixture to a preferred starting temperature of 110 to 150 ° C; furthermore, the water formed is to be removed in a suitable manner and the temperature is gradually increased to 220 to 250 ° C., the heating being continued until samples taken indicate that the esterification has essentially ended.

The starting hydantoins containing the two hydroxyethyl groups can be obtained as follows:

One ethoxylates hydantoin or a corresponding 5-mono or disubstituted hydantoin under suitable ethoxylation conditions with the required number of moles of ethylene oxide, so that the desired average sum for x and y is obtained. For this purpose, for example, (1) (a) a suitable amount of the starting hydantoin in (b) will be sufficient to dissolve the starting hydantoin under the elevated temperature and pressure conditions of the reaction

Dissolved in an amount of dioxane, polychloroethane or another compatible solvent, together with (c) an effective amount of an ethoxylation catalyst catalyzing the ethoxylation in a limited reaction zone (e.g. an autoclave equipped with a stirrer), (2) this mixture at an elevated temperature heated to at least about 50 ° C to dissolve the starting hydantoin, and (3) at the elevated temperature, the required number of moles of ethylene oxide were introduced under increasing pressure, io wherein the ethylene oxide and starting hydantoin reacted under these reaction conditions until the ethylene oxide was consumed, which by a sharp drop in the reaction pressure is precisely detectable.

The amount of ethylene oxide introduced into the limited reaction zone should be less than that which may cause the ethoxylation to go through under the temperature and pressure conditions given for the type and amount of catalyst used.

The ratio of starting hydantoin to solvent 20 is not critical. The maximum amount of starting hydantoin is that which is soluble in the solvent under the reaction conditions, even if it initially forms a slurry with it at the mixing temperature. However, this concentration is not critical. 25 If necessary, only one part by weight of starting hydantoin per 10 to 11 parts of solvent can be used. A practical ratio is about 40 to about 55 parts by weight of hydantoin and about 60 to 45 parts by weight of solvent. A generally practical quantitative ratio is found for approximately equal parts by weight of starting hydantoin and solvent.

Any catalyst which catalyzes the ethoxylation can be used in a catalytically effective amount to carry out the reaction. The catalyst should expediently be at least partially soluble in the reaction medium. At least with dioxane as the solvent, alkali metal hydroxides such as sodium hydroxide or expediently potassium hydroxide (because of its greater solubility) in aqueous solution of suitable concentration are generally very effective, a 45% strength aqueous potassium hydroxide solution advantageously being used.

Other alkaline catalysts such as tertiary amines can also be used, and possibly better together with 1,1,2-trichloroethane as the solvent, although the alkali metal hydroxides and especially potassium hydroxide can also be used with this solvent. Boron trifluoride can be used as a non-alkaline catalyst. The amount of catalyst can be relatively small since the substance is only intended to suitably catalyze the reaction, i.e. should produce a satisfactory reaction rate in practice, as can be seen from the stability of the process temperature.

It is therefore possible to use such small amounts of only about 0.5% of catalyst, based on the weight of the starting hydan-55 toin, and the maximum amount need not exceed about 1.5%. Amounts of approximately 1.0% by weight of the starting hydantoin are generally advantageous, especially when using the 45% aqueous potassium hydroxide solution. In this case, the 1.0% actually make up 0.45% KOH, based on the weight of the starting hydantoin.

The amounts of starting hydantoin and solvent, suitably equal amounts by weight, and the catalyst are usually placed in a pressure vessel, e.g. an autoclave, which is equipped with a stirrer and jacket for water vapor and water, and has an option for adding liquids. With stirring, the feed is preferably by indirect

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Heat exchange to at least about 50 ° C, better at least about 60 ° C and suitably heated to about 70 ° C, or even up to the boiling point of the solvent, so that the starting hydantoin dissolves. It is then advisable to flush the autoclave with nitrogen to remove oxygen from the system.

The ethylene oxide can be introduced when the solution has a temperature between 120 and 150 ° C, although the ethoxylation at any temperature in the range of 50 to 200 ° C and at an (autoclave) internal pressure of 3.49 to 4.55 or even up to 5.60 kg / cm2 can be carried out. In order to prevent the addition condensation from going through, the ethylene oxide is expediently fed in at a controlled rate.

For example, after consumption of ethylene oxide and a pressure drop to about 3.49 to 4.19 kg / cm2, a further amount of ethylene oxide is added until the pressure has again reached 4.55 to 5.60 kg / cm2, and the temperature is again at 140 to Maintained 150 ° C until the pressure drops again to about 3.49 to 4.19 kg / cm2. Additional portions of ethylene oxide are added as soon as the pressure drops to about 3.49 to 4.19 kg / cm 2 until it rises to about 4.55 to 5.60 kg / cm 2 until the amount required to achieve the desired substitution Ethylene oxide is used up.

The reaction mixture is then generally transferred to a distillation device in which the solvent is distilled off and recovered. The catalyst can optionally be neutralized, suitably before the distillation, depending on the intended use for the end product.

Although the reaction is described above as being feasible at temperatures up to 150 ° C., the reaction can take place under certain conditions at higher temperatures and corresponding pressures, but it is necessary to work below the temperature and the pressure at which the hydantoin ring breaks down under the reaction conditions (ie split), or undesirable discoloration, which cannot be removed by the usual means, occurs in the end product. For example, 200 ° C can be regarded as the practical maximum temperature and 29.1 kg / cm2 as the maximum pressure.

The bis-hydroxyethyl-hydantoins used as starting material in the process according to the invention can also according to the specification of GB-PS 1 290 728 (example C, page 8, example F, page 9, example J, page 11 and example M, page 12) and the specification of GB-PS 1 290 729 are produced.

The bis-hydroxyethyl-hydantoins used as starting material correspond to the structural formula I above, but have hydrogen as Rx and R2. Examples of these substituted hydantoins are compounds of the above formula in which R3 and R, methyl and R, and R2 are hydrogen and x plus y are the average value 5, 6, 10, 20 or 50; further examples are compounds in which R3 is methyl and R4 is ethyl, and those in which one or both of the radicals R3 and R4 represent any other alkyl, alkoxy or Petra or pentamethylene radical.

As already described in the description of the products obtained according to the invention, the carboxylic acid reactant required for the reaction according to the invention is benzoic acid or any fatty acid with 2 to 22 carbon atoms e.g. a fatty acid from acetic acid to caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachidic acid and behenic acid, the isostearic acids already mentioned, and unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid and various commercially available mixtures of saturated acids up to about 22 carbon atoms or mixtures thereof with oleic acid, linoleic acid and / or linolenic acid.

The carboxylic acid monoesters and diesters which can be prepared according to the invention are illustrated by the following examples:

example 1

"Mono" oleate of 1- (CH2. CH20) x. H, 3- (CH2. CH20) v. H-5,5-dimethyl-hydantoins, in which x + y are 6.2 on average (molar ratio acid: diol 1.06: 1):

2420 g (8.64 mol) "white oil" (technical oleic acid) and 6080 g (7.21 mol) 1- (CH ,. CH20) x. H, 3- (CH2. CH20) y. H-5,5-dimethylhydantoin, in which x + y is 6.2 on average (average molecular weight 844, preparation see preparation C below) and 17 g of hypophosphorous acid (50% aqueous solution) as catalyst are introduced into a 101 three-necked round bottom flask , which is equipped with a stirrer, the possibility of introducing nitrogen protective gas and a vertical air-cooled reflux condenser of 15 cm length, which is connected to a horizontal water-cooled condenser.

The batch is heated to about 250 ° C. over a period of about 2 hours using a glass-Col heating jacket with stirring and a slow nitrogen introduction rate. After further heating at 250 ° C. for about 4 hours, the esterification is considered to be essentially complete after a withdrawn sample has an acid number of only 1.1. The mixture is then cooled to 70 ° C. and decolorized by adding 0.2% by weight of 35% hydrogen peroxide and heating to 110 ° C. for one hour. After the addition of filter aids as in Example 1 and filtration, 8175.6 g (99.8% of theory) of the “mono” oleate of the 1,3-bis- (polyethoxy) dimethyl-hydantoin used as starting material, in which x + y be an average of 17, which has the acid number 1.1, the hydroxyl number 38.7 and the saponification number 61.1.

Example 2

"Mono" stearate of 1- (CH2. CH20) x. H, 3- (CH2. CH20) y. H-5,5-dimethylhydantoins, in which x + y is on average 17 (molar ratio acid: diol 1.1: 1):

2754 g (10.2 mol) technical stearic acid (type 55%, average molecular weight 270) and 8046 g (9.18 mol) 1- (CH2. CH20) x. H, 3- (CH2. CH20),. H-5,5-dimethyl-hydantoin, in which x + y is 17 on average (average molecular weight 876, preparation see preparation C) and 16.2 g of hypophosphorous acid (50% aqueous solution) as a catalyst are mixed with a stirrer, possibility filled with 20 1 three-neck round-bottom flasks equipped to form a surface protection from nitrogen gas and a small water-cooled horizontal cooler.

The batch is heated to 200 ° C. over a period of 2 hours using a glass-Col heating jacket with stirring and under nitrogen protection. After further heating at 200 ° C. for about 10 hours, the esterification is regarded as essentially complete. The reaction mixture is then cooled to 80 ° C. and decolorized by mixing it with 0.13% by weight of 35% hydrogen peroxide, which contains sufficient potassium hydroxide to adjust the pH of the batch to 5.9, and to 110 ° C heated. Then filter aid from diatomaceous earth is added and the mixture is filtered, the filtrate being 1029.1 g (98.6% of theory) of the “mono” stearate of 1,3-bis (polyethoxy) -5,5-dimethylhydane toins, in which x + y is 18 on average, with the acid number 2.4, the hydroxyl number 47.6, the saponification number 54.4 and the neutralization number 0.

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Example 3

Distearate of 1- (CH2.CH20) x. H, 3- (CH2. CH20) y. H, 5,5-dimethylhydantoins, wherein x + y 6.7 on average (molar ratio acid: diol 2: 1):

4842 g (17.543 mol) of the usual technical 70% stearic acid (from tallow, about 70% stearic acid, the rest mainly palmitic acid and a little myristic acid, average molecular weight 276) and 3658 g (8.772 mol) 1- (CH2. CH20) x. H, 3- (CH2. CH20) yH-5,5-dimethylhydantoin, in which x + y an average of 6.7 (average molecular weight 417, preparation see preparation D below) and 17 g of hypophosphorous acid (50% strength aqueous solution) as catalyst are filled into a 12 1 round-bottom flask which is equipped with a stirrer, a vertical fractionation column packed with a Goodloe sieve, which is connected at the top to a horizontal cooler with a water jacket, and means for providing nitrogen shielding gas and a glass Col heating coat is equipped.

The batch is heated to 240 ° C. over the course of 2 hours and then held at this temperature for about 16 hours, whereupon it has an acid number of 3.9 and the esterification is regarded as complete. The reaction mixture is then cooled to 70.degree. C. and decolorized by admixing 0.2% by weight of 35% hydrogen peroxide and heating to 110.degree. C. under constant nitrogen and holding at this temperature for 1 hour. The reaction mixture is then cooled to 70 ° C. and 50% aqueous sodium hydroxide solution is added in order to neutralize the acidic catalyst and adjust the pH to about 7.5. Then 1 wt .-% diatomaceous earth is added as a filter aid and the still liquid crude ester product is suctioned off. Finally, 8 075 g of end product (95%, based on the total charge) are obtained with the following properties:

Color (Gardner) 1 acid number 3.9

Saponification number 124.8 hydroxyl number 3.1

pH (5% solution) 7.2 F. 37.2 ° C.

Example 4

Di-laurate of 1- (CH2. CH, 0) x. H, 3- (CH2. CH20) y. H-5,5-dimethylhydantoins, in which x + y averages 20.9 (molar ratio acid: diol 2: 1):

This product is obtained by esterifying 2414 g (11.606 mol) of lauric acid (from hydrogenated coconut oil fatty acids, average molecular weight 208) with 6086 g (5.802 mol) of 1- (CH2. CH, 0) x. H, 3- (CH2. CH, 0) y. H-5,5-dimethyl-hydantoin, where x + y averages 2.9 (average molecular weight 1049). The device according to Example 3 and the procedure of this example are used with the same amount of catalyst, but at an esterification temperature of 245 ° C (instead of 240 ° C).

8016 g of end product (94.3% of the total charge) are obtained with the following properties:

Color (Gardner) below 1 acid number 2.5 saponification number 80.7 hydroxyl number 4.0

pH (5% solution) 6.1 F. -3 ° C.

Example 5

“Mono” oleate of 1- (CH2. ŒLO) ,. H, 3- (CH2. CH20) y. H-5,5-dimethylhydantoins, in which x + y 6.7 on average (molar ratio acid: diol 1.2: 1):

2840 kg (23.307 mol) "white oil" (technical oleic acid) and 3520 kg (18.595 mol) 1- (CH2. CH20) x. H, 3- (CH2. CH20) yH-5,5-dimethylhydantoin, in which x + y are 6.7 on average (average molecular weight 417) and 9.07 g of hypophosphorous acid (50% strength aqueous solution) as a catalyst are combined in one Reactor made of stainless steel with 8330 1 capacity filled, which with options for heating by means of steam or Dowtherm,

a vertical, air-cooled reflux condenser, which communicates with the atmosphere at the top, and is equipped with options for providing a protective layer against carbon dioxide.

The batch is heated to 240 ° C. and held at this temperature for about 16 hours, whereupon the acid number of a sample is less than 2, so that the esterification is regarded as complete. The crude ester is cooled to 70.degree. C. and decolorized by adding 12.7 kg of 35% hydrogen peroxide and heating to 110.degree. C. with stirring and holding at this temperature for 1 hour, with increasing amounts of flushing with carbon dioxide.

The decolorized liquid ester product is cooled to 70 ° C., mixed with about 22.7 kg of diatomaceous earth as a filter aid, then it is filtered on a filter press. The clarified end product, which is obtained in a yield of 5930 kg (92.9% of the total feed), shows the following properties:

Color (Gardner) less than 1 acid number 1.2 saponification number 95.3 hydroxyl number 57.0

pH (5% solution) 6.3 F. - 24 ° C.

Example 6

"Mono" oleate of 1- (CH2. CH20) x. H, 3- (CH2. CH20) y. H-5,5-dimethylhydantoins, where x + y averages 11.8 (molar ratio acid: diol 1.2: 1):

2180 kg (17.129 mol) of the "white oil" according to the above example (technical oleic acid) and 4170 kg (14.27 mol) of 1- (CH2. CH20) x. H, 3- (CH2. CH20) y. H-5,5-Dimethylhy-dantoin, in which x + y an average of 11.8 (average molecular weight 645, preparation see preparation D below are esterified with the same amount by weight of catalyst in the device according to FIG. 5 and according to the procedure of example 5, but only after decolorization with hydrogen peroxide the pH of the liquid crude ester is adjusted to 6.1 with 0.454 kg sodium hydroxide (as a 5% aqueous solution) The final product obtained in a yield of 6140 kg (94.7% of the total charge) shows the following properties:

Color (Garder) less than 1 acid number 1.1 saponification number 70.9 hydroxyl number 45.6

pH (5% solution) 6.1 F. - 16 ° C.

Example 7

"Mono" oleate of 1- (CH2. CH20) x. H, 3- (CH2. CH20) y. H-5,5-dimethylhydantoins, where x + y averages 16.2 (molar ratio acid: diol 1.2: 1):

904 kg (7.118 mol) of the "white oil" (technical oleic acid) used in the above example and 2273 kg (5.932 mol) 1- (CH2. CH20) x. H, 3- (CH,. CH20) y. H-5,5-dimethyl-hydantoin, in which x + y averages 16.2 (average molecular weight 844, preparation see preparation D below) and 6.35 kg of the catalyst used in the above example in the form of the aqueous acid solution are in a reactor made of stainless steel of 3785 1 capacity, which is equipped like the reaction vessel of Examples 17 and 18, implemented in the same way, but the esterification temperature is 250 ° C. The esterification continues until a sample has an acid number less than 2.

The end product thus obtained, which is obtained in a yield of 3035 kg (94.7% of the total feed), has the following properties:

Color (Gardner) less than 1 acid number 1.3 saponification number 59.8 hydroxyl number 37.0

pH (5% solution) 6.2 clear point - 3 ° C.

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The specific 1,3-bis- (polyethoxy) -5,5-dimethylhydantoin used in each of Examples 1 to 7 can be replaced by any other 1,3-bis- (polyethoxy) -5,5-dimethylhydantoin, where x + y, corresponding to the definition given following the structural formula above, can on average represent any sum between 3 and 100, except 17 or 18. In Examples 1 to 7, too, the molar ratio of starting fatty acid to diol can be increased to 1.5 mol of fatty acid per mol of diol, the corresponding sesqui esters being obtained, or to about 2 to about 2.1 mol of acid per mol of diol, the corresponding diesters being formed.

In all examples, including Examples 1 to 7, the N, N'-substituted dimethylhydantoin can be replaced by any 5-mono- or disubstituted hydantoins, the 5-position being able to carry any substituents R3 and R4. The corresponding end products are formed, which differ in the substituents on the 5-carbon atom.

Any bis-hydroxyethyl hydantoin (unsubstituted or substituted) can be formed with the desired value for the sum of x + y by ethoxylation, the corresponding hydantoin or 5-mono- or disubstituted hydantoin having the required number of moles of ethylene oxide ethoxylated by the method mentioned at the beginning.

Any such substitution on the 5-carbon atom of the hydantoin ring and any ethoxylation within the specified limits therefore represent further examples for the preparation of starting materials which, with the respective fatty acid, give the corresponding esters of 1,3-bis-hydroxyethyl-, 1,3-bis- - (Hydroxyethoxyethyl) - or 1,3-bis (hydroxyethoxypoly-ethoxyethyl) hydantoins with corresponding substitution in the 5-position, the amide nitrogen being in the 1-position and imide nitrogen in the 3-position. Suitable starting materials are thus e.g. 1,3-bis-hydroxyethyl-5-methylhydantoin, 1,3-bis (β-hydroxyethyl) -5-ethylhydantoin, 1,3-bis (β-hydroxyethyl) -5-propylhydantoin,

l- (ethoxy) x. H, 3- (ethoxy) y. H-5-methyl-hydantoin,

where x + y averages 2 to about 70, or even about 100,

1,3-bis- (β-hydroxyethyl) -5-methyl-5-ethoxyethyl hydantoin,

1,3-bis- (β-hydroxyethyI) -5,5-spirotetramethylenehydantoin and the like.

In Examples 1 to 7, the technical hydantoin diol used as the starting material can be replaced by a crystalline diol or by modified starting compounds such as the compounds which are otherwise substituted or unsubstituted on the 5-carbon atom, or by other polyoxyethanes on one or both nitrogen atoms Output connections.

The technical fatty acids from animal or vegetable sources used as starting material (e.g. from tallow or fats or coconut oil or known seed oils such as cottonseed oil or soybean oil) contain a fatty acid mixture. Therefore the final products, e.g. the products of Examples 1 to 5 and 11 to 19 actually a mixture of fatty acid esters of the diol in question, the ester with the main component of the technical fatty acid dominating in the ester mixture and, in addition to smaller amounts of the esters of other fatty acids present in the starting mixture, being proportional to them Proportions is mixed. The situation in the mixture of caprate and caprylate according to example 6 is analogous.

The technical stearic acids, oleic acids and lauric acids used as starting materials in Examples 1-7 or the mixture of capric acid and caprylic acid according to Example 6 can therefore be replaced by any other mixtures which are different in quantity, the corresponding mixed esters being obtained as products. The fatty acid mixtures used as the starting material can also be replaced by a single fatty acid having 2 to about 22 carbon atoms.

If, for example in Examples 2 and 3, the technical stearic acid is replaced by the corresponding molar amount of essentially pure stearic acid, the corresponding ester is obtained, the acyl residue of which only comes from stearic acid.

The other technical fatty acid mixtures can also be replaced by the essentially pure fatty acid which dominates, e.g. by replacing the technical hydrogenated coconut fatty acids according to Example 5 with lauric acid, whereby an ester end product is obtained, the acyl radical of which is derived exclusively from the corresponding fatty acid, e.g. Lauric acid comes from.

The same can be done with capric and caprylic acid, with esters with the acyl residue being obtained exclusively from capric acid or caprylic acid. Technical N, N'-bis-hydroxy-ethyl-dimethylhydantoin can also be replaced by the crystalline product, the corresponding defined ester being obtained together with the pure fatty acid.

In any case, however, even when using one or both reactants in pure form, when striving for the monoester as in Examples 1 and 2, the product consists of a mixture of 1-monoester, 3-monoester and 1,3-di-ester , the total amount of the two monoesters far exceeding the amount of the di-ester, with unreacted diol corresponding to approximately half the molar proportion of di-ester remaining.

The following preparations illustrate the preparation of the 5,5-dimethylhydantoin diols used as the starting material for some examples:

Preparation A:

Technical 1,3-bis (ß-hydroxyethyl) -5,5-dimethylhy-dantoin for example 7:

A mixture of 5.44 kg of 5,5-dimethyIhydantoin and 5.44 kg of 1,4-dioxane and 0.54 kg of aqueous 45% potassium hydroxide solution (catalyst) is in a jacketed Doyle-Roth autoclave with a capacity of 19 l (equipped with stirrer and liquid inlet) to dissolve the dimethylhydantoin, flushing the autoclave with nitrogen. The resulting solution is then heated to 95 ° C, the pressure is released to the atmosphere, then heated to 120 ° C.

With the drain valve closed, heating is continued to maintain the temperature between 120 and 140 ° C, while ethylene oxide is automatically fed intermittently to the autoclave via an automatic pressure-controlled valve, the valve releasing the feed when the internal pressure reaches 5.25 kg / cm2 has dropped and the supply stops as soon as the pressure has reached 5.32 kg / cm 2 until a total of 3.79 kg (0.19 mol) of ethylene oxide in the specified temperature range has been supplied over the course of 2 hours. As soon as the last ethylene oxide is used up, the pressure drops sharply.

The mixture is then cooled to about 80 ° C. and transferred to a 2 1 three-necked still. There it is mixed for about 15 minutes with the amount of 85% phosphoric acid required to neutralize the catalyst. The dioxane is then distilled off at 140 ° C. and 5 mm Hg pressure. Filtration of the liquid distillation residue gives the technical grade 1,3- as a light yellow viscous filtrate.

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-Bis- (ß-hydroxyethyl) -5,5-dimethylhydantoin with the following values in gas-liquid chromatography:

1,3-bis (ß-hydroxyethyl) -5,5-dimethyl-hydantoin 84.6%

Monohydroxyethyl-5,5-dimethylhydantoin (mixture of 1- and 3-isomers, the latter predominantly) 8.5%

Tri-ethoxylated 5,5-dimethylhydantoin (mixture of l-hydroxyethoxyethyl-3-hydroxyethyl-5,5-dimethylhydantoin and l-hydroxyethyl-3-hydroxy-ethoxyethyl-5-5-dimethylhydantoin, the latter predominantly) 5.5%

Tetraethoxylated 5,5-dimethylhydantoin with x + y an average of 4 (mixture of l-hydroxyethyl-3-hydroxyethoxy-ethoxyethyl-5,5-dimethylhydantoin, l-hydroxyethoxyethoxyethyl-3-hydroxyethyl-5,5-dimethylhydantoin and l, 3- Bis- (ß-hydroxyethoxy-ethyI) -5,5-dimethylhydantoin, the latter predominantly 0.6%

5,5-dimethylhydantoin 0.8%

Repeated on Example A, but with an increase in the amount of ethylene oxide to 2.2 moles per mole of 5,5-dimethylhydantoin, an end product of the following composition (gas / liquid chromatography) is obtained: 1,3-bis- (β-hydroxyethyl) - 5,5-dimethylhydantoin 82.6%

Monohydroxyethyl-5,5-dimethylhydantoin

(same mixture as in the first attempt) 1.8%

Tri-ethoxylated 5,5-dimethylhydantoin

(same mixture as in the first attempt) 14.7%

Tetraethoxylated 5,5-dimethylhydantoin

(same mixture as in the first attempt) 0.9%

Preparation B:

Crystalline 1,3-bis (β-hydroxyethyl) -5,5-dimethylhydantoin for Examples 11 and 12:

250 g of the viscous liquid filtrate according to preparation A are dissolved at room temperature in a mixture of 62.5 g of isopropyl alcohol and 1187.5 g of benzene and with a trace of crystalline 1,3-bis (β-hydroxyethyl) -5,5-dimethyl -hydantoin (obtained by crystallizing 20 g of viscous liquid product from the same solvent mixture) inoculated. The solution becomes cloudy and a crystal layer separates as soon as the container is placed in a water bath at 11 ° C. 4 days later, the crystals are suctioned off in a Buchner funnel and dried on a rotary vacuum dryer at normal pressure. If the container is returned to the water bath at 11 ° C, no further crystals will separate, not even on the following day. The gas / liquid chromatography of the crystals gives the following result:

1,3-bis (ß-hydroxyethyl) -5,5-dimethylhydantoin

97.9

%

Monohydroxyethyl-5,5-dimethylhydantoin

0.8

%

Tri-ethoxylated 5,5-dimethylhydantoin

0.8

%

Tetraethoxylated 5,5-dimethylhydantoin

0.1

%

unreacted 5,5-dimethylhydantoin

0.4

%

These mono-, tri- and tetra-ethoxylated components contain a mixture of the same corresponding isomers as in preparation A.

Preparation C:

Ethoxylated 5,5-dimethylhydantoin with x + y an average of 17 for example 14:

Following the procedure of Preparation A, 128 parts (1 mole) of 5,5-dimethylhydantoin are dissolved with heating in 354 parts of dioxane and 2.48 parts of 45% aqueous potassium hydroxide solution. Then 748 parts (17 moles) of ethylene oxide are automatically and intermittently fed into the autoclave over the course of about 6 hours, the pressure being kept between 4.55 and 4.90 kg / cm 2 and the temperature being kept at about 140 ° C. After cooling, the mixture is transferred to a distillation flask, neutralized with 1.15 parts of 85% phosphoric acid, then the solvent is stripped off, leaving a clear, viscous, light yellow liquid of ethoxylated 5,5-dimethylhydantoin with an average of 17 x + y.

Analogously, the ethoxylated 5,5-dimethylhydantoin with x + y is produced on average 20 for example 16 according to the instructions of preparation C, but using about 400 parts of dioxane, 2.6 parts of 45% aqueous potassium hydroxide solution and 880 parts ( 20 moles) of ethylene oxide, which are added over the course of about 7 hours. The potassium hydroxide catalyst is neutralized with 1.2 parts of 85% phosphoric acid.

Preparation D:

Ethoxylated 5,5-dimethylhydantoin with x + y 6.7 on average for Examples 15 and 17:

The preparation is carried out according to the instructions of preparation C, but using 128 parts of dioxane and 0.65 parts of 45% aqueous potassium hydroxide solution. In an analogous manner, 289 parts (6.7 mol) of ethylene oxide are fed in over the course of about 3 hours, the pressure being kept between 4.19 and 4.55 kg / cm 2 and the temperature being kept at about 140.degree. After the mixture has cooled, it is transferred to a distillation flask, neutralized with 0.3 part of 85% phosphoric acid, and then the solvent is stripped off.

The ethoxylated 5,5-dimethylhydantoin with x + y averaging 11.8 for Example 18 is prepared according to the procedure of Example D, but using 1.3 parts of 45% aqueous potassium hydroxide solution and 517 parts (11.8 mol) of ethylene oxide which are fed in the course of 4 hours and 15 minutes. The potassium hydroxide is neutralized with 0.6 part of 85% phosphoric acid.

The technical oleic acid referred to as "white oil" and used in Examples 1, 4, 11 to 13 and 17 to 19 is essentially colorless oleic acid, which is sometimes also referred to as "white oleic acid". It is generally obtained by distilling crude oleic acid, known as "red oil", at least twice, the latter coming from common sources such as tallow and various animal fats. The 80 to about 88.5% white oil (technical oleic acid) which was used in the examples mentioned consists of about 72.5% 9-cis-octadecenoic acid, 8.6% linoleic acid, 5.7 palmitolic acid, 1, 4% Mvristolic acid, 0.9% stearic acid, 21% hepadecanoic acid, 5% palmitic acid, 3.2% myristic acid and 0.5% lauric acid.

The term "total oleic acids", which was used in the above description, is common in the fatty acid industry and denotes the total amount of the individual acids oleic acid, linoleic acid, linolenic acid, palmitolenic acid and myristoleic acid, which in different, often very similar amounts in the various technical oleic acids different sources.

Examples 1, 2 and 3 each use the same

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technical stearic acid. The lauric acid from hydrogenated coconut oil fatty acids used in Example 4 and the technical hydrogenated coconut fatty acids represent the same starting material containing lauric acid. In the same way, any other available technical lauric acid, oleic acid or stearic acid (e.g. the so-called 70/30) can be used.

Since the various technical fatty acids are a mixture of a main component and other accompanying acids, the ester products obtained according to Examples 1 to 6 and 11 to 19 are actually ester mixtures.

The prefix «mono» is used in the title of Examples 1, 2, 5,

6 and 7 in quotation marks. In these examples, acid and diol are charged in essentially equimolar amounts, but the respective end products actually do not consist of a single ester whose acyl group is exclusively bound to one of the nitrogen atoms. Rather, the end products of these examples consist of a major amount of both monoesters, wherein one acyl group is attached to the 1-nitrogen atom and the other to the 3-nitrogen atom, and a lesser amount of 10-di-ester, and if the molar amount of fatty acid, such as e.g. In Examples 4 and 6, which is slightly less than the molar amount of hydantoin diol, there is also a small amount of unreacted diol.

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Claims (15)

617190 2. The method according to claim 1, characterized in that one produces ester or ester mixtures of the above formula, wherein R3 and R4 represent the methyl radical. 2nd PATENT CLAIMS 1. Process for the preparation of 1,3-bis-hydroxyethyl hydantoin esters of the formula R. c CO v-'l I I I R ^ OCl ^ C ^) ^ 'NCCh2CH00)' R2 (I) \ ~ \ / c ö or mixtures thereof, in which R3 and R4 individually denote hydrogen, a lower alkyl radical, cycloalkyl or alkoxy radical, where if one or both radicals R3 and R4 are alkyl, cycloalkyl or alkoxy, these together have at most 7 carbon atoms, or R3 and R4 together form the divalent tetramethylene or pentamethylene radical, one of the radicals R, or R2 can be hydrogen, while the other, or both radicals Rt or R., the benzoyl, oleoyl, linoleoyl, linolenoyl or a saturated fatty acid acyl radical with 2 to 22 carbon atoms or a mixture of saturated fatty acid acyl residues with 8 to 22 carbon atoms, or a mixture of any of the aforementioned saturated fatty acid acyl residues and the oleoyl, linoleoyl, linolenoyl, palmitoleoyl or myristoleoyl residue, and x + y are any sum of 3 to 100, characterized in that (a) a bis-hydroxyethyl hydantoin of the above formula, but in which Rj and R are hydrogen, with (b) benzoic acid or a saturated fatty acid with 2 to 22 carbon atoms or oleic acid, linoleic acid or linolenic acid, or a mixture of saturated fatty acids with 8 to 22 carbon atoms, optionally in a mixture with oleic acid, linoleic acid, linolenic acid, palmitolic acid and / or myristic acid, in the ratio from 1 mole of bis-hy-hydroxyethyl hydantoin to 1 to 2 moles of carboxylic acid under esterification conditions in the presence of a catalytically effective amount of a compatible esterification catalyst by heating the reaction mixture to the initial temperature of the esterification, separating the water of reaction, the temperature to 220 to 250 ° C. increases and continues heating until a sample taken indicates the essentially completed esterification. 3. The method according to claim 1, characterized in that one of the radicals Rj or R "is the isostearoyl radical. 4. The method according to claim 2, characterized in that with technical oleic acid mixtures of esters of the above formula are prepared, wherein Rt and R; represent the mixture of the acyl groups of the fatty acids contained in technical oleic acid. 5. The method according to claim 4, characterized in that technical oleic acid is used which consists of 80 to 88.5% of unsaturated acids and the rest of saturated fatty acids. 6. The method according to claim 2, characterized in that one produces ester or ester mixtures of the above formula, wherein the sum of x and y is on average 5 to 20. 7. The method according to claim 6, characterized in that (a) esterified with technical hydrogenated coconut oil fatty acids, (b) technical stearic acid or (c) technical oleic acid. 8. The method according to claim 7, characterized in that mixtures of esters of the above formula are prepared, wherein the sum of x and y is on average 20. 9. The method according to claim 7, characterized in that esterified with technical oleic acid, so that a major portion (a) of the reaction product from the two monoesters, namely (1) the monoester, wherein R2 is hydrogen and (2) the monoester wherein Rj is hydrogen and a minor portion (b) consists of the di-ester, wherein if the molar ratio of the acyl groups in the monoester and di-ester to that of the hydantoin portion is less than 1, a small amount of unreacted starting material is simultaneously present -Hydantoin is present. 10. The method according to claim 9, characterized in that one produces ester of the above formula, wherein the sum of x and y is on average 5, and the lower proportion of the ester product consists essentially of di-ester. 11. The method according to claim 9, characterized in that one produces ester of the above formula, in which the sum of x and y is on average 10, and the lower proportion of the ester product consists essentially of di-ester. 12. The method according to claim 9, characterized in that one produces esters of the above formula, wherein the sum of x and y is on average 15 and the lower proportion of the ester product consists essentially of di-ester. 13. The method according to claim 7, characterized in that technical oleic acid is used which consists of 80 to 88.5% of unsaturated acids and the rest of saturated fatty acids. 14. The method according to claim 1, characterized in that the catalyst used is hypophosphorous acid. 15. The method according to claim 1, characterized in that one carries out the esterification in an inert gas atmosphere, preferably in a nitrogen atmosphere, and that one flushes the reaction mixture with nitrogen.