LT3805B - N,n-disubstituted beta-aminopropionic acids - Google Patents

Abstract

The invention relates to new compounds of the general formula I: R1 - N - CH2CH - COOX A - R2 in which: R1 is a saturated or unsaturated alkyl radical or alkoxyl radical having 1-22 carbon atoms, preferably 12-18 carbon atoms, R2 is an alkyl radical having 1-18 carbon atoms, a saturated or unsaturated carboxyalkyl radical having 3-4 carbon atoms, a carboxyphenyl radical or a carboxyl radical (-COOH), R3 is hydrogen or CH3, X is hydrogen, an alkali metal, an alkaline earth metal, ammonium, alkylammonium or alkanolammonium and A is a) C=O, b) SO2, c) -CONH- or d) an alkylene radical having 0-3 carbon atoms, having emulsifying and surface-active properties, and it is proposed to use them for hydrophobization of hides and furs.

Description

The invention is directed to N,N-disubstituted β-aminopropane acids, which have hydrophobic properties and are intended for the impregnation of hides and skins, and to a method for obtaining these acids.

Alkylaminopropanoic acids, alkylaminodipropanoic acids and acylated alkylaminopropanoic acids are known. For example, U.S. Patent No. 2,462,012 describes the preparation of N-alkylaminopropanoic acids and their use as detergents, emulsifiers and foam stabilizers. Oleic acid sarcoside and oleylaminopropanoic acid are proposed for use as hydrophobic agents for the impregnation of leather. However, a disadvantage of using these compounds for this purpose is that the leather treated with them has a high water absorption.

The aim of this invention is to find materials that have better properties in terms of water absorption and longitudinal bending of leathers.

The above-mentioned objective is achieved by using materials having the general formula I:

Ra l

Ri - N - CH ₂ CH - COOX (I)

AR ₂ in which: Ri is a saturated or unsaturated alkyl radical or an alkoxyalkyl radical having 1-22 carbon atoms, preferably 12-18 carbon atoms,

R ₂ is an alkyl radical having 1-18 carbon atoms, a saturated or unsaturated carboxyalkyl radical having 3-4 carbon atoms, a carboxyphenyl radical or a carboxyl radical (-COOH),

R ₃ is hydrogen or CH3,

X is hydrogen, an alkali metal, an alkaline earth metal, ammonium, alkylammonium or alkanolammonium and

A is a) C=O, b) SO ₂ , c) -CONH- or d) an alkylene radical having 0-3 carbon atoms.

N-Alkylaminopropanoic acids, described in U.S. Patent No. 2,468,012, are prepared by coupling primary amines to acrylic acid esters and hydrolyzing the resulting N-alkylaminopropanoic acid esters to the corresponding acids or salts.

The VFR patent application No. 2054649 describes N-acyl-N-alkylaminopropanoic acids, which are obtained by reacting amines with acrylic acid derivatives, namely acrylic acid esters, acrylonitrile or acrylamide, and further reacting with anhydrides. In the final stage of the synthesis, the functional groups - ester, nitrile and amide - are hydrolyzed to the acid. The resulting products are solutions in water or a mixture of water and alcohol.

These known methods of obtaining have a number of disadvantages:

According to the method of preparation, the required hydrolysis stage can only be used to obtain products in solution, and to obtain 100% material, additional technological stages are required. After the formation of gelatinous structures, only 20-30% solutions of a paste consistency can be obtained in water. Only by using alcohols together, which is not beneficial, can the concentration be increased by approximately 50%. Since the hydrolysis takes place in a very alkaline medium, after neutralization to a pH of 5 to 8, products widely used, for example in textiles, contain large amounts of salts, which are often undesirable.

When using solid alkylamines, the coupling to acrylic acid derivatives must be carried out at high temperatures (above the melting point of the alkylamine), which, in the presence of reactive acrylic acid derivatives, accelerates the undesirable side reaction of diadduct formation. During this side reaction, a second molecule of acrylic acid derivative combines with the already formed N-alkylaminopropanoic acid derivative, forming a tertiary amine, which can no longer be acylated in the next step of the synthesis.

Finally, a disadvantage is also the smell of residual amounts of acrylic acid ester or acrylonitrile in the product, as even 0.1% of acrylic acid ester is noticeable.

Thus, another object of the present invention is to obtain a product which does not have the above-mentioned disadvantages, namely a product without undesirable large amounts of additional salts and without undesirable by-products.

It has unexpectedly been found that alkylamines can couple to (meth)acrylic acid at temperatures of 40-130 °C, preferably at temperatures of 70-100 °C. Although an organic salt is formed upon mixing the reaction components, the coupling is complete after 1-4 hours and occurs completely. No diadduct formation is observed under these conditions. No solvent is used.

With amines with a boiling point below the so-called reaction temperature, the reaction is carried out mainly under pressure, for example in an autoclave.

The interaction of alkylamine with (meth)acrylic acid occurs mainly in equimolar amounts.

As alkylamines of the formula RiNH ₂ , the following primary amines can be used, for example: methylamine, propylamine, butylamine, hexylamine, nonylamine, decylamine, dodecylamine, tridecylamine, isotridecylamine, hexadecylamine, octadecylamine, propoxypropylamine, octyloxypropylamine, oleylamine, oleyloxypropylamine, laurylamine, coconut oil amine, stearylamine, tallow amine or mixtures of the above amines. Particularly suitable amines are laurylamine, coconut oil amine, tallow amine and oleylamine.

Further conversion of N-alkyl-N-(2-carboxyethyl)amines in the case of acylation is carried out using anhydrides, isocyanates, carboxylic acid chloranhydrides or sulfuric acid chloranhydrides. The acylating agent is used in equimolar amounts at a temperature of 50-100 °C, in a small excess (about 5%).

The reaction with anhydrides or isocyanates is complete within 1-2 hours and the required N-alkyl-N-(2-carboxyethyl)amides are obtained in 100% yield. When using monocarboxylic acid anhydrides, for example acetic anhydride, the monocarboxylic acid obtained in equivalent amounts is separated by distillation or washing with water.

Examples of anhydrides include: acetic anhydride, propanoic anhydride, butyric anhydride, maleic anhydride, succinic anhydride, phthalic anhydride.

Examples of isocyanates include: butyl isocyanate, toluene isocyanate, isopropyl isocyanate.

The second reaction stage, the acylation stage, is also carried out in equimolar amounts of the reaction components.

If the acylation reaction is carried out with carboxylic acid chlorides, the acid-binding agent is soda ash or tertiary amines. The salt formed during the reaction can be filtered or washed with water.

Examples of carboxylic acid chloranhydrides include: acetic acid chloranhydride, propanoic acid chloranhydride, butyric acid chloranhydride, and suitable sulfuric acid chloranhydrides include, for example, methanesulfuric acid chloranhydride, ethanesulfuric acid chloranhydride, para-toluenesulfuric acid chloranhydride.

The subsequent reaction of the resulting N-alkylaminopropanoic acid can also be carried out with carboxylic acids having halogen substituents, preferably chlorine substituents (for example, with chloroformic acid, chloroacetic acid, chloropropanoic acid and chlorobutyric acid) or with (meth)acrylic acid.

The new method allows obtaining the Ν,Ν-disubstituted β-aminopropanoic acid derivatives proposed in the invention in two stages without the formation of a by-product. 100% of the product is obtained, without solvent.

During neutralization, N,N-disubstituted β-aminopropanoic acid derivatives are mixed with an aqueous solution of an alkali metal hydroxide, an alkaline earth metal hydroxide, or ammonium hydroxide. Depending on the concentration and the neutralizing agent, viscous to pasty aqueous solutions are obtained.

Neutralization is usually carried out with organic bases. Primary, secondary and tertiary amines, such as alkylamines and alkanolamines, are most suitable as organic bases. Ethanolamines and isopropanolamines are particularly suitable. The neutralizing agent can be used in equivalent amounts to the acid or in smaller amounts.

Derivatives of N,N-disubstituted β-aminopropanoic acids and their salts are used as emulsifiers and humectants or as skin-protecting surfactants in cleaning products. Another area of application is in mixtures intended to impart hydrophobic properties to the skin.

Waterproof leather is mainly obtained in two ways:

1. Filling capillary-like water-absorbing fiber gaps with compacting materials.

Water-insoluble substances, such as fats, paraffins, waxes or certain polymers, have an undesirable property, namely that they have a negative effect on wear-relevant properties, such as breathability and vapor permeability. Compounds that swell when they absorb water and at the same time have the effect of swelling and densifying the leather fibers are preferable. The products used in this way are classified as water-in-oil (w/o) emulsifiers.

2. Coating the fiber with hydrophobic materials.

Emulsifiers that can form complex compounds with polyvalent metal ions (cations) can in many cases also enter the chromium-collagen complex and cause hydrophobization. Such emulsifiers chemically bind to the leather fibers affected by chromium and aluminum tanning and, due to the hydrophobic coating, reduce the wettability and absorbency. The reduction in spreading properties is manifested by the formation of spherical droplets (water repelling (hydrophobic) effect).

The greatly increased requirements for hydrophobic leather are almost impossible to achieve with known hydrophobicization methods or can only be achieved at the expense of other important properties. Upper leather intended for everyday wear must currently meet the same requirements as leather intended for military clothing a few years ago, keeping up with comfort of wear, fashionable appearance, etc.

For this reason, hydrophobization was performed in two stages.

Prepared dried or tanned leather can be further treated with silicone oils dissolved in organic solvents. Another disadvantage is the drying temperature required after wetting (90-100 °C), which causes significant size losses. In addition, there is the problem of large amounts of solvent emissions into the environment.

From the point of view of rational production, the fact that additional processing requires an additional work stage is particularly undesirable.

By using the proposed materials, sufficient oiling and sufficient hydrophobicization are achieved not only during the finishing stage, but also with a single product.

The invention provides products for hydrophobization, the formula of which is used either in a partially neutralized form, as a low-water product, in most cases in the form of a paste, or in an unneutralized form. In most cases, the paste-like products are dissolved in hydrocarbons and/or chlorinated hydrocarbons, if necessary using solvents, and then at least partially neutralized. Bases are used for this purpose, in particular primary, secondary and tertiary amines and alkanolamines, as well as aqueous solutions of ammonia and alkali metal hydroxides.

0.1-25, usually 1-25% by weight of the compound of the invention is used, calculated based on the weight of the cut skin or wet fur, at a pH of 4-9, then the pH is reduced to 3.5-5.0 and, if necessary, fixed with 2-, 3- and 4-valent metal salts.

The product used for hydrophobization proposed in the invention contains (depending on the purpose) 5-80 wt. %, usually 10-70 wt. % of compounds of general formula I and, if necessary, 20-70 wt. %, usually 30-60 wt. % of chlorinated hydrocarbons, if necessary, with solvents such as high-boiling oxosynthesis products, and the remainder up to 100% is water.

Although excellent greasing and excellent hydrophobization are achieved by using only one of the compounds proposed in the invention, the hydrophobization agents proposed in the invention can also be used in combination with known greasing agents and/or hydrophobization agents, such as partially esterified phosphoric acids, oleic acid silicone sarcoside and/or (chloro)paraffins.

If partially esterified phosphoric acids are used, preference is given to acids partially esterified with alcohols having a chain length from C4 to C20, usually from C11 to C12, which, if necessary, can be oxyethylated, taking them in the following amounts: from 0.5 to 30% by weight, usually 1-20% by weight (calculated per 100 g of hydrophobization agent).

The combined use of acidic phosphoric acid esters can be realized by using them together with the compounds proposed in the invention, diluting and then neutralizing them together with the latter. Phosphoric acid esters in neutral form can also be used. Phosphoric acid esters are proposed to be used in cases where it is necessary, for example, to reduce the amount of extractable fat; this is important in the case of leathers intended for clothing, since their resistance to dry cleaning is improved.

When silicone oils are used together with the compounds proposed in the invention, their amounts are as follows: from 0.5 to 80 wt%, usually 1-20 wt% (calculated per 100 g of the mixture of hydrophobizing agents).

As silicone oils, commercial polysiloxanes can be used, namely dimethyl or methylphenyl polysiloxane. The most suitable viscosity ranges are from 100 to 500 mPa.s. In addition, the silicone oil with the compounds proposed in the invention is, if necessary, used together with hydrocarbons and/or chlorinated hydrocarbons or solvents. The use of silicones allows for certain desired surface effects to be obtained, such as softening the skin's surface.

In order to further increase the softness and achieve a higher degree of greasing, it is also possible to use oleic acid sarcoside as an additive. Any combination of partially esterified phosphoric acid, silicone oil oleic acid sarcoside and the compounds proposed in the invention can generally be used to obtain certain effects.

Oleic acid sarcoside together with the compounds proposed in the invention can be used in the following amounts: from 0.5 to 50 wt%, usually 2-20 wt% (calculated per 100 g of the mixture used).

The invention is illustrated by the following examples.

example

534 g (2 mol.) of oleylamine are placed in a flask with a stirrer, thermometer and reflux condenser and heated to 60 °C. 144 g (2 mol.) of acrylic acid are added dropwise over 30 min. The temperature rises to approximately 90 °C. Stirring is then continued for another 2.5 hours at 90 °C. The reaction mixture is cooled to 70 °C and 196 g (2 mol.) of maleic anhydride are added in portions. To complete the reaction, stir for 2 h at 70-80 °C. N-oleyl-N-(2-carboxyethyl)maleic acid monoamide is obtained as a light brown paste.

Acid value 250 mg KOH/g

Residual basic nitrogen content 0.2 mmol/g.

For neutralization, 122 g (2 mol) of monoethanolamine is added dropwise at 80 °C with stirring.

example

Analogously to Example 1, 269 g (1 mol.) of stearylamine is added to 72 g (1 mol.) of acrylic acid, and the reaction mixture is treated with 98 g (1 mol.) of maleic anhydride. The resulting N-stearyl-N-(2-carboxyethyl) maleic acid monoamide solidifies at room temperature to a light brown paste.

Acid number 251 mg KOH/g.

Residual basic nitrogen content 0.32 mmol/g.

Neutralize at 100 °C with 35.5 g (0.5 mol) of isopropanolamine.

example

Analogously to Example 1, 486 g (2.0 mol) of lauryloxypropylamine is added to 144 g (2 mol) of acrylic acid, and the reaction mixture is treated with 196 g (2.0 mol) of maleic anhydride. N-lauryloxypropyl-N-(2-carboxyethyl)maleic acid monoamide solidifies at room temperature into a dark brown, opaque paste.

Acid number 265 mg KOH/g.

Residual basic nitrogen content 0.3 mmol/g.

example

Analogously to Example 1, 785 g of coconut oil amine (3.72 mol.) (basic nitrogen content: 4.74 mmol/g) are added to 268 g (3.72 mol.) of acrylic acid, and the reaction product is treated with 364.8 g (3.72 mol.) of maleic anhydride. A red-brown, highly viscous oil is obtained.

Acid number 290 mg KOH/g.

Residual basic nitrogen content 0.25 mmol/g.

For neutralization at 80 °C, 554 g (3.72 mol) of triethylamine is added dropwise with stirring.

example

Analogously to Example 1, 101 g (1.0 mol.) of hexylamine is added to 72 g (1.0 mol.) of acrylic acid, and the reaction product is treated with 98 g (1.0 mol.) of maleic anhydride. N-hexyl-N-(2-carboxyethyl)maleic acid monoamide is obtained as a light brown oil.

Acid number 418 mg KOH/g.

Residual basic nitrogen content 0.15 mmol/g.

example

534 g (2 mol.) of oleylamine in a flask with a stirrer, thermometer and reflux condenser is heated to 60 °C. Over 30 min. 172 g (2 mol.) of methacrylic acid is added dropwise. The temperature rises to approximately 85 °C. In order for the reaction to occur completely, the mixture is stirred for 3 hours at a temperature of 100 °C. After determining the primary bases, it is assessed whether the reaction has occurred completely. Then it is cooled to 70 °C and 204 g (2 mol.) of acetic anhydride is added dropwise at a temperature of 70-80 °C. After another 2 hours, the formed acetic acid is evaporated in vacuo at a pressure of 20 mbar. N-oleyl-N-(2-carboxy-2-methylethyl)acet9 amide is obtained - a brown, clear oil.

Acidity 139 mg KOH/g.

Residual basic nitrogen content 0.1 mmol/g.

Neutralization is carried out at 80 °C with 112.2 g (2 mol) of KOH dissolved in 2402 g of water. An aqueous solution containing 25% solids is obtained.

example

Analogously to Example 1, 267 g (1.0 mol.) of oleylamine are added to 72 g (1.0 mol.) of acrylic acid. Then, 148 g (1.0 mol.) of phthalic anhydride are added in portions at 90 °C and stirred for 3 hours at 100 °C. N-Oleyl-N-(2-carboxyethyl)phthalic acid monoamide is a yellow-brown paste.

Acid number 225 mg KOH/g.

Residual basic nitrogen content 0.5 mmol/g.

example

Analogously to Example 1, 267 g of oleylamine are coupled to 72 g of acrylic acid. The coupling product is mixed with 55 g of anhydrous sodium carbonate and 301 g (1.0 mol) of oleic acid chloride are added dropwise over a period of approximately 2 hours at a temperature of 100 °C. After another 2 hours, the acylation is complete. The resulting edible salt is washed with water.

Acid number 94 mg KOH/g.

Residual basic nitrogen content 0.1 mmol/g.

example

Analogously to Example 6, 267 g (1.0 mol) of oleylamine is added to 86 g (1.0 mol) of methacrylic acid.

After addition, 101 g (1.0 mol.) of triethylamine is added to the reaction mixture and 190.5 g (1.0 mol.) of para-toluenesulfonic acid chloranhydride is added in portions at a temperature of 70-90 °C. After the exothermic reaction is complete, stirring is carried out for 2 hours at a temperature of 90 °C, then the salt is washed with water. N-oleyl-N-(2-carboxy-2methylethyl)-para-toluenesulfonic acid amide is obtained - a dark brown viscous oil.

Acid number 99 mg KOH/g. Residual base nitrogen 0 mmol/g. Infrared (IR) spectrum: C=O 1720 cm' ¹ c=c 1620 cm' ¹ (aryl group) so ₂ 1330 and 1170 cm' ¹ . nuclear magnetic resonance: 7-8 ppm (aromatic protons)

For neutralization at 90 °C, 105 g (1.0 mol) of diethanolamine is added with stirring.

example

Analogously to Example 1, 267 g (1.0 mol.) of oleylamine is added to 72 g (1.0 mol.) of acrylic acid.

After addition, 53 g (0.5 mol) of sodium carbonate powder is added and 114.4 g (1.0 mol) of methanesulfonic acid chloride is added dropwise at 110 °C. To complete the reaction, stirring is continued for another 2 hours at 110 °C. The salt formed is washed with water. N-oleyl-N-(2-carboxyethyl)methanesulfonic acid amide is obtained as a dark brown paste.

Acid number 129 mg KOH/g.

Residual basic nitrogen content 0 mmol/g.

IR spectrum: C=O 1730 cm' ¹ ,

SO ₂ N 1320 and 1160 cm' ¹ .

example

Analogously to Example 1, 267 g (1.0 mol.) of oleylamine is added to 72 g (1.0 mol.) of acrylic acid.

After addition, 115 g (1.0 mol.) of N-ethylmorpholine is added and 133 g (1.0 mol.) of toluene isocyanate is added dropwise at a temperature of 40-50 ° C. The mixture is kept for another 1 hour and N-oleyl-N-(2-carboxyethyl)-N-tolueneurea is obtained - a brown oil.

Acid number

IR spectrum: C=O (acid)

N-C=O

C=C (aryl group) mg KOH/g. 1720 cm' ¹ ,

1660 and 1560 cm' ¹ ,

1590 and 1610 cm' ¹ .

example

Analogously to Example 1, 267 g (1.0 mol.) of oleylamine is added to 72 g (1.0 mol.) of acrylic acid.

After addition, 115 g (1.0 mol.) of N-ethylmorpholine is added and 99 g (1.0 mol.) of n-butyl isocyanate is added dropwise at a temperature of 40-50 ° C. It is kept for another 1 hour and N-oleyl-N-(2-carboxyethyl)-N-butylurea is obtained - a light brown oil.

Acid number 96.4 mg KOH/g.

IR spectrum: C=O (acid) 1720 cm' ¹ ,

NC=O 1620 and 1540 cm' ¹ .

example

Analogously to Example 1, 204 g (0.6 mol.) of oleylaminopropanoic acid, 70 g of chloroacetic acid (sodium salt, 0.6 mol.), 54 g of water, and 108 g of isopropanol are added, heated to 80 °C, and a clear solution is obtained. 106.6 g of 45% sodium hydroxide solution (1.2 mol.) are added dropwise to this solution over 45 minutes. The viscosity of the reaction mixture has increased. Stirring is continued for 4 hours at 80 °C, then neutralized with concentrated hydrochloric acid, poured into excess water, and a precipitate precipitates. The product (N-oleyl-N-carboxymethylaminopropanoic acid) is separated and dried.

Acid number 245 mg KOH/g.

The coupling product used as starting material is obtained analogously to Example 1 from the reaction of oleylamine with acrylic acid (in equimolar amounts).

example

267.5 g of oleylamine and 0.2 g of HOME (hydroquinone monomethyl ester) are used. The addition is done dropwise with cooling so that the reaction temperature does not exceed 70 °C. Already from 80 °C the reaction proceeds exothermically, and the viscosity increases significantly. After about 10 minutes at 120 °C a paste-like mixture is obtained. Then stirring is continued for another 3 h at 140 °C. The product (N-oleyl-N-(2-carboxyethyl)aminopropanoic acid) has an acid number of 253 mg KOH/g.

example

a) 13.6 g of water and 22.7 g of sodium hydroxide solution (45%) are added to the apparatus with a mixer and heated to a temperature of approximately 50 °C. Then, while stirring, 63.7 g of N-oleyl-N(2-carboxyethyl)maleic acid monoamide from sample 1 are added and stirred until a homogeneous consistency is obtained.

b) The product obtained by method a) is used in the following waterproof leather preparation recipe and the hydrophobic effect is tested:

Leather from large bovine animals:

Type: waterproof.

Material: cowhide, blue color, thickness after cutting - 2.0 mm.

Percentages are calculated based on the weight of the cut skin.

Rinsing: 300% water 35 °C + 0.5% acetic acid 1:5* 15 min.

*(1 part by volume of acetic acid and 5 parts by volume of water)

Drain the washing solution.

Rinse: 300% water 35°C 10 minutes Drain the washing solution. Neutralization: 150% water 35°C Staining: 2% undissolved sodium formate 90 minutes Final tanning: + 2% undissolved dye 15 minutes + 4% undissolved tanigan QF** 30 minutes + 12% undissolved chestnut N 60 minutes at 8 revolutions per night + 250% water 60°C 10 minutes Drain the washing solution. Hydrophobicity: 100% water 60°C + 0.5% ammonia 1:5* 2 minutes *(1 part by volume of ammonia and 5 parts by volume of water)

+ 6.3 % Example 15 a proposes a hydrophobization solution for 60 min. 1:5* *(1 volume part of the product and 5 volumes of water) pH: 3.6 - 4.0 ** Product of Bayer AG, Leverkusen

Drain the washing solution. Washing 2 times: Drain the washing solution. 300% water 40°C after 10 minutes Fixation: 150% water 40°C Drain the washing solution. 3% Bauchrome A**, pH: 4.2 - 4.8 undissolved 60 minutes Washing 3 times: 300% water 20°C in 10 minutes

Dry the leather overnight on a goat, stretch it, dry it in a vacuum (80 °C/2 min.), air dry it, condition it, soften it, and smooth it (80 °C/0.5 min.).

Baily Penetrometer: (10% sediment)

Soaking time: >7/>7 hours.

Moisture absorption, %:

after 7 hours: 9.9/10.4.

Mezer:

Longitudinal bends 21924/19207

Moisture absorption, %:

After longitudinal bends 8.0/7.1.

example

The amide obtained according to Example 1 is used. 30 g of water and 7 g of diisopropylamine are added to the apparatus with a mixer at a temperature of about 50 ° C. Before starting the mixing, the organic phase is added, consisting of 14 g of the amide proposed in the invention, 3.5 g of the amino salt of the phosphoric acid ester (obtained by neutralizing alfol 16-18, a mixture of fatty alcohols from the Ziegler synthesis, P2O5, in a molar ratio of 3:1, with diisopropylamine) and 45.6 g of chloroparaffin, the chain of which contains 40% chlorine, and mixed until a homogeneous consistency is obtained.

This mixture is used in the following procedure to produce leather for military clothing:

Leather from large horned animals:

Type: leather for military clothing.

Material: cowhide, wet, blue color, thickness after cutting: 2.0 mm.

Percentages are calculated by weight after trimming.

Rinsing: 300% water 35 °C

0.5% formic acid 1:5* *(1 part by volume formic acid and 5 parts by volume water)

Drain the washing solution.

Neutralization: 100% water 35 °C % sodium formate, undissolved pH: 4.4 + 0.5% sodium bicarbonate 1:10 pH: 4.8.

Drain the washing solution.

Washing: 300% water 30 °C

Drain the washing solution.

Final tanning: 200% water 30°C % dye 1:20 + 4% undissolved tanigan** (QF) + 12% quebrach, undissolved Automatic overnight min.

min.

min.

min.

min.

min.

min.

Stillness/rotation 15 min/l min Drain the washing solution. + 200% water 60°C 20 minutes Washing: 300% water 60°C 10 minutes Hydrophobicity: 200% water 60°C

% hydrophobization agents from sample 16 diluted with water in a ratio of 1:5 (vol/vol) for 60 min.

+ 1% formic acid 1:5* *(1 volume part formic acid and 5 volumes of water) + 3% bichrome** F, undiluted 60 min.

Drain the washing solution Rinse 3 times: Drain the washing solution Rinse:

pH: 3.6 - 3.7.

300% water water °C °C after 10 min.

min.

Dry the leather overnight on a goat: stretch, dry in a vacuum (80 °C/3 min.), air dry, soften, smooth (80 °C/5 min.).

Baily penetrometer (10% sediment).

Soaking time: >420/>420 min.

Moisture absorption, %: after 7 hours 12/14

Mezer:

Longitudinal bends 29787/25971

Moisture absorption, %:

After longitudinal bends 10/12.

example

a) 30.5 g of water and 5.5 g of 45% aqueous sodium hydroxide solution are added to the apparatus with a stirrer at a temperature of 50 ° C. With slow stirring, the organic phase consisting of 18 g of amide (from example 1), 40 g of high-boiling mineral oil and 6 g of dimethylpolysiloxane with a viscosity of 350 mPa.s is added, then stirred until a homogeneous consistency is obtained.

(b) The mixture from part (a) is used in the process described in Example 16 and the following results are obtained:

Baily penetrometer (10% sediment)

Soaking time: >420/>420 min.

Moisture absorption, %:

after 7 hours. 7/8

Mezer:

Longitudinal bends 48123/48316

Moisture absorption, %:

after longitudinal bends 9/8.

example

The amide of Example 1 proposed in the invention was used.

39 g of water and 3 g of 45% sodium hydroxide solution are added to the apparatus with a mixer at a temperature of about 50 °C. Then, with slow stirring, the organic phase consisting of 6 g of the amide of example 1, 1.6 g of oleic acid sarcoside, 40 g of high-boiling mineral oil and 5 g of dimethylpolysiloxane with a viscosity of 35 mPa.s is added and homogenized.

The product thus obtained is used in the process for obtaining waterproof leather described in Example 16b. The following results are obtained:

Baily penetrometer (10% sediment).

Soaking time: >420/>420 min.

Moisture absorption, %:

after 7 hours 9/10

Mezer:

Longitudinal bends 29885/30147

Moisture absorption, %:

After longitudinal bends 14/11.6.

example

a) 39 g of water and 4 g of 45% sodium hydroxide are added to the apparatus with a stirrer at a temperature of about 50 ° C. While stirring, the organic phase is added, consisting of 12 g of the amide of example 4, 35 g of a high-boiling hydrocarbon, 5 g of dimethylpolysiloxane with a viscosity of 100 mPa.s, and 5 g of partially esterified phosphoric acid (alfolic 12-18, after reaction with P2O5, molar ratio 3:1) and stirred until a homogeneous consistency.

b) Using the procedure described in Example 16, the following results were obtained:

Baily penetrometer (10% sediment).

Soaking time: >7/>7 hours.

Moisture absorption, %:

after 7 hours: 13.3/12.0

Mezer:

Longitudinal bends 15849/16717

Moisture absorption, %:

After longitudinal bends 12/8 example

The product described in Example 13 is used. 20 g of this material and 68.4 g of chloroparaffin, which contains 40% chlorine in the chain, are placed in an apparatus with a mixer, stirred at a temperature of 100-105 ° C until a homogeneous consistency. After cooling to about 70 ° C, 11.6 g of diisopropylamine are added to the mixture for neutralization.

This mixture is used in the following process to obtain waterproof leather and its effects are being studied:

Material: cowhide, blue color, thickness after cutting - 2 mm.

Percentages are calculated by weight after trimming.

Rinsing: 300% water 35 °C

0.5% acetic acid 1:5 15 min.

Drain the washing solution.

Neutralization: 100% water 35 °C % sodium formate, undiluted 15 min.

+ 0.5% sodium bicarbonate 1:10 for 90 min.

Washing solutions - pH: 5.3

Cross-section of skin in relation to bromocresol green:cyan.

Drain the washing solution.

Rinse: 300% water 30 °C 10 min.

Drain the washing solution.

Dyeing: 100% water 30 °C

Final tanning: 1% black dye for chrome leather TU 141% 1:20 20 min.

+ 4% Tanigan QF**, undiluted 30 min.

+ 12% undissolved quebrach at 6 rpm overnight.

Tanning: + 200% water 60 °C 20 min.

Drain the washing solution.

Rinsing:

Drain the washing solution.

300% water °C min.

Hydrophobization:

100% water °C

Fixing:

Drain the washing solution.

Washing 3 times: 300% water % hydrophobization agent 1:4 + 1% formic acid 1:5 + 3% bichrome F Washing solutions - pH: 3.6 - 3.7.

°C min.

min.

min.

after 10 minutes

Drain the washing solution.

The leather is dried overnight on a goat, stretched, dried in a vacuum (80-85 °C, 2 min.), air-dried, moistened, softened, and smoothed in a vacuum (80-85 °C, 30 sec.). No exceptional observations were made during the wet work.

Baily penetrometer: (10% sediment).

Soaking time: >7/>7 hours.

Moisture absorption, %:

after 7 hours 13.1/8.2.

Mezer:

Longitudinal bends 15407/14320.

Moisture absorption, %:

After longitudinal bends 7.7/5.0.

Examples 21-25

25 g of the compound of formula I, 25 g of a high-boiling mineral oil and an amount of triethylamine required to neutralize the acidic group are mixed. The mixture is emulsified in 200 g of water at a temperature of 60 ° C. Such mixtures are used as hydrophobizing agents in the technical application recipe described in Example 16. The test results are given in Table 1.

table

Example Baily Penetrometer used, (10% imprint) Water absorption, number of hours water passage time (min.) %

21 amide (from example 6) about 360 8 6 22 sulfamide (from example 9) 23 55 1 23 sulfamide (from example 10) 135 13 1 24 urea derivative (from example 11) 48 58 2 25 urea derivative (from example 12) 10 67 2

comparative example

20 g of the product obtained according to the procedures described in Example 1, 6 or 13, or the same amount of known compounds from U.S. Patent No. 2,468,012 (oleic acid sarcoside or oleylaminopropanoic acid) were mixed with 68.4 g of a chloroparaffin containing 40% chlorine in the chain and the amount of diisopropylolamine required for neutralization. The test was carried out according to the procedure described in Example 20. The results are given in Table 2.

table

Compound V-test longitudinal bends Moisture absorption, % Example 1 25600/23900 9.0/9.8 Example 6 12000/14000 6.0/7.0 Example 13 15400/14300 7.7/5.0 Oleic acid sarcoside 13000/12600 15.0/22.1 (oleyl-CON(CH ₃ )CH ₂ COOH) Oleylaminopropanoic acid 4600/1400 11.0/7.6

(oleyl-NHCH ₂ CH ₂ COOH)

Claims (2)

DEFINITION OF INVENTION 1. N, N-substituted β-aminopropanoic acids of general formula I: Ra I Ri - N - CH ₂ CH - COOX (I) AR ₂ wherein: Ri is a saturated or unsaturated alkyl radical or an alkoxyalkyl radical having 1 to 22 carbon atoms, preferably 12 to 18 carbon atoms, R ₂ is an alkyl radical having from 1 to 18 carbon atoms, a saturated or unsaturated carboxyalkyl radical having from 3 to 4 carbon atoms, a carboxyphenyl radical or a carboxyl radical (-COOH), R ₃ is hydrogen or CH 3, X is hydrogen, alkali metal, alkaline earth metal, ammonium, alkylammonium or alkanolammonium, and A is a) C = O, b) SO ₂ , c) -CONH- or d) an alkylene radical having from 0 to 3 carbon atoms having emulsifying and surfactant properties for the hydrophobization of hides and skins. 2. A process for the preparation of N, N-substituted β-aminopropanoic acids according to claim 1, characterized in that (a) alkylamines are bonded to acrylic or methacrylic acid in equimolar amounts at 40 to 130 ° C; and b) N-acylating the resulting product with equimolar amounts of carboxylic anhydrides, isocyanates, carboxylic or sulfuric anhydrides to give a compound of formula I, not contaminated with by-products.