AU602171B2

AU602171B2 - A process for the production of N,N-disubstituted beta-aminopropionic acids and use of these as emulsifying agents, wetting agents and surfactants in cleaning agents and for waterproofing leather and skins

Info

Publication number: AU602171B2
Application number: AU80101/87A
Authority: AU
Inventors: Kurt Dahmen; Richard Mertens; Dolf Stockhausen
Original assignee: Chemische Fabrik Stockhausen GmbH
Current assignee: Stockhausen GmbH and Co KG
Priority date: 1986-10-27
Filing date: 1987-10-23
Publication date: 1990-10-04
Anticipated expiration: 2007-10-23
Also published as: JPS63112544A; EP0265818B1; EP0265818A2; LV11044B; NZ222310A; EP0265818A3; TR23997A; PT85994B; ES2003836A4; GR890300053T1; ES2003836T3; LV11044A; TR24291A; BR8705693A; JP2577011B2; PT85994A; ATE112259T1; AU8010187A; RU2062302C1

Abstract

A process for the preparation of compounds of the formula I <IMAGE> in which R1 denotes a saturated or unsaturated alkyl radical or alkoxyalkyl radical having 1 - 22 carbon atoms, preferably 12 - 18 carbon atoms, R2 denotes 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 denotes hydrogen or CH3 and X denotes hydrogen, alkali metal, alkaline earth metal, ammonium, alkylammonium or alkanolammonium and A represents <2bL>C=O, <2bL>SO2, <IMAGE> or an alkylene radical having 0-3 C atoms, which is characterised in that alkylamines of the formula R1-NH2, in which R1 has the meaning described above, are added to (meth)acrylic acid and the resulting N-alkylaminopropionic acids are reacted with carboxylic anhydrides, carbonyl chlorides, sulphonyl chlorides, isocyanates, halocarboxylic acids or (meth)acrylic acids and are then optionally at least partially neutralised. Novel N-alkyl-N-(2-carboxyethyl)sulphonamides and N-alkyl-N-(2-carboxyethyl)ureas are additionally described.

Description

COMMONWEALTH OF AUSTRALIA PATENTS ACT 2952-1969 602171 FORM COIMPLETE SPECIFICATION (Original) Application Number: Lodged: Complete specification Lodged: Accepted: Published: Class: Int. Class Priority: Related Art: ODGED AT SUB-OFFICE 2 3 O CT 1987 Me IbOuxn.

This documen1t contains the arnenniellts made under Section 49 and is correct for Prin ting, $1 Name of Applicant: Address of Applicant: Actual Tnventor/s: Chemische Fabrik Stockhausenl GmbH Bakerpfad 25, D-4150 Krefeld, Federal Republic of Germany.

DOLF STOCK(HAUSEN; KURT DAHMEN; and RICHARD MERTENS.

Address for Service: E. F. WELLINGTON CO., Patent and Trade Mark Attorneys,.

457 St. Kiltda Road, Melbourne, 3004, Vic.

Complete Specification for the invention entitled: "A PROCESS FOR TEE PRODUCTION OF NfN-DISJESTITUTED f3-AMINOPROP IONIC ACIDS AND THiE USE OF THESE AS EMULSIFYING AGENTS, WETTING AGENTS AND SURFACTANTS IN CLEANING AGENTS AND FOR WATERPROOFING LEATHER AND SK(INS" The following statement is~a full description of this invention including the best mnethod 8f performing it knowrn to mec/us: -1I- I 2 The present invention relates to a process for the production of N,N-disubstituted B-aminopropionic acids and the use of these as emulsifying agents, wetting agents, and surfactants in cleaning agents and for waterproofing leather and furskins, and in particular to a process for the production of Nalkyl-N(2-carboxyethyl) amides, new N-alkyl-N(2-carboxyethyl) sulfonamides, and N-alkyl-N(2-carboxyethyl) ureas, and the use of these.

Alkylaminopropionic acids, alkylaminodipropionic acids, and loSe the acylated alkylaminopropionic acids are known per se. Thus, o a 0° o° US-PS 2.468.012 describes the production of N-alkylaminoa pripionic acids and the use of these as detergents, emulsifiers, sooo and foam stabilizers. The production takes place by the 0 00 00 o° addition of primary amines to acrylic acid esters and saponification of the resulting N-alkylaminopropionic acid 00 esters to the corresponding acids or salts.

o 00 o° DE-OS 20 54 649 describes N-acyl-N-alkylaminopropionic 0ooo °oooo acids that are produced by conversion of amines with acrylic 0 0 acid derivatives such as the acrylic acid esters, acryl nitrile o or acryl amide and subsequent reaction with anhydrides. In the 0 0 0~o last step of this synthesis the ester-, nitrile-, or amide a 00 function is saponified to acid. The products are obtained as an aqueous or aqueous-alcoholic solution.

These known production processes entail a number of disadvantages:

I

3 The saponification stage, which is absolutely essential, results in the fact that the products can only be obtained in solution, and not as a 100% substance without additional process steps. Only 20- to 30-% solutions of a paste-like consistency can be obtained in water by the formation of gel structures.

Only the concurrent use of alcohols, which is disadvantageous, makes it possible to raise the concentration to approximately Since the saponification is carried out in a strongly alkaline range, the products have a very high salt content, 0 100 which is frequently undesirable, once the pH has been adjusted 0 o000 to 5 to 8, as is required for many applications, such as in the 400000 O 0 0o, textile field.

0 0 000 ,oo0 When'solid alkyl amines are used, the addition of the S0 0 acrylic acid derivatives must be carried out at elevated 1l 0 temperatures (above the melting point of the alkyl amine), 0 000 006 oo0, because of which, with the reactive acrylic derivatives, the 0 00 undesirable secondary reaction of diadduct formation is 000 Senhanced. During this secondary reaction a second molecule acr- 0 a ylic derivative is added to the already formed N-alkylamino- 2; -0 propionic acid derivative, and this results in a tertiary amine 0 that cannot be acylated during the following synthesis step.

Finally, the odour of the residual content of acrylic ester or acrylonitrile in the product is also a disadvantage.

A residual content of 0.1% acrylic ester can be detected.

It is the task of the present invention to create a process that does not have the disadvantages set out above; in r U I. I 4 particular, the production of products by the process, without an undesirably high salt content and without the formation of undesirable by-products.

A first aspect of the present invention provides a process for the production of compounds of the general formula: R N CH 2 CH COOX 1 i I r I I j Ij j 0 t

C

tt cL wherein R 1 is an alkyl radical, alkenyl radical, alkoxyalkyl radical, or alkoxyalkenyl radical, with 1-22 carbon atoms, preferably 12 18 carbon atoms,

R

2 is an alkyl radical with 1 18 carbon atoms, a carboxyalkyl radical or carboxyalkenyl radical with 3 4 carbon atoms, a carboxyphenyl radical, a toluene radical, or a carboxyl radical (-COOH),

R

3 is hydrogen or CH 3 X is hydrogen, alkali metal, alkaline earth metal, ammonium, alkylammonium, or hydroxyalkylammonium and A is >C 0, >S0 2 or It t comprising reacting an alkyl amine of the formula R1-NH 2 with (meth)-acrylic acid by adding the (meth)- acrylic acid in equimolar quantities to the alkylami, gradually thereby to form an N-alkylamino propionic acid, and subsequently reacting such N-alkylamino propionic acid with acid anhydride, acid chloride, or isocyanate containing the -AR 2 radical.

In preferred embodiments of the first aspect of the present invention, the process is characterized by: including the further step of neutralizing at least partially; or (ii) effecting the reaction of the alkyl amine with the (meth)acrylic acid at temperatures of about 40 130 0

C,

preferably about 70 100 0 C; or (iii) effecting the reaction under pressure; or I (iv) reacting the N-alkylaminopropionic acid that is produced 0 0 oj o in the first step, with the carboxylic acid anhydride, 0o oo.oo carboxylic acid chloride, sulfonic acid chloride, or 0 5o° isocyanate, at about 50 100C; or using the carboxylic acid anhydride, carboxylic acid chloride, sulfonic acid chloride, or isocyanate, in up to about molar excess relative to the N-alkylaminopropionic acid; or (vi) using a carboxylic acid chloride or sulfonic acid chloride for the second stage of the reaction, and having an acid binding agent present during the second step; or 14 (vii) selecting the acid binding agent from the group consisting of sodium carbonate and a tertiary amine; or (viii) effecting the neutralization with an alkyl. or hydroxyalkyl amine, preferably with a hydroxyethylamine or hydroxypropyl amine.

i A second aspect of the present invention provides an N-alkyl-N(2-carboxyethyl) sulfonamide or urea of the formula R3 R CH2CH COOX (I)

A

R

in which 1 is an alkyl radical, alkenyl radical, alkoxyalkyl radical, or alkoxyalkenyl radical, with 1-22 carbon atoms, t2 S* R 2 is an alkyl radical with 1-18 carbon atoms, a carboxyalkyl radical or carboxyalkenyl radical .lG with 3-4 carbon atoms, or a carboxyphenyl radical,

R

3 is hydrogen or CH3, X is hydrogen, alkali metal, alkaline earth metal, ammonium, aylammonium or hydroxyalkylammonium, and A is >S0 2 or-C-NH-, (f~r 0 .j Or p Swith the proviso that if A is SO 2 then R 2 cannot be an alkyl radical with 1-18 carbon atoms or a carboxyphenyl radical, and with the further proviso that if A is C=0-NH-, then R 2 cannot be an alkyl radical with 1-18 carbon atoms, Ai y\ i0 9 7 A third aspect of the present invention provides a process for waterproofing leather or fur-skins, comprising either during or after retanning, treating the leather or skins with a waterproofing agent of the formula

R

3 R N CH CH COOX

(I)

A

R

2 in which Ri is an alkyl radical, alkenyl radical, alkoxyalkyl 1radical or alkoxyalkenyl radical with 1-22 carbon atoms,

SR

2 is alkyl radical with 1-18 carbon atoms, a carboxyalkyl radical or carboxyalkenyl radical with 3-4 carbon atoms, a carboxy-phenyl radical, a toluene radical, or a carboxyl radical (-COOH),

R

3 is hydrogen or CH 3 X is hydrogen, alkali metal, alkaline earth metal, ammonium, alkylammonium or hydroxyalkylammonium, and A is >C 0, >S0 2 or -C-NH-, in a quantity from 0.1 to 25%-,wt; relative to the shaved weight of the leather or the wet weight of the fur-skin, at a pH of 4 to 9, finally adjusting the pH to the range from 3.5 to nd fixing the waterproofing agent in the leather or fur-skin.

o30 v~ A j zu of In preferred embodiments of the third aspect of the present invention, the process is characterized in that: prior to fixing of the leather or fur-skin, they are processed with a salt of a divalent, trivalent or tetravalent metal; or (ii) the waterproofing is effected with a composition comprising by weight 5 to 80% of a compound of the formula I, preferably in at least partially neutralized form, optionally to 70% of a hydrocarbon, optionally a solubilizer, and lO. water, more preferably: the waterproofing agent contains 0.5 to 30% by weight of a phosphoric acid partial ester of an optionally oxyalkylated alcohol of a chain length C 4 to C 2 0 relative to 100 g of the waterproofing agent that is used; or the waterproofing agent contains 0,5 to 80% by weight of a silicone oil relative to 100 g of the waterprooofing agent that Sis used; or the waterproofing agent contains 1 to 10% by weight of a dimethyl or methylphenyl polysiloxane; or (iii) the waterprooofing agent contains 0.5 to 50% by weight of oleic acid sarcoide, relative to 100 g of the waterproofing agent; or (iv) the waterproofing agent contains at least one of a paraffin and chloroparaffin.

We have found in relation to the first aspect of the present invention that alkylamines at 40 to 130 0 C, preferably to i00°C, can be added to (ieth)acrylic acid.

i Even though the components of the reaction are present as |organic salt after the mixing process, the addition reaction is terminated after one to four hours and has achieved a complete i conversion. No formation of diadduct was observed under these reaction conditions. No solvent is required. With amines having a boiling point below the so-called reaction temperatures, it is preferred that the conversion take place under pressure, in an autoclave.

It is preferred that the conversion of alkylamine with (meth)acrylic acid takes place in equimolar quantities.

r 'vi 9 The following primary amines can be used as alkyl amines of the formula R 1

-NH

2 methyl amine, propyl amine, butyl amine, haxyl amine, nonyl amine, decyl amine, dodecyl amine, tridecyl amine, isotridecyl amine, hexadecyl amine, octadecyl amine, propoxypropyl amine, octyloxypropyl amine, oleyl amine, aleyloxypropyl amine, lauryl amine, cocoa fat amine, stearyJ.

amine, tallow amine, or mixtures of the above amines.

Laury]. amine, cocoa fat amine! tallow amine and oleyl amine are preferred amines.

The further conversion of the N-alkyl-N~(2-carboxyethyl) amine inay- be carried out in substance with. anhydrides, isocyanates, carboxylic acid chlorides or sulfonic acid chlorides if acylation is involved. The acylation agent is ;preferably addeci to S the W-alky-lamino propionic acid in eguimolrqate pt sliqht excess (approximatel~y at temperatures of 50 to 100 0

C.

The reaction with anhydrides or ocaaeistrntd after I to 2 hours and provides the ,'esired N-alkyl-N(2-carboxyethyl) amideo In 100--O form. When using mmoocarboixylic acid anhydrides, acetic acid anhydride, the monocarboxylic acid that occurs in equivalent. quantities may be separated off by distillation or by washing with water.

For example the following anhydrides can be used.- acetic acid anhydridef propionic acid anhydlride, butyric acid anhydride, rnaleic acid anhydride, ;5uccinic acid anhydridd,

I

phthaic acid anhydride.

As an example, the following isocyanates are suitable-.

butyl isocyanate, toluyl isocyanate, isopropyl isocyantiat.

Zt is preferred that the second stage, the acylation reaction, also be~ carried out with eguimolar quantities of the reaction components.

If the acylation reaction is carried out with carboxylic 4 acid chlorides or sulfonic acid chlorides, powdered soda 1)r tertiary amnines -may be used as -th~e acid neutraliser. Th(, salt that is formed during the reaction can be filtered omt or washed out with water.

The following are examples of carboxylic acid chlorides: acetic acid chloride, propionic acid chloride, oleic acid chloride, and suitable sulfonic acid chlorides, methane sulfonic acid chloride, ethane sulfonic acid chloride, and p toluene sulfonic acid chloride.

The further conversion of the resulting alkylaminopropionic acid can also be effected with halogenated carboxylic acids prefePrably chiorocarboxylic acids chl.orof ormic acid, chloroaqetio acid, Qth!QrQpropionic acid, chJQrobutyric acid) ,or (meth) acrylic acid.

Using the new procoss, it is possible to Droduce the NN-disubstituted B-aminopropionic acid der~vatiVt9 in a single~vessel prdcess in two pyrithesis ztages Without the formation of secondary products. The products ave obtained in 100-t forVn without solvents.

For heutralisation, the N4'1-disubstitutid 3-anminoropionic acid derivatives may be rmixed with~ acxueoua 901tutiona dZakl metal hydroxide, alkaline earth metal hydroxide, or aionla, SViscous or pasty aqueous solutions are oJ~tained, depen'ding otx, the concentration and the neutralising agent, In a preferzed embod~Inent, n rttliiation is carr,.ed out ~with organic bases, eopecially priznary, 54oi4ry, and 4<aMines* Examples ot these art the alkyl. drdies ane' amin-n. Especial-ly preferred are the ethanol amii, 3'f 0 isopropanol amines. The nautratising 4ant cain be o quantities equivalent to the quantity of acid, or in smaller quantities than this.

The products produced by the novel process are of the formula

R

3

R

1 N CH COOX

A

.o

R

2 in which 0 o R 1 is a saturated or unsaturated alkyl radical or alkoxyalkyl radical with 1-22 carbon atoms, preferably 12-18 carbon atoms, 1$ oR 2 is an alkyl radical with 1-18 carbon atomns, a saturated or unsaturated carboxyalkyl radical with 3-4 carbou atoms, a carboxyphenyl radical, or a carboxyl radical (-COOH-

R

3 is hydrogen or CH 3 S1 X is hydrogen, alkali metal, earth alkali metal, ammonium, alkylammoniu~, hydroxyalkyla-mnonium, or alkanolammonium, and A is >C O0, >S0 2 -C-NH- or an alkylene radical with 0-3 C atoms.

0 O1 S)

JA

-'I

I J The N,N-disubstituted B-aminopropionic acid derivatives and their salts are used as emulsifiers and wetting agents, or as tensides in cleaning agents; when used as such tensides, they do not harm the skin. A further area of application is in formulations for rendering leather water-resistant. Thus, the present invention relates to both a process for waterproofing leather and fur-skins hy the use of the compounds according to the present invention, either alone or mixed with other }known waterproofing agents.

"O Essentially, the production of waterproof leather takes place accdrding to the following two processes: 1. Filling the capilliary-like, water-absorbing interfibre S spaces with substances to seal them against water.

I. Substances that are insoluble in water, such as fats, paraffins, wax, or specific polymers also display an undesirable accompanying characteristic in that they are impermeable to air and water vapour, which is important with regard to wearer comfort. Compounds that swell when they absorb water and S thereby augment the natural swelling and sealing effect of the leather fibres behave in a more favourable manner. The products that are used in this method belong to the water-in-oil (W/0) class of emulsifiers.

V2. The encasement of the fibre bundles with waterproofing substances.

11 Emulsifiers that can form complexes with multivalent metal ions (cations) -can in many cases also enter the chromiumcollagen complex and then cause water-repellancy. Emulsifiers of this type are chemically bonded to the chromium- or aluminumtanned leather fibres, and reduce their wettability and ability I to absorb water by this water-repellant encasement. The reduction of the ability to spread is seen in the formation of spherical droplets (the beading effect).

The demand for waterproof. leather, which has risen I dramatically during recent yearci, can scarcely be satisfied using knodn waterproofing methods, or can be met only by downgrading other important properties. upper or shaft leather that is intended for daily use is today required to satisfy I requirements that just a few years ago were imposed only on leather uoed for uniform, and In particular military, garments, without sacrificing any wearer comfort, fashionable appearance, I and the li~e.

2 For this reason, processors have resorted, for example, to a two-step waterproofing procoss. Leathers that have been finish dried or dressed can be treated with silicones dissolved in organic solvents. A disadvantage in this respect is the drying temperature* of between 90 0 C and 100 0 C that is required, for this leads to a considerable losses of size. In addition, the high proportion of organic solvents that is released into the environment also causes a problem.

Particularly tndesirable in the sense of rational finishing is the fact that subsequent treatment involves an addit-ional and unwanted stage in the processing cycle.

For this reason, it was also a task of the present invention to describe a process for waterproofing leathers and furskins, which is completed in a single stage, can be completed in an aqueous liquor and in a vat, and with which it is possible to achieve simultaneous fatting arnd massive waterproofing.

Furthermore, it should be possible to produce the secondary Sagents that are used as economically and as simply as possible, and they dhould miake it possible to achieve adequate fatting and Swaterproofing not only in one treatment step, but also by using a single product.

Th."s task has been solved by the use of compounds of the C general formula 1.

4 The products according to the present invention are used 1 for waterproofing either directly in their at least partially 200,0 neutralized form, as a product that contains some water, mostly 4: of a paste-like consistency, or the non-neutralised, mostly paste-like products are dissolved in hydrocarbons and/pr chlorinated hydrocarbons, optionally by means of solubilizers, and then partially neutralised. The bases mentioned above, particularly organic primary, secondary, and tertiary amines and I- -r alkanolamines, as well as aqueous solutions of ammonia and alkali hydroxides, are suitable for this. The emulsifying effect of the neutralized products also allows the formulation of water-containing products.

The products according to the present invention are used in a quantity of 0.1 to 25, preferably 1 to 15%-wt relative to the shaved weight of the leather or of the wet weight of the skin, at I pH values between 4 and 9; subsequently, the pH value is reduced to 3.5 to 5.0. An optionally fixation can be effected by means i 10 of a or 4-valent metal salt.

The product used for waterproofing according to the present Sinvention advantageously contains 5 to 80%-wt, .preferably 10 of the compounds according to the present invention, of the general formula I, optionally 20 to 70%-wt, preferably 30 to 4 15 60%-wt of 'hydrocarbons and/or chlorinated hydrocarbons, optionally with solubilizers such as the higher-boiling point products of the oxosynthesis. The remainder to 100% is water.

I Even though excellent oiling and waterproofing can be i achieved with the compounds according to the present invention alone, the waterproofing agents according to the present invention can be used together with known oiling and/or waterproofing agents such as phosphoric acid partial esters, silicone oils, oleic acid sarcoside and/or (chloro)paraffins.

Insofar as phosphoric acid partial esters are uqed, it l is preferred that partial esters of alcohols with chain lengths of C 4 to C 2 0 preferably C 16 to C 18 be used, these being optionally oxalkylated, in quantities from 0.5 to preferably 1 to 20%-wt (relative to 100 g waterproofing agent).

r I F t16 The co-application of acidic phosphoric acid esters can be such that they are produced together with the compounds according to the present invention, diluted, and then neutralised together with these. The phosphoric acid esters can also be used in already neutralised form. The phosphoric acid esters are used, for example, to reduce the extractable content of fat; this is a particular advantage for garment leathers because of the improved resistance to dry-cleaning that it brings about.

Insofar as silicone oils are used in addition to the compounds according to the present invention, they are used in S quantities of from 0.5 to 80%-wt, preferably 1 to (relative to 100 g of the waterproofing-agent formulation).

Commdrcially avaiable polysiloxanes such as dimethyl- or methylphenylpolysiloxane can be used as silicone oils.

Viscosity ranges from 100 to 500 mPa.s are preferred. The VI silicone oil is applied together with the compound according i to the present invention, optionally together with hydro- S carbons and/or chlorinated hydrocarbons or solubilizers. The use of silicones preferably assists in achieving specific desirable surface effects such as smoothness of grain.

It is also possible to use oleic acid sarcoside in order to i obtain improved softness and a more comfortable feel. In general, any combinatiLon of phosphoric acid partial ester, silicone oil, and oleic acid sarcoside can be used with the compounds according to the present invention in order to achieve a. specific effect.

r/4 /V71 0 r compounds according to the present invention, in quantities from to 50%-wt, preferably from 2 to 20%-wt (relative to 100 g of the formulation used).

The invention will be described by the examples that follow.

Example 1: 534 g (2 mol) oleyl amine is prepa*ed in a flask having a stirrer, a thermometer, and a cooler, and heated to 60 0

C.

Within 30 minutes, 144 g (2 mol) acrylic acid is added by drops, 0 t whereupon the temperature rises to approximately 90 0 C. Stirring is then continued for a further 2.5 hours at 900C. Complete conversioi is ascertained by determining the primary bases. The product of the reaction is cooled to 70 0 C and 196 g (2 mol) maleic acid anhydride is added by portions. In order to complete the reaction, stirring is continued for 2 hours at 70 o 800C. The N-oleyl-N(2-carboxyethyl) maleic acid monoamide is 9 obtained as a light-brown paste.

Us Acid number: 250 g KOH/g Residual content of basic nitrogen: 0.2 mmol/g 122 g (2 mol) monoethanol amine is added at 80C during stirring for neutralisation.

1 .18 Example 2: As in example 1, 269 g (1 mol) stearyl amine is added to 72 g (1 mol) acrylic acid and 98 g (1 mol) maleic acid anhydride is converted with the product of the reaction. The N-stearyl-N(2carboxyethyl) maleic acid monoamide solidifies at room temperature to form a light-brown paste.

Acid number: 251 mg KOH/g Residual content of basic nitrogen: 0.32 mmol/g Neutralisation is effected at 100 0 C with 37.5 g (0.5 mol) isopropanol amine.

S Example 3: a,*r As in example 1, 486 g (2.0 mol) lauryloxypropyl amine is added oV* to 144 g acrylic acid (2.0 mol) and the reaction product is ~converted with 196 g (2 mol) maleic acid anhydride. The Nlauryloxy- propyl-N(2-carboxyethyl) maleic acid monoamide V solidifies at room temperature to form a dark-brown, slightly I cloudy paste.

Acid number: 265 mg KOH/g Residual content of basic nitrogen: 0.3 mmol/g Example 4: As in example 1, 785 g cocoa fat amine (3.72 mol; content of basic nitrogen: 4.74 mtol/g) is added to 268 g acrylic acid (3.73 mol) and the reaction product is converted with 364.8 g naleic acid anhydride. A reddy-brown, highly viscous oil is obtained.

Acid number: 290 mg KOH/g Residual content of basic nitrogen: 0.25 meil/g 1.

I~

'19 554 g (3.72 mol) triethanol amine is added by drops at during stirring for neutralisation.

Example As in example 1, 101 g (1.0 mol) hexyl amine is added to 72 g (1.0 mol) acrylic acid and the reaction product is reacted with 98 g (1 mol) maleic acid anhydride. The N-hexyl-N(2carboxyethyl maleic acid monoamide is obtained as a light-brown oil.

Acid number: 418mg KOH/g Residual content of basic nitrogen: 0.15 mmol/g Example 6: S. 534 g (2 mol) oleyl amine is heated to 60°C in a flask fitted with a stirrer, a thermometer, and a cooler. Within 30 minutes, 172 g (2 tool) methacrylic acid is added by drops, whereupon the t temperature rises to approximately 85 0 C. In order to complete the reaction the mixure is stirred for 3 hours at 100C. A complete conversion is ascertained by determining the primary bases. Cooling the then effected to 70 0 C and 204 g (2 mol) S acetic acid anhydride is added in drops at 70 80 0 C. After a further 2 hours the resulting acetic acid is distilled off in a vacuum of 20 mbar, The N-oleyl-N(2-carboxy-2-methylethyl) acetaminde is obtained as a clear, brown oil.

Acid number: 139 mg KOH/g Residual content of basic nitrogen: 0.1 mmol/g This is neutralised at 80°C with 112.2 g (2 mol) KOH, dissolved in 2492 g water. An aqueous solution with 25% solids is obtained.

r iii

I

I li a a *i 4 9 4 9 sa a ii 4 4! i, 2 a 1 25 a a 4t a «n 7 4 5 Example 7: As in example 1, 267 g (1.0 mol) oleyl amine is added to 72 g mol) acrylic acid. Next, 148 g (1.0 mol) phthalic acid anhydride is added in portions at 90 0 °C and stirred for 3 hours at 100 0 The N-oleyl-N-(2-carboxyethyl) phthalic acid monoamide is a yellowish-brown paste.

Acid number: 225 mg KOH/g Residual content of basic nitrogen: 0.5 mmol/g Example 8! As in example 1, 267 g oleyl amine is added to 72 g acrylic acid. The product so obtained is mixed with 55 g of water-free sodium carbonate and 301 g (1 mol) oleic acid chloride is added by drops dt 100°C in approximately 2 hours. After a further 2 hours the acylation is ended. The common salt that is formed is washed out with water.

Acid number: 94 mg KOH/g Residual content of basic nitrogen: 0.1 mmol/g Example 9: As in example 6, 267 g (1,0 mol) oleyl amine is added to 86 g (1.0 mol) methacrylic acid.

After t..e addition, 101 g (1.0 mol) triethyl amine is added to the reaction mixture and 190.5 g (1.0 mol) p-toluenesulfonic acid chloride is added by portions at 70 90 0 After termination of the exothermic reaction, stirring is carried on for 2 hours at 90 0 °C and then the salt is washed out with water, -I 1 r 0 .,0o 000 f S00 0 ft0 0 mOO 9 a 0 00 906 00

I

lt I 4 I* 0 iv 9*09 t 6 04 i wF" ac^K«jB>^^ The N-oleyl-N(2-carboxy2-met 1 ethyl) p-toluenesulfonic acid amide is obtained as a dark-brown, viscous oil.

Acid number: 99 mg KOH/g Residual content of basic nitrogen: 0 mmol/g IR: C 0 1720 cm 1 C C 1620 cm-1 (aromatic compound)

SO

2 N 1330 cm i and 1170 cm-1 H-NMR 6 7 8 ppm aromatic protons 105 g (1 mol) diethanol amine is added whilst stirring at 90 0

C

for neutralisation.

Example As in example 1, 267 g (1.0 mol) oleyl amine is added to 72 g mol) 'acrylic acid.

After the addition, 53 g (0.5 mol) powdered sodium carbonate is added and 114.5 g (1.0 mol) methane sulfonic acid chloride is added by drops at 110 0 C. Stirring is continued for a further 2 hours at 100 0 C for post-reaction. The resulting salt is washed out with water. The N-oleyl-N(2-carboxethyl)methane sulfonic acid amide is obtained as a dark-brown paste.

Acid number: 129 mg KOH/g Residual content of basic nitrogen: 0 mmol/g IR: C 0 1730 cm 1 S0 2 -N 1320 cm 1 and 1160 cm- 1

L_

sr Example 11: As in example 1, 267 g (1.0 mol) oleyl amine is added to 72 g mol) acrylic acid.

After the addition, 115 g (1.0 mel) N-ethylmorpholine is added, and 133 g (1.0 mol) toluylisocyanate is added by drops at 500C. This is allowed to react for 1 hour; the N-oleyl- N(2-carboxyethyl)-N'-toluyl urea is obtained as a brown oil.

Acid number: 89 mg KOH/g IRI C 0 (Acid) 1720 cm- 1 N-C 0 1660 cm- 1 and 1560 cm-1 0 a C C (aromatic) 1590 cm- 1 and 1610 cm-1 Example 12: As in exaMple 1, 267 g (1.0 mol) oleyl amine is added to 72 g mol) acrylic acid.

After the addition, 115 g (1.0 mol) N-ethylmorpholine I added and 99 g (1.0 mol) n-butylisocyanate is added by drops at 40 0 C. This is allowed to react for 1 hour. N-oleyl=N(2- 00 a carboxethyl)-N'-butyl urea is obtained as a light-brown oils Acid number: 96,4 mg O1I/q aS 45 IR: C 0 (Acid) 1720 cm- N-C 0 1620 cm-'l and 1540 cm-1 Example 13: 204 g Oleylaminopropionic acid (0.6 mol), 70 g chloracetic acid (sodium salt; 0.6 mol), 54 g water, and 108 g isopropanol are mixed and heated to 8000; this results in a clear solution. 106.6 g 45-% caustic soda (1.2 mol) was added 3' odV OS Aq Wz 2- L-aa~ i~ by drops within 45 minutes, whereupon the viscosity of the reaction mixture increases. This is stirred for 4 hours at 82 0 C, then neutralized with concentrated hydrochloric acid and poured into an excess amount of water, whereupon the product precipitates out. The product (N-oleyl-N-carboxmethylaminopropionic acid) is separated off and dried, Acid number: 245 mg KOH/g The addition product used as the starting product is obtained, as i example 1, from the conversion of oleyl amine with acrylic acid in equimolar quantities.

Example 14: 267.5 g oleyl amine (1.0 mol) and 0.2 g HQME (hydroquinone m:onomethyl ether) are mixed, 144 g acrylic acid (2,0 mo01) is 4ddd to this by drops during cooling to a temperature of at most 70 0 C, and this is followed by Warming to 140oQ. From 80 0

C

the reaction proceeds exothermically and the viscosity increases ghqpl.y. After appoximately 10 minutes at 120 0 0 the mixture becomes paste-like. It is then stirred for q hours at 14004 The product (1-oey-N(2-carboxethylaminopropionic acid) has an acid umber of 253 mg KOH/g.

Example a) 13.6 9g water and 22,7 g 45-4 caustic sod& are mixed and warmed to approximately 50 0 C in a stirring vessel. Next, and while stirring, 63.7 g N-oleyl-N-(2-carboxethyl) maleic. acid monoamide as in example 1 is added, and subsequently stirred until homogeneous.

7 I b) The product from a) above was used in the following composition for the production of waterproof leather, and the water-repellancy so achieved was tested: Cattle hides: Type: waterproof Material: Cattle hides, wet blue Shaved substance: 2.0 mm Percentages based on shaved weight Washing: 300% water 35 0

C

0.5% acetic acid 1:5* 15 min 1 parts/vol conc. acetic acid and 5 parts/vol water Drain off bath Washing: 300% water 35 0 C 10 min Drain off bath Neutralisation/ Dyeing/ Retanning Drain off bath Washing: Drain off bath Waterproofing: 150% water 2% Na-formiate undissolved 2% dye undissolved 4% Tanigan QF** undissolved 12% KastanieXN undissolved at 8 rpm overnight 250% water 60 0

C

(x unsweetened chestnut) min rain min min 10 min 10 min 300% water 60OC 100% water 60 0

°C

0.5% ammonia 1:5 2 min 1 part/vol concentrated ammonia and 5 parts/vol water 6.3% of the waterproofing agent according to example 15a 1:5* 60 min I part/vol product and 5 parts/vol water 0.05 formic acid 1:5 15 min pH 3.6 nraif aff bath T P, Hy- I' 2 x Fix DraJ 3 x Draj Hori air Bali Wat, WatE aft Mae Fle Wagshjnq in off bath ation: 300% water 40 0 °C each 10 min 150% water 40 0

°C

3% Btychrom undissolved pH 4.2 4.8 60 min in off bath Washings: 300% water 20 0 °C each 10 Ln off bath se up overnight, sammy, set out, vacuum dry (80 C/2 min), -off, acclimatise, stake, iron (80 C/0.5 min) min products of Bayer, Leverkusen ly penetrometer: (10% upset) r penetration time: hours r absorption in r 7 hours 9.9/10.4 sertest <es 21S924/1920 7 7

N

I

i Water absorption in after water penetration 8.0/7.1 Example 16: The amide described in example 1 is used. 30 g water and 7 g diisopropanol amine are placed in a stirring flask at 0 C before the organic phase, consisting of 14 g of the amide according to the present invention, 3.5 g phosphoric acid ester amine salt.,(produced by conversion from Alfol 16-18, a mixture of fatty alcohols from the Ziegler synthesis, with P 2 0 5 molecular ratio 3:1, diisoporpanol amine for neutralisation) and r io ft g i, 26 45.5 g chloro- paraffin containing 40% chlorine in the chain is introduced during stirring, and mixed in homogeneously.

This formulation is used in the following process to produce military leather: Cattle hi'des: Type: military leather Material: Cattle hides, wet blue Shaved substance: 2,0 mm Percentage based on shaved weight Washing: 300% water 35 0

C

0.5% formic acid 1:5* 15 min 1 parts/vol conc. acetic acid and 5 parts/vol water Drain off bath Neutralisation: 100% water 35 0

C

3% Sodium formiate undissolved 15 min pH 4.4 0.5% Na-bicarbonate 1:20 90 min pH 4.8 .4 ft Au *r u 4

A'.

4 Drain off bath Washing: Drain off bath Retanninq Drain off bath Washing: Drain off bath 300% water 30 0 C 10 min 200% water 30 0

C

1% dye 1:10 20 min 4% Tanigan QF** undissolved 30 min 12% Quebracho undissolved 60 min Automatic run overnight Rest/run 15 min/1 min 200% water 60 0 C 20 min 300% water 60 0 C 10 min 42- Waterproofing: 200% water of the waterproofing agent according to example 16 diluted with water in proportion of 1:5 (vol/vol) 60 min 1% formic acid 1:5* 15 min 1 part/vol concentrated acid and 1 part/vol product and 5 parts/vol water 3% Baychrom**F undissolved 60 min pH: 3.6 3.7 B9 oim f 9 j a 9 9* I l tt 9 9 B 9 9 9 a a *9 26' Drain off bath 3 x Washing,: 300% water 25°C each 10 min Drain off bath Rinsing: Water 20°C 10 min Horse up overnight, sammy, set-out, vaciuum ,ry (80°C/3 min), air-off, acclimatise, stake, iron (80°C/0.5 min) products of Bayer, Leverkusen Bally penetrometer: (10% amplitude) Water penetration time: >420/>420 mins Water absorption in after 7 hours Maesertest Flexes Water absorption in 12/14 29785/25971 after water penetration 10/12 Example 17: 30.5 g water and 5.5 g 45-% caustic soda is prepared in a stirring vessel at approximately S0oC. The organic phase, consisting of 18 g of the amide as in example 1, 40 g of a higher boiling mineral oil, and 6 g dimethylpolysiloxane I I 28 with a viscosity of 350 mPa.s in added while stirring, and then stirred until homogeneous.

b) The formulation as in a) was used in a process as in example 16, and provided the following results: Bally penetrometer: (10% amplitude) Water penetration time: >420/>420 mins Water absorption in after 7 hours 7/8 Maesertest Flexes >48123/>48316 Water absorption in Safter water penetration 9/8 Example 18: The amide as in example 1 is used.

39 g water with 3 g 45-% caustic soda are placed in a stirring vessel at approximately 50 0 C. Then the organic phase, j consisting of 6 g of the amide described in example 1, 6 g oleic acid sarcoside, 40 g of a higher boiling point mineral oil and g dimethylpolysiloxane with a viscosity of 350 mPa.s is slowly introduced during stirring and then homogenized.

The product so obtained is used in the process for waterproofing as in example 16 whereupon the following results were obtained: I Bally penetrometer: (10% amplitude) SWater penetration time: >420/>420 Water absorption in after 7 hours 9/10 Maesertest Flexes Water absorption in 29885/30147 after water penetration 14/11.6 4 60 4 4o 0 4 1 5 008 4 *4 4 U6 *o a*, a Example 19: a) 39 g water and 4 g 45-% caustic soda are placed in a stirring vessel at approximately 50 0 C. Whilst stirring, the organic phase, consisting of 12 g of the amide as in example 4, g higher boiling hydrocarbon, 5 g dimethylpolysiloxane with a viscosity of 100 mPa.s, and 5 g phosphoric acid partial ester (Alfol 12-18 converted with P 2 0 5 mol ratio 3:1) was introduced and stirred until homogeneous.

b) Used in the process as in example 16, the following results were obtained: Bally penetrometer: (10% amplituFw Water penetration time: h Water absorption in after 7 hours Maesertest Flexes Water absorntion in 13.3/- 3 049/16717 after water penetration 12/8 Example The product described in example 13 was used. To this end, 20 g of this substance was placed with 68.4 g of a chloroparaffin with 40% chain chlorine in a stirring vessel and stirred at 100 to 105°C until homogeneous. After cooling to approximately i

I

700C, 11.6 g diisopropanol amine was added to the mixture for neutralisation.

This formulation was used in the following composition to produce waterproof leather, and tested with regard to its effect: Cattle hides: Type: waterproof Material: Cattle hides, wet blue Shaved substance Percentages based on shaved weight Washing: 300% water 350C 0.5% acetic acid 1:5 15 min Drain off bath Neutralisation: 100% water 35 0

C

0 4 44 '446( 4 44 0a0 I 4 00(.

0gt 4% 2Zo 2% Na-formiate undissolved 15 min 0.5% Na-bicarbonate 1:10 90 min bath pH: 5.3 Leather cross-section with bromocresol green: blue Drain off bath Washing: 300% water 300C 10 min Drain off bath Retanning: 1% Chrom leather fast black TU 14 1% 1:20 20 min 4% Tanigan QF** undissolved 30 min 12% Quebracho undissolved tanned at 6 rpm overnight 200% water 600C 20 min Drain off bath Washing: Drain off bath Waterproofing: Fixing: 300% water 600C 10 min 100% water 60 0

C

8% waterproofing agent 1:4 60 min i i

F

L 1 1% formic acid 3% Baychrom F Bath pH: 3.6 3.7 Drain off bath 3 x Washings: 300% water 25 0

C

Drain off bath Horse up overnight, sammy, set out, vacuum dry, (80 2 min), air-off condition, stake, vacuum iron (80 min). No unusual observations were made during the processing stage.

products of Bayer, Leverkusen Bally penetrometer: (10% amplitude) Water penetration time: hours 1:5 15 min 60 min each 10 min 85 0

C,

85

C

wet Water absorption in after 7 hours Maesertest Flexes Water absorption in 13.1/8.2 15407/14320 after water penetration 7.7/5.0

Claims

1. A process for the production of a compound of the formula 13 R N CH2CH COOX (I) A I R 2 wherein R 1 is an alkyl radical, alkenyl radical, alkoxyalkyl radical or alkoxyalkenyl radical with 1-22 carbon atoms, R2 is an alkyl radical with 1-18 carbon atoms, a carboxyalkyl radical or carboxyalkenyl radical with 3-4 carbon atoms, a carboxyphenyl radical, a toluene radical, or a carboxyl radical (-COOH), 4 R 3 is hydrogen or CH 3 Si X is hydrogen, alkali metal, alkaline metal earth, 'ammonium, alkylammonium or 'fydroxyalkylammonium, and A is >C 0, >S0 2 or -C-NH- 4 comprising reacting an alkyl amine of the formula RI-NH 2 with (meth)-acrylic acid by adding the (meth)-acrylic acid in equimolar quantities to the alkylamine gradually thereby to form an N-alkylamino propionic acid, and subsequently reacting such N-alkylamino propionic acid with acid anhydride,, acid 'chloride, or isocyanate containing the -AR 2 radical. \Alo e g~t~.if 33

2. A process according to claim 1, including the further step of neutralizing at least partially.

3. A process according to claim 1 or 2, wherein the reaction of the alkyl amine with the (meth)acrylic acid is effected at a temperature of 40 to 1300C.

4. A process according to any one of claims 1 to 3, wherein the reaction of the alkyl amine with the (meth)acrylic acid is effected at a temperature of 70 to '100 0 C. A process according to any one of claims 1 to 4, wherein the reaction is effected under pressure,

6. A process according to any one of claims 1 to Wherein the N-alkylamino propionic acid that is produced in the first step is reacted with the carboxylic acid anhydride, carboxylic acid chloride, sulfonic acid chloride, or isocyanate S at 50 to 1000C,

7. A process according to any one of claims 1 to 6, Swherein the carboxylic acid anhydride, carboxylic acid chloride, sulfonic acid chloride, or isocyanate, is used in up to 5% molar excess relative to the N-alkylamino propionic acid.

8. A process according to any one of claims 1 to 7, wherein a carboxylic acid chloride or sulfonic acid chloride is used for the second step of the reaction, and an acid binding <A agent is present during the second step. A- 0 A Lapn~ur~ l 34

9. A process according to claim 8, wherein the acid binding agent is selected from the group consisting of sodiuia carbonate and a tertiary amine. A process according to any one of claims 2 to 9, wherein the neutralization is effected with an alkyl or hydroxyalkyl amine.

11. A process according to claim 10, wherein the neutralization is effected with a hydroxyethylamine or hydroxypropyl amine.

12. N,N-disubstituted 8-aminopropionic acids obtained by the process according to any one of claims 1 to 11. 13, An N-alkyl-N(2-carboxyethyl) sulfonamide or urea of the formula R 3 i R 1 N CH2CH COOX (I) A R 2 in which R 1 is an alkyl radical, alkenyl radical, alkoxyalkyl or alkoxyalkenyl radical with 1-22 carbon atoms, R 2 is an alkyl radical with 1-18 carbon atoms, a carboxyalkyl radical or carboxyalkenyl radical with 3-4 carbon atoms, or a ca, soxyphenyl ,1Y^f^ radical, I i Y~LIWPn~r *t i R 3 is hydrogen or CH3, X is hydrogen, alkali metal, alkaline earth metal, ammonium, alkylammonium, or hydroxyalkylammonium, and A is >S0 2 or -C-NH-, II with the proviso that if A is S02, then R 2 cannot be an alkyl radical with 1-18 carbon atoms or a carboxyphenyl radical, and with the further proviso that if A is C=O-NH-, then R 2 cannot be an alkyl radical with 1-18 carbon atoms. 14, A compound according to claim 13 when obtained by the process according to any one of claims 1 to 11 respectively. A process for waterproofing leather or fur-skins comprising either during or after retanning, treating the leather or skins with a waterproofing agent of the formula I I It R I* N CH 2 CI-C COO r r 36 in which R1 is an alkyl radical, alkenyl radical, alkoxyalkyl radical or alkoxyalkenyl radical with 1-22 carbon atoms, R 2 is an alkyl radical with 1-18 carbon atoms, a carboxyalkyl radical or carboxyalkenyl radical with 3-4 carbon atoms, a carboxyphenyl radical, a toluene radical, or a carboxyl radical 3 is hydrogen or CH 3 X is hydrogen, alkali metal, alkaline earth metal, ammonium, alkylammonium, or hydroxyalkylammonium, tic, 0 and 44 Ae is >C 0, >$0 2 or -C-NH-, 04!it I 14t in a quantity from 0,1 to 25 -Wt, relative to the shaved weight of the leather or the wet weight of the fur-skin, at a pH of 4 2'1 to 9, finally adjusting the pH to the range from 3 ,5 to and fIxing the waterproofing agert in the leather or furskin 16, A process according to claim 15, wherein the 4 leather or skins is treated with the waterproofing agent in a quantity from 1 to 15% wt, relative to the shave( weight of the leather or the wet weight of the fur-skin 17, A process according to claim 15 or 16, wherein prior to fixing of the leather or fur-skin they are processed with a salt of a divalent, trivalent or tetravalent metal, 1',.o 0 cf 0 fo( 37 18, A process according to any one of claims 15 to 17, wherein the waterproofing is effected with a composition comprising by weight 5 to 80% of a compound of the formula I and water.

19. A process according to claim 18, wherein the waterproofing is effected with a qomposition comprising 5 to by weight of a compound of the formula I in at least partially neutralized form. A process according to claim 18 or 19, wherein the composition includes 20 to 70% by weight of a hydrocarbon, 21, A process according to any one of cJoaiias 18 to wherein the composition includes a solubilizer,

22. A process according to any one of claims 18 to 21, wherein the composition contains 0.5 to 30% by Weight of a phosphoric acid partial ester of an optionally oxyalkylated alcohol of a chain length C 4 to C 2 0 relative to 100 g of the composition that is used, 23, A process according to any one of claims 18 to 21, wherein the composition contains 0,5 to 80% by weight of a silicone oil relative to 100 g of the composition that is used. 24, A process according to any one of claims 18 to 21, wherein the composition contains I to 10% by weight of a 'dimethyl or methylphenyl polysiloxana, **I1 a#i A process according to any one of claims 18 to 24, wherein the composition contains 0.5 to 50% by weight of oleic acid sarcoside, relative to 100 g of the composition.

26. A process according to any one of claims 18 to 24, wherein the composition contains at least one of a paraffin and chloroparaffin.

27. Waterproofed leather or fur-skins obtained by the process according to any one of claims 15 to 26.

28. Cleaning agents having an emulsifier(s) or wetting agent(s) or surfactant(s) which consists of or comprises at least one compound according to any one of claims 12 to 14.

29. Leather and fur-skins waterproofing formulations having a water-resistant agent(s) which consists of or comprises at least one compound according to any one of claims 12 to 14. DATED this 23rd day of July, A.D, 1990 CHEMISCHE FABRIK STOCKHAUSEN GmbH, By its Patent Attorneys, F. WELLINGTQN CO., S. Wellingtoh)