DE19720771C2 - Process for the preparation of polyaspartic acid amides - Google Patents

Description

Field of the Invention

The invention relates to a process for the preparation of polyaspartic acid amides by aminolysis of polysuccinimide and the use of the substances for the production of surface-active agents.

State of the art

Polyaspartic acid is usually obtained by hydrolysis of polyaspartic acid (polysuccinimide) won and serves z. B. as an easily biodegradable builder in detergents. An overview on this, for example, by Kroner and Bertleff in SÖFW-Journal, 122, 756 (1996); in terms of the manufacturing process is representative of the extensive state of the art on the print ten DE-A1 42 44 031, DE-A1 43 00 020 and EP-A1 0686657.

If the ring of the polysuccinimide is not opened with water, but aminolysis with aminogrup Compound containing pen, polyaspartic acid amides are formed. The state of the art However, processes known in the art describe exclusively aminolysis in the presence of organic solvents, such as dimethylformamide (see EP-A1 0700950, EP-A1 0519119, DE-A1 22 53 190 and US 4,363,797). The use of organic solvents is However, from an economic point of view, it is undesirable because the solvents are very expensive must be separated again. From an application point of view, the materials come for one Numerous applications (e.g. cosmetics, pharmacy) are also out of the question, as they are still minor Amounts of solvent included.

Processes are known from the subsequently published documents DE-A1 196 31 379 and DE-A1 196 31 380 (BASF) for the production of polyaspartic acid amides by aminolysis of polysuccinimide with amines in Ab Presence of organic solvents known; however, the reaction is depressurized at around 60 ° C carried out.  

Accordingly, the object of the present invention was to provide a method for manufacturing Provision of polyaspartic acid amides to be made available that are free of the described after is to share.

Description of the invention

The invention relates to a process for the preparation of polyaspartic acid amides by Aminolysis of polysuccinimide in the absence of organic solvents, which is characterized by records that the reaction under autogenous pressure at temperatures in the range of 120 to 200 ° C.

Surprisingly, it has been found that the aminolysis of polysuccinimide changes in the absence of organic solvents can then be carried out quickly and completely if one under autogenous Pressure works at higher temperatures. The reaction products are free from disruptive Impurities and can therefore be easily used for cosmetic or pharmaceutical Use purposes. In a preferred embodiment of the invention, the aminolysis is carried out in aqueous Solution carried out, the use of surfactants as hydrotropes is particularly advantageous.

Amino compounds

In a first embodiment of the process according to the invention, primary amines and / or secondary amines which follow the formula (I) can be used as amino compounds,

R ¹ -NH-R ² (I)

in the R ¹ for an aliphatic or aromatic, linear or branched, saturated or unsaturated hydrocarbon radical having 1 to 22 carbon atoms and R ² for hydrogen or also an aliphatic or aromatic, linear or branched, saturated or unsaturated carbon residue with 1 to 22 carbon atoms stands. Typical examples of this are methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, di-n-propylamine, i-propylamine, di-i-propylamine, n-butylamine, di-n-butylamine, tert-butylamine, di-tert .-Butylamine and the fatty alkyl or difatty alkyl amines which are derived from the fatty alcohols having 6 to 22, preferably 12 to 18, carbon atoms. Before preferably laurylamine, dilaurylamine, cocoalkylamine, dicocoalkylamine, cetylamine, dicetylamine, stearylamine, distearylamine, isostearylamine, diisostearylamine, oleylamine, dioleylamine, behenylamine and dibehenylamine and their technical mixtures are used. In a further embodiment of the invention, aminoimidazoles of the formula (II) are used as amino compounds

where n stands for numbers from 1 to 6. Typical examples are 1- (3-aminomethyl) imidazole, 1- (3-amino ethyl) imidazole, 1- (3-aminopropyl) imidazole, 1- (3-aminobutyl) imidazole, 1- (3-aminopentyl) imidazole and 1- (3- Aminohexyl) imidazole.

Aminolysis

The aminolysis can be carried out in bulk. For this you put the polysuccinimide and the Amino compound in a pressure reactor, which is 1 to 10, preferably 3 to 5 h at 120 to 200, preferably heated to 140 to 160 ° C; the ring opening takes place under autogenous pressure. Here can the polysuccinimide and the amino compounds in a molar ratio of 1: 1 to 100: 1 preferably 50: 1 to 20: 1 are used. The crude polyaspartic acid amides are preferred wise absorbed in organic solvents and washed and then dried. In a be preferred because gentler embodiment of the method according to the invention takes the amino lysis in the presence of aqueous surfactant solutions at temperatures in the range from 40 to 90, preferably 50 to 70 ° C within 1 to 10 and preferably 3 to 5 h instead. The surfactants do not serve as Solvents, but as hydrotropes that improve mixing with the aqueous phase. As Solubilizers come, for example, from 10 to 30% by weight aqueous solutions of alkyl ether sulfates, Betaines or alkyl glucosides in question. This method also has the advantage that the Lö solutions, if appropriate after hydrolysis of the remaining succinimide rings by adding alkali, can be used without further processing to produce the desired preparations can.

Industrial applicability

The amides obtainable by the process according to the invention are notable for fine-pored, creamy foam and give skin and hair a pleasant soft feel. A Another object of the invention therefore relates to the use of the polyaspartic acid amides the method according to the invention for the production of cosmetic and / or pharmaceutical additives Preparations or for the production of detergents, dishwashing detergents and cleaning agents in which they are used in quantities from 1 to 50, preferably 2 to 25 and in particular 5 to 15% by weight, based on the composition can be hold.  

The polyaspartic acid amides obtainable by the process according to the invention can be combined men with conventional anionic, nonionic, cationic and / or amphoteric or zwitterionic Surfactants are used. Typical examples of anionic surfactants are soaps, alkylbenzenesul fonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sul fonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerin ether sulfates, hydroxy mixed ethers sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, Mo no- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, Fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as Acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. Provided the anionic surfactants contain polyglycol ether chains, these can be a conventional, preferred however, have a narrow homolog distribution. Typical examples of nonionic Surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fat acid amide polyglycol ether, fatty amine polyglycol ether, alkoxylated triglycerides, mixed ethers or mixed formal, alk (en) yl oligoglycosides, fatty acid-N-alkyl glucamides, protein hydrolyzates (especially plant products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and Amine oxides. If the nonionic surfactants contain polyglycol ether chains, these can be a conventional, but preferably have a narrow homolog distribution. Typical case games for cationic surfactants are quaternary ammonium compounds and ester quats, in particular quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterio African surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazoli nium betaines and sulfobetaines. The surfactants mentioned are exclusively known Links. With regard to the structure and manufacture of these substances, see relevant Über visual works, for example J.Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.), "Catalysts, surfactants and mineral oil additives", Thieme Verlag, Stuttgart, 1978, pp. 123-217. Preferably the polyasparagin acid amides used together with alkyl ether sulfates, alkyl oligoglycosides and / or betaines.

Cosmetic and / or pharmaceutical preparations

The cosmetic or pharmaceutical preparations, such as hair shampoos, hair loops ions, foam baths, creams, lotions or ointments, which are made using the method of the invention According to the method synthesized polyaspartic acid amides can also be prepared as further auxiliaries and additives, oil bodies, emulsifiers, superfatting agents, stabilizers, waxes, Consistency enhancers, thickeners, cation polymers, silicone compounds, biogenic agents, anti dandruff, film formers, preservatives, hydrotropes, solubilizers, UV light protection filters, Insect repellents, self-tanners, colors and fragrances included.  

Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear C ₆ -C ₂₂ fatty alcohols, esters of branched C ₆ -C ₁₃ carboxylic acids are, for example, oil bodies with linear C ₆ -C ₂₂ fatty alcohols, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or Trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -C ₂₀ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C ₆ -C ₂₂ - fatty alcohol carbonates, Guerbet carbonates, dialkyl ethers, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenisc hydrocarbons.

Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

• (1) Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear Fatty alcohols with 8 to 22 carbon atoms, on fatty acids with 12 to 22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group;
• (2) C _12/18 fatty acid _monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;
• (3) glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated Fatty acids with 6 to 22 carbon atoms and their ethylene oxide addition products;
• (4) Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxy analogs;
• (5) adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;
• (6) polyol and especially polyglycerol esters such. B. polyglycerol polyricinoleate or polyglyce rinpoly-12-hydroxystearate. Mixtures of compounds of several are also suitable of these substance classes;
• (7) adducts of 2 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;
• (8) Partial esters based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid as well as 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. Methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose);
• (9) trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates;
• (10) wool wax alcohols;
• (11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;  
• (12) Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 11 65 574 and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and Polyols, preferably glycerin as well
• (13) Polyalkylene glycols.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or with castor oil are known, commercially available products. These are mixtures of homologs, the middle of which Degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C _12/18 fatty acid _monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE-PS 20 24 051 as refatting agents for cosmetic preparations.

C _8/18 alkyl mono- and oligoglycosides, their preparation and their use as surface-active substances are, for example, from US 3,839,318, US 3,707,535, US 3,547,828, DE-OS 19 43 689, DE-OS 20 36 472 and DE-A1 30 01 064 and EP-A1 0077167 known. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds that have at least one quaternary in the molecule. Wear ammonium group and at least one carboxylate and one sulfonate group. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylamino propyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2-alkylethyl-3-carboxyl 3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C _8/18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts . Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12/18 acylsarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

Substances such as lanolin and lecithin and poly ethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fat Acid alkanolamides are used, the latter at the same time as foam stabilizers to serve. The main consistency agents are fatty alcohols with 12 to 22 and preferably 16 up to 18 carbon atoms and also partial glycerides. A combination is preferred of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates. Suitable thickeners are, for example Polysaccharides, especially xanthan gum, guar guar, agar agar, alginates and tyloses, carboxy methyl cellulose and hydroxyethyl cellulose, also higher molecular weight polyethylene glycol mono- and di esters of fatty acids, polyacrylates, (e.g. Carbopole® from Goodrich or Synthalene® from Sigma), Polyacrylamides, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as ethoxylated Fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethy lolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides as well Electrolytes such as table salt and ammonium chloride.

Suitable cationic polymers are, for example, cationic cellulose derivatives, such as. B. a qua ternated hydroxyethyl cellulose, available under the name Polymer JR 400® from Amerchol is, quaternized, cationic starch, copolymers of diallylammonium salts and acrylamides Vinyl pyrrolidone / vinyl imidazole polymers such. B. Luviquat® (BASF), condensation products from Poly glycols and amines, quaternized collagen polypeptides such as lauryldimonium hydroxy propyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such. B. amidomethicones, copolymers of adipic acid and dimethyl aminohydroxypropyldiethylenetrimamine (Cartaretine® / Sandoz), copolymers of acrylic acid with Dime thyldiallyl ammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides such as B. described in FR A 22 52 840 and their crosslinked water-soluble polymers, cationic chitin derivatives such as for example quaternized chitosan, optionally microcrystalline, condensation products from dihaloalkylene such. B. dibromobutane with bisdialkylamines such. B. bis-dimethylamino-1,3-propane, cationic guar gum such as B. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers such as B. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 der Miranol.

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones as well as amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or  alkyl modified silicone compounds that are both liquid and resinous at room temperature can be present. Typical examples of fats are glycerides. a. Beeswax, Carnauba wax, candelilla wax, montan wax, paraffin wax or micro waxes if necessary in Combination with hydrophilic waxes, e.g. B. cetylstearyl alcohol or partial glycerides in question. As Pearlescent waxes can in particular be mono- and difatty acid esters of polyalkylene glycols, Partial glycerides or esters of fatty alcohols with polyvalent carboxylic acids or hydroxycarbon acids are used. Metal salts of fatty acids such as. B. magnesium Aluminum and / or zinc stearate can be used. Biogenic active ingredients are, for example Tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, retinol, bisabolol, allantoin, Understand phytantriol, panthenol, AHA acids, plant extracts and vitamin complexes. As an anti Dandruff agents can be used as climbazole, octopirox and zinc pyrethione. Common Film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, poly vinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary Cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds.

UV light protection filters are organic substances that are able to ultra absorb violet rays and absorb the energy in the form of longer-wave radiation, e.g. B. To give off heat again. Typical examples are 4-aminobenzoic acid and its esters and derivatives (e.g. 2-ethylhexyl p-dimethylaminobenzoate or p-dimethylaminobenzoic acid octyl ester), methoxy cinnamic acid and its derivatives (e.g. 2-ethylhexyl 4-methoxycinnamate), benzophenones (e.g. oxybene zon, 2-hydroxy-4-methoxybenzophenone), dibenzoylmethane, salicylate ester, 2-phenylbenzimidazole-5-sul fonic acid, 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 3- (4'-methyl) benzylidene boron nan-2-one, methylbenzylidene camphor and the like. Continue to come for this purpose too finely dispersed metal oxides or salts, such as titanium dioxide, zinc oxide, iron oxide, Aluminum oxide, cerium oxide, zirconium oxide, silicates (talc) and barium sulfate. The particles should be egg NEN average diameter of less than 100 nm, preferably between 5 and 50 nm and ins have particular between 15 and 30 nm. You can have a spherical shape, it can however, such particles are also used that are ellipsoidal or in some other way from the spherical shape have different shape. In addition to the two aforementioned groups, primary Light stabilizers can also be used as secondary light stabilizers of the antioxidant type those that interrupt the photochemical reaction chain that is triggered when UV radiation penetrates the skin. Typical examples are superoxide dismutase, tocopherols (vitamin E) and ascorbic acid (vitamin C).

Hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used to improve the flow behavior. Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. Typical examples are

• - glycerin;
• Alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, Hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons;
• - Technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10, such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;
• Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, Pentaerythritol and dipentaerythritol;
• - Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical, such as wise methyl and butyl glucoside;
• - Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or mannitol;
• - Sugar with 5 to 12 carbon atoms, such as glucose or sucrose;
• - aminosugars, such as glucamine.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, para benzene, pentanediol or sorbic acid. As insect repellents there are N, N-diethyl-m-touluamid, 1,2- Pentanediol or Insect repellent 3535 in question, dihydroxyacetone is suitable as a self-tanner. As Dyes can use substances that are suitable and approved for cosmetic purposes as described, for example, in the publication "Cosmetic Colorants" by Dye Com mission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106 are compiled. These dyes are usually used in concentrations of 0.001 to 0.1 % By weight, based on the mixture as a whole.

The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40% by weight on the middle - amount. The agents can be produced by customary cold or hot processes respectively; the phase inversion temperature method is preferably used.

Detergents, dishwashing detergents and cleaning agents

Typical examples of detergents, dishwashing detergents and cleaning agents, in which those according to the invention Process available polyaspartic acid amides can be used are liquid to pasty Fabric softener, hand dishwashing detergent, automatic dishwashing detergent, rinse aid and Universal, household and sanitary cleaner. The agents can contain other typical ingredients such as for example builders, enzymes, enzyme stabilizers, bleaches, optical brighteners, thickeners agents, foam inhibitors, solubilizers, inorganic salts and fragrances and dyes point.  

Suitable builders are zeolites, phyllosilicates, phosphates and ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids. Among the compounds used as peroxy bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H ₂ O ₂ -producing peracid salts of peracids such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight. The use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent.

For example, hardened castor oil, salts of long-chain can be used as thickeners Fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium and titanium stearates or the Sodium and / or potassium salts of behenic acid, as well as other polymeric compounds become. The latter preferably include polyvinyl pyrrolidone, urethanes and the polymer salts Polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50 to 10% Maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably between 50,000 to 120,000, based on the free acid. In particular, water-soluble polyacrylates are also suitable for example, are cross-linked with about 1% of a polyallyl ether of sucrose and the one relative Molecular mass above 1,000,000 have examples of this are under the name Carbopol® 940 and 941 available polymers. The crosslinked polyacrylates are preferably not over in amounts 1 wt .-% particularly preferably used in amounts of 0.2 to 0.7 wt .-%.

Enzymes come from the class of proteases, lipase, amylases, cellulases or their Mixtures in question. Bacterial strains or fungi such as Bacillus are particularly suitable subtilis, Bacillus lichenformis and Strptomyces griseus enzymatic active ingredients obtained. Proteases of the subtilisin type and in particular proteases derived from Bacillus are preferred lentes are used. Their proportion can be about 0.2 to 2% by weight. The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature To protect decomposition.

In addition to mono- and polyfunctional alcohols and phosphonates, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

When used in the machine washing process, it can be advantageous to use the usual agents Add foam inhibitors. Suitable foam inhibitors include, for example, known ones Organopolysiloxanes, paraffins or waxes.  

Examples example 1

12.1 g (125 mmol) of polysuccinimide was mixed with 1.4 g (7.5 mmol) of n-dodecylamine and placed in an autoclave in a glass insert. The reactor was briefly purged with nitrogen and held at 150 ° C under autogenous pressure for 2 h. Then the reaction mixture cooled, relaxed and mixed with 250 ml of acetone for further work-up, stirred at 40 ° C. for 3 h, filtered again washed and the polyaspartic acid amide then to constant weight dried.

Example 2

12.1 g (125 mmol) polysuccinimide, 11.7 g (94 mmol) 1- (3-aminopropyl) imidazole and 75 ml a 5% by weight aqueous solution of 5 g sodium laureth sulfate (Texapon N, Henkel KGaA, pH = 8) were placed in a stirrer and stirred at 60 ° C for 3 h. The resulting solution of the Polyaspartic acid amides could be used without further processing.

Examples 3 and 4

In Table 1 are recipe examples using the according to the Invention Polyaspartic acid amides produced according to the method are shown. The in Examples 1 and 2 Polyaspartic acid amides prepared were first of all diluted with sodium hydroxide saponified solution and the solutions thus obtained are then used. The quantities are understood as% by weight.

Table 1

Recipe examples (water ad 100% by weight)

Claims (7)

1. A process for the preparation of polyaspartic acid amides by aminolysis of polysuccinimide in the absence of organic solvents, characterized in that the reaction is carried out under autogenous pressure at temperatures in the range from 120 to 200 ° C. 2. The method according to claim 1, characterized in that the aminolysis with amino compound carries out, which are selected from the group of primary amines, secondary amines, and aminoimidazoles. 3. The method according to claim 2, characterized in that amines of the formula (I) are used,
R ¹ -NH-R ² (I)
in which R ^{1 represents} an aliphatic or aromatic, linear or branched, saturated or unsaturated hydrocarbon radical having 1 to 22 carbon atoms and R ^{2 represents} hydrogen or likewise an aliphatic or aromatic, linear or branched, saturated or unsaturated hydrocarbon radical having 1 to 22 carbon atoms. 4. The method according to claim 2, characterized in that one uses aminoimidazoles of the formula (II),
where n stands for numbers from 1 to 6. 5. The method according to at least one of claims 1 to 4, characterized in that the Aminolysis in the presence of aqueous surfactant solutions at temperatures in the range from 40 to 90 ° C carries out. 6. Use of the polyaspartic acid amides by the process according to claims 1 to 5 Manufacture of cosmetic and / or pharmaceutical preparations.   7. Use of the polyaspartic acid amides by the process according to claims 1 to 5 Manufacture of washing, washing-up and cleaning agents.