Process of production of polyaminoacidesters through esterification of polyaminoacids or of transesterification of polyaminoacidesters

0001The invention describes a method for the preparation of Polyaminosäureestern by esterification of the side chain Carboxylic acid and / or carboxylate groups bearing polyamino acids - Hereinafter referred to as acidic polyamino - especially polyaspartic acid with alcohols, homogeneous products occur and the degree of esterification by the described Conditions can be specifically adjusted. Possibly , acidic polyamino are used whose acid groups Already partially esterified and whose alcohol component of the ester groups by the process according to the invention is replaced, hereinafter referred to as interesterification, optionally with simultaneous esterification of free carboxylic acid groups accompanied by an increase in the degree of esterification. Possibly is to accelerate the esterification or transesterification a catalyst with acid, lewis acidic, basic, or lewisbasischen properties used.

0002Polyaspartic acid, which as a biodegradable complexing and co-builders in detergents in the spotlight of interest is entered, can be known by alkaline Hydrolysis of the direct synthesis precursor Polysuccinimide (PSI, anhydropolyaspartic), obtained which, for example, by thermal condensation of aspartic acid are obtained or from ammonia and maleic can.

0003To polyamino with surface-active properties can be for Example pass by the free carboxylic acid groups of acidic transferred polyamino in N-alkylamides or esters will. The reaction described by several groups polysuccinimide with amines leads to polyaspartic acid amides (Kovacs et al, J. Med Chem 1967, 10, 904-7...; Neuse, Angew. Makromol. Chem., 1991, 192, 35-50). Neri et al. cause the ring opening of PSI by ethanolamine and receive Hydroxyethylaspartamide (J. Med. Chem. 1973, 16, 893-897, Macromol. Synth. 1982, 8, 25-29). DE 37 00 128 A and EP 0458079 A describes the subsequent esterification Such hydroxyethyl derivatives with carboxylic acid derivatives. Copolymers polyaspartic esters are, as in DE 195 45 678 A described, by condensation of monoalkyl esters of maleic or the fumaric acid addition of ammonia available. In DE 195 45 678 A is further disclosed that copolymers Polyaspartic esters by reacting polysuccinimide with Alcohols and a subsequent, if appropriate are hydrolysis accessible.

0004In DE 197 24 589 A is exemplified reported that reactions polyaspartic acid with fatty alcohols, in the eventualities Conditions not fully extend and inhomogeneous Products with comparatively unfavorable properties lead.

0005Depending on the degree of esterification and hydrophobicity of the alcohol component distinguished polyaspartic esters in addition to their pronounced Mildness and biodegradability excellent Properties as stabilizers for O / W and W / O emulsions, as foam-stabilizing and foam-enhancing co-surfactant in Detergents, dispersants as different pigments, as complexing of metal cations.

0006It has set itself the task to provide a method Polyaminosäureester, especially polyaspartic esters, by reacting the corresponding alcohols with polyamino establish, with homogeneous products are formed and the Esterification by discontinuing the process conditions can be determined.

0007This object is achieved by a process for the preparation of homogeneous Polyaminosäureestern by reacting polyamino acids, which contain in the side chains carboxylic acid and / or carboxylate groups with hydroxyl-containing Compounds by partial or complete esterification or by transesterification of partially esterified polyamino with alcohols, optionally with increasing the degree of esterification, under reaction conditions of high shear forces, optionally with the use of catalysts, solubilizers and / or reduced pressure.

0008Acidic polyamino are, for example polyaspartic Copolymers of aspartic acid and at least another proteinogenic amino acid glutamic acid in particular, Hydrolysates of polysuccinimide or reaction products of maleic acid derivatives, such as maleic anhydride, Maleic and / or with Maleinsäureamide Ammonia, optionally in the presence of a further amino acid, particularly glutamic acid. Particularly preferred is the use of polyaspartic acid.

0009The polyamino acids may also contain further monomers, preferably however, is that on average at least 30 mol .-%, particularly preferred that at least 60 mol .-% of the recurring Units in the side chain a carboxylic acid and / or Carboxylate exhibit. Other monomer units may, optionally in the form of their derivatives, for example, glutamic acid, Glutamine, asparagine, lysine, alanine, glycine, tyrosine, Tryptophan, serine, cysteine, non proteinogenic amino acids with in each case one or more amino or carboxy functions, such as For example, β-alanine or ω-amino-1-alkanoic acids, or di- Polycarboxylic acids such as maleic acid, fumaric acid, Itaconic acid, succinic acid, malonic acid, adipic acid, hydroxy carboxylic acids, such as tartaric acid, Citric acid, malic acid or its amides, di- or polyhydroxy compounds, Di- or poly-amino compounds, amino alcohols with a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon skeleton, optionally oxo or aza-analogs with oxygen or nitrogen atoms in the chain, or of polyalkylene glycols or ethylene oxide-propylene oxide copolymer include.

0010The respective manufacturing of Ausgangspolyaminosäuren usually have no effect on the process of the invention.

0011In the inventive method, the corresponding Ammonium, N-alkylammonium, N, N-dialkylammonium, N, N, N-trialkylammonium, alkali metal or alkaline earth metal salts of the described Polyamino be used.

0012It can be esterified or transesterified with all common connections be that contain at least one hydroxyl group. These include alcohols, including alkoxylated alcohols, Polyalkylene hydroxy polymers alkoxylated, Amines, carbohydrates, or hydroxycarboxylic acids including Sugar carboxylic acids.

0013In particular, monohydric alcohols in the sense of the present invention have 1 to 24 carbon atoms, for example methanol, Ethanol, 1-propanol, 2-propanol, allyl alcohol, propynol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2-methyl-1-butanol, 1-pentanol, 2-pentanol, 3-methyl-1-butanol, isopentanol (Mixture of isomers), 3-methyl-3-butenol, 1-hexanol, 2-hexanol, 5-hexen-1-ol, 3-hexene-1-ol, phenol, 1-heptanol, benzyl alcohol, 1-octanol, 2-ethyl-1-hexanol, 1-decanol, citronellol, linalool, 1-dodecanol, 1-tetradecanol, Farnesol, 1-hexadecanol, 1-octadecanol, Isostearyl alcohol (mixture of isomers), cis-9-octadecene-1-ol or 1-eicosanol.

0014Examples of alcohols having several hydroxyl groups are 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 2-butyne-1,4-diol, 1,6-hexanediol, trimethylolpropane, Pentaerythritol or sugar and sugar derivatives.

0015Alkoxylated alcohols are reaction products of alcohols with Epoxides, such as ethylene oxide, propylene oxide, butylene oxide or styrene or mixtures thereof.

0016Hydroxy polymers include polyethylene glycol, Polyoxyalkylenes, especially derived with monomer of ethylene oxide, propylene oxide, butylene oxide or styrene oxide, hydroxyalkyl acrylates and methacrylates or polyvinyl alcohol.

0017It can also be used mixtures of the alcohols described will.

0018For the purposes of the present invention are preferably between 0.1 and 5.0 mol of the hydroxyl-containing compound per Mole of free carboxylic acid and / or carboxylate group employed. For an average degree of esterification of 20% in the end product 0.2 to 0.4 mol of hydroxyl-containing compound per mole of free Carboxylic acid and / or carboxylate group is particularly preferred. For an average degree of esterification of 35% in the final product 0.35 to 0.7 mol of hydroxyl-containing compound per mole of free Carboxylic acid and / or carboxylate group is particularly preferred. For an average degree of esterification of 50% in the final product are 0.5 to 1.0 mole hydroxyl-containing compound per mole of free Carboxylic acid and / or carboxylate group is particularly preferred. For an average degree of esterification of 75% in the final product 0.75 to 1.5 mol of hydroxyl-containing compound per mole of free Carboxylic acid and / or carboxylate group is particularly preferred.

0019As acidic catalysts are all protic acids, for example, Sulfuric acid, sodium bisulfate, hydrochloric acid, Phosphoric acid, monosodium dihydrogen phosphate, disodium hydrogen phosphate, Pyrophosphoric acid, phosphorous acid, hypophosphorous Acid, nitric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, sulfonated or ion exchange resins.

0020Catalysts are also suitable Lewis acid or Lewis base or basic compounds, eg., LiOH, NaOH, Na₂O, N / A₂CO₃, NaHCO₃, NaF, NaH, NaNH₂, N / A₂SO₄, N / A₃PO₄, Sodium alcoholates, Sodium dodecyl sulfate, sodium trifluoroacetate, KOH, K₂O, K₂CO₃, KHCO₃, KCl, potassium alkoxides, KH, KNH₂, K₂SO₄, K₃PO₄, Copper acetate, Cu (CO₃)₂, CuN (C₄H₉)₂, Cu (II) alkoxides, CuF₂, Copper gluconate, Cu₃N, CuO, Ca (OH)₂, CaO, Calciumalkoholate, Ca (OOCCH₃)₂, CaCO₃, Ca (PO₄)₂, Mg (OH)₂, MgO, magnesium alcoholates, Mg (OOCCH₃)₂, MgCO₃, Mg (PO₄)₂ Zn (OOCCH₃)₂, Zn₃B₄O₉, ZnCl₂. Zn (OOCCH₂CH₃)₂, ZnF₂, Zinc gluconate, Zn (NO₃)₂, ZnCl₂O₄, Alumina, AlCl₃, AlPO₄, Al (PO₃)₃, Al₂Si₂O₇, AlNiZn, Al₂O (OOCCH₃)₄, AlBr₃. Aluminum alcoholates, Al (OC₃C₇)₂(C₆H₉O₃), Al (OH)₃. Aluminum lactate, Al₂(MoO₄)₃, Al₂(SO₄)₃, Ti, TiO₂. Titannitrilotriacetat, Titaniumalkoholate partially condensed, Titaniumalkoholate, TiAl₃, TiH₂, TiNi, TiO, Ti₂O₃, Ti₂(SO₄)₃. ZrO₂, Zirconiumalkoholate, ZrAl₃, ZrH₂, ZrO, Zr (SO₄)₂, SiO₂. Zeolites, silicates, GeO₂, Sn (OOCCH₃), SnCl₂, Tin alcoholates, PbO, PbO₂, VCl₃, VO, VO (C₅H₇O₂)₂, VOCl₃Tertiary amines such. B. trialkylamines particular triethylamine or Triisopropylamine, 1,4-diazabicyclo [2.2.2] octane, sulfonamides, such as. for example, para-toluenesulfonamide, triethanolamine, pyridine, Alkyl pyridines, piperazine, amine oxides, ammonium salts, such as, for example, Tetramethylammonium, tetrabutylammonium, Tetrabutylammonium, P₂O₅, PCl₃, PCl₅, PBr₃, PBr₅, POCl₃. POBr₃, Sb, Sb₂O₅, SbCl₃, SbF₃, K (SbO) (C₄H₄O₆) Antimonalkoholate, Bi, BiCl₃, Bi (OOCCH₃)₃, Bismutalkoholate, MoCl₃, MoCl₄, MoCl₅. Molybdänalkoholate, MoO₂, MoO₃, W, WO₃* K₂O, WO₃* SiO₂, Wolframalkoholate, WCl₆, WHERE₂Cl₂, Sulfonic acid chlorides such. B. para-toluene sulfonic acid chloride, SCl₂, SO₂Cl₂, SO₃, MnCl₂, MnCO₃. Mn (OOCCH₃)₂, MnPO₄, Manganalkoholate, FeCl₃, FeCl₂, FeBr₃, FeF₃. Eisenalkoholate, Fe (NO₃)₃, Fe₃N, iron acetate, CoCl₂ CoCO₃. Kobaltalkoholate, Ni, Rh, Pd, Pt, PtCl₂, PtCl₄, K₂PtCl₆, CeCl₃. Ce₂(CO₃)₃, Ce (OOCCH₃)₃, (NH₄)₂Ce (NO₃)₆, Ce (OH)₄ and / or Ceralkoholate.

0021It can employ mixtures of the catalysts described will. Optionally, the catalyst remains in the final product.

0022The catalysts are used in amounts of from 0.0001 wt .-% to 20 Wt .-%, preferably 0.001 wt .-% to 10 wt .-%, particularly preferably 0.1 wt .-% to 5 wt .-%, based on the total reaction mixture used.

0023As preferred reactors for carrying out the invention Such methods are used in which the reaction mixture a high shearing action is suspended, which both the mixing of the reaction components promotes, as well as the distillation of the esterification water formed during and / or the most Henden during a transesterification alcohol relieved from the viscous reaction mixture. This can For example, stirred reactors with shear-rich stirrers as about migration or Intermigrührer, cascade various stirred reactors, single- or multi-screw extruder, kneader, kneading reactors, single- or multi-screw high-viscosity, or paddle dryer be. Particularly preferred reactors with multistage Intermigrührern or high-viscosity, for example, the Types ORP, CRP or DTB LIST AG (Arisdorf, Switzerland).

0024Optionally, the inventive method includes directly the production on the poly, optionally wherein the to Reactor used can be used according to the invention or A method in a further, optionally cascaded connected, reactor follows.

0025Solubilizers commercial solvents can be used are such as n-alkanes, cycloalkanes, benzene, Toluene, alcohols, for example isopropanol, tert.-butanol, sec-butanol, isobutanol, cyclopentanol, cyclohexanol, Reaction products of alcohols with propylene oxide and / or Ethylene oxide, ketones, such as acetone, butanone, methyl isopropyl ketone, Methyl isobutyl ketone, esters, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.

0026Other solubilizers may hydrophobically modified polyamino especially partially esterified polyaspartic partially esterified polyaspartic acid-co-glutamic acids or N-alkylamides for example made of polyaspartic according to DE 195 45 678 A, be. The production of these Polyamino, especially the partially esterified polyaspartic or partially esterified polyaspartic acid-co-glutamic has practically no influence on their solubilizing Effect. If appropriate, these solubilizers be prepared according to the inventive method, in this specific case, 1 to 80 wt .-%, preferably 10 to 30 wt .-% of the product mixture remain in the reactor and serve as a solubilizer for a subsequent reaction.

0027Other solubilizers may be surfactant compounds, which are capable of at least partially an emulsion or a dispersion of the polyamino or Polyaminosäurederivates to stabilize in the hydroxyl-containing compound. This may be anionic, amphoteric, zwitterionic, cationic or nonionic surfactants, and mixtures thereof.

0028Anionic surfactants can be for example from the group of Sulfates, sulfonates, carboxylates and mixtures thereof be, for example, alkylbenzenesulfonates, α-olefinsulfonates, α-sulfonated fatty acid esters, fatty acid glycerol ester sulfates, Paraffin, alkyl sulfates, alkyl polyether, Sulfobernsteinsäurealkylester, Fatty acid salts (soaps), fatty acid esters of polylactic acid, N-acylamino acid ester, N-Acyltau-rate, Isethionates, Ethercarboxy-late, monoalkyl, N-acyl amino acid derivatives such as N-acyl aspartates or N-acyl glutamates, N-acyl sarcosinates, polyaspartic acid and others.

0029The anionic groups can in neutralized form present, with cationic counter ions from the group of alkali metals, Alkaline earth metals, ammonium or substituted ammonium. Amphoteric or zwitterionic surfactants are, for example, Alkylbetaines, alkyl amidoalkyl type cocoamidopropyl Sulfobetaines, phosphobetaines, sultaines and amidosultaines, Imidazolinium, amphoglycinates and others.

0030Non-ionic surfactants are, for example, ethoxylated fatty alcohols, ethoxylated alkylphenols, ethoxylated fatty acid esters, ethoxylated mono-, di- or triglycerides or Polyalkylenglykolfettsäureester. Other non-ionic surfactants may be selected from the Group of alkylpolysaccharides, for example alkyl or Alkenyl polyglucosides and their ethoxylation, Sugar esters, for example fatty acid esters of glucose, sucrose, Fructose or of methyl glucoside, sorbitol fatty acid esters and sorbitan (optionally ethoxylated) Polyglycerol, fatty acid, N-Acylaminozuckerderivate, For example, N-Acylglucamine, long chain tertiary Amine oxides or phosphine oxides and dialkyl originate.

0031Cationic surfactants may be selected from the group of quaternary ammonium compounds, quaternized protein hydrolysates, Alkylamidoamine, quaternary ester compounds, quaternary silicone oils, quaternary sugar derivatives and mixtures thereof be, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammoniumchloride, Tricetylmethylammonium chloride, stearyl and dialkylammonium.

0032The in combination with the novel polyaspartic acid derivatives Surfactants used can be any combinations from one or more surfactants of the above category.

0033Mixtures of solubilizers described be used. Optionally, the solubilizing agent remains in Final product, especially those solubilizers with a Boiling point greater than 200 ° C.

0034The solubilizing agent can in amounts from 0 to 95 wt .-%, preferably 0 to 50 wt .-%, particularly preferably 0 to 25 wt .-%, based be used on the total reaction mixture.

0035The temperature should be during the reaction 0 ° C to 250 ° C, preferably 50 ° C to 200 ° C, particularly preferably 90 ° C. to 150 ° C. Optionally, a temperature gradient is used to progress of the reaction.

0036The pressure should during the reaction values ​​between 5 bar and 0.0001 bar, more preferably between 1 bar and 0,001 bar to accomplish.

0037The water formed during the esterification is preferably water removed by distillation. Optionally, the distillation promoted by reduced pressure. The use of solvents, which form an azeotrope with water, facilitating also the progress of the esterification.

0038When partially esterified polyamino transesterification subjected, has the escaping alcohol component preferably a lower boiling point than the incoming hydroxygruppenhal-term Compound and can be prepared by distillation from optionally reduced pressure distillation.

0039Depending on the degree of esterification and hydrophobicity of the alcohol component can produced the method of the invention Polyaminosäureester as surfactants, as stabilizers for O / W and W / O emulsions, as foam stabilizing and foam-boosting Cosurfactants in cleaning agents, as dispersants different pigments or as a complexing agent for Metal cations and / or as a builder / co-builder in detergents be used.

0040The Polyaminosäureester produced by the inventive process have the O / W emulsifiers for cosmetic emulsions are used, for example, lotions with a comparatively low viscosity, or creams and ointments with a high viscosity, for application as skin care products such as day creams, night creams, care creams, Nourishing creams, body lotions, ointments and the like. Other Auxiliaries and additives conventional co, bodying agents, Oil components, superfatting agents, fats, waxes, stabilizers, contain active ingredients, glycerol, dyes and fragrances be.

0041Suitable bodying agents, hydrophilic waxes, for example, C₁₂-C₃₀Fatty alcohols, C₁₆-C₂₂Fatty acids, glycerol mono- and diesters and sorbitan mono- and diesters of saturated fatty acids be used with 12 to 22 carbon atoms.

0042Further coemulsifiers example in question: adducts 2-30 mol ethylene oxide and / or 0 to 5 Mol propylene oxide onto C₁₂-C₃₀Fatty alcohols and wool wax alcohols, preferably linear, saturated C₁₆-C₂₂fatty alcohols; Ethylene Oxide of glycerol and diesters and Sorbitan monoesters and diesters of saturated and unsaturated Fatty acids having 6 to 22 carbon atoms; Adducts of 2 to 30 mol ethylene oxide and / or 0 to 5 mol propylene oxide onto fatty acids with 12 to 22 C-atoms and to alkylphenols with 8 to 15 Carbon atoms in the alkyl group; C₁₂-C₁₈fatty acid partial esters of Addition products of 1 to 30 mol ethylene oxide onto glycerol; Adducts of ethylene oxide with fats and oils, for example, Castor oil or hydrogenated castor oil; partial of saturated or unsaturated C₁₂-C₂₂Fatty acids, and branched or hydroxy, with polyols, for example, Esters of glycerol, ethylene glycol, polyalkylene glycols, pentaerythritol, Polyglycerol, sugar alcohols such as sorbitol and polyglucosides such as cellulose; Polysiloxane-polyalkyl-polyether copolymers and derivatives thereof, and hydrophobically modified Polyaspartic acid.

0043As co-emulsifiers can be anionic, cationic, nonionic, amphoteric and / or zwitterionic surfactants, for example, designated from a compatibility promoting agents his group.

0044It can each Any mixtures of the above bodying and co-emulsifiers are used.

0045Suitable oil components are, for example, esters of linear C come₆-C₂₀fatty acids with linear C₆-C₂₀Fatty alcohols, esters of branched C₆-C₁₃Carboxylic acids with linear C₆-C₂₀fatty alcohols, Esters of linear C₆-C₂₀Fatty acids with branched alcohols, Esters of linear and / or branched C₆-C₂₀carboxylic acids with polyhydric alcohols and / or Guerbet alcohols, triglycerides based on C₆-C₁₀Fatty acids, vegetable and animal oils and fats, branched primary alcohols, substituted cyclohexanes, Guerbet carbonates, dialkyl ethers and / or aliphatic or naphthenic hydrocarbons.

0046As superfatting agents, for example, lanolin and lecithin derivatives and their ethoxylates, polyol esters, monoglycerides and fatty acid. It can silicone compounds such as polydimethylsiloxane, Cyclodimethicone and amino-, fatty acid-, epoxy-, fluorine, and / or modified silicone compounds and waxes, such as for example, beeswax, paraffin waxes or microwaxes be included. The emulsions may be thickeners such as Polyacrylic acid derivatives or cationic polymers such as cationic cellulose or starch derivatives, cationic chitin or chitosan derivatives, cationic silicone polymers, copolymers of diallyl ammonium salts eg with acrylamides, polyethylenimine contain. Further, metal salts of fatty acids, eg Magnesium, aluminum or zinc stearate as stabilizers or Zinc salts of ricinoleic acid may be contained as odor control. It Customary sunscreen active ingredients such as titanium dioxide, p-amino benzoic acid etc., fragrances, dyes, biogenic agents such as plant extracts or vitamin complexes and pharmaceutical Drugs be included. Furthermore, the Emulsions pearlescent agents such as ethylene glycol and usual preservatives such as parabens, sorbic acid, Phenoxyethanol and others.

0047The novel polyaspartic acid derivatives can also W / O emulsions are used, for example, as emulsifiers and / or co-emulsifiers for the production of skin care creams and lotions.

0048The novel polyaspartic acid derivatives with a natural Polyaminosäurerückgrat are mild surfactants which alone or in combination with anionic, cationic, nonionic, zwitterionic and / or amphoteric surfactants can be used. There are solid, liquid or pasty Preparations possible, including soap bars, washing lotions, Shower gels, shampoos.

0049The in combination with the process of the invention after the produced Polyaminosäureestern usable surfactants can anionic, cationic, amphoteric or zwitterionic or be non-ionic surfactants, for example from the already as Solubilizers mentioned compound classes.

0050The surfactant preparations according to the invention can further auxiliaries and Additives such as water and solvent for example, from the group of alcohols and polyols, thickening agent, Opacifiers such as glycol ester derivatives; Moisturizer, emollients such as animal and vegetable oils, carboxylic acid esters, Lanolin, beeswax, silicones; polymeric agents to improve the skin feel, conditioning, care or pharmaceutically active ingredients such as cationic or amphoteric polymers, proteins and protein derivatives, Lanolin derivatives, pantothenic acid, betaine, polydimethylsiloxanes or their derivatives, sunscreen agents and Solubilizers, stabilizers, fragrances, buffers, Preservatives and / or dyes.

0051Surfactant, the method according to the invention after the contain Polyaminosäureester produced, can be advantageously applied in for example, hair shampoos, shower, Schaumbadzubereitungen, Hand, facial and intimate cleansing lotions, Liquid soaps, bar soaps, shaving creams, hand washing pastes, skin-friendly dishwashing detergents, cleaners smooth surfaces and in toothpastes.

0052The Polyaminosäureester produced by the inventive process can be used as dispersants, for example, Paints and coatings are used. There they cause a favorable Development of color strength and improved rub-out properties.

0053The Polyaminosäureester produced by the inventive process be advantageous to the prior art appropriate neutralizing agents, in particular amines neutralized. here is particularly preferred to use of dimethyl ethanolamine or 2-amino-2-methylpropanol. For the production aqueous pigment pastes are 0.1-100 wt .-%, preferably 0.5-50 wt .-%, particularly 2 to 15 wt .-%, based on the weight of the pigments used. The according to the inventive Method Polyaminosäureester prepared can at either prior to dispersing the inventive use with the Pigments are mixed or directly in the dispersion medium (Water, any Glycolzusätze) before or simultaneously with the addition of the pigments and any other Solids are dissolved. The neutralization can occur before or during the preparation of the pigment pastes. Prefers be produced by the inventive process Polyaminosäureester used, the free carboxylic acid groups have already been partially or completely neutralized.

0054The Polyaminosäureester produced by the inventive process can in any mixtures with other, the prior art dispersion additives, for example, from the group of fatty acid alkoxylates, Poly (meth) acrylates, polyesters, polyethers, etc., are used.

0055As pigments, for example, in this connection, inorganic or organic pigments, and carbon blacks can be mentioned. Fillers dispersed, for example in aqueous coating materials can be, for example, are those based on kaolin, Talc, other silicates, chalk, glass fibers, glass beads or Metal powders. may be mentioned as examples of inorganic pigments Titanium dioxide and iron oxides. In consideration to withdrawing organic Examples of pigments are azo pigments, metal complex pigments, Phthalcyaninpigmente, anthraquinonoide pigments polycyclic Pigments, especially those of the thioindigo, Quinacridone, dioxazine, pyrrolopyrrole, naphthalenetetracarboxylic, Perylene, Isoamidolin (on) -, flavanthrone, pyranthrone or isoviolanthrone series.

0056Suitable coating systems into which the pigment pastes of the invention can be incorporated are any aqueous 1K or 2K paints into consideration. Examples include aqueous 1K coating such as those based on alkyd, acrylate, Epoxy, polyvinyl acetate, polyester or polyurethane resins or aqueous 2-component coatings, for example those based on hydroxyl-containing polyacrylate or polyester resins with Melamine resins or optionally blocked polyisocyanate as crosslinking agents. Similarly, are also made of polyepoxy resin called.

0057The Polyaminosäureester produced by the inventive process can be used as complexing agents, for example in detergents, as scale inhibitors, as metal in plastics, as auxiliaries in the leather and textile industries or as effectively enhancing additives to pesticides be used or insecticides. High molecular weight derivatives are also suitable as absorber materials.

Examples:

Comparative Example 1

0058In a 100 ml four neck round bottom flask fitted with a paddle, an internal thermometer and a distillation apparatus, were 11.5 g polyaspartic acid (M_W = 6000 n. GPC, calibration against Polyacrylate) with 9.3 g (0.05 mol, corr. 0.5 equivalents each aspartic acid) n-dodecanol and 1 g conc. sulfuric acid and heated to 150 ° C. This temperature was maintained under stirring and normal pressure for 8 h. After cooling gave an inhomogeneous product (mixture of polyaspartic acid, Fatty alcohol, polyaspartic esters), according ¹³C-NMR spectrum less than 10% of Asparaginsäuregruppen were esterified.

Comparative Example 2

0059In a 100 ml four neck round bottom flask equipped with a propeller, an internal thermometer and a distillation apparatus, were 11.5 g polyaspartic acid (M_W = 6000 n. GPC, calibration against polyacrylate) with 48.4 g (0.2 mol, corr. 2.0 equivalents each aspartic acid) n-hexadecanol, 3 g of phosphoric acid were added and 10 ml of dimethylformamide and heated to 150 ° C. This temperature was, with stirring, and a 100 mbar reduced pressure for 8 hours to maintain. After cooling gave an inhomogeneous product (mixture of polyaspartic acid, Fatty alcohol, polyaspartic esters), according ¹³C-NMR spectrum less than 10% of Asparaginsäuregruppen were esterified.

Comparative Example 3

0060In a 100 ml four neck round bottom flask equipped with a propeller, an internal thermometer and a distillation apparatus, were 5.75 g polyaspartic acid (M_W = 6000 n. GPC, calibration against polyacrylate) with 18.6 g (0.1 mol, corr. 1.0 equivalent each aspartic acid) of n-dodecanol and 1.7 g of methanesulfonic acid and heated to 150 ° C. This temperature was added under stirring and reduced pressure at 100 mbar maintained for 4 hours. After cooling to give an inhomogeneous Product (mixture of polyaspartic acid, fatty alcohol, polyaspartic esters) according to ¹³C-NMR spectrum was less than 10% the Asparaginsäuregruppen esterified.

example 1

0061In a 2 liter flange flask, equipped with a two-stage Intermigrührer, an internal thermometer and a distillation apparatus, were 575 g polyaspartic acid (M_W = 6000 n. GPC, Calibration against polyacrylate) with 807 g (3.3 mol, corr. 0.67 Equivalents per aspartic) n-dodecanol, 60 g of methane and added 140 ml of dimethylformamide and to 140 ° C heated. This temperature was under stirring and a to 100 mbar reduced pressure for 4 hours to maintain. After cooling gave a homogeneous product, according to ¹³C-NMR spectrum were 40% of the Asparaginsäuregruppen esterified.

example 2

0062The demand was met high-viscosity CRP 2.5 batch of company LIST AG with two horizontally arranged, homonyms, heated and self-cleaning agitator shafts and internal Discharge screw, the drive was carried out with a hydraulic power unit. The Brüdenausgang was with a reflux condenser with Water provided. In this apparatus, 1,295 g Polyaspartic acid (M_W = 1800 n. GPC, calibration against polyacrylate) with 415 g (5.6 moles, corr. 0.5 equivalents per aspartic) added n-butanol and 85 g of methane, conn. was the thermal oil in the heating jacket of Hochviskosreaktors heated to 140 ° C. The stirring speed was at 35/44 U / min. After 5 hours, the amount of water took in Water no longer. The reflux condenser was against exchanged a distillation bridge and under pressure reduction to 25 mbar, the residual butanol distilled. After cooling to give a homogeneous product, according to ¹³C-NMR spectrum was 34% of the Asparaginsäuregruppen esterified.

example 3

0063The demand was met high-viscosity CRP 2.5 batch of LIST AG with two horizontally arranged, co-rotating, heated and self-cleaning agitator shafts and internal discharge screw, the drive was carried out with a hydraulic power unit. Of the Brüdenausgang was fitted with a distillation bridge. In this apparatus were 805 g polyaspartic acid (M_W = 1800 n. GPC, calibration against polyacrylate) with 1016 g (4.2 mol, corr. 0.6 equivalents per aspartic) n-hexadecanol, 100 ml Dimethylformamide and 96 g of p-toluenesulfonic acid, conn. was the thermal oil in the heating jacket of Hochviskosreaktors heated to 150 ° C and the pressure reduced to 25 mbar. The Stirring speed was set at 35/44 U / min. After 6.5 h was stopped the reaction. After cooling, there was obtained a homogeneous product, according to ¹³C-NMR spectrum, 42% of Asparaginsäuregruppen esterified.

example 4

0064The demand was met high-viscosity CRP 2.5 batch of LIST AG with two horizontally arranged, co-rotating, heated and self-cleaning agitator shafts and internal discharge screw, the drive was carried out with a hydraulic power unit. Of the Brüdenausgang was fitted with a distillation bridge. In this apparatus 320 g Dodecylpolyaspartat (Degree of esterification: 20%), 1150 g of polyaspartic acid (M_W = 1800 n. GPC, calibration against polyacrylate) with 460 g (2.5 mol, corr. 0.25 equivalents per aspartic acid) of n-dodecanol and 80 g of added methane, conn., the heat transfer oil was in heated heating jacket of Hochviskosreaktors to 140 ° C and Pressure to 25 mbar reduced. The stirring speed was at 35/44 U / min. After 6.5 h, the reaction was terminated. Subsequently, 85 wt .-% of the reaction mixture were decreased the discharge screw, which to a homogeneous Product solidified and loud ¹³C-NMR spectrum of a degree of esterification 21% based on having the Asparaginsäuregruppen. To of in the reactor at elevated temperature (thermal oil: 140 ° C) remaining reaction mixture were added 1,150 g of polyaspartic acid (M_W= 1800 n. GPC, calibration against polyacrylate), 460 g (2.5 mol, corr. 0.25 equivalents per aspartic) n-dodecanol added and 68 g of methanesulfonic acid and the pressure to 25 mbar reduced. After 6 h, the reaction was terminated. This gave a homogeneous product, according to ¹³C-NMR spectrum was 19% of Asparaginsäuregruppen esterified.

example 5

0065The demand was met high-viscosity CRP 2.5 batch of LIST AG with two horizontally arranged, co-rotating, heated and self-cleaning agitator shafts and internal discharge screw, the drive was carried out with a hydraulic power unit. Of the Brüdenausgang was provided with a dropping funnel. In this Apparatus, 823 g (8.4 mole) maleic anhydride, 551.3 g submitted (2.6 mol) of glutamic acid and 280 g of water, the stirring speed was set at 35/44 r / min, conn. was the thermal oil in the heating jacket of Hochviskosreaktors heated to 100 ° C and, 582 g (8.6 mol) of 25% aqueous ammonia solution for 10 min through the dropping funnel. While the addition of ammonia, the temperature of the heat transfer oil raised to 120 ° C. to lower slowly depressurizing 7 mbar was raised to 150 ° C, the temperature of the heat transfer oil. After a total of 7 hours ended the distillation, it was on 120 ° C cooled. Following were 799 g (3.3 mol) of n-hexadecanol and 70 g of methanesulfonic acid to the reaction mixture distilled out given and the thermal oil for 6 h with reduction the pressure to 25 mbar heated to 140 ° C. After cooling gave a homogeneous product, according to ¹³C-NMR spectrum were 27% of Asparaginsäuregruppen esterified.

example 6

0066The demand was met high-viscosity CRP 2.5 batch of LIST AG with two horizontally arranged, co-rotating, heated and self-cleaning agitator shafts and internal discharge screw, the drive was carried out with a hydraulic power unit. Of the Brüdenausgang was fitted with a distillation bridge. In this apparatus, 900 g of Butylpolyaspartat (Degree of esterification: 34%) of Example 2 with 968 g (4.0 mol, corr. 1.75 equivalents per Asparaginsäurebutylestereinheit) n-hexadecanol added and 100 g of titanium tetraisopropoxide, conn. was the thermal oil in the heating jacket of Hochviskosreaktors heated to 140 ° C. The stirring speed was on 35/44 U / min. After 6.5 h, the reaction was terminated. one A homogeneous product, according to ¹³C-NMR spectrum was 37% the Asparaginsäuregruppen with hexadecyl and 8% of Asparaginsäuregruppen esterified with butyl radicals.

0067The examples clearly show that according to the invention with the Process homogeneous products are obtained with methods according to the prior art (Comparative Examples 1-3 or Comparative Examples 1-3 from DE 197 24 589) are not accessible.