DE1924301A1 - Polyaminopolytricarballyl acids - Google Patents

Description

Patent application D

Polyaniinopolytricarba lly acids

The invention relates to carboxyl and amino group-containing 011-gomers and polymers of the general formula

-C-C-N-

»Ι J

HHR _p

in which R ^ is hydrogen or a methyl group, R _{2 is} radicals of the formula

HC - COOX HC - COOX

hJ -

COOX

are,

in which X is a hydrogen or alkali metal atom or an inorganic or organic ammonium ion and η is a number 2 between 2 and 30.

Derived from polyethylene imine and polypropylene imine gurid bodies Polycarboxylic acids are already known. In DAS 1 060 8 ^ 9, acetic acid residues are substituted on nitrogen Polyäthjrlenimine described as stabilizers for perborate are usable. Furthermore, amber

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Acid radical substituted polyethyleneimines have been described. Polyalkylenimines which are wholly or partly substituted on the nitrogen by tricarballyl acid residues have not been used until now known.

The end groups to be supplemented in the above formula of the compounds according to the invention depend on the polymerization catalysts used in the preparation method to be discussed below. If a polar compound of the general Pormal K * - X is used as the catalyst, the radicals R - N - or -CH ₂ - CH ₂ X are to be expected as end groups.

R ₂

The compounds of the invention are amorphous products that react slightly acidic in aqueous solution and have a pronounced ability to form complexes against alkaline earth and heavy metal cations to have. Compared to other complex binders from the polyaminopolycarboxylic acid type - E.g. ethylenediaminetetraacetic acid and the above-mentioned N-acetic acid derivatives of polyethyleneimine - draw them are characterized by their stability towards active oxygen-containing compounds.

Preferred are those of the compounds according to the invention, which have an average degree of polymerization η between 5 and 25.

The compounds according to the invention can be prepared in such a way that tricarballyl acid residues which can be hydrolyzed on the nitrogen atom are produced substituted ethyleneimine or propyleneimine, optionally polymerized as a mixture with one another, the polymers saponified and removed the saponification solution in a known manner the free acid or wins the desired salts.

Among saponifiable tricarballyl acid residues are residues of tricarballyl acid esters » salts, amides and nitriles as

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stand. The N-substitution of ethyleneimine or prop'ylenimine by means of the residues mentioned can take place by reacting ethyleneimine or propyleneimine in an alkaline medium with aconitic acid in the form of their salts, esters, amides or nitriles.

Preferred starting materials are those formed by tricarballylic acid triester radicals substituted alkylenimines, especially those esterified with lower aliphatic alcohols having 1-4 carbon atoms are, e.g. N-yn-O ^ jjJ-triethoxy-carbonyl-propyl-jaziridine, N- (n- (l, 2,3-trimethoxy-carbonyl-) propyl-) aziridine, N- (n- (l, 2,3-triethoxycarbonyl-) propyl-) C-methyl-aziridine, N- (n- (1,2,15-tributoxycarbonyl) propyl) aziridine.

The polymerization of these compounds or their mixtures with one another can in the usual way in the presence of Lewis acids, e.g. boron trifluoride, neutral sulfuric or sulfonic acid esters, take place at temperatures between 15 and 95 ° C, about the temperature and by varying the amount of the polymerization catalyst, expediently in the range from 0.1 to 10 mol #>, based on the alkylenimine derivative used the degree of polymerization can be controlled within certain limits. Lower temperatures and lower catalyst concentrations favor, for example, the formation of high molecular weight products. However, there are always mixtures of compounds with different degrees of polymerization, their average molecular weight can be increased considerably by separating off the low molecular weight fractions by means of gel chromatography.

The polymeric esters can in a known manner with strong aqueous Alkalis are saponified.

The saponification solution is used to obtain the free acids expediently treated with strongly acidic cation exchangers, e.g. Lewatit S 100.

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The free acids can be neutralized in the usual way with bases such as sodium, potassium, lithium hydroxide, ammonia, mono-, di- and triethanolamine, mono-, di- and triethylamine, Morpholine or N-methylmorpholine into the corresponding Salts are transferred, whereby by applying substoichiometric Corresponding acidic salts can also be produced in amounts of base.

In the preparation of the trialkali salts of the polyaminopolytricarballyl acids it is generally possible to dispense with the isolation of the free acid. In this case, to saponify the polymeric ester an only slightly larger amount of alkali metal hydroxide than required to form the trialkali salt eats and recovers the trialkali salts by evaporation or spray drying the saponification solution.

The polyaminopolytrial arballyl acids according to the invention or their salts can be used in many areas of application due to their complexing properties. They can be used in analytical chemistry and in certain syntheses for masking heavy metal cations They can also be used to avoid the precipitation of hardness builders in cleaning processes, e.g. cleaning glass. They can also be added to dye baths for textiles in order to bind metal cations that can form undesirable color nuances. Finally, they can also be used to treat animal or plant life to supply so-called trace elements, with particular reference to the physiological harmlessness of the compounds according to the invention, and their use as complexing agents in processes in which aktivsa Oxygen-containing compounds are present, for example in bleach baths, since the polyaminopolytricarballyl acids are worthwhile over other complexing agents of the polyaminopolycarboxylic acid type due to their excellent stability towards active oxygen. 009847/1890

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example 1

In each case 301 g (1 mol) of N- (n- (1,2,3-triethoxycarbonyl) propyl) aziridine (boiling point 112-115 ° C / 0.1 mm Hg, η ^ ⁰ = 1.45 32) were 3 g (2 of diethyl sulfate were added under a nitrogen atmosphere and at room temperature. To initiate the polymerization, the reaction mixture was briefly heated to 80 ° C. and then kept for 8-15 hours at 40 ° C. Slightly yellowish, very viscous liquids resulted, the following osmometrically determined molecular weights had:

a) 1708, b) 2107, c) 2434. From this it follows for the degree of polymerization n: a) 5.7, b) 7.0. c) 8.1.

The reaction products of the three approaches were combined. 602 g of the oligomer mixture, corresponding to 2 basic moles of oligomeric esters, were admixed with 84 g of sodium hydroxide in the form of a 10% aqueous solution under a nitrogen atmosphere and heated to 90-95 ° C. After about 30 minutes, most of the polymeric ester had saponified; after 6 hours a clear solution was present, half of which was evaporated to isolate the sodium salt of the oligomeric acid until a precipitate was formed. After drying at 90 ° C., the sodium salt was in the form of a white powder which had the following analytical values: found: 34.24 % C; 3.25 % H; 4.37 % N j 24.69 % Na. calculated: 33 * 94 % C; 2.85 % H; 4.93 % N; 24.36 % Na.

The other part of the saponification solution was mixed with the same volume of acetone and passed through a strongly acidic cation exchanger (Lewatit S 100). The eluate was evaporated and the evaporation residue at 50 - 60 ° C over P ₂ ⁰ C in vacuo. A product was obtained in a yield of 70%, the analytical values of which corresponded satisfactorily with the values which can be calculated for the free oligomeric acid: found? 44.48 # C j 6.06 % H; 6.01 # N. Calculated: $ 44.24 C; 6.10 % H i 6.45 % N.

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A 5 g sample was taken from the remainder of the three batches of the oligomeric esters and dissolved in 90 ml of methanol. 10 ml of water were added to the solution and passed through a 1 m long column filled with 200 ml of swollen dextran (Sephadex LH 20). About 80 % of the eluate contained higher molecular weight fractions, the mean molecular weight of which was determined osmometrically to be 4870.

example 2

In the procedure according to Example 1, J515 β (1 mol) N- (n- (1,2,3-triethoxycarbonyl) propyl) C-methylaziridine (boiling point 122-125 ° C / 0.01 Torr, ⁿ § ° = 1.449 ² O ^{in the} presence of 3 g (2 mol #) of diethyl sulfate polymerized at 40 ° C. (initially 80 ° C.). The reaction time was 9 hours. The osmometrically determined molecular weight of the reaction product was 78IO, corresponding to a degree of polymerization of 24, 8th.

157.5 St, corresponding to 0.5 green moles of the polymeric ester, were admixed with 44 g of sodium hydroxide in the form of a 10% aqueous solution under an Ng atmosphere and saponified as described in Example! The free acid was obtained analogously to Example 1 from the cooled saponification solution. A pale yellowish amorphous product resulted, the analytical data of which showed a satisfactory agreement with the calculated values:

found: 47.2 % C ; 5.1 % H; 6.0 % N. Calculated: 46.7 % C- j 5.63 % Hj 6.07

Example 3

The ability of the polyaminopolytricarballyl acids to form complexes with respect to calcium, magnesium, copper and iron ions was determined as followsί To 10 ml of a 0.01 molar metal salt solution, χ ml of a 0.1 basic molar solution of the sodium salsa according to Example 1, (Ijj-x) ml of water and 5 ml of 0.01 molar soda solution were added, the pH being 10 being established. The number χ was varied between i and 9. The check for precipitation or

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Precipitation took place every hour. The trials were carried out once at room temperature and once at 100 ° C. The results are shown in the table below. The ones listed there Numbers indicate the ratio of basic mole of complexing agent to gram-mole of metal cation at which none Precipitation takes place. It is clear from the figures that each monomer unit 1 metal cation has bound.

Base mol complexing agent

1 1 1 1 1 1 1 1

cation temperature Ca ²⁺ 20 ° C 100 ° C Mg ²⁺ 20 ° C 100 ° C Cu ²⁺ 20 ° C 100 ° C Pe ⁵⁺ 20 ° C 100 ° C Example 4

In 1 1 of distilled water, which had been adjusted to pH 10 by adding NaOH, 0.615 g (4 m-mol) were added at 100 ° C. Na perborate tetrahydrate and 1.12 g (4 m basic mol) of the according to Example 1 given the Na salt of the oligomeric acid prepared. Samples of 100 ml each were taken at defined time intervals, in which the perborate content of the solution was determined iodometrically was determined. For comparison, analogous tests were carried out with the sodium salts of the known complexing agents ethylenediaminetetraacetic acid (EDTA) and nitridotriacetic acid (NTA). The results are summarized in the following overview:

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Complexing agents EDTA NT Tent (min.) 1 94 99 20th 43 79 40 13th 60 60 0 45 90 · - 27 120 - 19th 180 - 6th 240 0

Perborate content (in % of the initial amount)

Poly- (N- (n- (1,2, j5-tricarboxy) propyl) ethyleneimine, Na salt

99 92 92 90 87 83 71 61

Accordingly, in the presence of the complexing agents according to the invention, over 60 % of the originally present active acid carrier is still available after 4 hours, while when using NTA after 3 hours and EDTA 'after 1 hour the active oxygen content is less than 10 % of the original Value decreased 1st.

The starting materials used to produce the oligomeric esters were produced as follows:

a) N-n- (1,2,3-triethoxycarbonyl-) propyl-) azirldine A mixture of 1036 g (4 mol) of aconite curetriethyl ester, 252 g (6 moles) aziridine and 1 g of freshly prepared sodium methoxide kept at room temperature for 16 hours after homogenization by stirring. Excess aziridine was then added at 40 ° C la Yakut »is drawn off and the residue is fractionally distilled. There was a slight advance at 0.1 Torr and 112-115 ° C • In viscous oil over * the gas chromatograph was pure, one

Often

Refractive index nf «1.4532 and its structure could be confirmed by IR and MMt spectra. The yield, based on aconite tureryl ethyl ester, was 85 % of theory.

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b) Nn- (1,2,3-triethoxycarbony1-) propy1-) propyleneimine. In an analogous manner, 36 g (4 mol) of triethyl aoonitate and 342 g (6 mol) of propyleneimine were reacted in the presence of 1 g of sodium methylate and the reaction mixture was worked up. 125 ° C a viscous oil that had a refractive index of 1.4494. The product was pure by gas chromatography. IR and NMR spectrum confirmed the assumed structure. The yield, based on triethyl aconitate, was 90 % of theory.

The advantage that can be achieved with the invention is in particular that complexing agents have become available in which the known favorable properties of the complexing agents of the polyaminopolycarboxylic acid type with a remarkable oxidation stability are connected. This significantly expands the range of application of purely organic complexing agents.

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Claims (1)

Claims "in which X is a hydrogen or alkali metal atom or inorganic or organic ammonium ion and η is a number between 2 and 30. 2. Compounds according to claim 1-2, characterized in that the degree of polymerization η is a number between 5 and 25 * 5. Process for the preparation of the compounds according to claim 1-2, characterized in that ethyleneimine or substituted by residues of tricarballyl acid derivatives on the N atom Propylenimine optionally in a mixture with one another and / or in a mixture polymerized with unsubstituted ethylene imine and / or propylene imine and the polymers are then saponified, 009-347 / 1 ^r H) above -IL- COPY Patent department
D 3725 -U- . Use of the compounds according to claims 1-3 or their Alkali and / or ammonium salts and / or alkylammonium or alkylolammonium salts as complexing agents. H e η k e 1 A- (Dr. Haas) & C i e GmbH i.V. •• 9147 / 1S9Q copy