DE1171401B - Use of aminophosphonic acids or their derivatives as complexing agents for metal ions - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

LIBRARY

OESDEUTSCHEN PATEHT OFFICE

Boarding school Kl .: BOIj

German class: 12 g -1/01

Number:
File number:
Registration date:
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H 44723 IV a / 12 g
January 27, 1962
4th June 1964

It has been found that compounds of the formulas below or their water-soluble salts are particularly suitable as complexing agents for metal ions, in particular polyvalent metal ions.

O R "O HO - P - C - P - OH

RO NH ₂ OR ' O \ O

(D

HO — Ρ

RO

C-R "-C

, NH ₂ NH ₅

- P-OH

OR '

(II)

In these formulas, R and R 'denote hydrogen or aryl or aralkyl radicals or an aliphatic radical Remainder with 1 to 5 carbon atoms. R "means any organic radical. The inorganic Residues can be branched or unbranched and optionally also functional groups, such as Halogen, nitro, amino, alkoxy and carboxyl groups contain.

Compounds according to the formula I are obtained by reacting phosphorus trihalides with organic nitriles. The reaction is carried out at temperatures from 0 to 100 ^° C., about 2 moles of phosphorus trihalide being used per mole of nitrile. After the conversion has ended or possibly already during the reaction, organic acids, in particular glacial acetic acid, or inorganic oxygen-containing acids, in particular phosphorous acid, are added. After this treatment, the free acids are hydrolyzed with water or the mono- or diesters are reacted with corresponding alcohols or phenols, optionally in the presence of acid-binding agents.

The compounds of formula II can be prepared in a similar manner, but with an Instead of the nitriles, organic dinitriles can be used as starting substances. In these implementations about 4 moles of phosphorus trihalide are advantageously used per mole of dinitrile.

The aminophosphonic acids listed above can be used as complexing agents in a wide variety of forms. For example, calcium ions can be bound to a considerable extent with the help of these aminophosphonic acids and this property can be used in water softening. Furthermore, the complex formation can use aminophosphonic acids or
their derivatives as complexing agents
for metal ions

Applicant:

Henkel & Cie. G.m. b. H.,

Düsseldorf-Holthausen, Henkelstr. 67

Named as inventor:
Dr. Bruno Blaser, Düsseldorf-Urdenbach,
Hans Günther Germscheid, Hösel (RMd.),
Dr. Karl-Heinz Worms, Düsseldorf-Holthausen

serve to de-encrust fabrics in which alkaline earth salts have been deposited after washing processes and also to reduce ash build-up in such tissues.

In cleaning processes, such as bottle rinsing in particular, an additive is used to avoid Precipitation of hardness components, i.e. of sparingly soluble salts of calcium and magnesium, also an advantage. In such processes it is not necessary to use stoichiometric To work quantities, but also substoichiometric quantities are capable of precipitating considerably delay. A particular advantage, as has been found, is that even when hardness constituents are precipitated, the precipitates are largely in one form that do not adhere to metal and glass.

The ability to form complexes can also be used to advantage in Systems in which heavy metal ions, such as copper ions, have an undesirable influence to have. The avoidance of the decomposition of per compounds should be mentioned here as an example. Farther are the aminophosphonic acids used as an additive to dye baths from Textiles suitable for complex binding of metal ions that form undesirable color nuances.

Furthermore, the nitrogen-containing phosphonic acids with at least 2 phosphorus atoms in the molecule with advantage also in soap production as a rancidity preventive use.

Finally, the property of complex formation can also be used to produce animal or to supply so-called trace elements to plant life.

409 598/431

The surprisingly strong ability of these compounds to form complexes is also evident from the fact that in certain concentrations the Berliner-Blau reaction, which is otherwise characteristic of trivalent iron ions does not occur. The same applies to the well-known red coloration, which occurs when raw danide is added to solutions of trivalent iron is usually done. Even thioglycolate complexes, such as des Iron, can be decolorized by adding a small amount of aminophosphonic acids. Likewise, the Formation of the blue-colored copper tetramine and nickel complexes in the presence of these Connections suppressed. This property can be used technically for the deposition of To prevent iron compounds, especially iron hydroxide, on fabrics or when washing bottles. Rust stains can also be removed from fabrics.

The compounds detailed above can be in acidic, neutral or alkaline solution Find application. It is often also an advantage in practice instead of the aminophosphonic acids or their partial esters to use the corresponding water-soluble salts. These can generally be easily represented by neutralizing the acids with appropriate basic compounds. as Salts come in particular alkali, ammonium salts or salts of organic bases, such as, for example Mono-, di- and triethanolamine, alkyl- and arylamine, guanidine, urea, etc., into consideration. All compounds can be used individually or in a mixture with one another as complexing agents Find.

example 1

The calcite binding capacity of the above-mentioned compounds can be influenced by influencing the foaming capacity of soap solutions in hard water.

For this purpose, solutions are first prepared from 20 ecm of water, 20 ° d. H. and 2 drops Soap solution according to B ο u t r ο η and B ο u d e t. For this purpose, 5 ecm of a molar Soda solution added.

The sample solutions that can be prepared in this way do not foam when shaken. However, foaming occurs when an aqueous solution of the above-mentioned compounds is added to this. The concentration of this solution is chosen so that, arithmetically, 0.4 g of P ₂ O _{5 is contained} in 100 g of H ₂ O. With the selected initial weight, the number of cubic centimeters of solution used immediately indicates the lime titer. As is well known, this is defined by the amount of P ₂ O ₁ in grams which 1 g of calcium oxide is able to bind. If all of the CaO is bound, there are no more insoluble lime soaps, the solution is clear, and a constant foam is created when shaken vigorously.

link

1 -aminoethane-1,1 -diphosphonic acid-

. monoethyl ester

1-aminooctane-1,1-diphosphonic acid.
1-amino-2-phenylethane-1,1-diphosphonic acid

Example 2

ecm solution = calcium titer

6.3
5.6

5.3

To compare the scale prevention, solutions of pentasodium tripolyphosphate, ethylenediaminetetraacetic acid (ÄDTA) and 1-aminoethane-1,1-diphosphonic acid in Benrath water with a total hardness of 17.15 ° d were used. H. (carbonate hardness: 10.50 ° d. H.) in a concentration of 10 mg / 1 each. 100 ml each of these solutions were adjusted to a pH value of 9.0 and 10.0 (calomel glass electrode) with NaOH and heated to 80 ° C. in a thermostat for 1 hour (including the heating time). After the heating was immediately filtered off from the precipitate and the beakers with about 1% ^he ejected (NH 4) ₂ CO ₃ solution. The precipitate still adhering to the glass wall after this rinsing was dissolved with dilute HCl. In this solution and also in the filtrate, the hardness was determined by titration with ÄDTA. The figures in the following table represent the total precipitation in milligrams of CaO, the numbers in brackets behind it indicate the precipitation adhering to the wall. The data are average values from double or quadruple determinations.

additive

Ph 9

PhIO

No addition

Pentasodium tripolyphosphate

1-aminoethane-1,1-diphosphonic acid

Ethylenediaminetetraacetic acid

6.00 (3.2)
0.90 (0.2)
0.65 (0.05)
4.80 (2.3)

13.50 (6.1) 7.55 (2.25) 4.65 (1.35)

13.20 (3.2)

Example 3

The ability to form complexes with iron in a soda-alkaline solution compared with ethylene diamine tetraacetate (ÄDTA) can be found in the tables below. The following test set-up was used:

In each case 10 ecm of a 0.01 molar FeCl ₃ solution were mixed with 15 ecm of a solution which contained 5 mmol of Na ₂ CO ₃ . Increasing amounts of the complexing agents given in the tables were added to these solutions and the mixture was heated to the boil.

mmol

Precipitation Fe (OH) ₃ =

link

l-aminoethane-ljl-diphosphonic acid. 1-aminopropane-1,1-diphosphonic acid 1-aminobenzyl-1,1-diphosphonic acid .. 1,6-diaminohexane-l, 1,6,6-tetraphosphonic acid

ecm solution = calcium titer

7 7 5.5

5.6

ÄDTA

0.1
0.5
1

traces

1-aminoethane-1,1-diphosphonic acid
0.03

0.04
0.1

no
no

mmol Precipitation Fe (OH) ₃ = + Cloudiness + no + no + 5 mmol Precipitation CuO no
no cloudy ₊ no ₊ For s ρ - \ - 1 - aminopropane-1 , 1 -diphosphonic acid no Cloudiness weak opacity 1-aminobenzyl-1, -diphosphonic acid no green-yellow discoloration no green-yellow discoloration green-yellow discoloration 0.01
0.02 no no no 1,4-diaminobutane-1,1,4,4-tetraphosphonic acid 1-amino-2-phenylethane-1,1-diphosphonic acid no 0.01 + 6,6-tetraphosphonic acid 1-aminoethane-1,1-diphosphonic acid monoethyl ester no no no 0.05 no 1-aminoethane-1,1-diphosphonic acid monoethyl ester no 0.05 0.01 IO 0.02
0.04 + 0.03 4,4-tetraphosphonic acid l-aminopropane (2) -l, l-diphosphonic acid 1-amino-2-phenylethane-1,1-diphosphonic acid 1-aminobenzyl-1, 1 -diphosphonic acid 0.01 0.1 0.02 0.05 0.02 ) iel 5 0.02 + 0.02 -diphosphonic acid 0.03 1,6-diaminohexane-1,1, 0.1 + 0.05 0.03 The discoloration of the iron thioglycolate complex 0.04 weak opacity 0.03 0.03 1,4-diaminobutane-1,1, 0.08 0.04 was checked as follows: 0.05 no 0.05 no 0.05 0.05 1,6-diaminohexane-l, 1,6,6-tetraphosphonic acid no 0.1 0.025 5 ecm of a 0.01 molar FeCl ₃ solution 0.01 1-Aminooctane-1: 1-aminopropene- (2) -1,1-diphosphonic acid 0.04 with 5. 10 and 15 ecm of a 0.03 molar thioelvcol- 0.015 0.008 0.05 0.05 0.02 0.016 0.1 20th 0.04 25th 35 40

Example 4

The complex formation with copper in soda-alkaline solution compared with ethylenediaminetetraacetate (ÄDTA) is shown in the tables below. The experimental setup was the same as in Example 3; Instead of 0.01 molar FeQ ₃ solution, 0.01 molar solution of CuSO _{4 was} used.

mmol Precipitation CuO ÄDTA 0.1
0.2
0.25
0.3 low precipitation
clear 1-aminoethane- 1, -diphosphonic acid 0.02
0.03
0.04 +
cloudy in the cold
no 1-aminopropane-1, 1 -diphosphonic acid 0.01
0.02
0.04 cloudy
no
no

acid solution and 2, 3 and 4 ecm lmolar Soda solution adjusted to ph 10.3. To decolorize the deep red solutions, 0.5, 0.8 and 1.3 ecm a 0.1 molar l-aminoethane-l-diphosphonic acid solution needed. The pn value did not change during the addition.

Example 6

Solutions containing the metal ions listed in the table below became the aminophosphonic acids mentioned in each case are continuously added in smaller amounts in the form of a solution. The point was determined at which the polyvalent metal ions completely through this addition were bound. To determine this point, the dye was chosen as Eriochrome Black T used and worked at a pH of 10.

This determination can be used, for example, for magnesium, calcium and zinc. With bivalent Copper ions were used in place of eriochrome black T murexide (at pH = 8) while in the case of trivalent iron, the determination was carried out in hydrochloric acid solution against rhodanide.

The respective consumption, calculated in grams of compound per gram atom of metal, for these titrations shows the table below.

Metal ions

Consumption g mol / g atom of metal

-Aminoethane-1,1-diphosphonic acid

Mg ² -

Ca ² +

Cu ²⁺

Fe ² +

- aminopropane-1,1-diphosphonic acid

Ca ² +

Cu ²⁺

Fe ³⁺

-Aminobenzyl-1,1-diphosphonic acid

Ca ² +

Zn ² +

Cu ² +

Fe ³ +

-Aminodecane-1,1-diphosphonic acid
Fe ³ +

-Amino-2-phenylethane-1,1 -diphosphonic acid

Ca ² +

Fe ³⁺

1.4 0.7 0.9 1.0

0.75 0.92 1.22

0.7 2.36 0.96 1.48

3.0

2.0 2.0 Sufficient 35% H ₂ O _{2 was} added to this solution that the active oxygen content corresponded to the values given in the table below. In a comparative experiment, aminoethane-1,1-diphosphonic acid was also added in the concentration given below. The following table shows the active oxygen content at the beginning and after a certain period of time.

Addition to
Aminoethane
1,1-diphosphonic
acid
g / l Oxygen content
at the start
% Oxygen content
after 1 month
at 20 ^° C
7o 0.0
5 1.50
1.50 0.19
1.25

Example 7

In a 2% solution of 1-aminoethane-1,1-diphosphonic acid from pH 1.5 and 5 (adjusted with NaOH) were tissues about 2 years old Rust stains cooked for about 10 minutes. On another fabric with fresh rust stains, the Removal after about 3 minutes.

Example 8

A solution of the following composition was prepared:

203 g K ₄ P ₂ O ₇ ,

94 g sodium p-toluenesulfonate, 170 g of tetrapropylene benzene sulfonate, 70%> 12 g KOH,

23 g ethyl alcohol, 95%, 46 g ethoxylated coconut fatty acid monoethanol

amide,
406 g of water.

Claims (3)

Patent claims: 1. Use of compounds of the formulas below O R "O HO —PCP-OH RO NH ₂ OR ' ! I HO —P -
RO / II C —R "—Cl —P —OH I (II) ₂ NH ₂ NH ₂ \ OR ' (R or R '= hydrogen or aryl or aralkyl radicals or an aliphatic radical with 1 to 5 carbon atoms, R "= organic residue) or their water-soluble salts as complexing agents for metal ions. 2. Use of compounds according to claim 1 as complexing agents for bivalent and trivalent Metal ions. 3. Use of compounds according to claim 1 in sub-stoichiometric amounts, based on the metal ions. References considered: British Patent No. 703 181. 409 598/431 5.64 © Bundesdruckerei Berlin