DE2310451C2 - 1-chloro-1-phenylmethane-1,1-diphosphonic acid, its sodium, potassium, ammonium and triethanolammonium salts, processes for their preparation and their use as complexing agents for divalent and trivalent metal ions - Google Patents

Description

30th

For many technical purposes it is desirable to have the precipitation to prevent polyvalent metal ions. Connections come from different Structure to use. Known complexing agents are, for example, amino acids or their alkali salts, of which in particular nitrilotriacetic acid and alkylenedlamine tetraacetic acid are used because they in excellent catfish the hardeners of water to and also bind heavy metal ions. However, these substances have the disadvantage that they are used in stoichlometric amounts must be present in order to achieve a complexation. Polyphosphates are also used for such purposes used, which have the advantage also in sub-stoichlometric Amounts to be effective. However, polyphosphates are not under certain conditions hydrolysis stable.

One also already has phosphonic acids such as, for example Hydroxyäthandlphosphonsäure and Amlnoäthandlphosphonsäure used as complexing agents, since these Compounds can also be used in substoichlometric amounts and are stable to hydrolysis.

However, the compounds mentioned have inter alia. the disadvantage that they are not stable to sodium hypochlorite so that, for example, a use in NaOCl -haltlgen It is not very useful for industrial cleaners. Even when in use In steam boiler systems at which temperatures above 150 ° C can occur, a partial Hydrolysis.

It has now been found that 1-chloro-1-phenylmethane-1,1-dlphosphonic acid does not have this disadvantage and, moreover, has a particularly good ability to form complexes or a high level of effectiveness in sub-stoichiometric amounts (threshold effect). Instead of the acid, the corresponding water-soluble salts such as potassium, sodium and ammonium salts or salts with triethanolamine can also be used for the same purposes. It can be prepared by completely or partially neutralizing the acid with inorganic or organic bases such as NaOH, KOH, NH ₄ OH or triethanolamine, and also with alkali metal carbonates. However, some catfish also accrue the salts directly during production.

For the production of 1-chloro-l-phenylmethane-l,! - dlphosphonic acid phosphorous acid is reacted with benzoyl chloride by, for example, the components 1 be heated to 110 to 140 ° C for up to 3 hours. That Molar ratio of phosphorous acid: benzoyl chloride is between 1: 1 to 1: 2 and is preferably 1: 1.5.

Instead of phosphorous acid and benzoyl chloride, it is also possible to start from corresponding amounts of PCI ₃ and benzoic acid. The reaction product is then mixed with water and the benzoic acid formed is expediently separated off. The solution is then adjusted to a pH value above 7 and treated with bromine to oxidize by-products formed. It is advisable to first adjust the solution to a pH of 8 to 9 and, after the oxidation, to increase the alkalinity to pH 12. As a result, the sodium phosphate that occurs can be separated off particularly easily by crystallizing in the cold. Precipitation with alcohol gives the corresponding salt of 1-chloro-1-phenylmethane-1,1-diphosphonic acid, depending on the degree of neutralization that has taken place and the neutralizing agent used.

The free acid can either by acidification or by removing the alkali ions with the help of a Ion exchanger can be obtained.

Provided that the above-mentioned water-soluble Salts If desired, it is therefore not necessary, only to produce the free acid, but the neutralization can already before the oxidation of By-products or subsequent to them.

The above compounds are good complexing agents for polyvalent, in particular 2- and 3-value lengths, metal ions. You can use them specifically for operations of the Find water softening application. It is not necessary to work with stoichlometric amounts, but you can also considerably delay the precipitation of calcium by using sub-stoichiometric amounts.

The Hampshire test is often used in practice to determine the ability to complex calcium. In this test, 1 g of the complexing agent is dissolved in 100 ml of water and the solution is adjusted 10 ml of 2% soda solution are added to a pH of 12. Then under mechanical Stir and keep the alkalinity constant, a calcium salt solution was added dropwise until it remained cloudy. The test value results from the amount of mg calcium carbonate, which are required per gram of test substance until the cloudiness remains. This test value is when using the phosphonic acid according to the invention about three times as high as in the case of the hydroxyethyl phosphonic acid, which is known as an excellent complexing agent.

1-chloro-l-phenylmethane-1,1-dlphosphonic acid or Their water-soluble salts are therefore also used as corrosion and stone-preventing agents for cooling water, in particular ! n combination with additives known per se, ivle, for example, divalent zinc and / or cadmium salts, Orthophosphates, chromates or hydrazine hydrate are well suited.

What is to be regarded as the stoichlometric amount, depending on the compound used, can be

easily determined by a simple experiment. In general, the complexing agents are used in amounts of 1 mole per 2000 moles of metal ions up to six times stoichlometric Amount used.

The diphosphonic acids according to the invention and their water-soluble salts are also suitable for cleaning processes of rigid objects such as metal or glass in particular. In particular, the Use as an additive to bottle washing agents.

The ability to form complexes can also be used to advantage in systems In which copper ions have an undesirable influence. Examples include avoiding decomposition of per compounds or the stabilization of fats and soaps. Furthermore are the compounds mentioned are suitable as an additive to dye baths for textiles to avoid melallions, which are undesirable Form color nuances, bind complexly.

Finally, the ability to complex can also be used to supply plants with so-called trace elements. The good ability of these compounds to form complexes is also shown by the fact that the well-known red coloration does not occur, which is otherwise observed when Rhodanld is added to solutions containing trivalent Elsen. These properties can therefore also be used to advantage in order to prevent the deposition of elsenic compounds, in particular elsenic oxide, when washing bottles. The new compounds can also be used in electroplating baths instead of cyanides.

Finally, the above-mentioned phosphonic acid or its water-soluble salts are also used in industrial farms, which contain active chlorine-containing compounds, such as, in particular, NaOCl or sodium chloride isocyanurate Considered because it is resistant to these compounds. Resistance to relative high temperatures also enables use in steam boiler systems.

The new l-chloro-l-phenylmethane-U-diphosphonic acid is also a valuable starting product for the production of the corresponding esters, for example can be obtained by reaction with trlethyl orthoamelate. The esters are used as flame retardants suitable. Use as an insect floor is also possible.

In US-PS 35 60 608 agents for caries and tartar profllaxis are described. These contain as Active ingredient 0.05 to 5% by weight of a tin salt of a polyphosphonic acid. This makes the subject of the application, in which no tin salts are used, neither described nor suggested.

example 1

2 mol of phosphorous acid were heated ^{to 110 to 140 °} C. with 3 mol of benzoyl chloride for 3 hours. The melt was then taken up in one liter of water and the benzoic acid formed was separated off. The dissolved reaction mixture was adjusted to a pH value of 8 to 9 with sodium hydroxide solution and ^{oxidized at this pH value at 0} ° C. by introducing elemental bromine. After adjusting the solution to a pH of 12, the sodium phosphate formed was separated off in the cold. Ethanol was added to the phosphate-free solution to remove sodium bromide. The sodium salt of 1-chloro-1-phenylmethane-1,1-dlphosphonic acid is obtained in pure form.

If potassium hydroxide solution is used instead of sodium hydroxide solution for neutralization, the corresponding potassium salts are obtained.

To produce the free acid, the sodium salt was treated with an ion exchanger (Lewatit S 100). An oily concentrate is obtained from which the 1-chloro-1-phenylmethane-II-diphosphonic acid crystallizes out after prolonged standing. The yield was 40 _: 4 g.

. Analysis: found: 29.39 calculated: 29.32 % C found: 3.00 calculated: 3.14 %H found: 12.44 calculated: 12.39 % C1 found: 21.65 calculated: 21.64 15 Ο / ο ρ

Melting point: 287/288 ° C.

Molecular weight: determined by potentometric titration 288, calculated 286.5.

Example 2

For the production of the ammonium salt of 1-chloro-I-phenylmeth? .N-l, l-diphosphonic acid a concentrated aqueous solution of the acid - prepared according to example 1 - neutralized with ammonia and concentrated out of solution with alcohol or with excess Ammonia solution precipitates the corresponding salt. If trietnanolamine is used instead of ammonia, see above the corresponding triethanolammonium salt is obtained.

Example 3

Hampshire test

To determine the ability of calcium complexing, 1 g of the complexing agent was added to approx. 100 ml of water solved. After adjusting the solution to pH 12, 10 ml of 2% sodium carbonate solution were added. Subsequently was a calcium salt solution with mechanical stirring and keeping the alkalinity constant until it remains cloudy added dropwise.

For comparison, see the table below the values are also given that correspond to the corresponding hydroxy compound and that which is widely used in practice l-hydroxyethane-l, l-dlphosphonic acid can be obtained.

Complexing agents

mg CaCO ₃
g substance

l-hydroxyethane-U-diphosphonic acid 820

1-hydroxy-1-phenylmethane 990

1,1-diphosphonic acid

1-chloro-l-phenylmethane > 2 500

!, idiphosphonic acid

Example 4
Treshold-Effect In Sodaalkall's solution

When using the complexing agent as a hardness stabilizer In soda-alkaline solution and a calcium hardness of 20 °, d. H. at a temperature of 95 ° C., amounts of 150 mg / l were sufficient to cause a precipitation of sparingly soluble To completely prevent calcium leathers. Even at much lower concentrations were Calcium precipitation largely suppressed.

Example p

Was used for preventing scale deposits forming in a technical Kahl cycle of 5000 l content ^{3-chloro-l-phenyl} methane diphosphonic acid U-m used in Impfmengen from 1 to 'Y mg / m ^J. After a period of 6 to 8 weeks, hardly any stone-forming precipitates could be observed in the system. In order to improve the anti-corrosive effect, small amounts of alkali silicate were added in some cases.

Example 6

The ability to complex iron in a soda-alkaline solution of 1-chloro-1-phenylmethane-1,1-dlphosphonic acid can be seen from the table below. The following test arrangement was used. In each case 10 ml of a 0.01 molar FeCl ₃ solution were mixed with 15 ml of a solution which contained 5 mmol of soda. Increasing amounts of the abovementioned phosphonic acid were added to these solutions.

Table 1

Complexing agents

mmol precipitation

1 -Chlor-1 -phenylmethan- 0.01 opaque 1,1-diphosphonic acid 0.02 no 0.03 no

30th

Example 7

The ability to complex with copper in a soda-alkaline solution of 1-chloro-l-phenylmethane-1,1-diphosphonic acid Can be seen from the table below. The following test regulations were used applied:

In each case 10 ml of a 0.01 molar CuCl ₂ solution were mixed with 15 ml of a solution which contained 5 ml of soda. These solutions were used in increasing amounts of

oDcn called uipnospnonsa
Table 2 ure admitted. precipitation 45 30%
5% Complexing agents mmol opaque
no
no 5% 1-chloro-l-phenylmethane
1,1-diphosphonic acid 0.01
0.015
0.02 20%

50 60% caustic alkali

20% trisodium phosphate, anhydrous 5% sodium silicate (SiO ₂ : Na ₂ O = 3.35) 2.5% non-ionic antifoam 0.75% 1-chloro-l-phenylmethane

1,1-diphosphonic acid 1% aminotri (methylenephosphonic acid)

in the form of the sodium salt 10.75% sodium sulfate

Beer, lemonade and mineral water bottles were cleaned in a standard bottle washer. The application concentration was 1.5% * and the temperature of the cleaning solution was approx. 75 ° C. Even after No build-up of deposits or stones was observed in the dishwashers for a long period of time.

Example 10

For the cleaning of metal parts was in a concentration of 0.5% a cleaning agent of the following composition is used:

44% trisodium monophosphate

50.5% sodium metasilicate

1.5% non-ionic wetting agent

4% 1-chloro-1-phenylmethane-1,1 -diphosphonic acid

Example 11

Beer bottles were cleaned in a commercially available bottle washing machine with two lye zones. In A cleaning solution containing 1% sodium hydroxide solution was used in both caustic zones and the one in one Concentration of 0.2% an active ingredient concentrate of the following Composition:

phosphoric acid

1-chloro-1-phenylmelhan-1,1-diphosphonic acid
l-hydroxyethane-1,1-diphosphonic acid non-ionic wetting agent

(Reaction product of polyglycerine with 7 moles of propylene oxide)

water

rest

Example 8

A product with the following composition was used in a concentration of 1 to 2% as a bottle washing agent, which prevents distortions even after prolonged use in the warm water zone:

78% caustic soda

4.5% sodium silicate (SiO ₂ : Na ₂ O = 3.35) 1.75% antifoam agent

4% 1 -chloro-1-phenylmethane

1,1-diphosphonic acid
Remainder sodium sulfate

Example 9

55

60

65

MU a solid
Composition:

Detergent of the following was added. The cleaning solutions were at a temperature of about 60 ° C and, if necessary, by adding sodium hydroxide solution and active ingredient concentrate added. A stone formation in the warm water zone could not even after prolonged use to be established.

Example 12 A liquid bleach was prepared which

10% NaOCl

4% l-chloro-l-phenylmethane-1,1-diphosphonic acid in the form of the potassium salt, the remainder is water

contained. In practical use rum bleaching of cellulose-containing products such as straw or wooden

The hardness constituents also precipitated out higher temperatures. There was also no oxidation of the complexing agent by the chlorine liquor. Instead of the acid, you can also use the corresponding water-soluble potassium, sodium, or ammonium Use triethanolamine salts.

Example 13

For the manufacture of an industrial cleaning agent became

Parts of sodium dichloroisocyanurate

Parts of 1-chloro-1-phenylmethane-1,1-diphoic acid in the form of the sodium salt

Share anion active wetting agent
Parts of trisodium phosphate
Parts sodium sulfate

mixed. A solid preparation is obtained with a stable one high active chlorine content and a good disinfecting effect when used in aqueous solution.

Example 14

52 g of 1-chloro-1-phenylmethane-1,1-diphosphonic acid were esterified by heating with excess trlethyl orthoformate. The subsequent Fractionation yielded one at 188 ° C / 0.106 ίο mbar boiling pale yellow oily liquid.

Yield: 57.6 g = 79.6% of theory. Th.

Analysis: found: 45.33 calculated: 45.18 % C found: 6.46 calculated: 6.32 %H found: 8.50 calculated: 8.89 % C1 found: 15.43 calculated: 15.53 % P

Claims (3)

Patent claims:
1. Compounds of the formula
PO ₃ X: Po ₃ X ₂ , 10 where X is hydrogen, sodium, potassium, ammonium or triethanolammonium. 2. A process for the preparation of compounds according to claim 1, characterized in that phosphorous acid is reacted with benzoyl chloride in a molar ratio of 1: 1 to 1: 2, it being possible to use a corresponding amount of PCl ₃ and benzoic acid instead of phosphorous acid and benzoyl chloride, and the reaction mixture, optionally after separation of the benzoic acid, is oxidized in an alkaline solution with bromine or chlorine and the 1-chloro-1-phenylmethane-1,1-dlphosphonic acid formed or its salts In catfish known per se In the corresponding salts or the transferred free acid. 3. Use of compounds according to claim 1 as complexing agents for bivalent and trivalent Metal ions.