KR20010087419A - 1-Hydroxy-3-Sulfonoalkane-1, 1-Diphosphonous Acids - Google Patents

Abstract

The present invention relates to 1-hydroxy-3-sulfonopropane-1,1-diphosphonic acid, phosphonate-containing mixtures containing these acids, methods for their preparation, and their water treatment chemicals and metal ion sequestrants. It is about a use.

Description

1-hydroxy-3-sulfonoalkane-1,1-diphosphonic acid {1-Hydroxy-3-Sulfonoalkane-1, 1-Diphosphonous Acids}

The present invention relates to 1-hydroxy-3-sulfonopropane-1,1-diphosphonic acid and phosphonate mixtures containing these acids, methods for their preparation and their use as chemical and metal ion sequestrants for water treatment. It is about.

In industrial water systems, such as cooling water systems or steam generating systems, as well as in alkaline cleaning in the food industry, for example, against unwanted deposition (boiler scale) of almost insoluble calcium salts and, if appropriate, corrosion of iron materials. Water treatment chemicals and metal ion sequestrants are used to protect against.

1-hydroxyalkane-1,1-diphosphonic acid containing the structural element -C (OH)-(PO ₃ H ₂ ) ₂ has long been known as a chemical for water treatment. They are obtained by reacting a carboxylic acid or carboxylic acid derivative with an inorganic compound of trivalent phosphorus under dehydration conditions and then hydrolyzing.

The most well known representative 1-hydroxyalkane-1,1-diphosphonic acid is 1-hydroxyethane-1,1-diphosphonic acid (HEDP) having the formula:

CH ₃ -C (OH) (PO ₃ H ₂ ) ₂

HEDP is initially reacted with excess acetyl derivatives and trivalent phosphorus inorganic compounds under dehydration conditions, for example 2.4 mol of acetic acid, 1 mol of PCl ₃ and 0.6 mol of water, followed by hydrolysis and removal of excess acetic acid ( US-A-4 060 546 Example 2). The most important application of HEDP is the inhibition of boiler scale formation in cooling water [PR Puckorius, Strauss; Power, May 1995, pages 17-28, especially page 18].

One advantage of HEDP is single stage synthesis from inexpensive raw materials. One disadvantage of HEDP is the fact that it forms a calcium salt that is almost insoluble. When the calcium content is high in the cooling water, the HEDP Ca salt precipitates out, thus reducing the effective concentration of the inhibitor in the solution, and instead of the calcium carbonate deposition which should be prevented, deposition of the HEDP Ca salt may occur.

US-A-5 221 487 proposes the use of ω-sulfono-1,1-diphosphonic acid of the formula: as boiler scale and corrosion inhibitor.

Wherein n may have an integer value between 3 and 10, and X may be OH or NH ₂ . Compounds with X = OH are similar to HEDP in that both compounds have a 1-hydroxy-1,1-diphosphonic acid group -C (OH) (PO ₃ H ₂ ) ₂ . The advantage of sulfonated phosphonic acids over HEDP is their significantly higher calcium resistance. This was impressively demonstrated by Example 10 of US-A-5 221 487.

Calcium resistance of scale inhibitors can be readily determined by standardized turbidity testing by increasing the concentration of inhibitor at a fixed calcium concentration and a fixed pH until turbidity induced deposition occurs. The higher the dose of the inhibitor without causing significant deposition, the higher its calcium resistance. High calcium resistance means that using inhibitors in water with high calcium content, very effective inhibitor concentrations can be achieved. This is a very necessary condition for the use of inhibitors in hard water, but not enough. The actual activity of the inhibitor should be further demonstrated in the scale inhibition test.

However, US-A-5 221 487 lacks a scale inhibition test demonstrating the activity of ω-sulfono-1,1-diphosphonic acid as a scale inhibitor when compared to HEDP. Thus, no technical advantages have been demonstrated when compared to HEDP as the most recent prior art. The obvious disadvantage of the sulfonated compounds of this document when compared to HEDP is more precisely their expensive synthesis, ie to prepare 1-hydroxy-ω-sulfonoalkane-1,1-diphosphonic acid, Expensive ω-bromoalkane carboxylic acid is used as raw material. These are first reacted with phosphorus trichloride and water under dehydration conditions to obtain ω-bromo-1-hydroxyalkane-1,1-diphosphonic acid. The reaction mixture was then treated with aqueous sodium sulfite solution and alkali metal hydroxide solution to replace bromine with a sulfonic acid group. The bromide removed remains dissolved in the aqueous solution of the product. It cannot be recovered separately for reasonable consumption.

Formula

An additional 1-hydroxy-ω-sulfonoalkane-1,1-diphosphonic acid with (where n = 1) is referred to as an effective scale inhibitor in US-A-3 940 436 (described above). Literature, compound number 21 in column 8). The shortest possible synthetic route for this compound (see above, column 3, lines 1 to 29) begins with the dehydration of the solid HEDP sodium salt which then forms the vinylidenediphosphonic acid sodium salt which requires complex purification. The sodium vinylidenediphosphonic acid salt is then epoxidized with hydrogen peroxide in the presence of the catalyst sodium tungstate. The resulting epoxyethane-1,1-diphosphonic acid sodium salt should then be reacted with sodium disulphite in an aqueous solution (US-A-3 940 436, not reacting with sulfuric acid as incorrectly described in Example XI).

The object of the present invention

-Can be synthesized in high yield from inexpensive raw materials,

Has a good scale inhibitory action in a very wide range of water hardness, and

-Does not precipitate almost insoluble calcium salts, especially in water with very high calcium concentrations

To provide scale and corrosion inhibitors.

This object is in accordance with the invention of formula (I),

(In the above formula,

R ¹ and R ² independently of one another represent hydrogen or methyl,

M ¹ to M ⁵ independently of one another represent hydrogen ions, alkali metal ions, ammonium ions or alkylated ammonium ions) 1-hydroxy-3-sulfonopropane-1,1-diphosphonic acid and salts thereof, preferably Is a compound of formula (I) wherein R ¹ and R ² represent hydrogen and M ¹ to M ⁵ independently of one another represent a hydrogen ion, an alkali metal ion, an ammonium ion or an alkylated ammonium ion, or R ¹ represents methyl and R ² Is a compound of formula (I) wherein hydrogen represents and M ¹ to M ⁵ independently of one another represent a hydrogen ion, an alkali metal ion, an ammonium ion or an alkylated ammonium ion, or R ¹ represents hydrogen, R ² represents methyl and M By providing a compound of formula (I) in which ¹ to M ⁵ independently represent hydrogen ions, alkali metal ions, ammonium ions or alkylated ammonium ions and the following components, ie

At least one sulfonic acid of formula (II) or a salt thereof

At least one hydroxy acid of formula (III)

Phosphites of formula (IV)

M ¹ M ² HPO ₃

Phosphates of formula (V)

M ¹ M ² M ³ PO ₄

(Of the above formulas,

R ¹ and R ² independently of one another represent hydrogen or methyl,

M ¹ to M ⁵ and M ⁱ independently represent hydrogen ions, alkali metal ions, ammonium ions or alkylated ammonium ions,

Z represents a group of the formula -COOM ¹ or -C (OH) (PO ₃ M ¹ M ² ) ₂ ,

n can be assumed to be an integer value from 1 to 5, and the average value of n for all compounds of types (II) and (III) is between 1 and 2)

It is achieved by providing a phosphonate mixture, characterized in that consisting of. In the mixture, at least ^one compound of the formula (II), ie, a compound of the formula (I), wherein Z = -C (OH) (PO ₃ M ¹ M ² ) ₂ and n = 1 must be present.

In some cases, the mixtures of the present invention also include chlorides of formula (VI) or hypophosphite of formula (VII).

M ¹ Cl

M ¹ H ₂ PO ₂

The preferred quantitative ratio of the individual components in the phosphonate mixture is

At least 30%, particularly preferably at least 60% of the total phosphorus in the mixture is present in the compound of formula (I),

The molar ratio of the compound of formula (II) to the compound of formula (III) is at least 5: 1, particularly preferably at least 10: 1,

A molar ratio of the compounds of formulas (II) and (III) with Z = -C (OH) (PO ₃ M ₂ ) ₂ to the compounds of formulas (II) and (III) with Z = -COOM at least 1: 1 , Particularly preferably at least 2.3: 1,

At most 50%, particularly preferably at most 30%, of the total phosphorus of the mixture is present in the inorganic phosphorus compounds of the formulas (IV) and (V),

A ratio such that up to 15% of the total phosphorus in the mixture is present in the phosphate salt of formula (V).

The proportion of phosphorus in the individual compounds of the mixture is determined by the relative intensity of the signal of each compound in the ³¹ P-NMR spectrum (see Examples 1 and 2). Phosphonates of formula (I) exhibit characteristic triplets with a coupling constant of 14.8 Hz (aqueous solution of free acid at pH 0-1).

Type (II) compound to the type (III) molar ratio is ¹ (compounds of formula (II)) ¹ -CHR -SO ₃ H signal in the H-NMR spectrum for the signal -CHR ¹ -OH (general formula (III a compound of the Determined by the ratio of the strengths of the compounds). For example, when measured for 3- (trimethylsilyl) -tetraduterteropropionate sodium salt in D ₂ O at a pH of 0 to 3, the signal of the compound of formula (II) wherein R ¹ = H is 3.1 to 3.4 Signals of compounds of formula (III) with a chemical shift of ppm and R ¹ = H show chemical shifts of 3.75 to 4.0 ppm.

The molar ratio of compounds of Formulas (II) and (III) with Z = -C (OH) (PO ₃ M ₂ ) ₂ to compounds of Formulas (II) and (III) with Z = -COOM is ¹ H-NMR It is determined by the intensity ratio of the -CHR ² -C (OH) (PO ₃ M ₂ ) ₂ signal to the -CHR ² -COOM signal in the spectrum. For example, when measured for 3- (trimethylsilyl) -tetraduterropropionate sodium salt in D ₂ O at a pH of 0-3, the electron signal is 2.0-2.5 ppm chemical shift when R ² = H The latter signal shows a chemical shift of 2.5 to 3.0 ppm when R ² = H.

The mean value of the coefficient n, ie the average oligomerization degree n _mean , for all compounds of formulas (II) and (III) is also calculated from the ¹ H-NMR spectrum. If both radicals R ¹ and R ² represent hydrogen (raw acrylic acid), the intensities of the above-CH ₂ -SO ₃ H and -CH ₂ -OH signals are added and multiplied by two. The resulting parameter gives the relative signal strength of the external protons. The signal intensity of the internal protons ranges from 1.3 to 2.3 ppm (for pH 6-7, for 3- (trimethylsilyl) tetradeuteropropionate sodium salt in D ₂ O) and from 1.3 to 2.55 ppm (pH 0-3 Is determined from the intensity of very broad signals) for the 3- (trimethylsilyl) tetraduterropropionate sodium salt in D ₂ O). n _mean is calculated from the following equation:

n _mean = 4/3 (internal proton intensity / external proton intensity) + 1

The formula should be appropriately modified if the raw material is methacrylic acid or crotonic acid.

Compounds and mixtures of the present invention can be prepared according to the following reaction steps, wherein steps a), d) and e) are essential and steps b), c), f) and g) are optional:

a) at least 1 mol of sulfur dioxide and at least 1 mol of water, at least 1 mol of monovalent base and unsaturated carboxylic acid or carboxylic acid mixture, wherein

(Wherein R ¹ and R ² independently represent hydrogen or methyl)

Carboxylic acids are used) reaction of 0.9 to 2 mol;

b) optionally, treating the reaction mixture from step a) with a strongly acidic cation exchanger in the form of H ⁺ ;

c) optionally, dehydration of the reaction mixture from step b);

d) reaction under dehydration conditions with or without an amine salt with the reaction mixture from a) or c) and the P (III) raw material, wherein the molar amount of phosphorus used is from 1.6 to 2.4 mol;

e) hydrolysis of the reaction mixture from step d) by addition of a sufficient amount of water or aqueous hydrochloric acid;

f) optionally distillation for removal and recovery of volatile components;

g) recovery of the amine added in step a) or d), if desired, by alkalizing the reaction mixture with an alkali metal hydroxide solution, removing the released amine and reusing the amine in reaction step a) or d).

The unsaturated carboxylic acid used in reaction step a) is, for example, acrylic acid, methacrylic acid or crotonic acid, acrylic acid and crotonic acid are preferred, and acrylic acid is particularly preferred. Mixtures of the above carboxylic acids, such as mixtures of acrylic acid and crotonic acid, may also be used.

The monovalent base used in reaction step a) may be an alkali metal hydroxide, ammonia or an aliphatic primary, secondary or tertiary amine. Preferably, sodium hydroxide or tertiary amines are used, particularly preferably tributylamine.

The type of base used particularly affects the proportion of oligomers in the final product. For example, when sodium hydroxide is used as the base, significantly more oligomers are obtained when tributylamine is used as the base.

The preferred molar amount of added base should not be higher than the molar amount of sulfur dioxide and unsaturated carboxylic acid combined. With the minimum amount of base described above, the preferred base amount can be calculated using the following formula:

Preferred mole number of bases = mole number of SO ₂ + (mole number of factor-unsaturated carboxylic acid)

The factor in the above formula has a value of 0 to 1, particularly preferably a value of 0.3 to 0.9. Any amine salt formed in reaction step a) can advantageously be further used in this amount also in later reaction step d).

The preferred amount of water used is 20 to 30 mol when sodium hydroxide is used as the base. If tertiary amines are used as the base, the preferred amount of water is substantially less. The reason for this difference is that, firstly, the solubility of the salts is different, and secondly, when the dehydrated amine according to reaction step c) is used as the base and the amount of water in step a) is substantially greater than the amount desired in step d) This is due to the advantageous fact that less use can be made. In step a) when tributylamine is used as the base and in the subsequent reaction step d) PCl ₃ is used as the P (III) raw material, in reaction step a), preferably 3 to 5.8 mol, particularly preferably 3.8 to 4.6 mol of water is used. This amount of water already corresponds to the amount required in reaction step d) plus the amount of water consumed by the chemical reaction in reaction step a) (1 mol), and thus dehydration (reaction step c) and ion exchange (reaction step d) ) May be omitted.

The preferred amount of carboxylic acid used is 1 to 2 mol, particularly preferably 1.05 to 1.15 mol, when sodium hydroxide is used as the base. If tertiary amines are used as the base, preferably 0.90 to 0.98 mol of carboxylic acid are used.

The molar amount just mentioned is the total amount throughout reaction step a). The amount of base added and the amount of water can be easily divided when the reaction step a) is carried out step by step; Therefore, first

1) React 1 mol of SO _{2 with at least} 1 mol of water and at least 1 mol of base, and then

2) It has proved advantageous to react with 0.9 to 2 mol of unsaturated carboxylic acid, residual base and residual water.

The splitting into these two partial steps 1) and 2) has the advantage that the pH can be more easily maintained during the reaction with the unsaturated carboxylic acid. The preferred pH range for partial step 2) is 3 to 8, particularly preferably pH 5 to 6.

The method of reaction step a) is particularly simplified when sodium hydroxide is used as the base. Here, instead of the reaction of SO ₂ with sodium hydroxide solution and water, a commercially available solution of sodium bisulfite can be prepared directly in water and reacted with a solution of sodium hydroxide and carboxylic acid in water. When sodium bisulfite solution is introduced first and sodium carboxylate solution is added, the oligomer content in the final product is lower than when sodium carbonate solution is introduced first and then sodium bisulfite solution is added.

The preferred reaction temperature for partial step 1) is 0 to 40 ° C. In the case of partial step 2), 20 to 80 ° C. is preferred when using alkali metal hydroxide as base, and 40 to 100 ° C. when using amine as base.

Reaction step b) is necessary only when the alkali metal hydroxide is used as the base in step a). In the ion-exchange method, at least 50%, preferably at least 70% of all alkali metal ions must be exchanged with H ⁺ ions. When the amine is used as the base, step b) can be omitted.

The ion exchange group used is a resin containing a SO ₃ H group, for example LEWATIT® S 100.

Reaction step c) is necessary when there is more than 4.8 mol of water per mole of SO ₂ used in the aqueous solution from reaction steps a) or b). Reaction step c) is generally necessary after reaction step b) because the eluate from the ion exchanger resin generally contains too much water. When using an amine as the base, step c) can be omitted, provided that up to 5.8 mol of water must be used in step a).

Dehydration is preferably carried out by distillation under reduced pressure of at least 20 mbar at a bottom temperature of 90 ° C. or lower. Membrane processes for concentrating the solution are also suitable.

The P (III) feedstock used in reaction step d) can be either a pure compound of trivalent phosphorus or a mixture of these compounds: phosphorus trichloride (PCl ₃ ), phosphorus tribromide (PBr ₃ ), phosphorus trioxide (P ₄ O _6), blood phosphorus acid _{(H 4 P 2 O 5)} , phosphorous acid (H ₃ PO ₃₎ and mono alkyl phosphite, dialkyl and trialkyl esters (this time, preferably methyl and ethyl as the alkyl group are used ).

P (III) raw materials only provide the desired reaction under dehydration conditions. The dehydration condition is that, in the reaction mixture of step d), the initial molar ratio of phosphorus-bonded oxygen atoms (mol of O- _P -bonded to mol) to all phosphorus atoms (mol of P _{total amount} ) present in the mixture should be less than or equal to 2.4 Means. In order to calculate this initial molar ratio (O _{P-bonded amount} mol) / (mol _total P), all oxygen atoms from the phosphorus source other than oxygen atoms from any added water or water already present in the reaction mixture In addition, divide by the number of P atoms from all added phosphorus raw materials. Oxygen atoms from raw materials other than water and P (III) raw materials are not included in the total amount.

Preference is given to an initial molar ratio of 1 to 2.4 (O _{P-bonded amount} mol) / ( _{total amount} P of mol).

The raw material in question has an initial molar ratio (O _{P-bonded amount} mol) / (mol _total P) as pure material: phosphorus trichloride and phosphorus tribromide (0), phosphorus trioxide (1.5), pyrophosphoric acid (2.5 ), Phosphorous acid and esters thereof (3). According to the above conditions, only phosphorus trioxide can be used as pure material, and all other materials must be used as a mixture with other suitable P (III) raw materials or as a mixture with water in order to achieve the desired molar ratio.

Preferred P (III) raw materials are phosphorus trichloride and phosphoric acid, which are readily available and inexpensive chemicals. When these preferred raw materials are used, an initial molar ratio (mol of O _{P-bonded amount} ) / (mol of _total P) of 1.4 to 1.8 is particularly preferred. In order to achieve an initial molar ratio of 1.5 mol (O _{P-bonded amount} ) / (mol _total P), 1 mol of phosphorus trichloride must be used with 0.5 mol of phosphorous acid or 1.5 mol of water. Phosphorus trichloride, phosphorous acid and water can also be used in ternary combinations. In this case, it is particularly advantageous to use 3/3 mol of PCl _{3 to} 2/3 mol of water and 1/3 mol of H ₃ PO ₃ , since the phosphorous acid is then a particularly low 70% concentration which is a waste product from fatty acid chlorination. This can be used in the form of an aqueous solution.

Reaction step d) can be carried out in the presence of an amine salt, wherein preferably the amine salt used is the amine previously added in reaction step a). In the reaction step a), in addition to the amount of the amine, if the amount of water is also set according to the conditions of the reaction step d), only P (III) raw material needs to be added to the reaction mixture in step d).

If the amine is first added in reaction step d), the molar amount of the acid formed by the hydrolysis of the free acid + PCl ₃ , PBr ₃ or P ₄ O ₆ added in reaction step d) must be greater than the molar amount of free amine That is, the reaction mixture should have an acid excess. For example, when PCl ₃ , water and H ₃ PO ₃ are used as raw materials, this condition can be expressed by the following inequality:

2 (moles of H ₃ PO ₃ ) + 2 (moles of water)-(moles of amine)> 0

The amine salts accelerate the reaction to produce higher yields of phosphonates in less time. In the presence of an amine salt, the reaction in reaction step d) requires about 1 to 3 hours at 75 ° C.

The temperature in reaction step d) may be 40 to 180 ° C. The reaction temperature of 60-130 degreeC is used preferably. When low boiling point PCl ₃ is used as raw material, under some circumstances-depending on the amount of added amine and the amount of water-the reaction temperature of 130 ° C. cannot be achieved immediately, but only after a heating step of about 1 hour. During this time, most of the PCl ₃ reacts to form a nonvolatile secondary product.

The order in which the raw materials are added is arbitrary.

In reaction step e), the reaction mixture from reaction step d) is hydrolyzed. To this end, at least a large amount of water or aqueous hydrochloric acid is added so that all PCl or PBr bonds, or POP bonds used in reaction step d) can be hydrolyzed. Here consider the amount of water already used in reaction step d). In reaction step d), for example, if 1.5 mol of PCl ₃ and 1 mol of water are used in addition to the other raw materials, at least 2 mol of water must be added in reaction step c). The preferred amount of water is 1.1 to 20 times the minimum amount. The hydrolysis is preferably carried out at a temperature of 70 to 120 ° C, particularly preferably 90 to 110 ° C. Hydrolysis can also be performed at elevated pressure. Preferred hydrolysis periods are 1 hour to 24 hours, particularly preferably 12 to 20 hours.

In an optional reaction step f), the volatile components of the reaction mixture, in particular water and hydrogen chloride, are distilled off. To this end, the mixture is preferably heated to a temperature of up to 130 ° C. and the aqueous hydrochloric acid is removed overhead at atmospheric pressure or under reduced pressure.

If reaction step d) is carried out in the presence of an amine salt, the process ends with reaction step g). To this end, the alkali metal hydroxide solution, preferably sodium hydroxide solution, is added to adjust the reaction mixture to a pH greater than 7, preferably pH 10-14. As a result, the amine is liberated. In the case of trimethylamine, triethylamine or tripropylamine it can be removed by distillation. Tributylamine, tripentylamine or trihexylamine can be very easily removed from the phosphonate mixture by phase separation because of their low water solubility. The recovered amine can be reused in reaction step a) or d).

The materials and mixtures of the present invention may have a very broad range of uses, for example as scale inhibitors and also as corrosion inhibitors. Areas of use of such compositions include, for example, water treatment (eg, treatment of cooling water, process water and injection water in secondary oil extraction and water treatment in mining) and industrial and corporate cleaners (eg, Cleaning of containers and devices in the food industry, bottle cleaning, corporate dishwashers and washing machine detergents).

Compositions of this type are preferably 1-hydroxy-3-sulfonopropane-1,1-diphosphonic acid of formula (I) or (II) to (V) at a total phosphonic acid concentration of 1 to 20%. And optionally also contains a phosphonate mixture of the substances of (II) to (VII). The calculation of the concentration of free phosphonic acid is described in Example 1, reaction step g). Obviously, the compositions may also contain phosphonic acids in the form of their alkali metal salts, ammonium salts or alkylammonium salts.

The materials and mixtures of the present invention may be used alone or in admixture with one or more materials that have proven useful for each application. Examples of such additional components are based on zinc salts, molybdates, borates, silicates, azoles (eg tolyltriazole or benzotriazole), other phosphonic acids, acrylic acid, methacrylic acid, maleic acid and Thus mono-, co- and terpolymers containing comonomers having phosphonates, sulfonates and / or hydroxyl side groups, other polyaspartic acids, ligninsulfonates, tannins, phosphates, complexing agents, citric acid, tartaric acid And gluconic acid, surfactants, disinfectants, dispersants, and biocides. It is apparent to one of ordinary skill in the art that instead of acids (eg "phosphonic acids") their salts ("phosphonates") can be used and vice versa. .

The materials and mixtures of the present invention with the addition of polyaspartic acid and / or their salts as additional components have proven particularly advantageous. Preferred embodiments of polyaspartic acid are described in DE 4 439 193 A1, which is incorporated herein by reference.

The invention further relates to a water treatment method which comprises introducing a substance or mixture of the invention into the water to be treated.

The invention further relates to an alkaline cleaning method characterized by the use of the substance or mixture of the invention as an anti-skinning inhibitor / metal ion sequestrant.

The water treatment method will be described below using examples.

For example, when used in cooling systems with fresh water cooling, the materials or mixtures of the present invention are added to the influent water at concentrations between about 0.1 and 10 mg / l of active compound to prevent deposition and coating.

In the cooling circuit, additives for scale protection and / or corrosion protection are added in a rate dependent manner mainly based on the constituent water. The concentration is between about 1 to 50 mg / l of active compound in circulating cooling water, which generally has a significantly higher water hardness than in the case of fresh water cooling. Higher water hardness often occurs-at least occasionally-because of inadequate maintenance in the case of smaller cooling water systems, for example air conditioning systems for hospital or large office blocks. For such systems, additives with high calcium resistance are particularly preferred. The dosage is about 10 to 500 mg / l of active compound in circulating chilled water.

In seawater desalination by distillation in MSF (multi-stage flash) and VP (steam compression) systems, exfoliation of the heat exchanger surface is prevented by the addition of about 1 to 5 mg / l of active ingredient, added to the incoming seawater .

The dosage required for the RO (reverse osmosis) system is generally much lower because of the lower maximum temperature this method requires.

The method of using the materials and mixtures of the invention in alkaline cleaning is described as follows:

The active compound concentrations used for the inhibition of metal ion blockage and sclerosis in alkaline cleaning depend in particular on technical and physical conditions such as pH, residence time, temperature, water hardness.

In the weakly alkaline range (up to about 10 pH) at temperatures below 60 ° C. and relatively short residence times, the active compound concentrations, typically 5 to 80 mg / l, which are significantly lower than 100 mg / l, are mainly sufficient, At higher alkali concentrations and temperatures, sometimes a dose of about 100 mg / l to 1000 mg / l may be necessary.

The materials and mixtures of the present invention have the following advantages over commercially used product HEDP:

-In water with very high calcium concentration, it does not form almost insoluble calcium salts. Calcium resistance is significantly higher, which is evidenced by the low turbidity values in Table 1 of Example 3;

In water with a total hardness of 300 to 600 ppm CaCO ₃ , it is a more effective scale inhibitor because it prevents the formation of an adhesive coating (= scale) in these waters supersaturated with calcium carbonate even at lower doses than HEDP. (See symbols ★ for scale in Tables 2 and 3). In addition, among these waters, the proportion of calcium ions (= residual hardness RH [%]) that can be maintained in solution by the scale inhibitor is significantly higher than when HEDP was used (see Tables 2 and 3). Even very hard water with an overall hardness of 1200 ppm CaCO ₃ is stabilized by a correspondingly high dose of the inhibitor of the present invention to form a clear solution, while HEDP, due to its low calcium resistance, has a near insoluble calcium salt under the same conditions. Results in precipitation (see Table 4, inhibitor concentration 400 mg / l).

Formula given in the literature

(Wherein n = 1 and n = 3 to 10 and X = OH)

Compared with 1-hydroxy-ω-sulfonoalkane-1,1-diphosphonic acid of, the materials and mixtures of the present invention have the following advantages:

Can be produced in good yields from inexpensive raw materials;

1-hydroxy-ω-sulfonoalkanes-1,1 described above having the above formula even at very low inhibitor doses of 2 to 5 mg / l in water with an overall hardness of 300 to 600 ppm CaCO ₃ It is a more effective scale inhibitor because it retains more calcium ions in solution than diphosphonic acid. This is evidenced by the residual hardness measured in Tables 2 and 3 (compare materials from Example 1 (according to the invention) with materials from Comparative Examples 3 and 4 (above)). In addition, the compositions of the present invention in water containing 600 ppm CaCO ₃ have an adhesive coating (= scale) even at much lower doses than the 1-hydroxy-ω-sulfonoalkane-1,1-diphosphonic acid described above. Prevents the formation of (see the symbol ★ for the scale in Table 3).

Formula

(Wherein n = 1 and n = 3 to 10 and X = OH)

Compared with the above-mentioned process for preparing 1-hydroxy-ω-sulfonoalkane-1,1-diphosphonic acid of, the process for preparing the material of the present invention has the following advantages:

a previously unknown compound having the above formula with n = 2 in good yield;

Produces good scale inhibitors with very high calcium resistance;

And further methyl-substituted compounds according to formula I, wherein R ¹ or R ² is methyl.

The preparation methods mentioned in the literature of 1-hydroxy-ω-sulfonoalkane-1,1-diphosphonic acid known in the literature of the above formula wherein n = 1 and n = 3 to 10 are all examples of the formula (I). It does not produce the compounds of the invention.

For example, the above-described preparation method for compounds with n = 3 to 10 from US-A-5 221 487 cannot be expanded to compounds with n = 2. The mixture obtained in this experiment contains no components of formula (I) at all or very low concentrations (see Comparative Examples 1 and 2). Therefore, in all the tests performed these mixtures show a much inferior scale inhibitor than the inventive mixtures of Example 1 (see Tables 1-4 under "Comparative Example 1 (C ₃ backbone)").

The preparation method also described above for the compound of n = 1 from US-A-3 940 436 is that the sulfono group and the -C (OH) (PO ₃ H ₂ ) ₂ group are epoxyethane-1,1-diphosphonic acid sodium. It is in principle not suitable for the preparation of compounds of formula (I), because they can be separated from each other only by at most one CH ₂ group and not by two CH ₂ groups because of the synthetic route through the salt.

The preparation process of the invention is therefore the only one which makes it possible to prepare compounds of formula (I) in high yield.

The invention will be explained in more detail on the basis of the following examples (see indications for the above reaction steps).

<Example 1>

Acrylic acid and tributylamine, SO ₂ Reaction according to the invention of water, water and phosphorus trichloride

Reaction step a), partial step 1)

740 g (4 mol) of tributylamine and 252 g (14 mol) of water are mixed with a stirrer, an internal thermometer, pH electrode, a gas inlet tube with a glass frit, a reflux condenser and a gas outlet tube attached thereto. Introduced to the flask. With strong stirring at 20 ° C. to 30 ° C., sulfur dioxide was introduced into this biphasic mixture until the mixture became one phase and measured to pH 4. The reaction mixture was weighed and the mass increased 263.6 g, which means that 4.12 mol of SO ₂ was absorbed. In order to set the starting molar ratio of sulfur dioxide / tributylamine / water to 1/1 / 3.5, additionally 22 g of tributylamine and 7.5 g of water were added to the mixture. Thus, 312 g of this total mixture corresponded to a starting amount of 1 mol of sulfur dioxide, 1 mol of tributylamine and 3.5 mol of water.

Reaction step a), partial step 2)

312 g of the solution was introduced into a 1 l multi-necked flask equipped with a stirrer, an internal thermometer, two dropping funnels, a reflux condenser with a pH electrode and a gas line. The mixture was preheated to 60 ° C. 72.42 g (1 mol) of acrylic acid (99.5% purity) and 78.5 g (0.42 mol) of tributylamine were then added dropwise from two separate dropping funnels at this temperature. During this time the pH of the reaction mixture is between 5 and 5.5. After the dropwise addition, the mixture was further stirred at 60 ° C. for at least 2 hours. Iodine measurement of sulfites is added to the stirring time after the first time of the SO ₂ used is added after the stirring time of 2 hours and 87.7% showed a 97.6% could not be detected any more sulfite. 462.9 g of the mixture obtained initially corresponded to an initial amount of 1 mol of SO _2, 1 mol of acrylic acid, 1.42 mol of amine and 3.5 mol of water. Since 1 mol of water has already been consumed by a chemical reaction per mol of SO ₂ in part 1), the amount of free water obtained is only 3.5-1 = 2.5 mol. The amount of free water is important for the reaction step d) below.

After removing the amine on a rotary evaporator at 20 mbar and 90 ° C., sodium hydroxide solution was added to the sample of concentrated solution. The ¹ H-NMR spectrum of this sample (containing 3- (trimethylsilyl) tetraduteropropionate sodium salt at 0 ppm internally) was 2.58 ppm (for the -CH ₂ -COONa group) and 3.13 ppm (-CH _2- Two triplets (for SO ₃ Na groups) represent Compound (II) with Z = COOH, R ¹ and R ² = H and n = 1. Signal groups for different -CH ₂ -OH species could be seen at 3.65 to 3.85 ppm. The molar ratio of —CH ₂ —SO ₃ Na to —CH ₂ —OH was 42. The average oligomerization degree n _mean is very close to 1, but cannot be accurately measured because tributylamine residues interfere with the spectrum.

Reaction step d)

126.62 g of the reaction mixture and 5.04 g (0.28 mol) of water were added to a stirrer, an internal thermometer, a dropping funnel, a reflux condenser (refrigerant temperature -15 ° C.), a gas outlet tube attached thereto, a safety vessel and HCl and entrained PCl ₃ . Into a 0.5 l four-necked flask equipped with an absorbent vessel containing 1 l of water for trapping, blanked with nitrogen and heated to 60 ° C. The introduced mixture initially corresponds to an initial amount of 0.274 mol SO ₂ , 0.388 mol amine, 0.274 mol acrylic acid and 1.236 mol water, and the amount of free water is only 0.964 mol. Then, while stirring and cooling, 77.0 g (0.561 mol) of phosphorus trichloride was added dropwise to the mixture over a period of 30 minutes at a temperature of 60 to 70 ° C. The amount of the added phosphorus trichloride in the molar amount of SO ₂ the amount of phosphorus used for using the ratio 2.05, so that the calculated amount for the amount of phosphorus used in the SO ₂ using a molar ratio of 0.49. In addition, the molar ratio of free water to used phosphorus before the addition of PCl ₃ was 1.72. After addition of PCl ₃ , the reaction mixture was stirred at 70-80 ° C. for an additional 3 hours.

Reaction step e)

Thereafter, 280 ml of water was added dropwise at first with slow stirring and then with more rapid stirring after the initial HCl gas evolution had declined, and the mixture was kept at 100 ° C. for an additional 18 hours. In an absorption vessel containing 1 l of water to escape HCl and PCl ₃ gas (see reaction step d)), 1.07 mol total HCl and 0.02 mol H ₃ PO ₃ were detected.

Reaction step g)

The reaction mixture was cooled to 40-50 ° C. and 136 g (1.53 mol) of 45% sodium hydroxide solution were added with stirring. At 60 ° C., the biphasic mixture was transferred to a separatory funnel. The lighter organic phase separated out consisted of 70.4 g of tributylamine, which can be reused in the synthesis without further purification (the recovery for tributylamine in this experiment is 97.9%).

490.4 g of the heavier aqueous phase is the preferred phosphonate mixture. From the mass of the aqueous phase, the molar amount of PCl ₃ used and the loss of PCl ₃ by evaporation, the phosphorus content of the solution was calculated to be 3.41%.

In the aqueous phase, according to ³¹ P-NMR analysis, 72.1% of the total phosphorus was present as a phosphonate of formula (I) wherein R ¹ and R ² = H (wherein% from NMR spectrum is as follows: Similarly, it corresponds to the percent relative area under the signal: Formula (I) appears as a triplet at a chemical shift of 18.6 ppm in the ³¹ P-NMR spectrum An additional triplet of 2.8% of the total signal intensity is apparent at 19.2 ppm. This signal has been experimentally named a compound of formula (III) with Z = -C (OH) (PO ₃ M ₂ ) ₂ , R ¹ and R ² = H and n = 1, and at 3.8 ppm Phosphate of IV) (5.4% of phosphorus) and phosphate of formula (V) (10.2% of phosphorus) at 3.4 ppm could be detected, together with other phosphonates with unknown structure, a total of 84.4% of phosphorus Total phosphonate content in mole% according to ³¹ P-NMR analysis, 3.4. From the calculated total phosphorus content of the 1 mass% solution and the molar weight of compound (I) with M and R = H of 300.1 g / mol, the phosphonic acid content was calculated to be 13.9 mass%. Initial weight was calculated in the test.

Samples of the aqueous phase were adjusted to pH 2-3 with hydrochloric acid, concentrated and dissolved in D ₂ O. The ¹ H-NMR spectrum of this sample (containing 3- (trimethylsilyl) tetraduteropropionate sodium salt on an internal basis at 0 ppm) is derived from Compound (I), which is mainly R ¹ and R ² = H. Group of signals: multiplet at 2.37 ppm (compound (I) and to some extent Z = -C (OH) (PO ₃ M ₂ ) ₂ , R ¹ and R ² = H and n = 1 For the -CH ₂ -C (OH) (PO ₃ M ₂ ) ₂ group of (III) and an additional multiplet at 3.24 ppm (of compound (I) and to some extent Z = COOH, R ¹ and R ² = H and n = 1 for the —CH ₂ —SO ₃ M group of formula (II)). Two triplets of less intensity at 2.6 and 2.75 ppm showed the —CH ₂ —COOH groups of compound (III) and similar compound (II) with Z = COOH, R ¹ and R ² = H and n = 1 . The —CH ₂ —OH groups of the compound of formula (III) could be seen in the signal group at 3.75 to 4 ppm. Residues of tributylammonium ions were found at 0.93, 1.38, 1.7 and 3.1 ppm. The molar ratio measured from the signal intensities of the compound of formula (II) to the compound of formula (III) was 18.8 (= molar ratio -CH ₂ -SO ₃ M / -CH ₂ -OH). The molar ratio of the compounds of formulas (II) and (III) with Z = -C (OH) (PO ₃ M ₂ ) ₂ to the compounds of formulas (II) and (III) with Z = COOM was 5.3 (= mol Non-C (OH) (PO ₃ M ₂ ) ₂ / COOM).

The ¹³ C-NMR spectrum (solvent D ₂ O, 3- (trimethylsilyl) tetraduteropropionate sodium salt as internal reference, set to 1.7 ppm) of the acidic mixture, with ¹ H decoupling, Chemical shift and coupling constants for: (1) for R ¹ and R ² = H: 1-C: 76.3 ppm (t, ¹ J _CP 149.8 Hz), 2-C: 33.0 ppm (s) , 3-C: 50.6 ppm (t, ³ J _CP 6.6 Hz). For compound (III) with Z = -C (OH) (PO ₃ M ₂ ) ₂ , R ¹ and R ² = H and n = 1: 1-C: 76.6 ppm (t, ¹ J _CP 149.1 Hz), 2-C: 35.7 ppm (s), 3-C: 62.1 ppm (t, ³ J _CP 7.3 Hz).

<Example 2>

Reaction according to the invention of acrylic acid and sodium hydroxide solution, sodium bisulfite, water and phosphorus trichloride

Reaction step a)

80.1 g (1.1 mol) of acrylic acid (99% purity) were placed in an evacuated device and 197.6 g (1.0 mol) of 20.24% sodium hydroxide solution were added with stirring at 20-25 ° C. over 30 minutes. The final pH of the sodium acrylate solution was 6.5.

95.1 g (0.5 mol) of sodium bisulfite were dissolved in 300 ml of water in a multi-necked flask equipped with a stirrer, dropping funnel, internal thermometer, pH electrode, reflux condenser and air line attached thereto. The pH of the solution was adjusted to pH 4.5 with 5 ml of 20% sodium hydroxide solution. Then, over 1.5 hours, the sodium acrylate solution described above was added dropwise with stirring and cooling at 35 to 40 ° C. The final pH of the reaction mixture was 6.3. The mixture was stirred at 30-35 ° C. for a further 1 hour. Iodine measurements of sulfite showed that after further stirring for 1 hour, 95.9% of the initial sulfite was no longer detected.

Samples of the solution were concentrated on a rotary evaporator at 25 mbar and 90 ° C. heating bath temperature. The ¹ H-NMR spectrum of this sample in D ₂ O indicates that acrylic acid is no longer present in the mixture. At 3.1 to 3.3 ppm (for the 3- (trimethylsilyl) tetraduteropropionate sodium salt as internal reference, set to 0 ppm), different species -CH ₂ -SO ₃ Na groups can be seen. At 3.8 ppm the triplet of the -CH ₂ -OH species appears and at 4.3 to 4.4 ppm the signal group for various compounds containing -CH ₂ -O-CO groups is shown. The molar ratio of -CH ₂ -SO ₃ Na to (-CH ₂ -OH + -CH ₂ -O-CO-) was 7.1. From 1.3 to 2.3 ppm there is a very wide signal for the internal protons of the different oligomers. The average oligomerization degree n _mean was calculated to be 1.8.

The total mixture corresponded to an initial amount of 1 mol of sulfur dioxide, 2.025 mol of sodium hydroxide solution, 1.1 mol of acrylic acid and 25.6 mol of water.

Reaction step b)

The solution from step a) was added to a column containing 1.4 l of ion exchanger RWATITE® S 100 (in acid form).

Reaction step c)

The eluate from reaction step b) was initially dehydrated on a rotary evaporator at 60 ° C. heating bath temperature and 50 mbar pressure, finally at 90 ° C. and 20 mbar for an additional 10 minutes. 161 g of solid residue were obtained. The Karl-Fischer titration showed a water content of 13.4%. Titration with sodium hydroxide solution provided a 5.435 mmol content of COOH group per gram of material from the difference between the first and second equivalence points. Only half of the -SO ₃ Na groups were converted to -SO ₃ H groups.

Samples of the solution were concentrated on a rotary evaporator at 25 mbar and 90 ° C. heating bath temperature. The ¹ H-NMR spectrum of this sample in D ₂ O is from 3.1 to 3.3 ppm (for 3- (trimethylsilyl) tetraduterropropionate sodium salt as internal reference, set to 0 ppm), Z = COOH, R ¹ and R ² = H and n = 1 in formula (II) of the -CH ₂ -SO ₃ M groups of the triplet, and broadened at the border band of the main signal n> 1 of similar species of -CH ₂ -SO ₃ M The flag was shown. At 3.85 ppm a triplet of -CH ₂ -OH species appeared, and at 4.25-4.45 ppm a signal group for various compounds containing -CH ₂ -O-CO groups was shown. The molar ratio of -CH ₂ -SO ₃ M to (-CH ₂ -OH + -CH ₂ -O-CO-) was 7.9. From 1.5 to 2.55 ppm there is a very wide signal for the internal protons of various oligomers. Average oligomerization degree n The _mean was calculated to be 1.18 (no change compared to the analysis after process step a).

Reaction step d)

18.42 g of the reaction mixture from reaction step c) containing 0.1 mol of COOH groups and 2.47 g (0.137 mol) of water, and further 2.93 g (0.163 mol) of water and 37.08 g (0.2 mol) of tributylamine were added inside the stirrer, It was introduced into a multi-necked flask equipped with a reflux condenser equipped with a thermometer, a dropping funnel and a gas outlet. Two liquid phases formed upon heating to a maximum of 60 ° C. under nitrogen.

The introduced mixture initially corresponded to an initial amount of 0.01 mol of SO ₂ and 0.1 mol of acrylic acid and 0.2 mol of current amine and 0.3 mol of water. 27.5 g (0.2 mol) of phosphorus trichloride was then added dropwise to this mixture with stirring and cooling at a temperature of 60-65 ° C. for 21 minutes. The amount of the phosphorus trichloride was added to the amount of moles of SO ₂ the amount of phosphorus used for using the ratio of 2.2 and was calculated so that the amount for the amount of phosphorus used in the SO ₂ using a molar ratio of 0.46. In addition, the molar ratio of free water to used phosphorus before the addition of PCl ₃ was 1.5. After the addition of PCl ₃ , the reaction mixture was stirred at 75 ° C. for a further 21 hours.

Reaction step e)

Then 100 ml of water were added dropwise at 30-40 ° C. with stirring over 15 minutes and the mixture was kept at 75 ° C. for an additional 21 hours. 40 ml of water were then added and traces of suspended material were filtered off.

Reaction step g)

70 g (0.79 mol) of sodium hydroxide solution at 45% concentration were added to the filtrate. At 60 ° C., the biphasic mixture was transferred to a separatory funnel. The lighter organic phase separated out consisted of tributylamine (the recovery for tributylamine in this experiment is about 94%), which can be reused for synthesis without further purification.

216 g of the heavier aqueous phase is the preferred phosphonate mixture. From the mass of the aqueous phase, the molar amount of PCl ₃ used and the estimated PCl ₃ loss of 8% by sampling for evaporation and analysis, the phosphorus content of the solution was calculated to be 2.72%.

In the aqueous phase, according to ³¹ P-NMR analysis, 37.6% of the total phosphorus was present as a phosphonate of formula (I) wherein R ¹ and R ² = H. This compound was found to be triplets ( ³ J _PH = 12.8 Hz) at a chemical shift of 18.7 ppm in the ³¹ P-NMR spectrum. An additional triplet with 7.7% of the total signal intensity was seen at 19.3 ppm. This signal was experimentally named as a compound of formula (III) wherein Z = -C (OH) (PO ₃ M ₂ ) ₂ , R ¹ and R ² = H and n = 1. It was also possible to detect phosphites of formula (IV) (1.1% of phosphorus) at 3.75 ppm and phosphates of formula (V) (19.7% of phosphorus) at 6.0 ppm. Along with other phosphonates with unknown structures, a total of 78.3% of phosphorus was present in the phosphonates.

<Example 3>

Crotonic Acid and Tributylamine, SO ₂ Reaction according to the invention of water, water and phosphorus trichloride

Reaction step a), partial step 1)

185 g (4 mol) of tributylamine and 63 g (14 mol) of water are introduced into a 500 ml multi-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube with a glass frit, a reflux condenser and a gas outlet tube attached thereto I was. Nitrogen was first injected into this biphasic mixture and sulfur dioxide was introduced into the biphasic mixture until vigorous stirring at 20 ° C.-30 ° C. disappeared and the mixture turned colorless to yellow. The reaction mixture was weighed and the mass increased by 65.5 g, indicating that 1.02 mol of SO ₂ was absorbed. In order to set the initial molar ratio of sulfur dioxide / tributylamine / water to 1/1 / 3.5, further 4.33 g of tributylamine and 1.47 g of water were added to the mixture. Thus, 312 g of this total mixture corresponded to the initial amount of 1 mol of sulfur dioxide, 1 mol of tributylamine and 3.5 mol of water.

Reaction step a), partial step 2)

312 g of the solution was introduced into a 1 l multi-necked flask equipped with a stirrer, internal thermometer, dropping funnel and pH electrode. The mixture was preheated to 60 ° C.

In a glass beaker 87.85 g (1 mol) of crotonic acid (98% purity) was dissolved with 16.2 g (0.9 mol) of water and 74.0 g (0.40 mol) of tributylamine were added with water cooling at 60 ° C. This single phase mixture was added dropwise to the solution obtained from reaction step a), partial step b) at 60 ° C. over 40 minutes. The mixture was reacted at 60 ° C. for 23 hours and 80 ° C. for 5 hours. The pH of the reaction mixture after the reaction was 5.8. The resulting mixture (490 g) initially corresponded to an initial amount of 1 mol of SO _2, 1 mol of crotonic acid, 1.4 mol of amine and 4.4 mol of water. Since 1 mol of water has already been consumed by the chemical reaction per mol of SO ₂ in part 1), the amount of free water obtained is only 3.4 mol. The amount of free water is important for the reaction step d) below.

After removing the amine on a rotary evaporator at 20 mbar and 90 ° C., sodium hydroxide solution was added to the sample of concentrated solution. The ¹ H-NMR spectrum of this sample (containing 3- (trimethylsilyl) tetraduteropropionate sodium salt at internal ppm at 0 ppm) is Z = COOH, R ¹ = methyl, R ² = H and n = 1 In the case of (II) the following signals were shown: -CH ₃ : 1.31 ppm (d), -CH ₂ -COONa: 2.22 ppm (dd) and 2.84 ppm (dd), -CH-SO ₃ Na: 3.26 ppm (m). No byproducts containing oligomers or —CH—OH groups could be detected.

Reaction step d)

196 g of the reaction mixture was mixed with a stirrer, internal thermometer, dropping funnel, reflux condenser (refrigerant temperature -15 ° C), 1 liter of water to trap the gas outlet tube, safety vessel and HCl and entrained PCl ₃ attached thereto. It was introduced into a 0.5 l four neck flask equipped with an absorbent vessel containing, blanked with nitrogen and heated to 60 ° C. The introduced mixture initially corresponds to an initial amount of 0.4 mol of SO _2, 0.4 mol of crotonic acid, 0.56 mol of amine and 1.76 mol of water, and the amount of free water is only 1.36 mol. Then, while stirring and cooling, 110 g (0.8 mol) of phosphorus trichloride was added dropwise to the mixture over 35 minutes at a temperature of 60 to 70 ° C. The amount of the added phosphorus trichloride in the molar amount of SO _2, the amount of phosphorus used for use is 2, such that the calculated amount for the amount of phosphorus used in the SO ₂ using a molar ratio of 0.5. In addition, the molar ratio of free water to used phosphorus before the addition of PCl ₃ was 1.7. After addition of PCl ₃ , the reaction mixture was stirred at 70-80 ° C. for an additional 3 hours.

Reaction step e)

Thereafter, 400 ml of water was added dropwise at first with slow stirring and then with stirring more rapidly after the initial HCl gas evolution had declined, and the mixture was kept at 100 ° C. for an additional 18 hours. In an absorption vessel containing 1 l of water to escape HCl and PCl ₃ gas (see reaction step d)), 1.69 mol total HCl and 0.072 mol of H ₃ PO ₃ were detected.

Reaction step g)

The reaction mixture was cooled to 60 ° C and 213 g (2.4 mol) of 45% sodium hydroxide solution was added with stirring. At 60 ° C., the biphasic mixture was transferred to a separatory funnel. The lighter organic phase separated out consisted of 102.5 g of tributylamine, which can be reused for synthesis without further purification (the recovery for tributylamine in this experiment is 98.9%).

Heavier aqueous phase (724.5 g) is the preferred phosphonate mixture. From the mass of the aqueous phase, the molar amount of PCl ₃ used and the loss of PCl ₃ by evaporation, the phosphorus content of the solution was calculated to be 3.11%.

In the aqueous phase, according to ³¹ P-NMR analysis, 52.2% of the total phosphorus was present as phosphonate of formula (I) with R ¹ = methyl, R ² = H. The compound appeared as multiplets in the form of two closely adjacent signals at 18.9 ppm to 19.0 ppm, with ¹ H decoupling in the ³¹ P-NMR spectrum. In addition, a phosphite of formula (IV) (11.1% of phosphorus) at 3.7 ppm and a phosphate of formula (V) (18.2% of phosphorus) at 4.5 ppm could be detected. Along with other phosphonates with unknown structures, a total of 70.7% of phosphorus was present in the phosphonates.

<Example 4>

Methacrylic acid and tributylamine, SO ₂ Reaction according to the invention of water, water and phosphorus trichloride

In a similar manner to Example 3, methacrylic acid was used instead of crotonic acid.

In reaction step a), part step 2), methacrylic acid was reacted starting at 80 ° C. To the sample of the reaction solution obtained there was added sodium hydroxide solution and after the amine was removed, the solution was concentrated on a rotary evaporator at 20 mbar and 90 ° C. The ¹ H-NMR spectrum of this sample (containing 3- (trimethylsilyl) tetraduteropropionate sodium salt at internal ppm at 0 ppm) is Z = COOH, R ¹ = H and R ² = methyl and n = 1 In the case of (II) the following signals were shown: -CH ₃ : 1.23 ppm (d), -CH-COONa: about 2.75 ppm (m), -CH ₂ -SO ₃ Na: 3.31 ppm (dd) and about 2.85 (m).

After reaction step g), 960.6 g of aqueous phase was obtained. From the mass of the aqueous phase, the molar amount of PCl ₃ used and the loss of PCl ₃ by evaporation, the phosphorus content of the solution was calculated to be 2.93%.

In the aqueous phase, according to ³¹ P-NMR analysis, 39.1% of the total phosphorus was present as phosphonates of formula (I) wherein R ¹ = H and R ² = methyl. This compound showed two polylines in the ³¹ P-NMR spectrum, which, together with ¹ H-decoupling, in each case were ^{2 at} 19.4 ppm and 18.0 ppm with a 2 J _PP coupling constant of 22.3 Hz. Switched to doublet. It was also possible to detect phosphites of formula (IV) (29.4% of phosphorus) at 3.7 ppm and phosphates of formula (V) (16.1% of phosphorus) at 4.6 ppm. Along with other phosphonates with unknown structures, a total of 54.5% of phosphorus was present in the phosphonates.

Comparative Example 1

In a similar manner to Example 7 from US-A-5 221 487, 3-bromopropionic acid was first reacted with PCl ₃ and water, followed by sodium sulfite and KOH. As compared with this Example 7, the starting amount of the raw material was three times.

13.8 g (90 mmol) of 3-bromopropionic acid and 4.05 g (225 mmol) of water were placed in a multi-necked flask equipped with a stirrer, a dropping funnel, a reflux condenser and a gas outlet attached thereto, and warmed to 40 ° C. 150 mmol of phosphorus trichloride was added dropwise at a temperature of 40-50 ° C. with stirring over 20 minutes. At the end of the addition, the batch was heated under reflux in an oil bath at 150 ° C. for 3 hours. During this time the mixture sometimes became a solid. After 3 hours, the mixture was cooled to room temperature and a solution of 9.9 g (150 mmol) of potassium hydroxide and 11.3 g (90 mol) of sodium sulfite in 90 g of water was added dropwise while cooling over 15 minutes. The solution was then heated to 100 ° C. for 19 hours with stirring. The clear solution had a final pH of 4.85 and was evaporated to dryness. 38 g of solid was obtained.

³¹ P-NMR spectrum (solvent D ₂ O) showed a triplet characterizing the -CH ₂ -C (OH) (PO ₃ M ₂ ) ₂ group of the achiral compound at 18.8 ppm. In this -CH ₂ -C (OH) (PO ₃ M ₂ ) ₂ group only 13.2% of phosphorus was present. In addition, the following chemical formula

The compound of can be detected through two doublets at 37.2 ppm (in-ring phosphorus) and 16.7 ppm (out-ring phosphorus) with a coupling constant ² J _PP of 35.9 Hz in a ¹ H-decoupled ³¹ P-NMR spectrum. Can be. 19.0% of phosphorus was present in this compound. Along with other phosphonates with unknown structure, a total of 93.4% of phosphorus was present in the phosphonates. Most of the phosphonates present cannot be named by their structure. 5.8% of phosphorus was present as phosphate of formula (V) with chemical shift at 1.0 ppm.

The ¹ H-NMR spectrum of this sample (containing 3- (trimethylsilyl) tetraduteropropionate sodium salt on an internal basis at 0 ppm) is mainly Z = COOM, R ¹ and R ² = H and n = 1 Two triplets derived from II), one triplet at 2.62 ppm (for the -CH ₂ -COOM group of this compound) and an additional triplet at 3.15 ppm (-CH ₂ -SO ₃ of this compound) For group M). In addition to the triplets described above, in the representative region of 3 to 3.3 ppm of -CH ₂ -SO ₃ M, no additional signal was seen. This means that the majority of sulfonic acids are not present in compounds of type (I) but in compounds of formula (II) with Z = COOM. Compounds of type (I) should exhibit complex multiplets (see Example 1), not just triplets, due to P, H coupling to the protons of the —CH ₂ —SO ₃ M group. The -CH ₂ -OH groups of the compound of formula (III) can be seen as two triplets at 3.75 to 4 ppm. The molar ratio calculated from the signal strength of the compound of formula (II) to the compound of formula (III) was 4 (= molar ratio -CH ₂ -SO ₃ M / -CH ₂ -OH).

Comparative Example 2

In a similar manner to Comparative Example 1, 3-bromopropionic acid was first reacted with PCl ₃ and water, followed by an increased amount of sodium sulfite and KOH.

The reaction was carried out as in Comparative Example 1 except that 210 mmol of KOH was used instead of 150 mmol and 145 mmol of sodium sulfite was used instead of 90 mmol. The final reaction mixture before evaporation has a pH of 6.45.

³¹ P-NMR spectrum (solvent D ₂ O) showed two triplets that were characteristic of the —CH ₂ —C (OH) (PO ₃ M ₂ ) ₂ group of the achiral compound. That is, one with 2.9% of the total phosphorus signal intensity at 18.7 ppm and one representing 15.4% of the total signal intensity at 19.5 ppm. By adding the sample from Example 1 and measuring the sample mixtures again, it was shown that a signal smaller than the original containing 2.9% of phosphorus had a markedly increased intensity. Thus, this corresponds to compounds of formula (I) wherein R ¹ and R ² = H and n = 1. Signals larger than the original containing 15.4% of phosphorus may be designated as compounds of the formula (III) wherein Z = -C (OH) (PO ₃ M ₂ ) ₂ , R ¹ and R ² = H and n = 1. In addition, the following chemical formula

Can be detected as a pure sample from Comparative Example 2. 11.5% of phosphorus was present in this compound. Along with other phosphonates with unknown structures, a total of 91.0% of phosphorus was present in the phosphonates. Most of the phosphonates present cannot be named by the structure in this case either. 8.0% of phosphorus was present as phosphate of formula (V) with chemical shift at 2.9 ppm.

The ¹ H-NMR spectrum of this sample (containing 3- (trimethylsilyl) tetraduteropropionate sodium salt on an internal basis at 0 ppm) is mainly Z = COOM, R ¹ and R ² = H and n = 1 Two triplets derived from II), one triplet at 2.60 ppm (for the -CH ₂ -COOM group of this compound (II)) and an additional triplet at 3.16 ppm (this compound (II) For the —CH ₂ —SO ₃ M group. In addition to the triplets described above, in the representative region of 3 to 3.3 ppm of -CH ₂ -SO ₃ M, no additional signal was seen. This means that the majority of sulfonic acids are not present in compounds of type (I) but in compounds of formula (II) with Z = COOM. The —CH ₂ —OH groups of the compound of formula (III) could be seen as two triplets at 3.75 to 4 ppm. The molar ratio calculated from the signal strength of the compound of formula (II) to the compound of formula (III) was 7.7 (= molar ratio -CH ₂ -SO ₃ M / -CH ₂ -OH).

Comparative Example 3

In a manner similar to Example 5 of US-A-5 221 487, a cognate 4-bromobutyric acid was first reacted with PCl ₃ and water followed by sodium sulfite and KOH instead of 5-bromovaleric acid. The amount of raw material used was 6 times as compared with this example.

14.0 g (84 mmol) of 4-bromobutyric acid and 3.8 g (210 mmol) of water were introduced into a multi-necked flask equipped with a stirrer, a reflux condenser and a gas outlet attached thereto and heated to 40 ° C. 19.0 g (138 mmol) of phosphorus trichloride was added dropwise with stirring over 40 minutes at 40 ° C to 50 ° C. After addition, the batch was heated to 130 ° C. oil bath under reflux for 3 hours. In this case, the internal temperature was approximately 120 ° C. After 3 hours the mixture was cooled to room temperature and a solution of 8.9 g (138 mmol) of potassium hydroxide and 10.8 g (85.6 mol) of sodium sulfite in 90 g of water was added dropwise cooled at 25 ° C to 30 ° C for 15 minutes. . As soon as this solution was added dropwise, the reaction compound was alkaline. After heating to 95-100 ° C., the pH was reduced to 5-6. The mixture was heated at 100 ° C. for 19 hours with stirring. The clear solution obtained (124.3 g) had a final pH of 4.7.

³¹ P-NMR spectrum (solvent D ₂ O) showed a triplet characterizing the —CH ₂ —C (OH) (PO ₃ M ₂ ) ₂ group of the achiral compound at 19.1 ppm. During this phase, only 6.0% of phosphorus was present. In addition, the following chemical formula

The compound of can be detected via two doublets at 15.0 ppm (in-ring phosphorus) and 17.7 ppm (out-ring phosphorus) with a coupling constant ² J _PP of 25.4 Hz in a ¹ H-decoupled ³¹ P-NMR spectrum. Can be. 27.0% of phosphorus was present in this compound. Along with other phosphonates with unknown structures, a total of 90.4% of phosphorus was present in the phosphonates. Most of the phosphonates present cannot be named by their structure. 9.6% of phosphorus was present as phosphate of formula (V) with chemical shift at 0.7 ppm.

Comparative Example 4

In a manner similar to Example 5 of US-A-5 221 487, 5-bromovaleric acid was first reacted with PCl ₃ and water, followed by sodium sulfite and KOH. In comparison with the patent example, only the initial amount of raw material was 6 times.

15.2 g (84 mmol) of 4-bromobutyric acid and 3.8 g (210 mmol) of water were introduced into a multi-necked flask equipped with a stirrer, a dropping funnel, a reflux condenser and a gas outlet attached thereto and heated to 40 ° C. 19.0 g (138 mmol) of phosphorus trichloride was added dropwise with stirring over 40 minutes at 40 ° C to 45 ° C. After addition, the reaction compound was heated to 130 ° C. for 15 minutes and 120 ° C. for 2.75 hours. Reflux first occurs at an internal temperature of 110 ° C. Thereafter, the compound was cooled to room temperature and a solution of 8.9 g (138 mmol) of 86.7% purity potassium hydroxide and 10.8 g (85.6 mol) of sodium sulfite was added dropwise cooled to 25 g at 30 ° C. in 15 g of water. As soon as this solution was added dropwise, the reaction compound was alkaline. After heating to 95-100 ° C., the pH was reduced to approximately 6. The mixture was heated at 100 ° C. for 19 hours with stirring. The resulting solution (129.9 g) finally had a pH of 4.3.

³¹ P-NMR spectrum (solvent D ₂ O) showed a triplet characterizing the -CH ₂ -C (OH) (PO ₃ M ₂ ) ₂ group of the achiral compound at 19.0 ppm. During this phase, 23.1% of phosphorus was present. Along with other phosphonates with unknown structures, a total of 87.8% of phosphorus was present in the phosphonates. Most of the phosphonates present cannot be named by their structure. 8.9% of phosphorus was present as phosphate of formula (V) with chemical shift at 0.7 ppm.

Example 5

Calcium Resistance Test

700 ml of demineralized water was introduced into a 1 l glass flask and 10 ml of solution containing 183.4 g of inhibitor solution and CaCl ₂ · 2H ₂ O / l were added with stirring. The inhibitor solution used is generally a neutralized solution containing 10,000 mg / l of active compound, so the addition of 5, 10 or 20 ml is equivalent to the inhibitor concentration of 50, 100 and 200 mg / l.

The pH of the solution was adjusted to 9.0 by addition of sodium hydroxide solution or hydrochloric acid, then the volume was brought to 1 l. This solution contained Ca ²⁺ 500 mg / l.

The closed flask was stored in a circulating air drying cabinet at 75 ° C. for 24 hours. After cooling, the pH is measured (adjusted),-after resuspension of any precipitated salts for homogenization-the turbidity of the sample is measured in a 50 mm cuvette with a Nephel photometer as specified in EN 27027, Reported in FNU (formazine nefello unit).

The higher the turbidity value, the more calcium inhibitor salt precipitated. Therefore low turbidity values correspond to high calcium resistance. High calcium resistance is a prerequisite for effective calcium carbonate inhibition in water with high calcium concentrations.

As shown in Table 1, the Ca resistance of the material of the invention from Example 1 and the Ca resistance of the material from Comparative Examples 3 and 4 described by US-A-5 221 487 are significantly higher than the value of HEDP. . With the extension of the method presented in US-A-5 221 487, samples made with shorter carbon chain lengths from 3-bromopropionic acid are somewhat better than HEDP, but somewhat worse than the inventive material of Example 1.

Samples from Comparative Examples 1 and 3, in contrast to other materials, are not stable under experimental conditions of calcium tolerance measurements. The pH drops significantly during the measurement.

Calcium resistance measurement through turbidity experiment product Turbidity in FNU units at the inhibitor concentration 50 mg / l 100 mg / l 200 mg / l Material Example 1 0 0 0 Compare: HDEP 88 109 157 Substance Comparison Example 1 ^* (C ₃ backbone) 20 40 83 Substance Comparison Example 3 ^* (C ₄ backbone) 0 0 0 Substance Comparison Example 4 (C ₅ backbone) 0 0 0 Significant pH decrease during storage over 24 hours at * 75 ° C

<Example 6>

Test of Scale Inhibition Activity

Three different waters (eg, Examples 6a) to 6c) supersaturated in calcium carbonate were prepared synthetically from demineralized water by dissolving the salt and adjusting the pH with sodium hydroxide solution or hydrochloric acid. In these waters, deposition of solids during storage was studied as a function of added scale inhibitors having different structures and concentrations.

<Example 6a)>

To test scale inhibitory activity, synthetic tap water having the following composition was prepared:

Total hardness of Ca ²⁺ 100 mg / l and Mg ²⁺ 12 mol / l and CaCO ₃ 300 ppm equivalent to 3 mmol / l alkaline earth metal ions or 17 ° total German hardness,

3.2 mmol / l is equivalent to HCO ₃ ^- 195 mg / l and the carbonate hardness or 9. German carbonate hardness,

^{Na + 145 mg / l, SO} 4 2- 197 mg / l and Cl ^- 177 mg / l.

The total hardness (initial hardness) of this water was measured by titration with EDTA.

A small amount of inhibitor was added to this water and its concentration in the test solution was 2, 5, 10 and 25 ppm, calculated as the free inhibitor acid. The pH of the solution was adjusted to 11.0 by addition of sodium hydroxide solution (c = 1 mol / l) and stored in a dry cabinet at 60 ° C. for 24 hours in a closed glass flask containing glass rods. After storage, the solution was visually observed for the deposited crystals and filtered through a 0.45 μm membrane filter. In the filtrate, the total remaining hardness was determined by titration with EDTA. The "residual hardness in%" (RH [%]) listed in Tables 2-4 was calculated using the following formula:

a = residual hardness in the filtrate of the test sample

b = residual hardness in the filtrate of the blank sample without inhibitor

c = initial hardness

The higher the RH [%] value in the filtrate, the more effectively the CaCO ₃ precipitation is inhibited.

Any deposition on the scale, ie any deposition of adherent deposits on the glass surface, is particularly severe and is indicated by stars in Tables 2-4.

As shown in Table 2, the scale formation from 1-fold concentrations of synthetic water uses only the inventive material from Example 1 and also from Comparative Examples 3 and 4, which is claimed in US-A-5 221 487. Achievement at inhibitor concentrations of 25 mg / l was achieved only with. With the extension of HEDP and the methods presented therein, samples prepared with shorter carbon chain lengths from 3-bromopropionic acid (see Comparative Example 1) were unable to inhibit scale formation even at inhibitor concentrations of 25 mg / l.

At lower doses (inhibitor <10 mg / l), the materials of the present invention can stabilize higher residual hardness than all other comparative materials.

Residual hardness in synthetic water at 1-fold concentration after 24 hours at 60 ° C and pH 11 product Residual hardness RH [%] at the following active compound concentration 2 mg / l 5 mg / l 10 mg / l 25 mg / l Material Example 1 64 ^★ 77 ^★ 81 ^★ 98 Compare: HEDP Could not measure 49 ^★ 76 ^★ 78 ^★ Substance Comparison Example 1 ^* (C ₃ backbone) 26 ^★ 47 ^★ 53 ^★ 61 ^★ Substance Comparison Example 3 ^* (C ₄ backbone) 30 ^★ 49 ^★ 87 ^★ 96 Substance Comparison Example 4 (C ₅ backbone) 33 ^★ 58 ^★ 79 ^★ 99 Scale = scale

<Example 6b)>

In comparison with Example 6a), synthetic water having a double ion concentration was used. The pH of the inhibitor containing test solution was adjusted to 9.0 by addition of sodium hydroxide solution (c = 1 mol / l) and stored at 80 ° C. for 24 hours. See Table 3 for the results.

According to Table 3, the minimum inhibitor concentration that still prevents scale deposition from double concentrations of synthetic water is 5 mg / l for the inventive material from Example 1 and is claimed by US-A-5 221 487. 10 mg / l for materials from Comparative Examples 3 and 4, 25 mg / l for samples from Comparative Example 1 prepared with an extension to the preparation method described therein, and 25 mg / l for HEDP. It was more than l. Therefore, the substance of the present invention has already achieved the same effect as the substance described in half the dosage.

Residual hardness in double concentration of synthetic water after 24 hours at 80 ° C and pH 9 product Residual hardness RH [%] at the following active compound concentration 2 mg / l 5 mg / l 10 mg / l 25 mg / l Material Example 1 92 ^★ 100 100 100 Compare: HEDP 88 ^★ 79 ^★ 79 ^★ 77 ^★ Substance Comparison Example 1 ^* (C ₃ backbone) 60 ^★ 82 ^★ 82 ^★ 88 Substance Comparison Example 3 ^* (C ₄ backbone) 67 ^★ 90 ^★ 100 97 Substance Comparison Example 4 (C ₅ backbone) 72 ^★ 91 ^★ 100 100 Scale = scale

Example 6c)

In comparison with Example 6a), synthetic water having a four-fold ion concentration was used. The pH of the inhibitor containing test solution was adjusted to 9.0 by addition of sodium hydroxide solution (c = 1 mol / l) and stored at 60 ° C. for 24 hours. See Table 4 for the results.

Residual hardness in 4-fold concentration of synthetic water after 24 hours at 60 ° C and pH 9 product Residue hardness at the following active compound concentration: RH [%] 20 mg / l 50 mg / l 100 mg / l 400 mg / l Material Example 1 54 ^★ 49 ^★ 55 ^★ 86 Compare: HEDP 56 ^★ 54 ^★ 53 ^★ -6 ○ Substance Comparison Example 1 ^* (C ₃ backbone) 38 ^★ 48 ^★ 59 ^★ 25 ○ Substance Comparison Example 3 ^* (C ₄ backbone) 53 ^★ 55 ^★ 77 ○ 55 ○ Substance Comparison Example 4 (C ₅ backbone) 53 ^★ 54 ^★ 58 ^★ 92 ★ = scale deposition, ○ = sludge formation

According to Table 4, the four-fold concentration of synthetic water was obtained at 60 ° C. and pH 9 only at very high inhibitor concentrations of at least 400 mg / l and the inhibitors of the invention according to example 1 or the inhibitors according to comparative example 4 It was stable only when used to give a clear solution. The material from HEDP and Comparative Examples 1 and 3 resulted in sludge formation at this dose. The negative value for% residual hardness in the 400 mg / l HEDP test is noteworthy. A negative RH [%] value is lower at the end of the experiment with the inhibitor (in this case CaCO ₃ 723 ppm) than in the comparative test without the inhibitor (CaCO ₃ 750 ppm). In this experiment, HEDP acts to precipitate calcium ions. This behavior is consistent with the low calcium resistance of HEDP (see Table 1).

<Example 7>

Test of Corrosion Inhibition Activity

In order to test the corrosion inhibiting activity, synthetic water having a ionic concentration twice as compared with Example 6a) was prepared. In 12 liters of this synthetic water, the inhibitor concentration was set to 30 mg / l by adding the pre-neutralized inhibitor. This solution was charged to a 12 liter capacity vessel in which four steel tube rings made of C steel (St 37), pretreated with acetone and degreased, were stirred through the solution on a stirrer at a rate of 0.6 m / s. During the entire experiment, 1.4 l / h of fresh aqueous solution containing 20 mg / l of inhibitor, in contrast to 122 liters of initial solution, were added to the vessel and the same flow of solution was allowed to flow through the overflow. After 72 hours, the rings were removed and pickled with hydrochloric acid. The loss of mass of the ring was measured and related to the surface area of the ring and the experiment time. From this, a corrosion rate of 0.06 mm / yr for the material from Example 1 and 0.05 mm / yr for HEDP was calculated. In the blank test without inhibitor, the corrosion rate was 0.17 mm / yr.

Claims (31)

The compounds of formula (I) and salts thereof. <Formula I> In the above formula, R ¹ and R ² independently of one another represent hydrogen or methyl, M ¹ to M ⁵ independently represent hydrogen ions, alkali metal ions, ammonium ions or alkylated ammonium ions. A compound according to claim 1, wherein in formula (I) R ¹ and R ² represent hydrogen and M ¹ to M ⁵ independently of one another represent a hydrogen ion, an alkali metal ion, an ammonium ion or an alkylated ammonium ion . The compound of claim 1, wherein in formula (I), R ¹ represents methyl, R ² represents hydrogen, and M ¹ to M ⁵ independently represent hydrogen ions, alkali metal ions, ammonium ions, or alkylated ammonium ions. Compound made into. A compound according to claim 1, wherein in formula (I) R ¹ represents hydrogen, R ² represents methyl and M ¹ to M ⁵ independently represent hydrogen ions, alkali metal ions, ammonium ions or alkylated ammonium ions Characterized by a compound. In addition to the compound of formula (I) according to any one of claims 1 to 4, a mixture characterized in that the following other components are present. At least one sulfonic acid of formula (II) or a salt thereof <Formula II> At least one hydroxy acid of formula (III) <Formula III> Phosphites of formula (IV) <Formula IV> M ¹ M ² HPO ₃ Phosphates of formula (V) <Formula V> M ¹ M ² M ³ PO ₄ Among the above formulas, R ¹ and R ² independently of one another represent hydrogen or methyl, M ¹ to M ⁵ and M ⁱ independently represent hydrogen ions, alkali metal ions, ammonium ions or alkylated ammonium ions, Z represents a group of the formula -COOM ¹ or -C (OH) (PO ₃ M ¹ M ² ) ₂ , n can be assumed to be an integer value from 1 to 5, and the mean value of n for all compounds of types (II) and (III) is between 1 and 2. 6. Mixture according to claim 5, wherein at least 30% of the total phosphorus in the mixture is present in the compound of formula (I). 6. Mixture according to claim 5, wherein at least 60% of the total phosphorus of the mixture is present in the compound of formula (I). A mixture according to claim 5, wherein at most 15% of the total phosphorus of the mixture is in the phosphate salt of formula (V). A mixture according to claim 5, wherein the molar ratio of the compound of formula (II) to the compound of formula (III) is at least 5 to 1. 7. The compound of formulas (II) and (III) according to claim 5, wherein the compounds of formulas (II) and (III) above Z = -C (OH) (PO ₃ M ₂ ) ₂ vs. Z = -COOM Mixture having a molar ratio of at least 1 to 1. a) 1 mol of sulfur dioxide is at least 1 mol of water, at least 1 mol of monovalent base and unsaturated carboxylic acid or carboxylic acid mixture, wherein (Wherein R ¹ and R ² independently represent hydrogen or methyl) Carboxylic acids are used] with 0.9 to 2 mol; b) treating the reaction mixture from step a) optionally with a strongly acidic cation exchanger in the form of H ⁺ ; c) optionally dehydrating the reaction mixture from step b); d) reacting the reaction mixture from step a) or c) with the P (III) raw material, wherein the molar amount of phosphorus used is 1.6 to 2.4 mol, in the presence or absence of an amine salt under dehydration conditions; e) hydrolyzing the reaction mixture from step d) by adding a sufficient amount of water or aqueous hydrochloric acid; f) the reaction mixture from step e) is optionally distilled for removal and recovery of volatile components; g) the compound according to claim 1 and 5, characterized in that the reaction mixture from step e) or f) is optionally alkalized with an alkali metal hydroxide solution and the amine is removed and reused in step a) or d). Process for the preparation of the mixture of the above description. The method according to claim 11, wherein the carboxylic acid used is acrylic acid, methacrylic acid or crotonic acid. The method according to claim 11, wherein the carboxylic acid used is acrylic acid, crotonic acid or mixtures thereof. 12. The method of claim 11, wherein the carboxylic acid used is acrylic acid. 12. The process of claim 11 wherein the base used is an alkali metal hydroxide or an aliphatic primary, secondary or tertiary amine. 12. The process according to claim 11, wherein the molar amount of base added in step a) is equal to or less than the sum of the molar amounts of sulfur dioxide and carboxylic acid together. 12. The method of claim 11, wherein step d) in, and the P (III) material is phosphorus trichloride used, PCl ₃ is added before the reaction mixture, characterized in that the addition contains water of PCl ₃ mol of 1 to 2.4 mol per that Way. 12. The method of claim 11, wherein step d) in, and the P (III) material is phosphorus trichloride used, PCl ₃ is added before the reaction mixture, characterized in that the addition contains water of PCl ₃ 1.4 to 1.8 mol per mol Way. The process according to claim 11, wherein reaction step d) is carried out at a temperature of 40 to 180 ° C and reaction step e) is carried out at a temperature of 70 to 120 ° C. The method of claim 11, a) in a first partial step, 1 mol of sulfur dioxide is reacted with 3 to 5.8 mol of water and 1 mol of tertiary aliphatic amine, and in a second partial step, the resulting product mixture is subjected to the same amine 0.9 to 2 mol and unsaturated carboxylic acid or Carboxylic acid mixture [wherein Carboxylic acids of which R ¹ and R ² independently of one another represent hydrogen or methyl are used; react with at least the same molar amount, but at most 2 mol; d) reacting the reaction mixture from step a) with 1.6-2.4 mol of phosphorus trichloride; e) hydrolysis of the reaction mixture from step d) by adding 5.2-100 mol of water, f) optionally distilling the reaction mixture from step e) to remove and recover volatile components; g) reaction steps b) and c) are omitted by alkalizing the reaction mixture from step e) or f) with an alkali metal hydroxide solution and removing tertiary aliphatic amines and reusing in step a). 21. The method of claim 20, wherein the carboxylic acid used is acrylic acid, methacrylic acid or crotonic acid. 21. The method of claim 20, wherein the carboxylic acid used is acrylic acid, crotonic acid or mixtures thereof. The method of claim 20, wherein the carboxylic acid used is acrylic acid. 21. The method of claim 20, wherein the base used is tributylamine. The process of claim 20, wherein the first partial step of reaction step a) is performed at a temperature of 0 to 40 ° C. and the second partial step is performed at a temperature of 40 to 100 ° C. 21. The process according to claim 20, wherein the reaction step d) is carried out at a temperature of 40 to 180 ° C and the reaction step e) is carried out at a temperature of 70 to 120 ° C. The process according to claim 20, wherein the reaction step d) is carried out at a temperature of 60 to 130 ° C and the reaction step e) is carried out at a temperature of 90 to 110 ° C. The 1-hydroxy-3-sulfonoalkane-1,1-diphosphonic acid of claim 1 or the phosphonate mixture of claim 5 is present at a total phosphonic acid concentration of 1 to 20%. Compositions for use in water treatment and alkaline cleaners. A water treatment method comprising adding the composition of claim 28 to water to set the total phosphonic acid concentration to 1 ppm to 500 ppm in water to be treated. An alkaline cleaning method comprising adding the composition of claim 28 to water to set the total phosphonic acid concentration to 1 ppm to 1000 ppm in water to be treated. 1-hydroxy-3-sul as described in claim 1 for inhibiting metal corrosion and scale deposition in the feed water in cooling water systems, sea water evaporators, steam generating systems, gas scrubbing systems, cooling and heating systems and secondary oil extraction. Use of Phonoalk-1,1-diphosphonic acid or phosphonate mixtures according to claim 5.