Method for synthesis of aminopolyalkylene phosphonic acid compounds

FIELD: chemistry.

SUBSTANCE: aminopolyalkylene phosphonic acid is obtained in the presence of not more than 0.4 wt % halogen of hydrogen acid with respect to phosphorous acid, wherein all N-H groups of the amine are converted to 50% or more of the corresponding alkylene phophonic acids. Reaction of phosphorous acid (a), amine (b) and formaldehyde (c) takes place in the presence of an acid catalyst (d) with pKa ≤ 3.1, which is homogeneous with respect to the reaction medium, in the ratio: (a):(b) between 0.1:1 and 1.5:1, (c):(b) between 0.2:1 and 2:1, (c):(a) between 3:1 and 0.5:1 and (b):(d) between 40:1 and 1:5, where (a) and (c) denote number of moles, (b) denotes number of moles multiplied by number of N-H groups in the amine, (d) denotes number of moles multiplied by number of free protons in one mole of catalyst.

EFFECT: shorter duration of the single-step cycle, prevention of corrosion, achieving better environmental and economical factors.

20 cl, 64 ex, 35 tbl

The technical FIELD

The invention relates to a method for producing compounds aminoalkylphosphonic acid, in particular to compounds in which all the available N-H in most parts of the amine or ammonia raw materials alkylenediamine, essentially, with the exception halogenation acid, by-products and intermediates (intermediates). More specifically, the compounds aminoalkylphosphonic acid can be successfully obtained by reaction of phosphorous acid, amine and formaldehyde in a precisely defined proportions and in the presence of an acid catalyst, characterized by a pKa value equal to or less than 3.1, provided that the acid catalyst may be homogeneous introduced into the reaction environment.

PRIOR art

Connection aminoalkylphosphonic acids are widely known and find a variety of commercial recognition in a variety of applications, including water purification, slow process of scale formation, detergents, airing, adjuvants during oil extraction at sea fields as pharmaceutical ingredients. It is well known that such industrial application preferably needs aminoalkylphosphonic acids, where most of the functional N-H groups am the IAK/amine starting material (raw material) is converted into the corresponding alkylammonium acid. Therefore, it is logical to assume that in this field of technology there are many ways of making such compounds. The existing prior art receiving aminoalkylphosphonic acids is based on the transformation of phosphorous acid obtained by the hydrolysis of trichloride phosphorus, or on the transformation of phosphorous acid by adding hydrochloric acid, and hydrochloric acid may be partially or fully be added in the form of amine hydrochloride.

Getting aminoalkylphosphonic acid described in the patent document GB 1142294. This method is based on the exclusive use of trihalides phosphorus, usually trichloride phosphorus as a source of reagent is phosphorous acid. For this reaction usually requires the presence of substantial quantities of water, often up to 7 moles per 1 mole of trihalide phosphorus. Water used for hydrolysis of trichloride phosphorus, resulting in phosphorus and hydrochloric acid. Loss of formaldehyde occur during the reaction, which is carried out at low temperatures in the range from 30°C to 60°C, followed by a short stage of heating at 100°C-120°C. In the patent document GB 1230121 disclosed the improvement of the method described in patent document GB 1142294, consisting in the fact that alkilalkoksimyetilfosfinov acid can be obtained odnos adinam way by applying trihalide phosphorus instead of phosphorous acid, this provides economic benefits. Synthesis of aminomethylene phosphonic acids described in Moedritzer and Irani, J. Org. Chem., Vol 31, str-1607 (1966). Currently, the mechanisms of the reaction of manniche and other canonical reactions are known. The most favorable conditions for the reaction of manniche require low pH values, such as those that result from the use of 2-3 moles of concentrated hydrochloric acid to 1 mol of the amine hydrochloride. Formaldehyde is added dropwise to the liquid reaction mixture containing the amine hydrochloride, phosphorous acid and concentrated hydrochloric acid, at the boiling point. In the patent US 3,288,846 also describes a method for aminoalkylphosphonic acids through the formation of a water mixture having a pH value below 4 and containing amine, an organic carbonyl compound such as aldehyde or ketone, followed by heating the mixture to temperatures above 70°C, resulting in aminoalkylphosphonic acid. The reaction is carried out in the presence of halogen ions to inhibit the oxidation orthophosphoric acid in phosphoric acid. Patent document WO 96/40698 applies to obtain the N-phosphonomethyliminodiacetic acid by simultaneous injection into the reaction mixture of water, aminoacetyl the red acid, formaldehyde, a source of phosphorous acid and a strong acid. The source of phosphorous acid and a strong acid is trichloride phosphorus.

In addition, the use of trichloride phosphorus to obtain aminoalkylphosphonic acids are illustrated and it drew the attention of many authors, such as Long, etc. and Tang and others in Huaxue Yu Nianhe, 1993 (1), 27-9 and 1993 34(3), 111-14, respectively. A comparable method is also known from patent application Hungary No. 36825 and patent Hungary No. 199488. In the patent document EP 125766 similarly described the synthesis of such compounds in the presence of hydrochloric acid, which includes the same stages, in the patent document JP 57075990 recommended to obtain these kinds of connections, using as source material phosphorous acid through further interaction with the amine in the presence of concentrated hydrochloric acid.

In the patent application of Japan 57075990 describes a method for tetrathiofulvalene by the interaction of formaldehyde with diaminoalkanes and phosphorous acid in the presence of a large number of concentrated hydrochloric acid.

The INVENTION

Main objective of the present invention is a method of obtaining aminoalkylphosphonic acid (ROS) essentially in the absence of hydrogenogenic, h the particular hydrochloric acid, by-products and intermediates. Another objective of the present invention is concerned with the obtaining aminoalkylphosphonic acids using as source material ammonium or amine source material (raw material), in which substantially all of the free N-H groups are converted to corresponding derivatives alquilerfurgoneta acid. In particular, all N-H groups in 50% or more of the raw material amine/ammonia interact with obtaining derivatives alquilerfurgoneta acid. Not more than 60%, preferably not more than 40%, unreacted amine starting material, expressed relative to the amine source material, where all N-H groups were converted into alkylester acid (100%)contain at least one N-H group, which was not transformed into a derived alquilerfurgoneta acid. Another objective of the present invention is a more efficient use of formaldehyde reagent, which, in the presence of halogenation acid, can form formaldehyde distillate, in the process of obtaining the AFC. The next task of the present invention is the implementation of the method of producing ROS in such a way as to minimize the oxidation of phosphorous acid to phosphoric acid. Another objective of the present invention is a method of obtaining ROS, p. and which essentially completely eliminates the release into the atmosphere or reduced (by, for example, thermal oxidation) release unwanted environmental side products, such as methyl chloride. Another objective of the present invention is to provide such a method of obtaining the AFC, where substantial corrosion problems would be minor. Another objective of the present invention is to provide an efficient, does not require a large investment method of producing ROS. Another object of the present invention to provide an acid catalyst to obtain AFK essentially in the absence of hydrohalogen acids or their precursors. The above and other objectives of the present invention can be solved by the inventive technical solutions described below.

The term "percent" or "%"as defined in the present description, means, unless otherwise stated, the mass percentage. The term "phosphonic acid" and "phosphonate" can be used in the description and claims interchangeably. The term "poly" in the term "aminoalkylphosphonic acid" means that at least two fragments alquilerfurgoneta acid present in this connection. Determination reagent "phosphorous acid" includes essentially individual reagent and its precursors (precursors). The term"amine" includes amines as such and ammonia. The term "formaldehyde" means interchangeable formaldehyde, in the literal sense of the word, as well as aldehydes and ketones.

INFORMATION CONFIRMING the POSSIBILITY of carrying out the INVENTION

It was found that the compounds unapolegetically acid can be obtained in a favorable manner in the presence of not more than 0.4% (expressed with respect to a component of phosphorous acid, taken as 100%) hydrohalogen acid, whereby all the available N-H group in 50% or more amine raw material (source material) is converted into the corresponding alkylenediamine acid by reacting:

(a): phosphoric acid;

(b): Amin;

(in): formaldehyde;

in the following ratio of components:

(C):(a) from 5:1 to 0.25:1;

(a):(b) from 0.05:1 to 2:1;

(C):(b) from 0.05:1 to 5:1;

where (a) and (b) denote the number of moles, and (b) represents the number of moles multiplied by the number of N-H groups in Amina, in the presence of an acid catalyst having a pKa value equal to or less than 3.1, and specified an acid catalyst (g) is homogeneous with respect to the reaction medium and is used in the following ratio of components:

(b):(d) from 40:1 to 1:5;

where (g) denotes the number of moles of catalyst multiplied by the number of free protons in one mole of catalysis is ora, followed by separation obtained aminoalkylphosphonic acid essentially known manner.

In preferred embodiments of the invention apply the following ratio of components:

(a):(b) from 0.1:1 to 1.5:1,

(C):(b) from 0.2:1 to 2:1,

(C):(a) from 3:1 to 0.5: 1.

In particularly preferred versions of the invention, the ratio of components precisely defined as follows:

(a):(b) from 0.4:1 to 1.0:1.0,the

(C):(b) from 0.4:1 to 1.5:1,

(C):(a)from 2:1 to 1.0:1.

Component of phosphorous acid can be used by itself or can be entered in the form of its P-oxide. Phosphorous acid and the corresponding P-oxides can be obtained from any suitable precursors (precursors), including phosphorus of natural origin, contained in rocks, which can be converted in a known manner in elementary phosphorus, with subsequent oxidation to P-oxides and, if possible, of phosphorous acid. The reagent is phosphorous acid can also be obtained by hydrolysis of PCl₃and purification of the thus obtained phosphor acid by removal of hydrochloric acid and other intermediate compounds containing chlorine and the resulting hydrolysis.

The method described in the present invention, is carried out in the presence of not more than 0.4%, predpochtitel is about 2000 ppm or less, more preferably 200 ppm or less, expressed in relation to a component of phosphorous acid (100%), hydrochloric acid.

While obtaining phosphorous acid by direct oxidation of elemental phosphorus and hydrolysis of the resulting P-oxides, as you know, is quite time-consuming, there are different ways in which this relationship can be economically acceptable. In the patent application Canada 2070949 disclosed is a method of obtaining phosphorous acid or the corresponding P₂O₃oxide by introducing gaseous phosphorus and water vapor in a plasma reaction zone at a temperature in the range from 1500 To 2500 K for efficient conversion in P₂About₃with subsequent rapid cooling of the oxides of phosphorus, the temperature of which is above 1500 K, the water to a temperature below 1100 For obtaining N₃RHO₃high purity. According to another approach, the oxides of phosphorus (I) and (III) can be obtained by catalytic reduction of oxides of phosphorus (V), as described in patent US 6440380. The oxides can be hydrolyzed with obtaining phosphorous acid. In the patent document EP-A-1008552 disclosed is a method of obtaining phosphorous acid by oxidation of elemental phosphorus in the presence of alcohol with the production of esters of P(III) and P(V) with subsequent selective hydrolysis of EF is RA phosphorous acid phosphorous acid. In the patent document WO 99/43612 described the selective catalytic method of obtaining P(III) hydroxy acids. Catalytic oxidation of elemental phosphorus to phosphorus, having a degree of oxidation is also known from patent US 6476256 and 6238637.

According to another approach phosphorous acid can be successfully obtained through the interaction of trichloride phosphorus reagent, which represents or carboxylic acid or sulfonic acid, or alcohol. PCl₃reacts with reagent with the formation of phosphorous acid and acid chloride, in the case of acid reagent, or chloride, such as alkylchloride, resulting in the interaction of PCl₃with the appropriate alcohol. Products containing chlorine, for example, alkylchloride and/or the acid chloride can be easily separated from the phosphoric acid by methods known in the art, for example, via distillation. While phosphorous acid, thus obtained, essentially can be applied as specified in the claims, it may be desirable, and is often preferable to purify the obtained phosphoric acid by essentially eliminate or mitigate concentrations of products containing chlorine and unreacted raw materials (starting materials). Such cleaning methods are horoscopist and the de-facto standard in the field, appropriate technology for. Suitable examples of the above cleaning methods include selective adsorption of organic impurities on the active carbon or the application of separation of aqueous phase to highlight the component of phosphorous acid. Material information relating to the interaction of trichloride phosphorus reagent, such as carboxylic acid or alcohol, may be found in Kirk-Othmer, Encyclopedia of Chemical Technology, Chapter Phosphorous Compounds, December 4, 2000, John Wiley & Sons Inc.

In a preferred embodiment of the invention the reagent is phosphorous acid used according to the method of the present invention, represents the products obtained essentially with the exception of halogen. Such methods of obtaining phosphoric acid with the exception of halogen are well known in the art. Specific examples of methods that can be used to obtain reagents phosphorous acid, described below.

According to one of the approaches (i), phosphorous acid may be obtained by reaction of elemental phosphorus, preferably of tetraphosphorus, with water at temperatures below 200°C, in the presence of a catalyst such as a noble metal, such as Pd, is effective in activating the process of oxidation of phosphorus in the interaction of water with the receipt fo forestay acid with high selectivity. This method is described in patent US 6238637 B1, essentially similar descriptions of the inventions can be seen in patent documents WO 99/43612 and US 6476256 B1. According to another approach (ii), mainly species of R.(III), such as phosphoric acid, can be obtained by interaction of species P(V) with a reducing agent, such as hydrogen, in the presence of a catalyst reaction recovery. This method is described in detail in US patent 6440380 B1. According to another approach (iii), phosphorous acid may be obtained by selective hydrolysis of esters of phosphorous acid. The initial hydrolysis reaction mixture containing esters of phosphorous acid and esters of phosphoric acid, is carried out with liquid water and steam for the selective hydrolysis of esters of phosphorous acid to phosphoric acid. Patent document EP 1008552 A1 provides enough to play this way disclosure of this technology.

The required amine component may be represented, for example, traditional reagents containing nitrogen. In particular, the amine component may be selected from the group consisting of:

- ammonia;

- primary and secondary amines containing separate hydrocarbon groups, comprising from 1 to 100, preferably from 1 to 50 carbon atoms, the said Ugledar the derivative fragments may represent primocane linear or branched alkyl fragments or aromatic, or polyaromatic fragments, or combinations thereof;

- polyamines;

- primary and secondary amines and polyamines containing alkoxysilane or dialkoxybenzene radicals and/or functional groups, including functionalityand silyl groups such as trialkylsilyl, hydroxyl, carboxylic acid or sulfonic acid, or esters of such acids, or combinations thereof.

Specific examples of alkylamines followed are methylamine, ethylamine, butylamine, octylamine, decylamine, dodecylamine, stearylamine, dimethylamine, diethylamine, dibutylamine, naphtylamine, benzylamine, aniline and cyclohexylamine. Can also be used primary and secondary aliphatic amines containing a substituted alkyl group.

Acceptable types of polyamines include Ethylenediamine, Diethylenetriamine, Triethylenetetramine, di(propylene)etilanfetamina, di(hexamethylene)triamine, hexamethylenediamine were and polymeric amines, such as polyethylenimine and allylamine.

Despite the fact that amines can be used in the form of a free base, it is often preferred their application in the form of a salt, such as sulfate.

The required formaldehyde component is a well-known and widely used ingredient. Formaldehyde literally known as oxymethylene, has the formula CH_{2/sub> Oh, it is produced and sold in the form of aqueous solutions containing various, often subtle, such as 0.3 to 3%, the amounts of methanol and usually represents a 37% solution of formaldehyde, although there may be various concentrations. Solutions of formaldehyde exist as a mixture of oligomers. The precursors of formaldehyde can, for example, be represented by paraformaldehyde, a solid mixture of linear poly(oxymethyluracili), usually rather short, with chain length n=8-100, cyclic trimers and tetramera formaldehyde, indicated by the terms of trioxane and tetraoxane respectively.}

_{Formaldehyde component can also be represented aldehydes and ketones having the formula R1R2C=0, where R1and R2may be the same or different and selected from the group consisting of hydrogen and organic radicals. When R1represents hydrogen, the material is an aldehyde. When and R1and R2represent organic radicals, the material is a ketone. Types of suitable aldehydes, in addition to formaldehyde, are acetaldehyde, Caproic aldehyde, nicotinic aldehyde, CROTONALDEHYDE, glutaric aldehyde, para-Truelove aldehyde, benzaldehyde, naphthaldehyde and 3-aminobenzaldehyde. Acceptable for the present invention kinds of the ketones are acetone, methyl ethyl ketone, 2-pentanone, bution, acetophenone and 2-acetylcyclohexanone.}

The method described in the present invention requires the presence of an acid catalyst, characterized by a pKa value equal to or less than 3.1, preferably equal to or less than a 2.75, more preferably equal to or less than 1.9, especially less than 1.9;

the specified catalyst is a homogeneous miscible with the reaction medium. The value of pKa is a well-known variable that can be expressed as follows:

pKa=-log₁₀Ka,

where Ka is the acidity constant thermodynamic equilibrium.

PKa value of almost all acidic substances known from the literature or, if necessary, can be easily determined. Homogeneous catalysts are the catalysts suitable for the formation of a single liquid phase reaction medium in the specific conditions of the reaction. It is evident that the catalysts which are insoluble or immiscible with the reaction medium and, thus, which is inhomogeneous in environmental conditions, for example at 20°C, can be miscible or soluble at the temperature of the reaction and, thus, to be recognized as "homogeneous". The acid catalyst may be-is from the reaction medium by known methods, for example, filtering the insoluble acids, separation of the immiscible phases acids or by other conventional methods, such as ion exchange, nanofiltration or electrodialysis. The homogeneous nature of the acid catalyst can be easily installed by, for example, visual examination of the deposition or properties of phase separation.

In the reaction medium an acid catalyst is used in the ratio: (b):(g) in the range from 40:1 to 1:5, preferably from 20:1 to 1:3, more preferably from 10:1 to 1:2. In this respect, (b) represents the number of moles of the amine, multiplied by the number of N-H groups in Amina; (g) is expressed as the number of moles of an acid catalyst, multiplied by the number of free protons in one mole of catalyst. Varieties of acid catalyst suitable for use according to the present invention may, for example, be represented as sulfuric acid, sulfurous acid, triperoxonane acid, triftormetilfullerenov acid, methanesulfonate acid, oxalic acid, para-toluensulfonate acid and naphtalenesulfonic acid. Can also be used mixtures of the aforementioned types of acid catalysts.

The reaction according to the present invention is carried out in accordance with methods well known in the art. As a Shire is to is illustrated in the experimental data, the method can be performed by combining the necessary reagents and heating the reaction mixture to a temperature usually in the range from 45°C to 200°C and up to higher temperatures if they apply high pressure, more preferably from 70°to 150°C. Typically, the temperature increase limit is intended to prevent any inherently undesirable thermal decomposition of the reagent is phosphorous acid. It is obvious and well known that the decomposition temperature of the reagent is phosphorous acid and in General most any other individual reagents can in most cases may vary depending on other physical parameters such as pressure, and qualitative and quantitative parameters coreagent contained in the reaction medium.

The reaction according to the present invention can be carried out at atmospheric pressure and, depending on the reaction temperature, the distillation of water, which also reduces the minimum amount of unreacted formaldehyde. The duration of the reaction can vary from almost instantaneous, for example 1 minute, until an extended period of time, for example 4 hours. The specified duration, typically involves the gradual addition during the reaction formalize the IDA or other reagents. According to one well-tested method phosphorous acid, amine and an acid catalyst are added to the reactor followed by heating the mixture and with the gradual addition of the formaldehyde component, starting at a temperature of, for example, in the range from 70°to 150°C. This reaction can be conducted at atmospheric pressure distillation or without distillation, usually water and a certain amount of unreacted formaldehyde.

According to another example of the method, the reaction can be carried out in a closed vessel under an increasing autogenous pressure. According to this method, the reactants are partially or completely added to the reaction vessel at the beginning of the reaction. In the case of incomplete reaction mixtures additional reagents can be gradually added one by one or with one or more other reagents, as soon as it reached the working temperature of the reaction. Gradually adding formaldehyde directly or mixed with other reagents during the actual reaction is illustrated in the Examples. Reagent formaldehyde may, for example, is gradually added during the reaction itself, or with parts of the amine, or phosphorous acid, or acid catalyst.

According to another example of the method, the reaction may be conducted in Association sist the m distillation and pressure regulation. In particular, the reaction vessel containing the reaction medium is maintained at atmospheric pressure and the selected reaction temperature. The mixture is then, perhaps, is continuously circulated through the reactor operating at increasing autogenous (autoclave) pressure, thus in accordance with the necessity gradually added formaldehyde or additional reagents. The reaction is essentially completed under pressure, and then the reaction mixture is removed from the closed vessel and returned to the reactor, in which, depending on the reaction parameters, particularly temperature, can occur distillation of water and other unreacted ingredients.

Thus, the above-described variants of the method show that the reaction can be carried out through diverse and essentially complementary approaches for implementing the method. Thus, the reaction may be performed as a periodic process by heating the initial reagents, typically phosphorous acid, amine and acid catalyst (1) a closed vessel under conditions of increasing autogenous pressure, or (2) under conditions of boiling under reflux, or (3) by distillation of water and minimal amounts of unreacted formaldehyde to a temperature preferably in the range from 70°to 150°is, and gradually during the reaction, adding formaldehyde component, as illustrated in the Examples. According to a particularly preferred variant of the invention, the reaction is carried out in a closed vessel at a temperature in the range from 100°C to 150°C, in the implementation, in particular by the progressive addition of formaldehyde, when the duration of the reaction is from 1 minute to 30 minutes, more preferably from 1 minute to 10 minutes.

According to another approach, the reaction is carried out as a continuous process, is possible with autogenous pressure and continuous injection of reagents into the reaction mixture at a temperature in the range from 70°C to 150°C, and the reaction product (phosphonic acid) is extracted continuously.

According to another variant, the method may be a semi-continuous process, the reaction of obtaining phosphonic acid is carried out continuously, while the preliminary reaction between the reagents may be carried out serially.

The method according to the present invention is illustrated by the following specific examples.

DESCRIPTION of embodiments of the INVENTION

Example 1

Aminotrimethylene acid (ATMP) produced by interaction of phosphorous acid, ammonia and formaldehyde in the presence of a catalyst - methanesulfonic acid. Indiv the dual components used in the following proportions.

The first reactor add phosphorous acid, then water, methansulfonate acid and ammonia. Thus obtained reaction mixture is heated to 105°C and at this temperature, begin gradual addition of formaldehyde. Formaldehyde is added dropwise within 2 hours. After adding formaldehyde reaction continued for another 2 hours at the boil under reflux.

The reaction product is analyzed by 31P-NMR spectral method. It was found that ATMP get access to 59.1 per cent.

Additional methods of obtaining ATMP carried out using the method described in Example 1,and conducting the reaction in accordance with Example 1, except that the catalyst - methansulfonate acid is used in the following concentrations.

The reaction product analyzed as described in Example 1, ATMP get the output:

The above Examples (1-3), compared with the methods known from the prior art that use a connection PCl₃demonstrate the unexpected advantages of the method according to the present invention and illustrate that aminoalkylphosphonic acid can be obtained without the use of hydrohalogenation reagents for short cycle times and high yields. According to the Example 1, in addition to contained 59.1% of ATMP get 15,9% N-Methylenebis(methylenephosphonic) acid (N-MelBMPA) and 16.5% phosphorous acid. According to Example 2 receive 76.8% of ATMP, 6.8% OF N-MelBMPA and 9% fo forestay acid. According to Example 3 get ATMP high yield, 8.3% of N-MelBMPA and 12% phosphorous acid. Compared with multi-stage procedures lasting more than 6 hours and use as source material trichloride phosphorus, in all three examples, the reaction is carried out in one stage, and complete within 4 hours.

Samples ATMP receive, using the method in accordance with Example 1, except that the reaction was carried out under continuous distillation at the reaction temperature. Individual reagents, with the exception of the catalyst and added water, in Examples 4-8 are applied in identical proportions, the following:

Methansulfonate acid and add water is used in the following concentrations.

The reagents are added according to the sequence described in Example 1. Formaldehyde type, starting at 105°C for 3 hours (Example 4) or 1.5 hours (Examples 5-8). Methods of obtaining these Examples is carried out with continuous distillation of water at the reaction temperature, thereby also reducing the minimum amount of unreacted formaldehyde. The reaction products analyzed as described in Example 1. Analytical results are presented below.

The above results illustrate the extremely important advantages associated with the method according to the present invention, in particular high outputs aminoalkylphosphonic acids obtained in a short one-step production cycle, essentially with the exception of the negative outcomes associated with the use of the method with hydrochloric acid, are known from the prior art. Especially noteworthy is the fact that the obtained distillate can be recycled/used without additional purification stages, to whom it is required for the method, carried out in the presence of hydrochloric acid. Special attention should be paid to the absence of methyl chloride, especially in the gaseous by-products.

Additional methods of obtaining aminoalkylphosphonic acid is carried out as described in Examples 4-8, except as specifically described below. In Examples 9, 11-13 listed ingredients are used in identical concentrations, below.

The concentration and type of catalyst, and the amount of added water is chosen as follows.

The reagents are added according to the sequence given in Example 1. Formaldehyde added, starting at a temperature of 105°C, for:

1.5 hours in Examples 9 and 11,

3 hours in Examples 12 and 13,

in continuous distillation at the reaction temperature. The reaction products are analyzed according to Example 1, contain the above products in specified concentrations.

Aminoalkylphosphonic acid obtained according to Example 1, have the following compositions.

Concentrations and types of catalysts are shown below.

The reagents are added with the according sequence, specified in Example 1. Formaldehyde added, starting at a temperature of 105°C, for:

3 hours in Examples 16 and 17;

2 hours in Example 15,

in continuous distillation, as in Examples 9, 10-13. The reaction products are analyzed according to Example 1, contain the following phosphonate components.

Ethylenediaminetetra(methylene)phosphonic acid (EDTMPA) (Examples 18, 20 and 21) are obtained by the reaction described in Example 1, the same for these examples, the number of listed ingredients listed below.

Catalyst - methansulfonate acid alone or in combination with sulfuric acid is used in the following quantities.

The ingredients are added as described in Example 1. According to Example 18 formaldehyde added, starting at a temperature of 105°C. when distillation over a period of time equal to 4 hours. According to Example 20, 90% of Ethylenediamine added together with formaldehyde, starting at a temperature of 105°C. when distillation over a period of time equal to 4 hours. According to Example 21, 90% Ethylenediamine EXT the keys together with formaldehyde, starting at a temperature of 105°C. when distillation over a period of time is 4 hours and 20 minutes.

The reaction products are analyzed according to Example 1, contains:

Diethylenetriaminepenta(methylene)phosphonic acid (DTPMP) receive (Examples 22-24) via the reaction described in Example 1, the above ingredients are in the established proportions.

Catalyst - methansulfonate acid, is used in the following quantities.

The reagents are added according to the sequence described in Example 1. According to Example 22 formaldehyde added during distillation, starting at a temperature of 105°C, over a period of time equal to 3 hours. Example 23 is identical to Example 22, except that the formaldehyde was added over a period of time equal to 2 hours and 40 minutes. Example 24 perform the same way as Example 23, except that 10% of Diethylenetriamine add other reagents, whereas 90% of the analogue type together with formaldehyde over a period of time is 4 hours and 20 minutes.

The reaction products are analyzed according to Example 1, contain the following connections:

The reaction product obtained according to comparative Example 22 contains 86% phosphoric acid and does not contain DTPMP.

Aminoalkylphosphonic acid (Examples 25-30) get through the interactions that take place in a closed vessel under an increasing autogenous pressure, concentration of reagents used in the procedure described in Example 1, are listed below.

Catalyst - methansulfonate acid is used in the following quantities.

The reagents are added according to Example 1. According to Example 25 10% Diethylenetriamine add other reagents, whereas 90% triamino material type together with formaldehyde, starting at a temperature of 115°C, over a period of time equal to 3 hours. The method described is output in Example 26, identical to the method described in Example 25, except that the formaldehyde/triamine are added dropwise within a period of time of 1 hour and 30 minutes. According to Example 27 40% Diethylenetriamine add other reagents, whereas 60% triamino ingredient added together with formaldehyde over a period of time equal to 30 minutes, starting at a temperature of 125°C. the Sequence of operations of Example 28 is identical to the procedure described in Example 27, except that the formaldehyde-triamine ingredient added dropwise within a period of time equal to 4 minutes. The method described in Example 29, identical to the method described in Example 28, except that the formaldehyde-triamine ingredient added dropwise within a period of time equal to 30 minutes. The sequence of operations of Example 30 is identical to the sequence described in Example 28, except that the formaldehyde-triamine ingredient added dropwise within a period of time equal to 3 minutes.

The reaction products are analyzed according to Example 1 includes the following components:

Example 31 (s)

Comparative compound aminoalkylphosphonic acid get through interactions described in Example 1, the quantities of ingredients listed below.

Formaldehyde added during distillation, starting at a temperature of 105°C, over a period of time equal to 4 hours.

The reaction product is analyzed according to Example 1, contains 0.4 percent EDTMPA, 3.7% of phosphorous acid and 58,1% phosphoric acid.

Example 32

Connection aminoalkylphosphonic acid get according to the method described in Example 1, through the interactions that take place in a closed vessel under an increasing autogenous pressure, the ingredients are listed below.

10% ammonia added with other reagents, whereas the remaining 90% of the ammonia added together with formaldehyde, starting at a temperature of 105°C, over a period of time equal to 3 hours.

The reaction product is analyzed according to Example 1, contains the following connections:

Additional aminoalkylphosphonic acid (Examples 33-46) are obtained according to the method described in Example 1, through the interactions that take place in a closed vessel under an increasing autogenous pressure, the ingredients in the initial proportions are listed below.

obuvki formaldehyde/ammonia in the individual examples are as follows.

Examples:

33. 10% ammonia added at the beginning and 90% of type together with formaldehyde over a period of time is 90 minutes, starting at a temperature of 115°C;

34. As described in Example 33, except that 40% of the ammonia is added at the beginning and formaldehyde/ammonia reagent is added dropwise within a period of time equal to 30 minutes;

35. As described in Example 34, except that the formaldehyde/ammonia added, starting at a temperature of 120°C;

36. As described in Example 34, except that the formaldehyde/ammonia added, starting at a temperature of 125°C;

37. As described in Example 33, except that the formaldehyde/ammonia added, starting at a temperature of 115°C for a period of time equal to 30 minutes;

38. As described in Example 37, except that the formaldehyde/ammonia added, starting at a temperature of 125°C;

39. As described in Example 38, except that the formaldehyde/ammonia is added dropwise within a period of time equal to 30 minutes, starting at a temperature of 120°C;

40. As described in Example 39, except that 30% ammonia added at the beginning, while the remaining 70% is added together with formaldehyde;

41. As described in Example 37, except that 70% of the ammonia is added at the beginning and 30% add together with formaldehyde;

42. As described in Example 41, except for the receiving, the formaldehyde/ammonia added, starting at a temperature of 120°C;

43. As described in Example 42, except that the formaldehyde/ammonia added during the period of 3 minutes, starting at a temperature of 115°C;

44-46. As described in Example 43, except that the formaldehyde/ammonia added, starting at a temperature of 125°C; the reaction products are analyzed according to Example 1, contain the following phosphonate compounds:

A series of compounds aminoalkylphosphonic acid (Examples 47-59) get in a closed vessel under an increasing autogenous pressure, thereby applying the method described in Example 1, with certain changes, as indicated below.

Types of acid catalyst used in the following proportions.

Sequence reactions performed as described in Example 1, it includes the following modified conditions.

Examples:

47, 48. As described in Example 1, except that 70% of the ammonia is added at the beginning and 30% add together with formaldehyde, starting at a temperature of 125°C, over a period of time equal to 30 minutes;

51-55. As described in Example 47, except that the formaldehyde/ammonia type, starting the ri temperature 145°C for a period of time, equal to 3 minutes;

49, 50. As described in Example 51, except that the formaldehyde/ammonia added, starting at a temperature of 135°C (Example 49) or 140°C (Example 50);

56, 57. As described in Example 1, except that the formaldehyde is added dropwise within 3 minutes, starting at a temperature of 145°C;

58. As described in Example 1, except that 70% N₃RHO₃add with formaldehyde under mechanical stirring, starting at a temperature of 125°C, over a period of time equal to 3 minutes;

59. As described in Example 1, except that the formaldehyde added under stirring, starting at a temperature of 125°C, over a period of time equal to 30 minutes;

The reaction products are analyzed according to Example 1, containing phosphonate compounds listed below:

Used in Example 47, the catalyst - small is the new acid may undergo decomposition during the reaction at temperatures exceeding, for example, about 125°C, acetic acid, characterized by a pKa value equal to 4.75 V and CO₂. Therefore, the output of the phosphonic acid is low, this disadvantage arises primarily from the limited thermal stability of malonic acid as a catalyst at the reaction temperature.

EDTM-phosphonic acid (Example 60) are obtained by the reaction sequence described in Example 1; the ingredients in the specified proportions are listed below.

Reagents, including 20% amine, load at the beginning of the reaction; 80% of the amine with formaldehyde added during the reaction, nacinal a temperature of 130°C, over a period of time equal to 30 minutes.

The reaction product is analyzed according to Example 1, contains the following connections.

The above result illustrates the importance of the option of an acid catalyst. Also noteworthy is the fact that the preferred concentration of acid catalyst effectively increase the conversion of phosphorous acid phosphonic acid, thereby simultaneously (and preferably) by inhibiting the oxidation of phosphorous acid to phosphoric acid.

DTPMP product (comparative Example 61) are obtained by reaction described in Example 1. Amounts of reactants are listed below.

Reagents, including 40% amine, load at the beginning of the reaction; 60% of the amine with formaldehyde added during a period of time equal to 30 minutes of reaction, starting at a temperature of 130°C.

The reaction product is analyzed according to Example 1, contains the following connections.

These data demonstrate the need to apply the appropriate acid catalyst. The minimum concentration of an acid catalyst, as claimed in the present invention, necessary to ensure the education of acceptable concentrations aminoalkylphosphonic acids.

An acid catalyst is used in the following proportions.

Reagents, in addition to formaldehyde, is added to the reactor at the beginning of the reaction at room temperature. Then the reaction mixture is heated to 125°C. and at this temperature, begin gradual addition of formaldehyde, which lasts for a period of time equal to 30 minutes. The reaction is carried out in a closed vessel under an increasing autogenous pressure.

The reaction products were analyzed using the method specified in Example 1, indicate that the following compounds are formed.

Compared with the traditional is nymi ways of obtaining the results demonstrate the advantages fixed the claimed method, in particular the high yields obtained in a short cycle, with the additional condition that there is sufficient scope for optimizing the way, given the significant concentration of unreacted phosphorous acid.

1. The method of obtaining aminoalkylphosphonic acid in the presence of not more than 0.4 wt.% (expressed in relation to a component of phosphorous acid, taken as 100%) hydrohalogen acid, whereby all the available N-H group in 50% or more amine starting material are converted to corresponding alkylenediamine acid by reacting:
(a): phosphoric acid;
(b): Amin; and
(in): formaldehyde;
in the following ratio of components:
(a):(b) from 0.1:1 to 1.5:1,
(C):(b) from 0.2:1 to 2:1, and
(C):(a)from 3:1 to 0.5:1,
where (a) and (b) denote the number of moles, and (b) represents the number of moles multiplied by the number of N-H groups in Amina, in the presence of an acid catalyst having a pKa value equal to or less than 3.1, and specified an acid catalyst (g) is homogeneous with respect to the reaction medium and is used in the following ratio of components:
(b):(d) from 40:1 to 1:5;
where (g) denotes the number of moles of catalyst multiplied by the number of free protons in one m the Le of the catalyst, followed by separation obtained aminoalkylphosphonic acid, essentially, in a known manner.

2. The method according to claim 1, characterized in that the acid catalyst used in the ratio (b):(g)in the range from 20:1 to 1:3.

3. The method according to claim 1, characterized in that the reaction is carried out at a temperature in the range from 45 to 200°C.

4. The method according to claim 1, characterized in that the acid catalyst is selected from the group consisting of sulfuric acid, sulfurous acid, triperoxonane acid, triftormetilfullerenov acid, methanesulfonic acid, oxalic acid, malonic acid, para-toluensulfonate acid and naphtalenesulfonic acid, and mixtures thereof.

5. The method according to claim 1, characterized in that the ratios of the reagents are as follows:
(a):(b) from 0.4:1 to 1.0:1.0,the
(C):(b) from 0.4:1 to 1.5:1, and
(C):(a) from 2:1 to 1.0:1.

6. The method according to claim 1, characterized in that the acid catalyst is used in the ratio (b):(g)in the range from 10:1 to 1:2.

7. The method according to any one of claims 1 to 6, characterized in that the reaction is carried out at a temperature in the range from 70 to 150°C., in combination with the approach selected from the following:
carrying out the reaction under atmospheric pressure distillation or without distillation of water and unreacted formaldehyde;
in a closed vessel under an increasing auto is hinnon pressure;
in the combined equipment for distillation and pressure control, whereby the reaction vessel containing the reaction medium, support at atmospheric pressure and selected reaction temperature, followed by circulating the reaction mixture through the reactor operating at increasing autogenous pressure, thus, in accordance with the need to gradually add the formaldehyde and other selected reagents; and
as a continuous process, possibly with increasing autogenous pressure, and the reagents are continuously injected into the reaction mixture, and the reaction product phosphonic acid is extracted on a continuous basis.

8. The method according to claim 1, characterized in that the amine is selected from the group consisting of:
ammonia;
primary and secondary amines containing individual hydrocarbon group comprising from 1 to 100 carbon atoms, and these hydrocarbon fragments may represent primocane linear or branched alkyl fragments or cyclic alkyl fragments, or aromatic or polyaromatic fragments, or combinations thereof;
polyamines; and
primary and secondary amines and polyamines containing alkoxysilane or dialkoxybenzene radicals and/or functional groups, including trialkylsilyl, hydroxyl, carboxylic acid or with Lanovoy acid, or esters of such acids, or combinations thereof.

9. The method according to claim 8, characterized in that alkylamino chosen from:
of methylamine, ethylamine, butylamine, octylamine, decylamine, dodecylamine, stearylamine, dimethylamine, diethylamine, dibutylamine, naphtylamine, benzylamine, aniline and cyclohexylamine.

10. The method according to claim 1, characterized in that the acid catalyst has a pKa value equal to or less than 2.75V.

11. The method according to claim 1, characterized in that the phosphorous acid get in a known manner, essentially, with the exception of halogen.

12. The method according to claim 11, characterized in that the phosphorous acid get, essentially, with the exception of halogen,
(i) by reaction of elemental phosphorus with water at temperatures below 200°C, in the presence of a catalyst effective to activate the oxidation of phosphorus in the interaction with water; or
(ii) through the interaction of species P(V) with a reducing agent, such as hydrogen, in the presence of a catalyst of the reaction of recovery; or
(iii) by reaction of hydrolytic initial mixture containing esters of phosphorous acid and esters of phosphoric acid, liquid water and steam, resulting in the hydrolysis of esters of phosphorous acid to phosphoric acid.

13. The method according to item 12, distinguish the different topics that elemental phosphorus is tetrapolar.

14. The method according to claim 1, characterized in that the polyamine is selected from the group consisting of Ethylenediamine, Diethylenetriamine, Triethylenetetramine, di(propylene)etilanfetamina, di(hexamethylene)analogue, diamine, polyethylenimine and allylamine.

15. The method according to claim 1, wherein the phosphorous acid is obtained by reaction of trichloride phosphorus reagent selected from the group consisting of: carboxylic acid, sulfonic acid and alcohol, with the subsequent removal of the formed products containing chlorine and unreacted starting materials by distillation or phase separation.

16. The method according to item 15, wherein the products containing chlorine, to remove content of 2000 ppm or less, expressed relative to the quantity of the component of phosphorous acid (100%).

17. The method according to claim 1, wherein the phosphorous acid is obtained by hydrolysis of trichloride phosphorus, followed by substantial removal of hydrochloric acid containing chlorine and other intermediate compounds obtained by hydrolysis.

18. The method according to 17, characterized in that the hydrochloric acid and chlorine intermediate compounds are removed to a concentration of 2000 ppm from the phosphor component CI is lots (100%).

19. The method according to claim 1, characterized in that the acid catalyst has a pKa value of less than 1.9.

20. The method according to claim 8, characterized in that the individual hydrocarbon groups in the primary and secondary amines have had include from 1 to 50 carbon atoms.