Method of producing aminopolyalkylenephosphonic acid compounds in presence of heterogeneous catalyst

FIELD: chemistry.

SUBSTANCE: disclosed is a method of producing aminoalkylenephosphonic acid which can be used in water purification, inhibiting scum formation, in detergent additives, sequestering agents, activating additives during oil extraction and as pharmaceutical components. The proposed method of producing aminoalkylenephosphonic acid is realised in the presence of not more than 0.4 wt % hydrohalogenic acid, where all available N-H groups in 50% or more of the amine starting material are converted to the corresponding alkylenephosphonic acid. The proposed method involves reacting (a) phosphorous acid, (b) amine and (c) formaldehyde, where the ratio (a): (b) ranges from 0.05:1 to 2:1, (c):(b) ranges from 0.05:1 to 5:1, and (c):(a) ranges from 5:1 to 0.25:1; where (a) and (c) denote number of moles and (b) number of moles multiplied by the number of N-H groups in the amine, in the presence of a Bronsted acid catalyst which is heterogeneous with respect to the reaction medium, with subsequent extraction of the obtained aminoalkylenephosphonic acid.

EFFECT: design of a method of producing aminoalkylenephosphonic acid, which has economical, technological and ecological advantages.

19 cl, 8 ex

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 a heterogeneous with respect to the reaction medium acid catalyst.

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 ammonia/amine starting material (raw material) is converted into the corresponding alkylammonium acid. So can predpolojite, in the art there are many methods for obtaining 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, which produces 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. the Synthesis of aminomethylene phosphonic acids described in Moedritzer and Irani, J. Org. Chem., Vol 31, str-1607 (1966). The most favorable conditions for the reaction of manniche require low pH values, such as that obtained in the results is the use of 2-3 moles of concentrated hydrochloric acid to 1 mol of the amine hydrochloride. This high acidity increases output and inhibits the oxidation of phosphite in phosphate. Formaldehyde is added dropwise to the liquid reaction mixture containing the amine hydrochloride, phosphorous acid and concentrated hydrochloric acid, at the boiling point. Patent document WO 96/40698 applies to obtain the N-phosphonomethyliminodiacetic acid by simultaneous injection into the reaction mixture of water, iminodiacetic 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 its further interaction with the amine in the presence 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, in particular hydrochloric acid, by-products and intermediates. Another objective of the present invention is concerned with the obtaining aminoalkylphosphonic acids using is the quality of raw materials ammonium or amine starting materials, have mostly all free N-H groups are converted to corresponding derivatives alquilerfurgoneta acid. In particular, all N-H groups in 50% or more amine/ammonia source material interact with obtaining derivatives alquilerfurgoneta acid. Not more than 60%, preferably not more than 40% of the reacted 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 in accordance with the method of obtaining the AFC is a more efficient use of formaldehyde, which, in the presence of halogenation acid, can form formaldehyde distillate. The next task of the present invention is a method of obtaining the AFC, which essentially completely eliminates the release into the atmosphere or reduced (through, 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. More about the objective of the present invention is to provide an efficient, not capital intensive 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 (precursors). Another objective of the present invention is the discovery of an effective acid catalyst, which can be reused with regeneration or without regeneration, and which makes it possible to obtain reaction products without using the methods of separation and/or purification. 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. Definition of reagents such as phosphorous acid" and "amine" refers to an individual reagents directly and their precursors (precursors). The term "formaldehyde" means interchangeable formaldehyde, in the literal sense of the word, as well as aldehydes and ketones. The term "amine starting material" refers interchangeably to "ammonia" and/or "Amin".

REDUCED THE I, CONFIRMING the POSSIBILITY of carrying out the INVENTION

It was found that the compounds aminoacetophenone acid can be obtained 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 starting material (raw materials) are converted to 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, and

(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 acid catalyst (g), which is heterogeneous with respect to the reaction medium, and the specified acid catalyst Branstad (Broensted) selected from the group consisting of:

(1) combinations of a solid acidic metal oxide as such or deposited on the material media;

(2) cation exchange resin selected from the group comprising copolymers of styrene, ethylvinylbenzene and divinylbenzene, functionalityand thus, in order to instill SO₃H fragments on the aromatic group, and perftorirovannyh the resin;

(3) organic sulfonic and carboxylic acids Branstad, which at the reaction temperature are essentially not miscible with the reaction medium;

(4) acid catalyst obtained:

(i) the interaction of solid media, have not shared pair of electrons with the applied organic acid Bronsted; or

(ii) the interaction of solid media, have not shared pair of electrons, coated with a compound having an acid center Lewis;

(iii) from heterogeneous solids functionalized by chemical grafting of the acid group of Bronsted or its precursors (precursors), and

(5) heterogeneous heteropolyacids General formula H_xPM_yO_zwhere R is selected from phosphorus and silicon, and M is selected from tungsten and molybdenum and combinations thereof, followed by separation obtained aminoalkylphosphonic acid in a known manner.

Component of phosphorous acid can be used as such, or may be introduced in the form of its P-oxide. Phosphorous acid and the corresponding P-oxides can be obtained from any suitable 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, in Sogno, 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.

According to a preferred variant of the invention, the purification of phosphoric acid includes a reduction in the level of chloride content lower than 0.4%, preferably below 2000 ppm or less, more preferably 200 ppm or less, expressed in relation to the phosphorous acid (100%).

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

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 R₂About₃oxide by introducing the gaseous fostoria water vapor in a plasma reaction zone at a temperature in the range from 1500 to 2500 K for efficient conversion in P ₂O₃with 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 6,440,380. The oxides can be hydrolyzed with obtaining phosphorous acid. In the patent document EP-A-1.008.552 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 the ester of phosphorous acid to phosphoric 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 6,476,256 and 6,238,637.

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, for example, alkylchloride, policyscope interaction PCl ₃with 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 preferred to purify the obtained phosphoric acid by essentially eliminate or mitigate concentrations of products containing chlorine and unreacted starting materials. Such purification methods are well known and the de-facto standard in the area corresponding to the production technology. 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,is a 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 methods (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, with the receipt of phosphorous acid with high selectivity. This method is described in patent US 6,238,637 B1. Essentially similar descriptions of the inventions can be seen in patent documents WO 99/43612 and US 6,476,256 B1. According to another method (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 the patent US 6,440,380 B1. According to another method (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 the FOSFA the nuclear biological chemical (NBC acid, performed with liquid water and steam for the selective hydrolysis of esters of phosphorous acid to phosphoric acid. Patent document EP 1.008.552 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 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 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, steer the Lamin, 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. Usually formaldehyde receive and sell in the form of aqueous solutions containing various, often minor, for example, 0.3 to 3%, the amounts of methanol and usually represents a 37% solution of formaldehyde. 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, and cyclic trimers and tetramera formaldehyde, indicated by the terms of trioxane and tetraoxane respectively.

Formaldehyde component can also be made the flax aldehydes and ketones, having the formula R₁R₂C=O, 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 ketones are acetone, methyl ethyl ketone, bution, acetophenone and 2-acetylcyclohexanone.

The method described in the present invention requires as a necessary component of a heterogeneous acid catalyst Branstad. Pentecosta properties are the ability to deliver protons. The term "heterogeneous" means that the acid catalyst is essentially insoluble in the reaction medium under the reaction conditions, or essentially immiscible, thus liquid, reaction medium under the reaction conditions. Properties of insolubility and/or necesitamos catalyst can be installed on cnym way for example, on the basis of visual observation. Pentecosta acidity can also be derived from the properties of a Lewis acid after coordinating interaction centers Lewis on the catalyst is not shared pair of electrons in the coordinating partner, for example, water. Pentecosta acidity can also be obtained by joining the Lewis acid, for example, BF₃the precursor acid catalyst Branstad who have not shared pair of electrons and which is capable of coordinating interaction with a Lewis acid, for example, silicon dioxide.

Pentecosta properties of any catalysts of this type are easily detectable by conventional means. As an example, Pentecosta acidity can be determined for a thermally stable inorganic products through, for example, thermal desorption Isopropylamine with the subsequent use of microbalance in accordance with the method described R.J. Gorte and others, J.Catal. 129, 88, (1991) and 138, 714, (1992).

Heterogeneous catalyst having the properties of acid Bronsted may, for example, be represented by the following species are independently selected subclasses, namely:

(1) Solid catalysts are represented by combinations of acidic metal oxide, which can be applied to conventional materials media, such as on the silicon oxide, carbon, a combination of silica-alumina or alumina. Such combinations of metal oxide can be applied directly or with the addition of inorganic or organic acids. Suitable examples of catalysts of this class are amorphous silica-alumina, acidic clays, such as smectites, clay-treated inorganic or organic acid, cross-linked clays, zeolites, usually in their proton form, and metal oxides, such as ZrO₂-TiO₂in a molar ratio of approximately 1:1 and sulfated metal oxides, for example, sulfonated ZrO₂. Other suitable examples of combinations of metal oxides, expressed in molar ratios, are: TiO₂-SiO₂in the ratio of 1:1 and ZrO₂-SiO₂in a 1:1 ratio.

(2) Different types of cation exchange resins can be used as acid catalyst when carrying out a reaction between an amine, phosphorous acid and formaldehyde. Typically, such resins include copolymers of styrene, ethylvinylbenzene and divinylbenzene, functionalityand thus, in order to instill SO₃H groups on the aromatic group. Such resins are used as acid catalysts in numerous commercial products, such, for example, the following: tert-butyl is Fira, derived from methanol and isobutene, or bisphenol a, is obtained from acetone and phenol. Such acid resin can be applied in various physical configurations, such as in gel form, in macrostate configuration, or applied on a material carrier, such as silicon dioxide, or carbon, or carbon nanotubes. Another type resin includes perforated resin bearing the carboxylic group or sulfonic acid, or group, and carboxylic, and sulfonic acids. Known examples of such resins are: NAFION⁽™⁾, FLEMION⁽™⁾and NEOSEPTA-F⁽™⁾. Fluorinated resin can be applied both directly and deposited on inert material such as silica or carbon, or carbon nanotubes, enclosed in a highly dispersed network of metal oxide and/or silicon dioxide.

FLEMION is a trademark owned by the company Asahi Glass, Japan.

NEOSEPTA is a trademark owned company Tokuyama Soda, Japan.

NAFION is a trademark owned by the DuPont company, USA.

(3) an Acid catalyst Branstad, such as organic acid Branstad, is essentially insoluble or not miscible with the reaction medium. When the reaction conditions, in particular when the reaction rate is the atur catalyst may form a second liquid phase and at the end of the reaction can be extracted using traditional methods such as filtering or separation of phases. Examples of suitable acid Regents include vysokopetrovsky (this means that 50% or more of the hydrogen atoms connected to carbon atoms, substituted with fluorine atoms), long-chain sulfonic or carboxylic acids, such as perfluorinated undecisive acid or, in particular, perfluorinated carboxylic acid and perfluorinated sulfonic acid having from 6 to 24 carbon atoms. Such perfluorinated acid catalysts can be essentially not miscible with the reaction medium. The reaction will be carried out in a reactor with continuous stirring in order to ensure sufficient dispersion of the acid phase in the aqueous phase. Himself acidic reagent may be diluted insoluble in the water phase, such as water-insoluble ionic liquid.

(4) Heterogeneous substances, usually having a lone pair of electrons, such as silicon dioxide, a combination of silica-alumina, alumina, zeolites, activated carbon, sand and/or silica gel, may be used as a carrier for the acid catalyst Branstad, for example, methanesulfonic acid or para-toluensulfonate acid, or compounds having an acid center Lewis, such as SbF₅so that interaction led to the floor is to obtain a strong Pentecostal acidity. Heterogeneous solids, such as zeolites, silica or mesoporous silica, for example, MCM-41 or 48, or polymers, such as, for example, polysiloxane can be functionalized by chemical grafting of the acid group of Bronsted or its precursor with obtaining, thus, acid groups such as sulfonic and/or carboxylic acid or their precursors. The functionalization can be carried out in various ways known in the art, for example, direct inoculation on solid through, for example, reaction of SiOH groups of the silicon dioxide with chlorosulfonic acid, or may be performed by joining the solid matter using organic bridges, which can be, for example, a derivative of performanceline. Silica, functionalized acid Bronsted, can also be obtained using the Sol-gel method with obtaining, for example, silicon oxide, functionalized with thiol, through co-condensation of Si(OR)₄and, for example, 3-mercaptopropionylglycine using either neutral or ionic formulaic ways, with subsequent oxidation of the thiol to the corresponding sulfonic acid by using, for example, N₂About₂. Functionalityand substances can primantis is as it is, for example, in the form of a powder, in the form of zeolite membranes or in many other forms, for example, in the form of a mixture with other polymers in membranes or in the form of solid extrudates, or floor, for example, structural inorganic carrier, for example, cordierite monoliths; and

(5) Heterogeneous heteroalicyclic, typically having the formula H_xPM_yO_z. In this formula R acts as a Central atom, usually silicon or phosphorus. Peripheral atoms surround the Central atom, usually symmetrically. The most common peripheral elements M are usually Mo or W, while V, Nb, and TA are also acceptable. The indices x, y, z in a known manner to determine the ratio of atoms in the molecule and can be determined by conventional methods. As is well known, the polyacid exist in many crystalline forms, but the most common for heterogeneous types of crystalline form is called the structure of Keggin (Keggin structure). Such heteroalicyclic exhibit high thermal stability and are non-corroding cast. Heterogeneous heteroalicyclic preferably applied on the media selected from silica gel, diatomaceous earth, carbon, carbon nanotubes and ion exchange resins. Preferred heteroalicyclic according to the present from which retenu can be represented by the formula H ₃RM₁₂About₄₀where M represents W and/or Mo. Examples of preferred RM fragments may represent a PW₁₂, PMo₁₂, PW₁₂/SiO₂, PW₁₂/carbon and SiW₁₂.

The heterogeneous catalyst according to the present invention, as generally used in well-known from the prior art concentrations. The main criterion for determining the concentration of the catalyst is, of course, the completion of the reaction, i.e. the conversion of phosphorous acid in connection phosphonic acid. Thus, quantitatively, the concentration of the catalyst in this regard can be optimized in the usual ways. Given that the catalyst can be used in the whole volume of the reaction medium, for example, dispersed immiscible catalyst, or locally, for example, in a fixed bed, or in the membrane, or equivalent structure, it is obvious that in such cases the amount of the catalyst cannot be determined in relation to coreagent. Regardless of the correlation between relative concentrations of reagents, such as amine and the catalyst, it has been experimentally established within the method according to the present invention that a very low concentration of catalyst can lead to high conversion with getting phosphonic acid. In particular, it found the network, in the device for periodic process, for example, in the case reactor with continuous stirring (CRNP) the ratio of the amine (b) in direct (CRNP) contact with a heterogeneous catalyst (g)generally is in the range from 40:1 to 1:5, (b) is expressed as the number of moles multiplied by the number of N-H groups in Amina. The catalyst (d) is expressed as the number of proton equivalents of the catalyst. It is believed that in the case of fixed configuration layer only amine (b) is in direct contact with a heterogeneous catalyst (g). In the case of fixed configuration layer the ratio of the amine (b) and catalyst (d), expressed as specified for CRNP, often is in the range from 10:1 to 1: 40.

Heterogeneous acid catalyst Branstad can be applied to many existing production facilities, which are well known in the art. The catalyst may be used, for example, in the configuration of the fixed layer or in the hull reactor with continuous stirring (CRNP), or with a membrane, or to be suspended in the reaction mixture, or in a mixture with the reaction mixture. Special attention deserves the fact that the heterogeneous catalyst provides significant operational and economic advantages. The catalyst may, for example, be repeatedly IP is alsoan, as a rule, directly, although it may be prescribed minimum non-destructive processing, for example, water or washing with acidified water.

The reaction according to the present invention is carried out in accordance with the regulations, are well known in the art. As 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. the upper Limit temperature limit actually has as its goal the prevention of any essentially 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 be dependent on additional physical parameters such as pressure, and qualitative and quantitative parameters coreagent contained in the reaction mixture.

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 min the minimum amount of unreacted formaldehyde. The duration of the reaction may vary from a short period of time, for example, 30 minutes, up to an extended period of time, for example, 4 hours. The specified duration, typically involves the gradual addition during the reaction of formaldehyde and possibly other reagents. According to one well-tested method, phosphoric 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 technical solution 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. The gradual addition of formaldehyde in the process of the reaction is illustrated in the Examples. Formaldehyde reagent can,for example, gradually add in the course of the reaction itself, or with parts of the amine, or phosphorous acid.

According to another sequence, the reaction may be carried out when combining distillation systems and pressure control. In particular, the reaction vessel containing the reaction mixture, support at atmospheric pressure and the selected reaction temperature. The mixture is then possible to continuously circulates through the reactor operating at increasing autogenous (autoclave) pressure, therefore, in accordance with necessity is gradually added formaldehyde or additional reagents. According to a preferred variant of the invention, the closed reactor may contain a heterogeneous acid catalyst Branstad in any configuration that is acceptable for the specified reaction. The reaction is essentially completed under pressure, and then the reaction mixture is removed from the reaction vessel and return 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 method show that the reaction can be carried out through diverse and essentially complementary podhod is 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 non-reacted formaldehyde, to a temperature preferably in the range from 70°C to 150°C, 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, combining, in particular, the gradual addition of formaldehyde.

According to another approach, the reaction is carried out as a continuous process, if possible, at 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 approach, the method can 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 astasia the invention is illustrated by the following examples, to facilitate understanding.

DESCRIPTION of embodiments of the INVENTION

Example 1

Connection aminoalkylphosphonic acid get through interaction of the following ingredients in the specified proportions.

A mixture containing phosphoric acid, Amberlyst 36 and ammonia, while stirring, heated to 105°C, since at this temperature the gradual addition of formaldehyde by distillation over a period of time is 4 hours and 20 minutes.

The reaction product is analyzed by 31P-NMR spectral method. It was found that in the reaction product are present in significant concentrations below aminotrimethylene acid (ATMP) and N-Methylenebis(meth lenfestey acid) (N-MelBMPA).

Example 2

Additional aminoalkylphosphonic acid get through interaction, the sequence of operations described in Example 1, except for the duration of the addition of formaldehyde, the materials listed below.

Formaldehyde added, starting at a temperature of 105°C. when distillation over a period of time equal to 2 hours and 30 minutes.

Analysis of the reaction product is carried out according to the Example , showed the following concentrations of components:

Example 3

Composition ATMP get through interaction of the following ingredients in the specified proportions.

Catalyst - perftorpolietilena acid is not miscible with the reaction medium under the reaction conditions. All reagents, except formaldehyde, prior to the heating load in the autoclave, which creates the necessary dilleniidae formaldehyde begin at a temperature of 120°C for a period of time, equal to 2 hours.

The reaction product is analyzed according to the method described in Example 1, and it contains the following main connection.

Next song aminoalkylphosphonic acid get through interaction of the listed ingredients as set forth below.

The reaction mixture is produced by adding to the reactor at ambient conditions of phosphorous acid, perfluroundecanoic acid and ammonia. Then the reaction mixture is heated to 120°C and gradually add formaldehyde, starting at a temperature of 120°C, over a period of time equal to 120 minutes.

The reaction products analyzed according to the method described in Example 1, and the results confirm the formation of high concentrations of components phosphonic acid as follows:

The results of the analysis confirm the formation of high concentrations of the desired phosphonic acid compounds. In addition, it was found that the conditions of the reaction provide sufficient space for the optimization method, given the significant concentration of unreacted phosphorous acid and a simultaneous reduction in the formation of phosphoric acid.

Additional compositions aminoalkylphosphonic acid was obtained as follows.

Example 7

114 g of a commercially available resin - wet Amberlyst 36, with an average of 56% of the water several times impregnated by immersion in 100 g of solution containing 87,14% phosphorous acid in water, each time the impregnated resin is shaken for 15 minutes, followed by the separation of the aqueous phase and replacing it with fresh solution of the FOSFA Ristau acid. Stage impregnation is repeated three times, and the thus obtained resin Amberlyst contains a mixture consisting of 52,37 g of phosphorous acid and 11,46 g of water. Because according to this method, you must 67,80 g of phosphorous acid, 15,43 g H₃RHO₃add to the additional amount available in the catalyst. Ingredient of phosphorous acid is added to the catalyst (Amberlyst), followed by stirring the mixture at room temperature and adding 14,34 g of ammonia (32% solution). Then to the resulting mixture while stirring the autoclave high pressure, starting at a temperature of 125°C, over a period of time equal to 60 minutes, add formaldehyde (36,6% solution). After that, the resin is separated from the reaction mixture by filtration, and she essentially can be used as catalyst in the following Example.

Example 8

Reusable catalyst of Example 7 at room temperature is mixed with 67.8 g (0,8268 mol) of phosphorous acid and 14,34 g (0,8505 mol) of ammonia (32% solution). Then to the resulting mixture in the high pressure autoclave over a period of time equal to 60 minutes, starting at a temperature of 125°C, add 69,70 g (0,8505 mol) of formaldehyde (36,6% solution).

The reaction products obtained in Examples 7 and 8, analyzed according to the method described in Example 1, the results played the comfort, what phosphonic acid is formed in high concentrations as set forth below.

Experimental data show that repeated application of the catalyst is successful in the synthesis of aminomethylene phosphonic acids.

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
(in): formaldehyde;
in the following ratio of components:
(a):(b) from 0.05:1 to 2:1;
(C):(b) from 0.05:1 to 5:1 and
(C):(a) from 5:1 to 0.25:1,
where (a) and (b) about the mean 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 a heterogeneous with respect to the reaction medium acid catalyst Branstad selected from the group consisting of:
(1) combinations of a solid acidic metal oxide as such or deposited on the material media;
(2) cation exchange resin selected from the group comprising copolymers of styrene, ethylvinylbenzene and divinylbenzene, functionalityand thus, in order to instill SO₃N fragments on the aromatic group, and perforated resin bearing carboxylic groups and/or sulfonic acid;
(3) organic sulfonic and carboxylic acids Branstad, which at the reaction temperature are essentially immiscible with the reaction environment;
(4) acid catalyst obtained:
(i) a rigid carrier having lone-pair electrons with the applied organic acid Bronsted; or
(ii) the interaction of solid media having lone-pair electrons, coated with a compound having an acid center Lewis;
(iii) from heterogeneous solids functionalized by chemically grafted group acid Bronsted or its precursors, and
(5) heterogeneous heteropolyacids General formula H_xPM_y zwhere R is selected from phosphorus and silicon, and M is selected from tungsten and molybdenum and combinations thereof,
followed by separation obtained aminoalkylphosphonic acid in a known manner.

2. The method according to claim 1, characterized in that the ratios of the reagents are as follows:
(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.

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 ratios of the reagents are as follows:
(a):(b) from 0.4:1 to 1.0:1,0;
(C):(b) from 0.4:1 to 1.5:1 and
(C):(a) from 2:1 to 1.0:1.

5. The method according to any one of claims 1 to 4, 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 autogenous 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, therefore, under the necessity gradually add the formaldehyde and other selected chemicals. 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.

6. The method according to claim 1, characterized in that the amine is selected from the group consisting of:
ammonia;
primary and secondary amines containing separate hydrocarbon groups, 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 sulfonic acid, or esters of such acids, or combinations thereof.

7. The method according to claim 1 or 6, characterized in that the amine is selected from the group consisting of methylamine, ethylamine, butylamine, octylamine, decylamine, dodecylamine, stearylamine, dimethylamine, diethylamine, dibutylamine, naphtylamine, benzylamine, aniline and cyclohexylamine.

8. The method according to claim 1 or 6, characterized in that the amine is a polyamine, selected from the group, ostoja of Ethylenediamine, Diethylenetriamine, Triethylenetetramine, di(propylene)etilanfetamina, di(hexalen)analogue, polyethylenimine and polyallylamine.

9. The method according to claim 1, characterized in that the reagent is phosphorous acid get in a known manner in the presence of not more than 2000 ppm hydrohalogen acid.

10. The method according to claim 9, wherein the phosphorous acid is obtained in the presence of not more than 0.2 wt.% hydrohalogen acid, expressed relative to the concentration of phosphorous acid (100%):
(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.

11. The method according to claim 10, wherein the elemental phosphorus is tetrapolar.

12. The method according to claim 1, wherein the phosphorous acid is obtained by reaction Proc. of the chloride with 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.

13. The method according to item 12, characterized in that products containing chlorine, essentially removed to a concentration of 2000 ppm or less, expressed in relation to the content component of phosphorous acid (100%).

14. The method according to claim 1, wherein the phosphorous acid is obtained by hydrolysis of trichloride phosphorus with the subsequent removal of hydrochloric acid and other intermediate compounds containing chlorine, to a concentration of not more than 2000 ppm, expressed in relation to the content of phosphorous acid (100%).

15. The method according to claim 1, characterized in that the organic acid Bronsted selected from fluorinated carboxylic acids and fluorinated sulfonic acids having from 6 to 24 carbon atoms in the hydrocarbon chain.

16. The method according to item 15, wherein the acid catalyst Branstad represents a perfluorinated undecisive acid.

17. The method according to claim 1, characterized in that the RM fragment in a heterogeneous heteroalicyclic is selected from the group consisting of PW₁₂, PMo₁₂, PW₁₂/SiO₂, PW₁₂/carbon and SiW 12.

18. The method according to claim 1, characterized in that the reaction is carried out in a setting selected from a tank reactor with continuous stirring (CRNP) and the fixed layer, and the ratio of the amine (b)being in direct contact with the heterogeneous catalyst, heterogeneous catalyst (g) in CRNP is in the range from 40:1 to 1:5, and the fixed layer is in the range from 10:1 to 1:40, while (d) is expressed as the number of proton equivalents of the catalyst.

19. The method according to claim 6, characterized in that a separate hydrocarbon groups in the primary and secondary amines have had include from 1 to 50 carbon atoms.