MXPA97000587A - Procedure for the obtaining of polymers recurring succin conunities - Google Patents

Abstract

The present invention relates to a process for the preparation of a polymer having recurring succinyl units, characterized in that it comprises the reaction of A, a dicarboxylic acid with unsaturated carbon atoms or a derivative thereof, with B, a supply or donor compound of nitrogen, in a first reaction step which is carried out batchwise to give a reaction mixture comprising at least one low molecular weight reaction product of A and B and / or a prepolymer of A and B, and subsequent feeding continuous of the reaction mixture in a continuously operating or working reactor and treatment of the reaction mixture at a temperature of 140 to 350 ° C to give the polymer having recurring succinyl units and a molecular weight Mw > 1300 in a second stage of reaction

Description

PROCEDURE FOR THE OBTAINING OF POLYMERS WITH RECURRING UNITS OF SUCCINILQ. DESCRIPTION OF THE INVENTION. The invention relates to a process for obtaining polymers with recurring suc-cinyl units. The polymers prepared in this way can be hydrolyzed to give the corresponding derivatives by means of organic and inorganic bases. The production of polymers containing succinyl units, especially polyasparaginic acid and polysuccinimide, has been the subject of intensive research for some years. US-A 4 839 461 (= EP 0 256 366) describes the preparation of polyaspartic acid from maleic acid anhydride, water and ammonia. It is known from US-A 4 590 260 that amino acids can be polymerized together with malic acid, maleic acid and / or fumaric acid derivatives at 100 to 225 ° C. According to US Pat. No. 4,698,981, microwaves can be used to carry out a reaction of this type. US-A 5 288 783 describes the preparation of polyaspartic acid from maleic acid or fumaric acid, water and ammonia at temperatures of 190 to 350 ° C and at temperatures of 160 to 200 ° C, by extrusion. The polysuccinimide, prepared by one of the two process routes, is then hydrolyzed in an alkaline fashion to give the polyaspartic acid. EP-A 0 625 531 describes a continuous process for obtaining polymers from monoethylenically unsaturated acids or anhydrides and a hydrogenated component, a fluidizing agent can be present. The present invention relates to a process for obtaining polymers with succinyl-containing units by reacting A, an unsaturated C 4 -carboxylic acid or a derivative thereof, with B, a nitrogen-containing compound in a first reaction step, obtaining a reaction mixture, containing at least one low molecular weight reaction product consisting of A and B and / or a polymer consisting of A and B, preferably with a molecular weight M , ^ < 1300 and then continuous feeding of the reaction mixture to a continuously working reactor, treatment of the reaction mixture at a temperature of 140 to 350 ° C with obtaining the polymer with recurring succinyl units and with a molecular weight Mw > 1300 in a second reaction stage. Preferred compounds A are maleic acid anhydride, maleic acid and fumaric acid. They can be used alone or as a mixture. Preferred compounds B are ammonia or ammonia-releasing compounds, especially suitable are ammonium salts and carbonic acid amides such as, for example, ammonium bicarbonate, diammonium carbonate, urea, isourea (cyanurate ammonium), carbamide acid or ammonium carbamide. It is also possible to use other organic and inorganic ammonium salts. These educts can be used alone or as a mixture in substance or solution. When ammonia B is used as an adduct, it can also be used in gaseous form. The preparation of the reaction mixture is preferably carried out either by reacting the maleic anhydride with ammonia or with the ammonia derivative or by reacting maleic acid anhydride first with water to give maleic acid and subsequently reaction with ammonia and with ammonia derivatives. In a preferred embodiment, maleic anhydride is reacted with ammonia or with ammonia derivatives. In this case, suitable solvents can be used. Water is a preferred application. According to the conditions of the embodiment, maleic anhydride derivatives are formed, such as, for example, maleinamide acid, ammonium maleinamidate, monoammonium maleinate, diammonium maleinate, asparaginic acid., monoammonium asparaginate, diammonium asparaginate, mono-, di-tri-, tetraammonium iminodisuccinate, asparagine, ammonium asparaginate, diammonium iminodisuccinatodiamide and the resulting condensation products thereof. In the presence of water, the corresponding ammonium salts are also formed by the hydrolysis of the acid amides. In another preferred embodiment, maleic anhydride is first reacted with water to give maleic acid, which is then reacted in aqueous solution with ammonia or with ammonia derivatives to give a reaction mixture. According to the invention, reaction mixtures can also be formed, which can additionally contain the corresponding derivatives of fumaric acid and malic acid. In addition, all the components containing amino groups can be presented in condensed form with the remaining carboxylic acid-containing components, with formation of peptide bonds. The maleic acid anhydride or its derivatives in the form of educt A will be used, preferably in amounts such that the molar ratio between the nitrogen in the reactant B, in relation to the maleic anhydride or a derivative thereof in the reactant A is find between 0.1 and 25, preferably between 0.5 and 8, and very particularly preferably between 0.9 and 4. The first stage of the reaction is a rapid, strongly exothermic reaction, during which, in If the reaction is non-specific, for example by a sharp increase in temperature, product deterioration may occur. According to the invention, however, a specific temperature conduction can be ensured with preferably constant reaction conditions, in order to obtain a desired reaction mixture. Preferred reaction conditions are temperatures between 60 and 250 ° C, especially between 70 and 170 ° C, and particularly preferably between 80 and 150 ° C. The residence times can vary especially between 1 minute and 20 hours, preferably between 2 minutes and 3 hours. The pressures are established specifically depending on the conduction of the reaction or the temperature. If necessary, the pressure can be adjusted by adding inert gas. In order to carry out the first stage of the reaction, all reactors which allow a good regulation of the reaction conditions are particularly suitable. It is advantageous to carry out the reaction in discontinuously operating apparatuses which can provide a sufficient residence time. In this case, the volume of the reaction can be used for the dilution of the educt stream and thus reduce the reaction rate and, in spite of this, make a sufficient reaction temperature, which enables the formation of the intermediate products desired. The preferred reactors are all types of stirred tank reactors with and without a closed pumping circuit, cascades of stirred tanks, coil reactors, tubular reactors with recycling etc. When gaseous ammonia is used, examples of reactors should be mentioned: bubble columns, gas agitation tank and bubbling coil reactors. Preferably, the first stage of the reaction will be carried out in a tank with discontinuous stirring. In this case, one of the educts A or B can be arranged, if appropriate in a solvent, and the other educ-to be added. In another embodiment, the educts A and B are fed simultaneously to a discontinuous reactor (semi-continuous work form). If necessary, the educts will be fed premixed to the batch reactor. In this case, all types of mixers can be used. Examples which may be mentioned are jet mixers such as, for example, nozzle mixers, static mixers or dynamic mixers. When gaseous ammonia is used, it will be fed to the reactor preferably through suitable gas distributors. You can imagine all types of static gasifiers (for example perforated plates), sintered plates, annular gasifiers, gasified lances etc) and dynamic gasifiers (for example injectors, ejectors, agitators-gasifiers, etc.). The gaseous ammonia feed can also be carried out in a closed pumping circuit using a suitable direct mixer (nozzles, mixers, static, injectors, ejectors). Once the dosing in the reactor has been completed, the reaction mixture can be directly polyered or, preferably, heated to the desired reaction temperature and kept for a certain time at the reaction temperature. In this case, the reactor under pressure will generally be operated. In this way, the solvent and / or the reaction water formed from the reaction mixture are prevented from evaporating. In another embodiment, the solvent and / or, if appropriate, the water of the reaction formed is specifically evaporated by controlling the pressure, in order to specifically control the temperature and / or the properties of the reaction mixture. . The complex reaction mixtures, obtained in the first batch reaction stage, have not yet been described for obtaining polymers with recurring succinyl units. These differ from the known starting products for the preparation of polyaspartic acid by its complex composition. First of all, the amino group necessary for the formation of the aspartic acid polypeptides in the iminodisuccinates is blocked by the addition of another unit with 4 carbon atoms. Therefore it was not evident that such compounds or mixtures in which these compounds are contained, were suitable for the formation of polymers.

The reaction mixture, formed in the first stage of the reaction, also encompasses mixtures of various reaction mixtures, prepared in advance, or, if appropriate, mixtures of a reaction mixture or of different reaction mixtures with the reaction mixture. the educts A and / or B, is thermally polymerized in the second stage of the reaction in a suitable installation to give the desired product. In this case the choice of the reaction mixture depends on the desired quality of the product for the various fields of application of the products. In a preferred embodiment, several continuous reactors for the first reaction stage are operated in a plant in parallel with the reactor for the subsequent thermal polymerization. In this way a high flexibility of the production facility is achieved. For the thermal polymerization, preferably all the apparatuses that make available the minimum residence times necessary for the polymerization with a narrow distribution of the residence times of the viscous-liquid phase, which allow the necessary conduction of the temperature and at the same time, are suitable. time, an evaporation, at least partial, of the solvent, especially water, as well as the water formed during the reaction. Furthermore, the thermal polymerization should be carried out, for the formation of the polymer chains with homogeneous chain lengths, as far as possible, during equal residence times for all molecules with, as far as possible, identical reaction conditions. Suitable reactors with a narrow spectrum of residence time are known from the literature of the branch (for example Ullmann: Encyclopedia of Industrial Chemistry, 1992, Vol. B4, 97-120). The preferred devices for thermal polymerization are therefore all apparatuses having a defined residence time with a narrow distribution of the residence times for the solid or highly viscous phase and which at the same time enable a good tempering by evaporation, at least partial, of the solvent and / or of the water of the reaction formed during the polymerization. Such preferred devices can be, for example, singly or in combination: a) Residence tubes, see O. Levenspiel The Chemical Reactor Ommiboo OSU Book Stores Inc. Corralis Oregon Jan. 1989, Chap. 3-5. b) Reactors for high viscosity with movable inserts, preferably spindles, List reactor, such as those described in EP-A 0 6122 784 Al c) Driers (for example pallet dryers, spray drying) preferably as those have been described in DE-A-4 425 952. d) Cascade of stirred tanks, especially as those described by Levenspiel (see above) e) Thin-film evaporators, especially as those described by W.L. McCade, JCSmith, Unit operations of chemical engineering, McGrace Hill, 2nd edition, 1967, chapter 16, page 445. f) Reactors for high viscosity without moving inserts (eg reactors with polyphase coil tubes (MP R )), especially as those described in DT 1 667 051, DE 219 967. g) Microwave reactors, especially as those described in US Pat. No. 4,698,981. Especially good results are obtained when has used a tubular reactor or an MPWR. These apparatuses have been specially accredited for carrying out the method according to the invention. In order to control the reactor temperature of the reactions carried out, a complete or even partial closed-loop operation of the reaction mixture can be carried out in combination with dissipation or heat input. For a reaction reaction of this type, all reactors of the above-mentioned type are particularly suitable for recycling the reaction mixture in combination with heat input or dissolution as well as all coil reactors. In a preferred embodiment, it can be dosed, for the desired conduction of the reaction,. a mixture of the reaction formed in the first step of the invention or a mixture of various reaction mixtures, previously prepared or optionally mixtures of a reaction mixture or of different polymers with the educts A and / or B or a component of the product A and / or B or a solvent, at various points suitably along the tubular reactor or the polyphase coil reactor so that an optimum profile of the temperature and optimum properties of the product can be achieved. The number of the dosing points is preferably in the range of up to 10. The type of feed will be chosen in such a way that a good mixing with the reaction solution is verified. The polymer generated in the first stage of the reaction or mixtures of various prepolymers, prepared previously, or optionally mixtures of a prepolymer or of various prepolymers with the educts A and / or B are fed, according to the products used, at temperatures between 50 ° C and 270 ° C in the polymerization reactor. The contribution or dissipation of the heat in the reactor is controlled in such a way that the second stage of the reaction can take place, depending on the type and concentration of the products used, at 120 to 350 ° C, preferably at 140 to 300 ° C. ° C and especially preferentially at 140 to 270 ° C. Advantageously, the temperature will be adjusted by means of the pressure in the reactor and the quantitative streams of the feed prepolymer, formed in the first stage of the reaction, or mixtures of various prepolymers, previously prepared or, if necessary, mixtures of a prepolymer or various prepolymers with the educts A and / or B as well as by the solvent content. In addition, product-product zones with different temperatures in the reaction system can be contacted directly or indirectly in order to verify a thermal exchange. The residence times in the reactor system to be used in the second stage of the reaction, up to 120 minutes inclusive. Residence times of up to 30 minutes inclusive are preferred. Particularly preferred are decreasing residence times as the temperature increases, ie at temperatures between 120 and 200 ° C corresponds a time of less than 30 minutes; at temperatures between 200 and 250 ° C, less than 10 minutes, at temperatures between 250 and 300 ° C less than 5 minutes, at temperatures above 300 ° C, less than 2 minutes. The residence time will preferably be chosen in such a way that practically complete polymerization is verified. The reaction products obtained are hot solutions or fusions containing solvent or containing water, depending on the content of water or solvent due to the enthalpy of the liberated reaction as well as to the supply or to the dissipation of heat. The polymers prepared according to the process of the invention have recurring succinyl units on at least one of the following structures: R = ONH4, NH2 or structures 1, 2, 3, 4, 5 and 6.

In general, the polymers have mainly recurring units 1, 2 and 3. In addition, other recurring units can be contained, due to the conduction of the suitable reaction and to the choice of the educts, for example a) Alic acid units of the formula b) Maleic acid and fumaric acid units of the formula The analysis of the chemical structure is carried out preferably with 13 C-NMR, FT-IR and after complete hydrolysis with HPLC, GC and GC / MS. According to a further development of the invention, the structure of the obtained polysuccinimide can be influenced by means of the stoichiometric ratio.

The polymerization products can be solved. Suitable reaction components are hydroxides or carbonates of alkali metals and alkali metal teas such as, for example, sodium hydroxide solution, potassium hydroxide solution, sodium carbonate or potassium carbonate, ammonia and amines such as triethylamine, triethanolamine, diethylamine, diethanolamine, alkylamine etc. In this case, hydrolysis at a pH value of 7 to 12 is preferred. The products obtained contain asparaginic acid-containing units, which correspond, in the form of the free acid, to the following formulas: CH - CO - NH CH2 - CO - NH - | Y I CH2 COOH - CH COOH Form to Form ß __ When the polymer is constituted totally or fundamentally by these recurring units, it will therefore be constituted by a polyaspartic acid. In general, the proportion of the β-form is greater than 50%, preferably greater than 70%. The temperature in the hydrolysis is conveniently in the range that includes up to the boiling point of the polymer suspension and preferably between 20 and 150 ° C. The hydrolysis will be carried out under pressure if necessary. In this case, a salt will usually be obtained. However, it is also possible to obtain the free acid by pure aqueous hydrolysis or by treating the salt with acids or with acid ion exchangers. Depending on the reaction conditions, for example the residence time and the temperature of the polymerization, different chain lengths or molecular weights can be adjusted. According to the analysis by gel permeation chromatography molecular weights are obtained, in particular from Mw = 1,300 to 10,000, preferably from 1,300 to 1,500, particularly preferably from 1,300 to 4,500. The polymers prepared according to the invention can be used, in non-hydrolyzed form, preferably in hydrolyzed form, as additives in phosphate-free or phosphate-free washing and cleaning agents. These are adjuvants for washing agents and cause a reduction in the scale and grayness on the washed textile during the washing process. Furthermore, the polymers prepared according to the invention are suitable as agents for the treatment of water. These can be added to the water in refrigeration circuits evaporators or installations for the desalination of seawater. In addition, they can be used, inhibitors of the sedimentation in the concentration by evaporation of sugary juices. They are also suitable as dispersants, stabilizers for bleaching agents and as corrosion inhibitors, for the dispersion of organic and inorganic pigments, as additives in fertilizers and as auxiliary agents for grinding. Due to their good dispersion properties, the polymers according to the invention are also suitable as dispersing agents for inorganic pigments and for the production of highly concentrated dispersions in solids (slurries) for example of alkaline earth metal hydroxides, such as, for example, (OH) 2 or Mg (OH) 2 or even their oxides and carbonates, as well as as additives for cement or as cement blenders. The invention also relates to a process for obtaining modifying polymers, in which 0.1 to 99.9 mol% of the educts A and B b) 99.9 to 0.1 mol% of fatty acids, fatty acid amides, polybasic carboxylic acids are reacted. their anhydrides and amides, polybasic hydroxycarboxylic acids, their anhydrides and amides, polyhydroxycarboxylic acids, aminocarboxylic acids, saccharidocarboxylic acids, alcohols, polyols, amines, polyamines, alkoxylated alcohols and amines, aminoalcohols, or sugars, carbohydrates, acids ethylenically unsaturated mono- and polycarboxyles as well as their anhydrides and amides, protein hydrolysates, for example corn protein hydrolyzate, soy protein hydrolyzate, aminosulfonic acids and aminophosphonic acids, according to the process of the invention. The educts A and B, described under a), are used in the polymerization according to the invention from 0.1 to 99.9 mol%, preferably from 60 to 99.9 mol%, and particularly preferably from 75 to 99.9 mol%. All fatty acids are considered as component (b) of the polymers. These can be saturated or ethylenically unsaturated. Examples are formic acid, acetic acid, propionic acid, butyric acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, sorbic acid, myristic acid, undecanoic acid, as well as all mixtures of fatty acids of natural origin, for example mixtures of fatty acids with 12/14 carbon atoms or with 16/18 carbon atoms. As unsaturated fatty acids, acrylic acid and / or methacrylic acid can also be used. In addition, these acids can also be used in the form of their amides. Polyphasic carboxylic acids which may be used are, for example, oxalic acid, succinic acid, glutaric acid, adipic acid, malonic acid, suberic acid, aconitic acid, itaconic acid, sulfosuccinic acid, alkenylsuccinic acids ( with 1 to 26 carbon atoms), 1,2,3-pro-panotric-carboxylic acid, butanetetracarboxylic acid, furanodicarboxylic acid, pyridinedicarboxylic acid. The anhydrides of the polyphasic carboxylic acids can also be used, for example succinic acid anhydride, itaconic anhydride, aconitic acid anhydride and phthalic anhydride. In addition, polybasic hydroxycarboxylic acids and polyhydroxycarboxylic acids also come into consideration as component (b). The polybasic hydroxycarboxylic acids carry, in addition to at least one hydroxy group, at least two or more carboxyl groups. Examples which may be mentioned include malic acid, tartaric acid, racemic acid, citric acid and isocitric acid. The monobasic polyhydroxycarboxylic acids carry, in addition to a carboxylic acid group, two or more hydroxy groups, for example glycerinic acid, dimethylolpropionic acid, dimethylolbutyric acid, gluconic acid. Monovalent alcohols are also suitable, for example with 1 to 22 carbon atoms, such as, for example, methanol, ethanol, n-propanol, i-propanol, butanol, pentanol, hexanol, octanol, lauryl alcohol, stearyl alcohol, etc. The alcohols can optionally also have a double bond, such as allyl alcohol or oleyl alcohol. In addition, these alcohols can be alkoxylated, for example with ethylene oxide or with propylene oxide. The adducts of 3 to 50 moles of ethylene acid on fatty alcohols or on oxoalco-holes are of primary technical interest. Furthermore, it is possible to use, as component (b), either saturated or unsaturated polyols, such as, for example, ethylene glycol, propylene glycol, butanediol, butenediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, neopentyl glycol and alkoxylated polyols such as polyethylene glycols, polypropylene glycols, trimethylolpropane. ethoxylates, glycerin or pentaerythritol with molecular weights of up to 6,000. Further suitable are comonomer (b) also amines such as alkylamine with 1 to 22 carbon atoms, for example methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, octylamine, isooctylamine (ethylhexylamine), stearylamine, allylamine, oleylamine, ethylenediamine, diethylenetriamine, hexamethylene diamine, piperazine, diaminobutane, dimethylamine, diethylamine, hydroxylamine, hydrazine, ethanolamine, diethanolamine, aminopropanediol as well as polyalkyleneamines such as polyethyleneamines with molecular weights of up to 6,000. The amines can also be alkoxylated, for example the addition products of 3 to 30 moles of ethylene oxide on fatty amines such as oleylamine, palmitylamine, or stearylamine. In addition, amino sugars such as aminosorbit or quitosamine are also suitable. They are also suitable as component (b) carbohydrates, such as glucose, sucrose, maltose, dextrin, starches or saccharide carboxylic acids, for example, mungic acid, gluconic acid, glucuronic acid, glutaric acid. In addition amino acids, proteinogens such as glycine, alanine, glutamine and lysine or non-proteinogenic acids such as 4-aminoglutaric acid, diaminosuccinic acid, "11-aminoundecanoic acid and 6-aminocaproic acid as component (b) can be used. The compounds of component (b) are used in amounts of 0.1 to 99.9 mol%, preferably 0.1 to 40 mol%, more preferably 0.1 to 25 mol%, for polymerization A single compound of component (b) or mixtures of two or more compounds of (b) may be used Compounds of component (b) may be mixed in the desired ratio with one of the main educts (a) and used in the of mixing in the first stage of the reaction In another embodiment, the compounds of component (b) are added to the reaction mixture at the completion of the second stage of the reaction at the entrance to the reactor for the reaction. polymer It is also possible to dose the compounds of the component (b) simultaneously with the main starting material (a) in the first stage of the reaction. When monofunctional compounds such as alcohols, amines, fatty acids or fatty acid amides are used as component (b), they will be incorporated at the end of the chain. These act as chain switches and reduce molecular weight. The polyvalent compounds of component (b) can be incorporated in the finished polymer both at the end of the chain and distributed statistically through the polymer chain. The crude polymers can be freed from the monomer parts by customary working methods, for example by extraction with water and hydrochloric acid 1-n- or by filtration through membranes. The analysis of the copolymers is carried out by 13C and 15N-NMR spectroscopy, FT-IR spectroscopy and after total hydrolysis with HPLC, GC and GC-MS. The modified polymers are prepared from the polysuccinimides, preferably by aqueous hydrolysis at 20 ° C to 150 ° C and pH from 7 to 12, optionally under pressure. However, this reaction can also be carried out at temperatures outside the indicated temperature range and at other pH values. Suitable bases are alkali or alkaline earth metal hydroxides or carbonates such as, for example, sodium hydroxide solution, potassium hydroxide solution, sodium carbonate or potassium carbonate, ammonia and amines such as triethylamine, triethanolamine, diethylamine, diethanolamine, alkylamines, etc. Totally or partially neutralized copolymers are obtained, which contain, incorporated by polymerization, from 0.1 to 99.9 mol% asparaginic acid and from 99.9 to 0.1 mol% of at least one compound (b). When primary amines or bases carrying primary amino groups are used for hydrolysis, the amine salts formed, by dehydration, in the corresponding amides can be transformed. The dissociation of the water can be carried out by tempering at temperatures of 30 ° C to 250 ° C, if appropriate, by means of a vacuum. The modified polymers according to the invention can be used as additives in phosphate-free and phosphate-free washing and cleaning agents. The polymers are adjuvants for washing agents and cause, during the washing process, a reduction of the incrustation and grayness on the washed textile material. Furthermore, the polymers modified according to the invention are suitable as agents for the treatment of water. It can be added to water in refrigeration circuits, evaporators or facilities for seawater desalination. They can also be used as deposit inhibitors during the evaporation of sugary juices. Due to their good dispersion properties, the modified polymers according to the invention are also suitable as dispersants for organic pigments and for the production of highly concentrated dispersions in solids (slurries) for example of alkaline earth metal hydroxides such as, for example, Ca (0H) 2 and Mg (0H) 2, or also of its oxides and carbonates as well as as additives for the cement or as cement blenders. The invention is explained in more detail below with reference to exemplary embodiments. Examples Polymers with recurring succinyl units are obtained in the following manner: The abbreviations used mean MS acid maleic acid polyaspartic acid MSA maleic acid anhydride. Example 1. 1.1 Obtaining a solution of 74.5% by weight of malonate_of_INH4l1 ^? ^. 51.7 kg of water are placed in a tank with agitator and heated to 60 ° C. 75.0 kg approximately 0.765 kmoles of maleic anhydride are added in portions, the temperature is increased to 80 ° C. Then 22.1 kg approximately 1.3 kmole of gaseous ammonia are added. In this case the temperature is increased until the end of the ammonia dosing at 100 ° C. 148.8 kg of a 74.5% by weight solution of the MS (NH4) 1/7 salt are obtained. 1.2 Atemperado of the solution. The solution obtained is tempered for 16 hours at 100 ° C. 1.3 Polymerization of the tempered solution. The tempered solution is pumped approximately at a flow rate of 21 kg / hour in a heated coil tube with a length of 58 mm and a section of 15 mm. The polymerization is carried out there at approximately 190-200 ° C. In this case, the solvent and the water of the reaction can largely be removed by evaporation. At the end of the tube, the raw polymer product is discharged by the current that is formed individually in the coil tube without forced circulation. The hot raw product is treated with water in a tub connected below. The analysis shows the following composition referred to carbon (units with 4 carbon atoms): total nitrogen (N): 177% of the theory. 1.4. Hydrolysis to give the sodium salt of polyasnacrinic acid. The amount of sodium hydroxide solution necessary for a complete hydrolysis of the carboxyl groups is determined by the saponification number (VSZ). Peptide bonds are not hydrolyzed by the determination methods. The VSZ for the obtained crude product is 3.08 mmoles NaOH / g of crude product solution. The hydrolysis is carried out with sodium hydroxide solution at 130 ° C for 3 hours under pressure. The ammonia released is then removed by distillation. 1.5 Analysis of the PAS-Na solution. The solution obtained from the PAS-Na salt shows a content of 30% in carbon. The determination of the molecular weight by gel permeation chromatography (GPC) leads to a weight average value Mw of 1390. The determination of the dispersion capacity of calcium carbonate at 25 ° C, pH 11, leads to a value CCK of 22 mg of Ca C03 / g salt of PAS-Na. The ZnO content of an aqueous dispersion of 10 g of ZnO supplemented with water up to 200 ml, shows after 2 hours with a salt amount of PAS-Na of 20 mg, 67% of the theory, with a quantity used of 50 mg, of 74% of the theory and with an employed quantity of 100 mg, of 64% of the theory. The data shows that by polymerizing a salt solution of MS-NH4, which has a heterogeneous composition, a sodium salt of polyaspartic acid can be obtained, which has dispersing and sequestering properties. "Example 2. The tempered solution of example 1 , it is used for the polymerization again with an amount of 21 kg / hour The temperature of the reaction in the coil tubular reactor of 58 m, is from 200 to 210 ° C. The analysis of the crude product introduced in water sample The following composition: Total N 177% of the theory, with a VSZ of 3.46 mmol of NaOH / g of crude product solution PAS, the hydrolysis is carried out accordingly The solution at 24% by weight of PAS-Na salt shows the following analysis values and properties: Mw (per GPC) = 1690; CCDK = 35 mg CaCO3 / g salt of PAS-Na; ZnO content of an aqueous dispersion at 20 ° C, pH 9.5 = 71% of theory with 20 mg of PAS-Na salt, = 76% of theory with 50 mg of salt PAS-Na, = 78 % of the theory with 100 mg of salt PAS-Na and = 73% of theory with 200 mg of salt PAS-Na. Example 3. 3.1 Obtaining a 73.6% solution of NH4l1 / 3i maleinate The procedure is as in Example 1.l. In this case, 51.7 kg of water, 75 kg of MSA and 16.9 kg of gaseous ammonia were used. 143.6 kg of solution were obtained. 3.2 Atemperado of the solution. The solution is tempered for 5 hours at 100 ° C. 3. 3 Polymerization of the tempered solution. The tempered solution is pumped continuously with a flow rate of 20 kg / h in a 58 m heated coil tube. The polymerization is carried out preponderantly (due to the development of the temperature that is established) at temperatures of 185-200 ° C. The raw product introduced in water shows the following N content. Total N = 139% of the theory. 3.4 Hydrolysis of the sodium salt of polyasparaainic acid. The VSZ for the raw product of PAS was 3.22 mmole NaOH / g. After hydrolysis at 130 ° C, 3 hours the ammonia released is distilled off. The almost odor-free solution is analyzed. 3.5 Analysis of the PAS-Na salt solution. The PAS-Na salt solution shows a content of 33% by weight in carbon. Total N = 83% of the theory. Mw per GPC = 1790; the ZnO content of an aqueous dispersion is, when using 20, 50, 100 and 200 mg of the PAS-Na salt, of 69% of the theory, of 76% of the theory, of 78% of the theory and of the 77% of the theory. Example 4. 4.1 Obtaining an 80.4% solution of maleinate of NH4l1 3 ^ The procedure is as indicated in Example 1.1. 39.5 kg of water, 75 kg of MSA and 16.9 kg of gaseous ammonia are used. 131.4 kg of solution are obtained. The temperature level is increased due to the concentrated form of realization at 10-15 ° C. Therefore, the ammonium salt in solution at 110-115 ° C is obtained. 4.2 Atemperado of the solution. The solution is tempered for 1.5 hours at 110 ° C. 4.3 Polymerization of the tempered solution. __ With a quantitative flow of 20 kg / h the solution is heated first in a preheater, with a length of 8 m, up to 215 ° C. The polymerization is then carried out in a coil tube with a length of 11.5 m at temperatures of 145-215 ° C. The raw product introduced in water shows the following N content: total N = 131% of the theory. 4.4 Hydrolysis to give the PAS-Na salt. The VSZ for the crude product solution of PAS is 1.96 mmol / g. The hydrolysis is carried out as described in the previous examples at 130 ° C, for 3 hours and then distilling off the ammonia-water. 4.5 Analysis of the PAS-Na salt solution. The PAS-Na salt solution shows a content of 38% by weight in carbon. Total N = 75% of the theory. The CCDK value is 28 mg of CaCO3 / g of the PAS-Na salt; The ZnO content of an aqueous dispersion is, when using 20, 50 and 100 mg of PAS-Na salt, 67% of the theory, 73% of the theory and 69% of the theory. Example 5. A solution of 73.6% by weight of the salt MS (NH) 1 3 is used for the tempering at 100 ° C, as already described in Example 3.1. After a tempering of 3 hours this solution is used by a quantitative stream of 30 kg / hour for the polymerization. In this case the solution is heated in a pre-heater, with a length of 8 to 235 ° C and then polymerized in a serpentine tube, with a length of 21 m, at temperatures of 185-215 ° C with evaporation elimination of the water. The crude product is introduced into water and shows the following N content: total N = 135% of the theory. With a saponification number of 1.96 mmole NaOH / g, the hydrolysis is carried out in the manner described. The resulting solution at 29% of the PAS-Na salt shows the following analysis and properties: N total = 80% of the theory, Mw (per GPC) = 1720; CCDK = 23 mg of CaCO3 / g; the ZnO content is, when using 10, 25, 50, 100 and 200 mg of the PAS-Na salt per 10 g of ZnO in an aqueous dispersion (200 ml in volume) of 66% of the theory, of 82% of theory, 83% of theory, 84% of theory and 76% of theory. Example 6. 6.1 Obtaining a 73.6% solution of malenose from iNH4l1 # 3- The preparation is carried out as described in example 3.1. 6.2 Atemperado of the solution. The solution is tempered for 6 hours at 100 ° C. The analysis provides a total N = 130% of the theory. 6.3 Polymerization of the tempered solution. With a quantitative current of 40 kg / hour, the solution is first heated in a preheater with a length of 8 m, up to 230 ° C. The polymerization is then carried out with evaporation removal of the water of the reaction mixture at temperatures of 170-205 ° C in a 21 m coil tube. By evaporating a part of the solvent and the water of the reaction, the viscosity of the liquid mass increases. However, the flowability of the reaction mixture is maintained. The hot reaction mixture is further conducted through an extruder heated to 100 ° C. In this case, it is an extruder with two self-cleaning trees, which rotate in identical directions, with a cross section of 59 mm per tree and with a length of 1,050 mm (such extruders have already been described in DBP 862 668 of 1944) . The power absorption was 6.8 kW with a speed of 130 revolutions / -minute. A pulverulent brown product was discharged from the extruder into flakes. It had the following N content: Total N = 111% of the theory. 6.4 Hydrolysis to give the PAS-Na salt. The VSZ of the polysuccinimide is 10.3 mmoles NaOH / g. The hydrolysis is carried out as described in the previous examples at 130 ° C for 3 hours in the autoclave with subsequent elimination by distillation of the ammonia water. 6.5 Analysis of the PAS-Na salt solution. The PAS-Na salt solution shows a content of 31% by weight in carbon (units with 4 carbon atoms). Total N = 89% of the theory; CCDK = 15 mg CaCO3 / g of salt PAS-Na: the ZnO content of an aqueous dispersion is, when using 20, 50, 100, 200 and 300 mg of the PAS-Na salt, 64, 75, 76 , 77 and 71% of the theory; Mw (by GPC) = 2040. In this way it has been shown that a clearer formation of the molecular mass was obtained in this example when an extruder is used. The polymer shows a broad profile in the behavior of the dispersion from the point of view of the application technique. The dis persant effect also occurs for a large number of other pigments (for example titanium oxides, iron oxides), mineral salts (for example calcium carbonate, magnesium carbonate, as well as calcium and magnesium hydroxides and oxides). ) and ceramic powders. The determination of the ZnO content of an aqueous dispersion is carried out according to the following routine: 1 g of the substance to be tested is dissolved in 100 ml of distilled water. The pH of the sample must be 10 and must be corrected, if necessary, by the addition of hydrochloric acid ln or sodium hydroxide ln. The prepared SAMPLE is transferred to a 100 ml volumetric flask and exactly 100 ml of standard solution is filled with distilled water. 10.0 g of ZnO p.A (Merck) are placed in a 250 ml mixing burette and suspended with 140 to 170 ml of water. For the assay of the activity of the concentrations mentioned, the following quantities of standard solution are required: 10 mg in 1 ml of standard solution 20 mg in 2 ml of standard solution 50 mg in 5 ml of standard solution 100 mg in 10 ml of solution 200 mg standard in 20 ml of standard solution 300 mg in 30 ml of standard solution. The mixture is stirred for 30 seconds at 24,000 min-1 with an Ultraturrax agitator, the agitator is rinsed with distilled water, the suspension is completed to 200 ml. The suspension of the sample thus prepared is shaken three times by hand and allowed to stand for 3 hours at room temperature. An aliquot is then collected at the 150 ml mark with a volumetric pipette of 5 ml and transferred to a 50 ml graduated burette, in which 10 ml of ln hydrochloric acid and approximately 20 ml of water have been placed. After completion of the graduated burette, an aliquot of 100 ml is removed from this and it is titrated at pH 11 (ammonium chloride / ammonium chloride) with 0, 1 EDTA solution against the black eriocer or. Evaluation:% ZnO = V • t • 16.27 where V = my of EDTA solution t = title of the EDTA solution. __ It is stated that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property:

Claims (17)

1. CLAIMS 1. - Process for obtaining polymers with recurring succinyl units, characterized in that it is carried out by means of the reaction of A, a dicarboxylic acid with 4 unsaturated carpono atoms or a derivative thereof with B, a compound supplying nitrogen in a first reaction stage with obtaining a reaction mixture, containing at least one low molecular weight reaction product consisting of A and B and / or a prepolymer formed by A and B and then continuous feeding of the reaction mixture in a continuously working reactor, treatment of the reaction mixture at a temperature of 140 ° C to 350 ° C and obtaining the polymer with recurring units of succinyl and with a molecular weight of 1 ^, > 1300 in a second reaction stage.
2. 2. Method according to claim 1, characterized in that the first stage of the reaction is carried out discontinuously.
3. 3. Process according to at least one of the preceding claims, characterized in that the polymerization is carried out with removal of water.
4. 4. Process according to at least one of the preceding claims, characterized in that the product obtained has essentially recurrent units of succinimide.
5. 5. Process according to at least one of the preceding claims, characterized in that the polymer is hydrolyzed to obtain a polymer with mainly recurring asparaginic acid units.
6. 6. Method according to claim 5, characterized in that the polymer has essentially recurring units with the following structure or a salt thereof: CH - CO - NH CH2 - CO - NH - I and I CH2 COOH - CH COOH Form or Form ß where, referring to the sum of the linked parts a and ß, the linked proportion ß is present in a proportion greater than 50%.
7. 7. Process according to at least one of the preceding claims, characterized in that in the first stage of the reaction, anhydride of maleic acid, malic acid or a mixture thereof is used as the starting material A and essentially ammonia as the starting material B.
8. 8. Process according to at least one of the preceding claims, characterized in that the first stage of the reaction is carried out at a temperature comprised between 60 and 250 ° C, especially between 80 and 150 ° C, and with a time of residence between 1 minute and 20 hours.
9. 9. - Process according to at least one of the preceding claims, characterized in that the polymerization is carried out in a second stage of the reaction at a temperature of 120 to 350 ° C, especially of 140 ° C to 270 ° C.
10. 10. Process according to at least one of the preceding claims, characterized in that the first step of the reaction is carried out in a discontinuous reactor described.
11. 11. Process according to at least one of the preceding claims, characterized in that the second stage of the reaction is carried out in a residence tube, a high viscosity reactor, a drier, a cascade of stirred tanks, an evaporator thin layer or in a microwave device.
12. 12. Process according to at least one of the preceding claims, characterized in that the second step of the reaction is carried out in a polyphase coil reactor.
13. 13. Process according to at least one of the preceding claims, characterized in that the polymerization is controlled in the second stage of the reaction in such a way that the polymers obtained have open-chain succinyl units.
14. 14. Process according to at least one of the preceding claims, characterized in that the polymers obtained in the second stage of the reaction are then subjected to a solvolysis, preferably to a hydrolysis.
15. 15. Process according to at least one of the preceding claims, characterized in that the obtained polymers, if necessary after hydrolysis, they mainly have recurring asparaginic acid units.
16. 16. Use of the polymers obtained according to at least one of the preceding claims, in aqueous systems, especially for the treatment of water, for the inhibition of precipitates and for dispersion.
17. 17. Use of the polymers obtained according to at least one of the preceding claims for the dispersion of inorganic or organic particles in non-aqueous systems.