MXPA01011197A - Method for fractionation of water soluble or dispersible polymers containing amino groups with a broad molar mass distribution - Google Patents

Abstract

The invention relates to a method for fractionation of water soluble or dispersible synthetic polymers containing amino groups with a broad molar mass distribution by means of ultrafiltration. The polymer solution or dispersion which is to be fractionated is continuously fed into an utltrafiltration circuit comprising at least one ultrafiltration unit and the retentate with a narrower molar mass distribution and the permeate are continuously discharged in such a way that the ultrafiltration circuit is placed in a substantially stationary state. The invention also relates to polymers which can be obtained according to the inventive method and to the use thereof.

Description

METHOD OF FRACTIONATION OF SOLUBLE OR DISPERSE POLYMERS? BLESSED EM WATER CONTAINING AMINO GROUPS WITH A WIDE DISTRIBUTION OF MOLAR MASS.

The present invention relates to a process for fractionating water-soluble or water-dispersible amino-containing polymers, which have a broad molar mass distribution by ultrafiltration, and the use of the polymer contained in the retentate. Water-soluble amino-containing polymers they have been used for a long time as retention aids, drainage aids and fixation compositions in the production of paper, as promoters in paper sizing with aldicetenes, as flocculants for waste wastes, as adhesion promoters in production of laminated films. as additives in hair setting and skin care compositions and as compositions for immobilizing anionic active ingredients. As a rule, these amino-containing polymers are adducts and? Or condensates of amino-containing building blocks, such as alkylenimines. days and oligoamines, which may have been reacted with carboxylic acids. carboxylic acid derivatives, polyethers, polyethers and / or crosslinking agents, cf. for example DE-B-1 771 814. US-A-2 182 306, US-A3, 203 910, US-A-4 144 123. EP-A-0 411 400, DE-A-2 1672 567, US -A- 4,066,494, DE-A-2 916,356, WO-A-94/12560, WO-A-94/14873 and Journal of Applied Polymer Science, Vol. 30, 4099-4111 (1984). WO 97/25367 describes a process for preparing condensates containing ammo, soluble in water and adducts by ultrafiltration of aqueous solutions of condensates or adults through membranes, from 5 to 5% by weight of the condensates or adducts contained being separated. as permeate. The condensates and amino-containing adducts obtained by this process have a comparatively narrow molar mass distribution and very good operating characteristics such as retention aids, drainage aids and fixing compositions in papermaking. The disadvantage of these processes is that the adducts and condensates containing amino obtained have a very high Brookfield viscosity of up to 850 mPas, based on a strength of about 15% by weight of polymer solution, which has an adverse effect on the process of ul raf iltration. EP-B-0 442 866 describes a process for separating and reusing reams of urea / formaldehyde, melamma / formaldehyde and polyamidoamma / epichlorohydrin by ultrafiltration. This process is intended to prepare polymers having a high molecular weight and to reduce the concentration of contaminants, such as formaldehyde. The permeate separadc can be worked. if necessary, before recycling to the polymer preparation. A plant for the process is also described, which comprises a polymerization reactor, an ultrafiltration unit and a permeate work stage. The ultrafiltration described in a batch process, part of the polymer solution being removed from a storage container, subjected to ultrafiltration and then recycled to the container, and the process repeated until the contaminant content has been reduced to the desired degree until the desired concentration of the polymer has been reached. The possibility of a procedure is merely indicated, and no additional information is provided. The disadvantage of the batch process for the polymer filtration is that, in order to achieve sufficient separation, the retentate has to be recycled again and again to the product tank until the desired concentration has been reached. After sufficient separation, the product tank must be emptied and filled with fresh starting material and the ultrafiltration must be started and carried out again. This leads to interruption times during filling and emptying and to variable qualities of filtration product to filtration. To avoid interruption times during filling and emptying, a batch plant can be operated cyclically by means of two product tanks, that is, while the ultrafiltration is being carried out from one tank the other tank can be varied and refilled. However, additional plants for cyclic operation acquire a large amount of space and are expensive. To ensure a very uniform quality of the separation products, the filter units would have to be cleaned and / or maintained regularly in the case of batch operation, ie, as a rule after each batch. Another disadvantage is the large viscosity and pressure increase towards the end of the ultrafiltration, which results from the increased concentration of the retentate and requires efficient transport means and pressure resistant plants. Additionally, in the case of high viscosities, it must be increase either the pressure of traps embrana or reduce the incoming flow. Both can adversely affect the separation efficiency In Milk Science International 36 (11) 1981, J, Hiddink, P. De Boer and P.F.C. Nooy reported on investigations towards transmembrane flow in serum ultrafiltration. The effect of a thermal pre-treatment, of pH, of the salt content and of the type of membrane used is investigated. A batch and continuous ultraf iltration plant was used for research, and no dependence on the products was found on the continuous and batch process. It is an object of the present invention to provide a process for fractionating synthetic polymers containing amino, at least partially soluble in water, which is simple to carry out in practice and leads to an amino-containing polymer having a low viscosity and it has at least comparable performance characteristics, such as good drainage and retention action, in papermaking. It has been found that this object is achieved, according to the invention, by a process for the fractionation of water-soluble or water-dispersible synthetic polymers containing ammo having a wide molar mass distribution by ultrafiltration, wherein the solution or The polymer dispersion to be fractionated is continuously fed to at least one ultrafiltration circulation with at least one ultraflation unit. and the retentate having a narrower molar mass distribution and the permeate are continuously discharged, such that the circulation of ultrafiltration is essentially in a constant state. It has surprisingly been found that the amino-containing polymers obtained by this process have very good operating characteristics in combination with a lower viscosity. While polymer transmembrane flux decreases in batch processes at high concentration, in the continuous process an upper polymer transmembrane flux is surprisingly observed when reviewing at higher concentrations. Consequently, in the novel process, the relative requirement with respect to membrane area and delivery decreases substantially compared to the batch process if the process is carried out at high concentration, even when the final concentration of the polymer is constant. This makes it possible to save filtration water, and higher concentration permeate is obtained. As a result, the cost of any required reconcentration of the permeate can be substantially reduced.

Brief description of the figures Figure 1 shows a one stage ultrafiltration plant, suitable for the novel process. Figure 2 shows a four-stage ultrafiltration plant which is suitable for the novel process and in which stages I to IV are connected in series. In the novel process, the polymer is fed into an aqueous medium, preferably as an aqueous solution or aqueous dispersion, to an ultrafiltration, and the polymer-containing aqueous medium is separated into retentate and permeate. As a rule, franation of the amino-containing synthetic polymers used is achieved, i.e., separation into various portions or frans that differ in polymer concentration, polymer composition and / or molecular weight distribution. The novel process is explained in more detail below with reference to an aqueous polymer solution. All statements consequently apply to aqueous polymer dispersions. Ultrafiltration is as a rule a membrane separation process, or membrane filtration process, which is preferably suitable for the molar mass dependent separation of dissolved or dispersed substances. Membrane filtration processes include microfiltration, nanof iltration, and reverse osmosis. These processes differ substantially in the cuts, which depend essentially on the type and porosity of the used membranes ^ Ultrafiltration and microf iltración, in the context of this invention are combined under the term ultraf íltración, are particularly suitable for franating polymers that contain synthetic amino acids in the novel process. Reverse osmosis and iltracíón nanof are appropriate to work preferably permeate obtained in the novel process, for example by concentration, All membranes co ercialmente available that have a cut for polymers with molar masses, for example, from 1000 to 10,000,000 , preferably from 1000 to 500,000, can be used for ultrafiltration. Membranes having cuts for molar masses of 3000 to 300,000 are used particularly preferably. The cutting of the membrane used in each case can be adapted to the molecular weight distribution of water-soluble or water-dispersible amino-containing polymers, which are also referred to below as water-soluble polymers, amino-containing polymers or polymers for simplicity purposes, so that from 5 to 95%, preferably from 20 to 90% by weight of the polymer used can be separated. In ultrafiltration, the low molecular weight frans of polymers whose molar mass is less than the cut are separated as permeate. The high molecular weight frans of the polymer remain in the retentate. In the context of the present invention, the iltración ultraf also comprises, as described above, microf iltración through membranes, membranes having average pore diameter of 0.01 to 10 microns, preferably 0 05-1 icron in particular from 0.1 to 0.5 microns, being used. By separating the frans of low molecular weight with the permeate, polymers containing amino in which the fran of polymer particles having a higher molar mass is increased compared to the polymer used before ultraf iltración obtained in the retained. As a rule, polymers having a narrower molecular mass distribution are obtained by this process. The membranes used may be, for example, in the form of hollow fibers and tubes, plate and frame apparatus, hollow fiber modules or spiral bound modules. Diameters or channel widths are as a rule from 0.5 to 25 mm. In the case of tubes or hollow fibers, diameters of 0.5 to 2.5 mm are particularly suitable. In the case of filters based on plate and frame membranes, such as plate and frame devices or spiral linked modules, the channel widths from 1 to 5 mm are particularly appropriate. Suitable materials for the membranes are, for example, regenerated cellulose, cellulose acetate, cellulose triacetate, polyamide, polyacrylonitrile, copolymers of acrylonitrile, polysulfone, polyethersulphone, copolymers of vinyl chloride, polyimide, fluoride and polyvinylidene, polytetrafluoro oet i leño, polimeti tilmetac ilato. hydrolyzed copolymers of ethylene and vinyl acetate, having a degree of hydrolysis of at least 50% vinyl acetate groups, polycarbonate. polyethylene. prepared by high pressure polymerization of ethylene, and HDPE (very high density polyethylene), polypropylene, carbon, mineral or ceramic membranes and in particular mechanically stable membranes such as metal membranes, e.g., stainless steel membranes that are can combine with a secondary membrane The secondary membrane can consist of titanium oxide or zirconium oxide or one of the above-mentioned organic materials, such as polysulfone. the polysulfone-based membranes are preferably used. The summary relating to ultrafiltration and the membranes appropriate thereto is provided, for example, by Muñir Chryan in Ultrafiltration Handbook, Technomic Publishing Company, Inc., 1986. Membranes which are suitable for ultrafiltration are offered by numerous companies, for example. example atalog Internat ional Treffen für chemische Technik und Biotechnologie ACHEMA 94, Fra kfut am Main. An ultrafiltration unit usually comprises one or more modules which are connected in series and / or in parallel and contain the membrane arrangement. The term "modules" is used when the membranes are combined to form larger structures in order to increase the membrane surface for ullage filtration. In particular, the membranes in the form of tubes or hollow fibers are combined to provide modules, for example, in the form of hollow fiber modules or spirally bonded modules. An ultrafiltration circulation may have one or more ultrafiltration units arranged in series and / or in parallel (an ultrafiltration circulation having at least one ultrafiltration unit is also referred to below as an ultrafiltration step). As a rule, an ultrafiltration circulation has at least one means of transport, such as a pump. In the novel process, a plurality of ultrafiltration circulations connected in series, in general from 2 to 10, in particular from 2 to 6, can also be used. An ultrafiltration unit is preferably available in each circulation of ultrafiltration. Preferably, the ultrafiltration units of a multi-stage plant have membranes with essentially the same cuts. However, the invention is not limited thereto. Each circulation of a multi-stage plant, if required, may have its own pressure and / or flow control. The process can have a controlled feed for an aqueous medium essentially free of polymer, whose feed can preferably be used for concentration, viscosity, production, and / or pressure adjustment in the novel process. The parameters used for this controlled feeding can be in particular process parameters such as concentration, viscosity, conductivity, pressure, flow rate and / or production. Controlled feeding of the aqueous medium can preferably be carried out in the feed of all stages. In a further preferred embodiment of the process, the first and / or the last of a plurality of ultrafiltration stages does not have said controlled feeding. The feeding is effected expediently towards the line through which the polymer solution is fed into the circulation. The connection or coupling of the ultrafiltration stages of a multi-stage ultrafiltration process can be carried out at atmospheric pressure or under pressure control through a valve at the inlet or outlet of the traffic unit. Preferably, the connection of the stages is carried out at atmospheric pressure, that is, the retention of an ultrafiltration stage serves as a feed for the next stage of infiltration. Preferably, the pressure at the inlet of the ultrafiltration unit it is carried from 1 to 20, preferably from 1.5 to 10, particularly preferably from 2 to 5. bar, eg, about 3 or about 4 bar (inlet pressure). A transmembrane pressure of 0.5 to 10, preferably from 1 to 7.5, particularly preferably from 1.5 to 5 bar is preferably established in the ultrafiltration unit. As stated, an ultrafiltration unit may comprise 1, 2, 3 or more ultrafiltration modules. In the case of modules connected in parallel, the inlet pressure is equal to the average of the inlet pressures of the respective modules. If a plurality of modules are connected in series, the module inlet pressure is always the inlet pressure at the first level in the flow direction. In a multi-stage ultraflation, units having a larger diameter or a larger channel width are preferably used in the last stage. For example, a comparable flow can be maintained in this way even in case of an increase in viscosity of the polymer-containing medium in the last stage at a pressure comparable to that in the previous steps, or a higher flow can be achieved in this way in the case of constant viscosity of the medium containing polymer at comparable pressure. For example, a diameter of 1.5 to 3 times or a channel width of 1.5 to 3 times is appropriate. In the context of this process, a constant state should be understood as meaning that at least the polymer feed and the discharge are retained continuously, that is, essentially constant as a function of time, Preferably, other process parameters essential for the process are also essentially constant as a function of time Preferably, other process parameters essential for the process they are also essentially constant as a function of time at any point in the novel process in the aqueous medium containing the amino-containing polymer. The essential process parameters in the novel process are at particular pressure, temperature, polymer concentration and mass distribution. molar. In the context of the invention, the constant state should not be understood as meaning that the relevant process parameters have to be constant during the entire process or in the complete ultrafiltration plant. for example, the pressure in the aqueous medium is as a rule not equal at all points throughout the plant, but in general it is higher in or after the means of transport that transports the aqueous medium through the plant than, for example , in the output of an ultraf iltration unit The inlet pressure (in the ultrafiltration unit or units) is also essentially constant during the novel process, as is the output pressure of the unit. means that each value or process parameter in one location may differ from the value in another location, but that the value in a location considered over a prolonged period is essentially constant. that is, it is essentially constant as a function of time. In those systems in which the starting materials are fed continuously and the product or products are continuously separated, the term flow equilibrium or flow equilibrium state is used in place of the term constant state. Water-soluble or water-dispersible amino-containing polymers that usually have a broad molar mass distribution can be separated by the novel process into polymers having a narrow distribution and high molecular weight fractions and toward polymers having low weight fractions. molecular. The amino-containing polymers are known. They describe, for example, in the prior art cited above. The publications mentioned therein are hereby incorporated by reference in their entirety. These are, for example, a) the reaction products of alkylene diamines or polyalkylene polyamines with crosslinking agents containing at least two functional groups, whose reaction products are described, for example in WO 97/25367. The polyethyleneimines obtainable in this manner have as a rule a broad molar mass distribution and MW of average molar masses, for example, from 120 to 2-1Q6, preferably from 430 to 1-106 This group includes polyamino amines which are grafted with ethylenimine and crosslinked with bisglycidyl ethers of polyethylene glycols and described in US-A 4 144 123 mentioned. Reaction products which can be obtained by reacting Michael adducts of polyalkylene polyamines, polyamidoamines, polyamidoamines grafted with ethylene imine and mixtures of said compounds and monoethically unsaturated carboxylic acids, salts, esters, amides or nitriles with at least one crosslinking agent. functional bi These reaction products are described, for example, in WO-A94 / 184743. in addition to the halogen-containing crosslinking agents, the described classes of halogen-free crosslinking agents are particularly suitable for their preparation, partially hydrolyzed, crosslinked, water-soluble polyethylene glycides described in WO-A-94/12560 and they can be obtained by reaction of polyethylene imines with monobasic carboxylic acids or their esters or anhydrides, acid chlorides or acid amides with formation of amide and reaction of knotted polyethylene glycol with crosslinking agents containing at least two functional groups. The average molar masses M "of the appropriate polyethyleneimines can be up to 2 million, preferably from 1000 to 50,000. The polyethyleneimines are partially nested with monobasic carboxylic acids so that. for example, from 0.1 to 90, preferably from 1 to 50% of the nitrogen atoms admired in the polyethyleneimines are present as a-groups. Suitable crosslinking agents containing at least two functional double bonds are shown above. Halogen-free crosslinking agents are preferably used. Polietieminimines and quaternized polyethyleneimines. For example, both ethylene imine homopolymers and polymers containing, for example, grafted ethylennirin (aziridine) are suitable for this purpose. The homopolymers are prepared, for example, by polymerizing ethyleneinine in aqueous solution in the presence of acids, Lewis acids or alkylating agents, such as methyl chloride. ethyl chloride, propyl chloride, ethylene chloride. chloroform or tetrachlorethylene. The polyethylene imines that can be obtained in this manner have a broad molar mass distribution and average molar masses M "of, for example, 129 to 2 106, preferably 430 to 1 106. The polyethyleneimines and the quaternized polyethylene nitrins, if if required, they may have been reacted with a cross-linking agent containing at least two functional groups (see above) The quaternization of the polyethylenimines may be carried out, for example, with alkyl halides, such as methyl chloride, ethyl chloride, Hexyl chloride, benzyl chloride or lauryl chloride, and with, for example, dimethyl sulfate. Additional suitable amino-containing polymers whose quality can be improved by ultrafiltration are polyethyleneimines modified by a Strecker reaction, for example the reaction products of polyethylenimines with formaldehyde and sodium cyanide with hydrolysis and the resulting nitnets to provide the corresponding carboxylic acids. These products, if required, may have been reacted with a crosslinking agent containing at least two functional groups (see above), polyalkylene phosphonimides and the alkoxylated polyethylenimines obtainable, for example, by reacting polyethylene glycol with ethylene oxide and / or propylene oxide and WO 97/25367 are described, and polyethylene glycol and alkoxylated polyols, if required, can be reacted with a crosslinking agent containing at least two functional groups (see above) The amino-containing polymers are preferably selected from polyalkyleneimines, polyalkylenepolylamines, polyarnidoamines, polyalkylene glycol polyamines, polyamideamines grafted with ethyleneimine and then reacted with at least one bi-functional crosslinking agents, and mixtures and copolymers thereof Polyalkyleneimines, in particular polyethylene imines, and derivatives thereof are preferred Polyamidoamines grafted with ethylene imine and then reacted with at least bi-functional crosslinking agents are particularly preferred. The aforementioned amino-containing polymers are selected in particular from the polymers described in DE-B-24 34 816, DE-A-196 21 300 and WO 97/25367. These publications are hereby incorporated by reference in their entirety. In a preferred embodiment of the novel process, polymers obtainable by condensation of C-C12 dicarboxylic acids. in particular, adipic acid. with pol i (alkylenedia in), in particular diethylenetriamine, ethylenetetramine and tetraethylenepentanine. or mono- bistris- or tetra (aminopropy 1) et i lendiamine or mixtures thereof, grafting of the polyaryoamides, obtained in the condensation, with ethylenimine and subsequent cross-linking are used. The grafting is preferably carried out with an amount of ethyleneimine so that the polydiamine drug contains from 2 to 50, preferably from 5 to 10, ethyleneimine units per basic nitrogen group. The grafted polyamidoamine is crosslinked by reaction with at least bi-functional halogen-free crosslinking agents, preferably bis-glycidyl ethers of polyalkylene glycols, polyglycid ethers of polyethylene glycols having molecular weights of from 400 to 5000, in particular from 500 to 3000, v.gr, about 600 or about 2000, are particularly preferred. The ultrafiltration of synthetic water-containing amino-containing polymers having a broad molar mass distribution is preferably carried out by a process in which an aqueous medium having a polymer content of 3 to 30, preferably 4 to 5% by weight it is continuously fed to the ultrafiltration, and at the end of the process, a retentate having a polymer content greater than 5, preferably greater than 7% by weight, is continuously discharged from the ultrafiltration circulation. As a rule, the retentate discharged from the ultrafiltration circulation has a polymer content of less than 50, particularly less than 30, particularly preferably less than 20% by weight. The ultrafiltration of the amino-containing polymers is preferably carried out in such a way that from 5 to 95, preferably from 20 to 90% by weight of the polymers used are separated as permeate and the polymers having a higher average molecular mass. , if required, they are isolated from the detainee. The amount of the low molecular weight polymers separated as permeate is from 30 to 70% by weight in a preferred embodiment. In the case of ultrafiltration, the temperature of the aqueous polymer solutions is as a rule from 0 to 100EC, but it can also be more than 100BC, in particular if the ultrafiltration is carried out under pressure. The ultrafiltration is preferably carried out at 40 to 90BC, particularly preferably 50 to 70SC. The ultrafiltration is generally carried out at superatmospheric pressure on the retentate side, for example from 0.5 to 50, preferably from 1 to 30 bar. In ultrafiltration the pH of the aqueous solutions of the amino-containing polymer is , for example, as a rule from 2 to 14, preferably from 4 to 13, in particular from 7 to 12. The novel process is carried out using an ultrafiltration plant having at least one feed for the aqueous medium (feed polymer) containing the amino-containing polymer to be filtered, at least one ultrafiltration circulation with at least one ultrafiltration unit, means for discharging the permeate, means for discharging the retentate and, if It is required, transport devices and feeds for aqueous medium free of polymer (feeding medium). To start the plant, the ultrafiltration circulation is fed with starting material (ie, aqueous medium containing unfiltered polymer) through the polymer feed, and the aqueous polymer-containing medium is circulated. When passing through the ultraf iltration unit. the medium containing aqueous polymer is separated into permeate and retained. The retentate remains in circulation while the permeate is continuously discharged from the circulation. The loss of aqueous medium due to continuous discharge of permeate is compensated by constantly feeding into the starting material and, if required, essentially polymer-free aqueous medium. If required, the distillate obtained from the concentration of the polymerization process by means of thin film evaporation or the permeate obtained by means of reverse osmosis can be used as aqueous medium for the ultration. The medium containing aqueous polymer is circulated until the desired degree of filtration has been achieved. During the start, the novel process, therefore, resembles the processes of the prior art. Once the desired degree of filtration in the novel process has been achieved, the retentate having the desired degree of filtration is continuously removed, and the starting material and, if required, aqueous medium essentially free of polymer, for example, distilled from the thin film evaporation or preferably the permeate of the reverse osmosis, they are constantly fed in an amount such that the degree of filtration and the retentate discharge remain constant, that is, the process is now in a constant state, the constant state, the aqueous medium containing the circulating polymer has essentially the desired degree of filtration and / or the desired concentration, i.e. is constantly present in a state corresponding to the final state of the batch process of the prior art. The continuous discharge of retained, that is, the amount of retentate that is continuously discharged per unit time of the ultrafiltration circulation, can be controlled by means of various process parameters, e.g., polymer concentration, viscosity, conductivity, production, pressure in dividing the inlet pressure of the ultraf iltration units, flow regime, in particular the inflow regime, and the flux. The discharge is preferably controlled by means of the inlet pressure of the ultrafiltration unit or by means of the polymer concentration, for example in the form of an in-line solids determination of the retentate obtained, alternatively by measuring the polymer concentration and the flow of the polymer (starting material) fed and of the retentate in the discharge of the process As a rule, the term discharge controlled by pressure or viscosity is used in the case of the first variant, and the term discharge controlled by separation in the case of the second variant. As a rule, polymers containing amino. Water-soluble solvents used in the novel process have a broad molar mass distribution (M "/ Mp, preferably an M, / M r, greater than 100, in particular greater than 200, particularly preferably from 300 to 1000. For example The crosslinked polyaminoamines grafted with ethyleneimine can have a molar mass distribution M "/ Mn of about 400. The molar mass distribution is determined by gel permeation chromatography, based on Pullulan standards, using water as eluent. Starting polymer dispersions having Brookfield viscosities (see below) of 10 to 100 mPas are preferred for the novel process.The retents prepared according to the invention have, for example, viscosities of 20 to 2500, preferably 50 to 800. , particularly preferably from 80 to 300 mPas (measured in a Broofield viscometer at 10% strength by weight of aqueous polymer solutions at 20 ° C and pH 10) and a molar mass ratio M "/ Mn, for example 2 to 350, preferably 10 to 300. The ultrafiltration is preferably carried out in such a way that the ratio of the molar mass distribution of the polymer fed into the distribution The molar mass of the retentate obtained by the process is greater than 1.1, in particular greater than 1.2. particularly preferably greater than 1.3, v.gr, about 1.5, about 2 or about 10. The novel process for the fractionation of amino-containing polymers by ultrafiltration preferably comprises the following steps: a) passage continuous of the solution or dispersion of polymer to an ultra filtration unit, b) separation of the solution or dispersion of polymer in the ultrafiltration unit towards a permeate and a retentate, c) discharge of the permeate from the process, d) discharge of part of the process retentate, mix the remainder of the retentate with the polymer solution or dispersion in step a) and, if required, essentially polymer-free aqueous medium and passage of the mixture to the ultrafiltration unit. the process is carried out in two stages, that part of the retentate that is discharged in d) is preferably subjected to additional fractionation by a process comprising steps aj ad). If the novel process comprises more than two stages, the steps of the process described above are preferably applied in context to the additional steps. The process preferably comprises an upstream start phase having the following steps: a) continuous passage of the solution or dispersion of polymer to an ultrafiltration unit, b) separation of the polymer solution or dispersion in the ultrafiltration unit towards a permeate and a retentate, c) discharge of the permeate from the process, d) mixing of the retentate total with the polymer solution or dispersion in step a) and, if required, with essentially polymer-free medium and passage of the mixture to the ultrafiltration unit until the desired degree of fractionation has been reached in the retentate. The low molecular weight polymer fractions separated as permeate in the fractionation can be recycled to the preparation process for the water soluble polymers used as starting materials in the ultrafiltration, that is, they are used for the synthesis of amino-containing, water-soluble polymers having a wide distribution, which can then be subjected again to ultrafiltration. If the concentration of the permeate of the fraction (content of amino-containing polymer) is lower than, for example. that desired to recycle to the preparation of the polymers. this permeate can be concentrated, for example, by distilling water, preferably by thin film evaporation, or by removing water by membrane filtration methods whose membranes preferably have smaller pore diameters than the membranes used in advance in the polymer actuation. . Membrane filtration methods particularly suitable for concentrating the permeate are narrow traffic, nanof iltration and reverse osmosis. These methods are mentioned together below by the term reverse osmosis. The concentration steps can be carried out as part of the novel process or separately in a separate plant. In both cases, the concentration of preference occurs outside the ultrafiltration circulation. In reverse osmosis, the membranes having a cut for electrically neutral molecules of 50 to 500 dalton are preferably used. For example, membranes having cuts of 50 to 200 dalton and NaCl retentions of 50 to 99.9% (generally referred to as reverse osmosis membrane), membranes having cuts of 150 to 2000 dalton and NaCl retention of 0 to 60 % (generally referred to as nanof iltration membranes) and membranes having cuts of 1000 to 5000 dalton and NaCl retention of 0 to 20% (generally referred to as membranes for narrow ultrafiltration) or combinations thereof are appropriate. Suitable membrane materials are preferably the above-mentioned materials and in particular polymeric materials, such as polyamide, polyimide, polysulfone and polyethersulphone, or non-polymeric materials, such as ceramic materials, for example based on AljOj or Ti02, or carbon . For example, membranes in the form of tubes, hollow fibers, hollow fiber modules, flat modules or spirally linked modules are suitable. The appropriate membranes, for example, are Desal 3 and Desal 5 and Desal and H051 from Osmonics. The permeate can be collected before concentration and then fed to the concentration stage. Preferably, the concentration of the permeate obtained from the novel continuous process is carried out continuously. In this case, the expensive collection of the permeate in collecting containers can be omitted, which represents a saving of time, space and costs compared with the prior art. A reverse osmosis of one stage, two stages or multiple stages is particularly appropriate for the continuous concentration of the permeate. For this purpose, the permeate stream obtained continuously is fed to the reverse osmosis, preferably at a process pressure of 10 to 120, particularly 40 to 70 bar and a process temperature of 5 to 150 aC, in particular 10 at 100 SC, particularly preferably from 30 to 70 BC. Reverse osmosis is preferably carried out at a membrane flow of 0.05 to 5, in particular 0.1 to 4 m / s. To carry out reverse osmosis in spirally bonded modules, the membrane fluxes of 0.1 to 15, in particular from 0 2 to 1 m / s have proven to be useful By coupling the novel continuous fractionation by ultrafiltration with a continuous concentration of the fractionation permeate by reverse osmosis, the following additional advantages are obtained in comparison with processes comprising ultrafiltration in batches with subsequent concentration of the permeate. Since the permeate discharged from the novel continuous ultrafiltration is obtained essentially in constant quantity, constant composition and constant polymer concentration, the subsequent continuous reverse osmosis can be carried out in a particularly advantageous manner with respect to, for example, efficiency and easy process control capability. In addition, the concentration does not require reserve capabilities, which are required in the batch process due to the concentration, composition and amount of permeate that change constantly. If the permeate is concentrated, for example, a concentration of 5 to 50, preferably 10 to 30% by weight of polymer is established. In a preferred embodiment of the novel process, a continuous ultrafiltration of a stage or of multiple steps as described above is carried out, and the continuously obtained permeate is fed at a continuous concentration, in particular at a concentration of one stage or multiple stages by reverse osmosis, in which the permeate of the ultrafiltration is concentrated at a polymer concentration of 5 to 35, preferably 10 to 30% by weight. In a particularly advantageous manner, the concentrate obtained is used to prepare the polymers to be fractionated according to the invention, preferably by grafting with ethyleneimam and subsequent crosslinking with crosslinking agents having at least 2 functional groups, and the polymers obtained from this way they are subjected to the novel continuous ultrafiltration. The permeate obtained from the reverse osmosis is again preferably used as an aqueous medium for the filtration. With respect to the continuous multistage ultrafiltration, it has surprisingly been found that, when operates at higher concentration, for example in a continuous four-stage ultrafiltration, the transmembrane polymer flows from the batch process can be achieved. The novel process thus has a large number of advantages over a batch process: lower water demand for separation higher permeate concentration less stress by concentrating the permeate constant permeate outlet (without ridges) Surprisingly, it has been found that retained and lost obtained by the novel process differ from those obtained in the batch ultratification of the prior art, even when the same processing units and the same ultrafiltration membranes are used in the same way. both cases. At the same polymer concentration, the same degree of concentration retained by the novel process generally have lower viscosities with the same efficiency. The present invention, therefore, is further related to a synthetic amino-containing polymer that can be obtained in the form of a solution, for example in the form of the retentate obtained in the novel ultrafiltration or a concentrate thereof or in solid form obtaining the polymer from the retentate. The polymers that can be obtained in the form of the retentate are preferably used as retention aids, drainage aids, flocculants and fixing compositions in the manufacture of paper For this purpose, they are added to the paper material in the usual amounts, by example, from 0.01 to 1% by weight. Compared with the same amount of amino-containing polymers of the same composition as were prepared by batch ultrafiltration, at least comparable retention and drainage effect are obtained with the fraction of the condensates and / or amino-containing adducts remaining in the same. the one held Surprisingly, however, the viscosity of the retentate is considerably lower. The retentate, therefore, is much easier to handle The polymers obtained as retentate are also very useful, in combination with polyacrylates of high molecular weight, anionic, neutral or cationic, such as retention aids, drainage aids or fixation compositions, Similar systems are described in the literature, for example, EP-A-0 223 223, EP-A-0 235 893 and EP-A-0 335 575.

The combinations of the polymers obtained as retained with colloidal silica or bentonites or additionally with neutral anionic, high molecular weight polyacrylamides, as a third component are also very particularly useful as retention aids, drainage aids or fixation compositions in the manufacture of paper. Processes for the production of paper using cationic assistants that do not undergo any particular post-treatment, for example, ultrafiltration, are described, for example, in EA-0 223 223, EP-A-0 235 893 and EP-A-0 335 575. If the retentates that can be obtained by the novel process are used, a significant improvement is achieved in the drainage and retention regime in papermaking. The polymer fractions obtained as retained in the ul Also, they are used as flocculants in waste sludges, as adhesion promoters in the production of laminated films, as hair setting additives and skin care compositions and as compositions that immobilize anionic active ingredients, for example in the preparation of medicines, in protection of harvest or in protection of material, for example, in the conservation of wood The retenidos that can be obtained in the ultrafiltration and comprising polyethylene imines having an average molar mass M "of, for example, from 105 to 2-106 are preferably used as adhesion promoters for the production of laminated films, These retainings provide stronger bonds having high strength aging. Since the low molecular weight components are separated from the polyethylenimines subjected to ultrafiltration, the retainers are particularly suitable as a primer for the production of food packaging and as additives in compositions for fixing the hair and for skin care. they continue to illustrate the invention without restricting it. The novel process is initially explained with reference to Figures 1 and 2. In the ultrafiltration plant of a stage of Figure 1, 1 indicates the feed point and the circulation direction of the aqueous polymer containing medium. The ultrafiltration circulation 2 comprises a circulation pump 3, a heat exchanger 4 (optional) and an ultrafiltration unit or a membrane module 5 and an outlet 11 for retentate and 12 for permeate, if required, the concentration desired, the desired viscosity and / or pressure can be adjusted by adding aqueous medium through 14 and valve 13. In addition, auxiliary means, such as throttle valves 6 and 7 and bypass 8, 9 and 10 are present, as well as Instrumentation Pl, P2, TI and Fl for pressure, temperature and flow, which controls the throttle valves 6 and 7, thermal exchanger 4 and circulation pump 3. To start the plant, circulation 2 is flooded through 1 with the polymer solution to be filtered. The polymer solution is then circulated through the ultrafiltration unit or the membrane module 5, the transmembrane pressure being controlled by means of the valve 6. The permeate is discharged freely through the branch 10 until it has been achieved the desired concentration of the polymer solution in the circulation. The retentate discharge is then adjusted to free discharge by means of the bypass 8. The position of the throttle valve 6 at this time is set and the inlet pressure before the traction unit 5 is kept constant at the value existing at this time by means of the throttle valve 7 In this manner, the retentate is discharged under pressure control, and the permeate runs freely. The retentate and permeate discharged are replaced by unfiltered, fresh polymer solution which is sucked to through 1 by suction of circulation pump 3. In the plant of Figure 2, the 4 ultrafiltration circulations I to IV are connected in series. The aqueous polymer solution is fed through 101. The ultrafiltration circulation 102 of each stage comprises a circulating pump 103., an optional thermal exchanger 104, an ultrafiltration unit or a membrane module 105 and an outlet for the permeate 106. In addition, each stage has auxiliary means, such as choke valves 107, taps 108 and measurement and control instrumentation. P, T, F and FF for pressure, temperature and flow (these are indicated by dashed lines). The retentate passes through lines 109 from an ultrafiltration stage to the next ultrafiltration stage and can be adjusted to the desired concentration, viscosity and / or pressure by adding aqueous medium through 110 and valves 113. The discharge The retentate is carried out through the outlet 111, and the discharge of the permeate through the outlet 112. The start is effected by flooding the plant with the polymer solution to be filtered. This is then circulated in each stage, in each stage. some case of the retentate of steps I to II being fed through line 109 to the next stage, until the desired concentration of the polymer solution in stage IV has been reached. The retentate is then discharged under pressure control through the outlet 111, and the permeate flows freely through the outlets 106 and 112. The retentate and permeate are replaced by fresh polymer solution, which is sucked through 101 through the suction of circulating circulation pump I If desired, water for dilution can be fed through lines 110 and a proportion control FF. The last stage (stage IV) can also be operated as a stage of pure concentration. For the rest, the following definitions are feasible: Trasrnembrane pressure = (pressure at the module inlet + pressure at the module outlet) / 2 -pressure at the permeate side; Polymer transmembrane flow = amount of polymer in kg, calculated as a solid, which is permeated through a filter area of 1 m2 per hour; Input flow rate = (volume of inflow / time) per input flow area; Inlet flow area (in the case of hollow fibers) - number of hollow fibers x (fiber inner diameter / 2) 2 x pi; Mass transfer = amount of water added, based on the amount of starting solution at the beginning of the ultrafiltration; In the examples that follow, the percentages are by weight, unless otherwise stated. Unless otherwise stated in the examples, the viscosities were measured in a Brookfield viscometer at 20aC, a concentration of 10% by weight and a pH of 10. In the examples in which an ultrafiltration is described, cartridges of hollow fiber from A / G-Technology Corp., Needham, MA, USA, were used, some of which were connected in series; examples of such cartridges are those of type UFP-100-E-4A (filter area of 0.042 m2, diameter of hollow fiber 1 mm, length 36 crn), type EFP-500-E-6A and UFP-500-H-6E filter area 0.56 and 0.44 nr respectively; hollow fiber diameter 1 mm and 2 mm, respectively), type UFP-50Q-E-85 (filter area 8.8 m2, hollow fiber diameter 1 mm), UFP-500-152M (total filter area 18.8 m2, diameter of hollow fiber 1 mm). unless explicitly stated otherwise, the total length of. Hollow fiber was 127 cm.

I. Preparation of polymers la. Polymer 1 In accordance with the methods disclosed in DE-B-24 34 816, Example 3, a polyamidoamine is prepared by condensation of adipic acid with diethylenetriamine and then grafted in aqueous solution with an amount of ethyleneimine so that the polyamidoamine contains 6.7 ethyleneimine units grafted by basic nitrogen group. An aqueous solution of 10% strength of this polymer (polymer la) has a viscosity of 22 mPas. The polymer is crosslinked by reaction with a bisglycidyl ether of a polyethylene glycol having an average molar mass of 2000, in accordance with the data in Example 3 of DE-B-24 34 816. A polymer (polymer 1) containing Ethyleneimine units and having a broad molar mass distribution (Mtl / Mn of 400) and a viscosity of 120 mPas (determined in aqueous solution of 10% strength at 20QC and pH of 10) is obtained. The concentration of the aqueous solution is 12.5% and the pH is 10.

Ib. Polymer 2 The polymer (polyamidoamine grafted with ethyleneimine) is crosslinked by reaction with a bisglycidyl ether of a polyethylene glycol having an average molar mass of 600, in accordance with the data in Example 3 of DE-B-24 34 816. A polymer (polymer 2) containing ethylene imine units and having a broad molar mass distribution (M «/ M- of 400) and a viscosity of 120 mPas (determined in aqueous solution of 10% strength at 202C and pH of 20) is obtained, The concentration of the aqueous solution is 12.5% and the pH is 10.

II. Comparison Examples Comparison Example VB1 Ultraf iltration in batches in diluted mode (lal and in concentration mode (Ib) 3.1 kg of polymer 1 having a solids content of 12.5% were initially taken in a storage container. was pumped by means of a displacement pump to an initial hollow fiber inlet flow rate of 1.0 m / s through a hollow fiber module having a filter area of 0.04 m2, a hollow fiber diameter of 1 mm and a length of 36.2 cm, and the retentate was again passed to the storage container, the transmembrane pressure at the beginning of the experiment was regulated at 2.1 bar by means of a valve at the module outlet. filtration, the inlet pressure was kept constant at 3.4 bar by adjusting pump delivery, the temperature in the experiment was 602 ° C. During ultrafiltration, the level of the storage container was maintained A constant flow was made by measuring additional water to the storage container, until a mass transfer of 4, that is, four times the amount of water, based on the quantity of the starting solution at the beginning of the ultrafiltration, had been reached. added The filtration was then continued without additional addition of water, with reduction of the level, and the retentate in this manner was concentrated. The results of this experiment are summarized in Table 6. Ib. During the ultrafiltration, only 91% of the quantity of liquid discharged as permeate was replaced by adding water, that is, the ultrafiltration was carried out with continuous reduction of the level. The results of this experiment are summarized in Table 6.

Comparison Example VB2. The operation is controlled by inlet pressure by batch in diluted mode (2a) and concentration mode (2b). The polymer 2 was initially taken into a storage container and pumped by means of a displacement pump to a constant hollow fiber inlet flow rate of 0., 5 m / s through hollow fiber modules (filter area 0.56 m2, hollow fiber diameter 1 mm, total length 127 cm) and was passed again to the storage container. The transmembrane pressure was regulated at 2.1 bar by means of a valve at the module outlet during the experiment. Towards the end of the experiment, the incoming flow rate was reduced to 0.3 m / s, so that the inlet pressure in the module did not exceed 4 bar. The temperature in the experiment was 65SC. VB2a: 10.3 kg of polymer 2 having a solids content of 12.3% was used. During ultrafiltration, the level in the storage vessel was kept constant until a mass transfer of 2.4 by measuring additional water to the storage vessel. The ultrafiltration was then carried out without addition of water, until the. Storage container level was 47% of the initial level. The results of this experiment are summarized in Table 6.

VB2b: 7.74 kg of polymer 2 having a solids content of 16% are taken initially, The water measurement was regulated in such a way that an inlet pressure of 4 bar was present in the ultrafiltration module throughout the entire duration of the experiment. The ultrafiltration was carried out until the solids content of the retentate was 10.5%, corresponding to a mass transfer of 1.75. The results of this experiment are summarized in Table 6.

Comparison Example VB3: Batch ultrafiltration to achieve a high solids content 2000 kg polymer 2 was initially taken in a storage vessel and pumped by means of a displacement pump at a constant inlet flow rate of 0 5 m / s through modules having a hollow fiber diameter of 1 m, a total length of 127 cm and a total filter area of 64 m2 and then passed back to the storage container. The transmembrane pressure was regulated at 2.1 bar during the experiment by means of a valve at the module outlet. By measuring additional water to the storage container, the level in the storage container was kept constant until a mass transfer of 2.5. Filtration was then continued without addition of water, until a polymer having a final concentration of 14.5% was sealed. Additional results for the experiment are summarized in Table 6.

III EXAMPLES OF COMPLIANCE WITH THE INVENTION Example Bl Four-stage continuous operation in diluted mode (Bla) and in concentrated mode (Blb) In Examples Bla and Blb, a one-stage continuous plant was used to simulate a continuous plant of four stages, and the retentate obtained in each stage was collected, and after adjusting the concentration with water, it was used as starting material for the next stage.

Bla: Continuous ultrafiltration was carried out with polymer 2 having a solids concentration of 12.5%, Two modules connected in series and having a hollow fiber diameter of 1 mm and a filter area of 0.56 m2 were used The data of the individual stages are summarized in Tables 1 and 6. "PC power" (PC = polymer concentration) is the polymer concentration of the feed at the input of an ultrafiltration stage, "PC bleeding" is the polymer concentration of the retentate at the outlet of this ultrafiltration step and "permeate PC" is the permeate polymer concentration of this step. The input pressure of the module of steps 1 to 3 was adjusted to 3.0 _ + 0.1 bar. The concentrations of the individual stages are shown in Table 1.

Table 1 Stage Addition of PC To i PC sanPC Per- PTMF1 water enta- tion water solution: polymer 1 1.0: 1 6.2% 8 .8% 3 .4% 0, 69 2 1.1: 1 4.2% 6 .9% 1. .7% 0. 42 3 1.2: 1 3.2% 5 .9% 1 .0% 0, 25 4 5.9% 10.5% 1 .6% 0, .15 1) Polymembrane flow of polymer in kg / m''h The additional results of this experiment are summarized in Table 6 Blb: This example was carried out analogously to Example Bla, except that less water was added in the individual steps. The input pressure of module from steps 1 to 3 was adjusted to 3.8 +. 0.1 bar. The data of the individual stages are summarized in Table 2, Table Stage Addition of PC aliPC sanPC per- PTMF1 water mentado grade water solution: polymer 1 0.2: 1 10.6% 13.2% 6.8% 0.86 2 0.7: 2 7.6% 10.8% 3, 7% 0, 51 3 0.8: 1 6.0% 9.4% 2.2% 0, 31 4 9.4% 10, 8% 2.1% 0.19 1) Flow of polymer transmembrane in kg / m2h The additional results of this experiment are summarized in Table 6.

EXAMPLE B2 Continuous two-stage ultrafiltration The ultrafiltration was carried out analogously to Example Bl, except that modules having a filter area of 0.56 m2 and a hollow fiber diameter of 1 mm were used in the first Stage and modules having a filter area of 0.44 m2 and a hollow fiber diameter of 2 mm were used in the second stage. Here, the input pressure of the module of the first stage was adjusted to 4 bar, the transmembrane pressure being 2.1 bar and the incoming flow being 0.5 m / s. The pressure was kept constant with variation of the starting concentration. The retentates obtained in stage 1 were fed, without extra water addition, to the second stage. The inlet pressure served as a fixed point value to regulate the retentate discharge. Under these conditions, five experiments B2a to B2e were carried out, the experiments differing essentially in the solids content of the retentate obtained. The data for the retentions obtained they are summarized in Table 3 and Table 6.

Table 3: Transmembrane polymer flows from stage 1 and stage 2 Transmembrane flow from polymer transmembrane flow - Stage] in polymer - Stage 2 kg / mh in kg / m: h B2a 0, 47 0, 16 B2b 0.42 0.12 B2c 0.40 0.12 B2d 0.35 0.11 B2e 0.31 0.07 VB3 0.20 (batch; Example B, Four stage continuous ultrafiltration coupled to atmospheric pressure and pressure controlled retentate discharge The ultrafiltration was carried out in an apparatus as described in Figure 2, which, however, also has, in the stage IV. a controlled feed (cf, Figure 2: 110/113) for aqueous medium. Water was measured in, stages II, III and IV through these feeds. Modules that have a filter area of 0.56 pr and a hollow fiber diameter of 1 mm were used in each stage, an incoming flux of 0.5 nV modules being adjusted in stages I to III, a resistance 9% by weight of polymer solution 2 was used. The measurement, based on the feed (relation to water to polymer solution) was 0.53 (stage II). 0 62 (stage III) and 0.43 (stage IV), The transmembrane pressure of the stages at III was regulated at 2.2 bar. The retentate was discharged under pressure control by means of the inlet pressure of the last stage (4.8 bar at 0.4 m / s of incoming flow). The results are summarized in IV Table 4 and Table 6.

IV Performance characteristics of the novel retainers not in accordance with the invention. The retentates obtained in Example VB3 Comparison and the novel Examples B2a to B2e and B3 are - if ¬ tested to determine their appropriate capacity as drainage aids and retention aids in papermaking, using two material models (model 1: non-deinked waste paper for cardboard and coating, model 2. improved bleached newspaper) Drainage according to Schopper-Riegler was determined as a measure of drainage efficiency. The optical transparency of the white water flowing out was used as a measure for the reduction of fibers, and fillers. The measurements were carried out with the help of a Lange photometer at 340 nm. The results shown below are average values of these measurements. For each model of material, in 4 measurements, retention aids and drainage aids were measured in concentrations of 0.055 and 0.1% and 0.15% and 0.2% (novel retainers of Examples B2a to B2e and B3, retained from Example VB3 not in accordance with the invention) and 0.1% and 0.2% and 0.3% and 0.4% (unfiltered polymer), Using cumulative parameters, the relative amount of retentate used to achieve the same performance as with unfiltered polymer it was calculated from these eight measurements, the respective amount of polymer being calculated as solid. The data and results are summarized in Table 4.

Table 4, Concentration of starting material and product properties after 2 stages Separating Material Retained Viscosity Quantity of solid splitting of Relative Concentrated Batching of D1 'B2a 6.3% 53% 14.2% 183 mPas 53% B2b 5.0% 55% 13.8% 190 mPas 51% B2c 4.2% 55% 13.1% 198 mPas 51% B2d 3.6% 56% 12.0% 159 mPas 52% B2e 3.1% 54% 10.2% 102 mPas 50% B3 9.0% 54% 10.5% 136 mPas 53% VB3 - (Lot) 54% 1 .5% 850 mPas 53% 1) Determined in accordance with Brookfield, 20BC 2) amount of polymer, calculated as solid, to achieve the same performance as with unfiltered starting polymer; the relative quantity used was determined for two material models of the mean value of the drainage time measurements in accordance with Schopper-Riegler and the optical transparency of the white water SAW. Coupling continuous ultrafiltration with continuous reverse osmosis A membrane test cell that is suitable for retaining flat membranes was used in the laboratory apparatus. The membrane area was 80 cm2 and the retentate flow channel was 40 mm wide and 1.2 mm high and fitted with a spacer. The cell is thus lowered to the scale of a rolled module. The cell was integrated into a circulation as follows: circulation vessel - high pressure pump heat exchanger - cell - pressure relief valve circulation vessel Circulation retention was approximately 2.5 1. - In circulation, the performance through the cell, the temperature and the pressure before and after the cell were measured The temperature (by means of the heat exchanger), the performance (by means of the pump speed) and the cell pressure ( by means of the pressure release valve) were regulated. The permeate flow was determined by weighing. Controlled by means of a level control in the circulation vessel, the feed solution (permeate fractionation) was fed into the circulation, and the retentate was removed from the circulation by means of a controllable pump. The pump circulation was filled to the controlled level with feed solution and the reverse osmosis was started. The following process parameters were maintained. Pressure before the cell = 50 bar - circulation temperature = 50EC - Performance through the cell = 66 1 / h (Membrane flow = 0 38 m / s) In a first phase, the concentration at the final solids content This was then carried out by means of permeate removal and controlled measurement by level of additional feed solution to the circulation. The plant was then matched through the continuous feed and bleeding operation, that is, the permeate and the retentate were removed and the feed solution was measured under level control. The removal of the retentate was regulated in such a way that the solids content in the circulation was maintained at the desired value. To simulate a two-stage feed and cascade of bleeding, the retentate was used a second time as a feed solution, as described above. After equilibrium had been established, all data measured for feeding and bleeding operation were recovered. The measured data obtained with the various membranes are shown in Table 5. Table 5: Results of the continuous concentration of permeate by means of membrane methods Membrane Stage Starting conditions Conc. from permeate flow to conc, feeding feed [kg / rn7 h] [%] Desal SDK 1 4 2 119 Desal 5DK 1 3.9 122 Desal 5DK 1 4.2 115 2 10 2 66 .4 Desal G 10 1 3.8 73 Osmonics H051 1 4 0 139 Table 5 (continued); Membrane Feeding and bleeding data Concentration flow regime. { %] Flow more (kg / h) of per- Ali- Rete- Permea- Rete- Permeate mennido de tion Desal 5DK 0, 254 0.052 0.202 20.2 0.078 25, 2 Desal 5DK 0.173 0.028 0.145 23.6 0.085 18.1 Desal SDK 0, 897 0.366 0.531 10.2 0, 061 66.4 0. 396 0.198 0.198 20.4 0.077 24.8 Desal G 10 0.201 0.039 0, 162 19.3 0.099 20, 2 Osmonics H051 0.363 0.080 0.283 16 8 0.419 35.4 NF membrane _ Desal 5DK (polyamide), UF membrane = Desal GIO (polyamide); Osmonics H051 (polysulfone) Table 6: Results of the polymer fraction (ultraf iltration) Membrane Modules Polymer Content No. 01) Area Length Material Retained (mm; (m2; (cm; torque (%.). Etatide pas (%) VBla 1 1 0.042 36.2 12.5 10.2 VBlb 1 1 0.042 36.2 12, 5 8.7 VB2a 1 1 0.56 127 12.3 9.7 VB2b 1 1 0.56 127 16 10 5 VB3 1 1 64.0 127 12.5 14.5 Bla 4 1 0.56 (x4) 127 6.2 10.5 Blb 4 1 0.56 (x4) 127 10.6 10 8 B2a 2 ly2 0.56 and 0.44 127 6.3 14.2 B2b 2 ly2 0.56 and 0.44 127 5.0 13.8 B2c 2 ly2 0, 56 and 0.44 127 4.2 13.1 B2d 2 ly2 0.56 and 0.44 127 3.6 12.0 B2e 2 ly2 0.56 and 0.44 127 3.1 10.2 B3 4 1 0.56 (x4) 127 9.0 10.5 Table 6 (continued) to VBla 0.50 4.0 53 dil. 60 VBlb 0, 35 4, 0 56 conc. 60 VB2a 0.53 2.5 60 dil. 65 VB2b 0.43 1.5 56 conc. 65 VB3 0.20 2, 3 54 dil, 65 Bla 0.34 3.4 58 cont. 65 dil. Blb 0 47 1 2 54 cont. 65 conc. B2a 0.32 1.0 53 cont 65 B2b 0 27 1 5 55 cont 65 B2c 0.26 2.0 56 cont 65 B2d 0 23 ¿* 54 cont 65 B2e 0 19 3.0 54 cont 65 B3 0.44 1.6 54 cont 65 conc 1) Diameter of hollow fibers 2) Transmembrane flow of average polymer 3) dil. = diluted; conc. = concentrated; cont. = continuous 4) MT = mass transfer, normalized to 12% strength of starting material solution (kg of H20 required per kg of starting material solution)

Claims (1)

1. CLAIMS 1. - A process for the fractionation of water-soluble or water-dispersible synthetic amino-containing polymers by ultrafiltration, wherein the process comprises the following steps: a) continuous passage of the polymer solution or dispersion to an ultrafiltration unit; , and mixing the recycled retentate of step d), and optionally, aqueous medium essentially free of polymer, b) separation of the mixture in the ultrafiltration unit towards a permeate and a retentate, c) discharge of the permeate from the process, d) discharge of part of the process retained; recycle the remainder of the retentate in step a), e) passage from that part of the retentate discharged in d) to at least one additional ultrafiltration unit, and treatment thereof by a process comprising steps a) to d), 2 - A process according to claim 1, comprising a start phase having the following steps: a) continuous passage of the solution or dispersion of polymer to an ultrafiltration unit, b) separation of the solution or dispersion of polymer in the ultrafiltration unit to a permeate and a retentate, c) discharge of the process permeate. d) mixing the total retentate with the polymer solution or dispersion in step a) and, optionally, with essentially polymer-free medium and passage of the mixture to the ultrafiltration unit until the desired degree of fractionation has been achieved. in the retained. 3. A process according to claim 1 or 2, wherein the polymer solution or dispersion has a polymer content of 3 to 30% by weight. 4. A process according to any of claims 1 to 3, wherein a retentate having a polymer content greater than 55 by weight is discharged. 5. A process according to any of the preceding claims, wherein from 20 to 90% by weight of the polymer used is separated as permeate. 6. A process according to any of the preceding claims, wherein the ultrafiltration is carried out through membranes having a cut for polymers with molar masses of at least 1000 to 500,000 or through membranes having a diameter of pore from 0 01 to 10 microns. 7 - A process according to any of the preceding claims, wherein the membranes are used in the form of tubes, hollow fibers, plate and frame apparatus, hollow fiber modules, coin modules or spirally linked modules, 8. A process according to any of the preceding claims, wherein the ultrafiltration is carried out at an inlet pressure of 1 to 20 bar. 9. A process according to any of the preceding claims, wherein the ultrafiltration it is carried out at a transmembrane pressure of 0.5 to 10 bar. 10. A process according to any of the preceding claims, wherein the ultra filtration is carried out in an inflow of 0.01 to 10 m / s. 11. A process according to any of the preceding claims wherein the filtration units having a larger diameter or a larger channel width are used in the last stage. 12. - A process according to any of the preceding claims, wherein the amino-containing polymers are selected from polyalkylene polyamines, polyamidoamines, polyalkylene glycol polyamines, polyamidoamines grafted with ethylene imine and then reacted with at least bi-functional cross-linking agents, and mixtures and copolymers thereof