DE102009054532A1 - Continuous preparation of polymer particles of water-soluble polymers in tube rector comprises producing a dispersion of liquid dispersed phase of monomers in e.g. liquid continuous phase and polymerizing monomers using radical initiators - Google Patents

Abstract

Continuous preparation of polymer particles of water-soluble polymers from monomers in a tube rector comprises: (a) producing a dispersion of a liquid dispersed phase in a liquid or gaseous continuous phase, where the dispersed phase comprises the monomers; and (b) polymerizing the monomers in the dispersed phase, using one or more radical initiators, to the water-soluble polymers during the transport of the dispersion in the tube reactor, where the tube reactor has a circular cross-section perpendicular to the flow direction and a constant inner diameter of 0.1-5 mm. Continuous preparation of polymer particles of water-soluble polymers from monomers in a tube rector comprises: (a) producing a dispersion of a liquid dispersed phase in a liquid or gaseous continuous phase, where the dispersed phase comprises the monomers; and (b) polymerizing the monomers in the dispersed phase, using one or more radical initiators, to the water-soluble polymers during the transport of the dispersion in the tube reactor, where the tube reactor has a circular cross-section perpendicular to the flow direction and a constant inner diameter of 0.1-5 mm or a semicircular cross-section perpendicular to the flow direction with constant geometry and a roundness of at most 14 with a maximum inner diameter of 0.1-5 mm and the maximum diameter of one, more or similar polymer particles prepared in the step (b) is perpendicular to the flow direction of at least 80% and less than 100% of the tube inner diameter and/or the maximum tube inner diameter. An independent claim is included for the polymer particle(s) obtained by the above method.

Description

The The present invention relates to a continuous process Preparation of polymer particles of a water-soluble Polymers of monomers in a tubular reactor. The invention relates also the polymer particles produced by this process. Further is the use of the method according to the invention prepared polymer particles for the preparation of solutions and preparations of the present invention, wherein the Polymer preferably as (i) thickener, as (ii) flocculant or (iii) adhesive in pressure-sensitive adhesives.

A Variety of manufacturing processes for water-soluble Polymers are known. Usual procedures for this are, for example, bulk polymerization, solution polymerization, Suspension polymerization, precipitation polymerization and emulsion polymerization. Some commercially important water-soluble polymers, such as for example, polyvinylpyrrolidone (PVP), polyacrylic acid (PAS) and polyvinyl acetate (PVA), are usually by radical Polymerization of vinyl group-containing monomers produced.

The Production of high molecular weight polymers can often be only in discontinuous Procedures are performed, which is usually low Space-time yield conditionally. The polymers produced are distinguished often by quite low molecular weights (molecular weights). polymers with very high molecular weights are conventional Methods often only with great effort and long cycle times produced. Due to the manufacturing process, the polymers are usually also with surfactants, stabilizers and the like contaminated.

water-soluble Polymers are usually (a) as dilute solutions or (b) as solids, usually in the form of powders. Highly concentrated solutions are usually at medium levels and high molecular weights highly viscous and therefore difficult to produce and bad to handle. You can not, for example be pumped. The commercial diluted Solutions lead because of the very high water content Of mostly 80-90 wt .-% to high transport costs. The solid Shapes, on the other hand, favor undesirable dust formation and have considerable irregularities in particle size, shape and morphology, which manifests itself in a large coefficient of variation of the particle size. powdery PVP is among other things due to the easier oxidation limited only due to the large powder surface storable. With longer storage reduces the average molecular weight. PVP powders are also available hygroscopic. You must be under these reasons Shielding gas are stored and are not unlimited even then storable. Additionally disadvantageous in the production of dry polymers such as in the form of powders the extra step for drying and the energy and time required for it.

As a method for carrying out chemical reactions, micro process engineering and microfluidics have been developed in recent years. The publication "Polymerizations in Microstructured Reactors: An Overview," Chemie Ingenieur Technik, 2005, 77, No. II, pp. 1693-1714 gives an overview of known uses of such processes for polymerization reactions. However, the preparation of water-soluble polymers is not described there. DE 10 2004 049 730 B4 and WO 01/64332 A1 describe apparatuses intended for use in micro process engineering and microfluidics; Furthermore, processes for the preparation of dispersions by means of such apparatuses are described.

In micro process engineering and microfluidics, methods for continuous droplet generation have been developed. Such processes make it possible to prepare dispersions with liquid dispersed phase, wherein the dispersed volumes have a monodisperse size distribution. Examples of such methods of continuous drop formation are well described in the art. Such is the magazine Int. J. Multiphase Flow 2003, 29, 813-840 a method for continuous drop generation by means of a static mixer is described. The use of the membrane technique is for example in Macromolecules 2004, 37, 2954-2964 described and the use of vibrating diaphragms for example in Colloids Interface Sci. 1985, 105, 560-569 , Capillary and nozzle technology will be in Chem. Eng. Sci. 2004, 59, 3045-3058 and in Science 2002, 295, 1695-1698 , Continuous droplet generation by flow-focussed microfluidic chips is described, for example, in US Pat Phys. Rev. Lett. 2001, 87, 274-501 . J. Am. Chem Soc. 2005, 127, 8058-8063 . Angew. Chem. Int. Ed. 2005, 44, 724-728 . Macromolecules 2005, 38, 4536-4538 and Langmuir 2005, 21, 11614-11622 described.

The present invention provides a process for producing water-soluble polymer particles and corresponding particles which meet a number of requirements. The requirements of water-soluble polymers include, in particular, when they are to be used as thickeners, Flocculation aids or are provided as adhesives in pressure-sensitive adhesives, the highest possible molecular weight and the smallest possible amount of impurities. Further requirements are ease of handling, in particular the possibility of transporting and portioning the polymers in a simple manner. For polymer particles, the smallest possible coefficient of variation of the particle size and the lowest possible dust development are desired. In addition, in the case of PVP, high molecular weight stability, long shelf life and the ability to retain the polymers under normal atmosphere without disadvantage are required. These requirements can not or only to a sufficient extent be met with conventional production methods.

It was a primary object of the present invention, individual or all of the above requirements fulfill and solve the corresponding problems or at least alleviate it.

• (a) Erzeugen einer Dispersion einer flüssigen dispergierten Phase in einer flüssigen oder gasförmigen kontinuierlichen Phase, wobei die dispergierte Phase Monomere umfasst,
• (b) Polymerisieren der Monomeren in der dispergierten Phase unter Verwendung eines oder mehrer Radikalinitiatoren, zu dem wasserlöslichen Polymer, während des Transports der Dispersion in dem Rohrreaktor,

wobei der Rohrreaktor (zumindest im Rahmen üblicher Toleranzen) einen kreisförmigen Querschnitt senkrecht zur Fließrichtung und einen konstanten Innendurchmesser im Bereich von 0,1 bis 5 mm oder einen kreisähnlichen Querschnitt senkrecht zur Fließrichtung mit (zumindest im Rahmen üblicher Toleranzen) konstanter Geometrie und einer Rundheit von höchstens 14 mit einem maximalen Innendurchmesser im Bereich von 0,1 bis 5 mm besitzt und worin der maximale Durchmesser eines, mehrerer oder sämtlicher in Schritt (b) hergestellter Polymerpartikel senkrecht zur Fließrichtung mindestens 80% und weniger als 100%, bevorzugt mindestens 95% und weniger als 100% und besonders bevorzugt mindestens 98% und weniger als 100%, des Rohrinnendurchmessers bzw. (im Falle eines kreisähnlichen Querschnitts) des maximalen Rohrinnendurchmessers beträgt.This object is achieved according to the invention by a process for the continuous production of polymer particles of a water-soluble polymer from monomers in a tubular reactor, with the following steps:

• (a) forming a dispersion of a liquid dispersed phase in a liquid or gaseous continuous phase, the dispersed phase comprising monomers,
• (b) polymerizing the monomers in the dispersed phase using one or more free-radical initiators to the water-soluble polymer during transport of the dispersion in the tubular reactor,

wherein the tubular reactor (at least within the usual tolerances) has a circular cross-section perpendicular to the flow direction and a constant inner diameter in the range of 0.1 to 5 mm or a circular cross-section perpendicular to the flow direction with (at least within usual tolerances) constant geometry and a roundness of at most 14 having a maximum inner diameter in the range of 0.1 to 5 mm, and wherein the maximum diameter of one, more or all of the polymer particles produced in step (b) is at least 80% and less than 100%, preferably at least 95%, perpendicular to the flow direction less than 100%, and more preferably at least 98% and less than 100% of the inner tube diameter or (in the case of a circular cross-section) of the maximum inner tube diameter.

The Word cross section always designates the cross section of the cavity (Interior) of the tubular reactor, through the inner wall of the tubular reactor is limited. Have preferred circular cross-sections a uniform or uniform Rounding, as well as, for example, ellipsoidal cross-sections. Preferred are for circular to be used according to the invention as well as in the context of a technical production and processing of Tubes and tubes accessible, circular ("round") Cross-sections. The roundness of planar objects (such as for example cross sections) is defined as the quotient of the square the size of the area divided by the size the area. The roundness of a circle is therefore 12.57, that of a square 16 and that of an equilateral triangle, for example 20.8. Preferred is a method as described above, wherein the tubular reactor has a cross-section with a roundness in the range from 12.57 to 13.5, preferably from 12.57 to 13, and more preferably from 12.57 to 12.8.

Of the Tubular reactor can be made of a rigid, non-flexible material ("Pipe") or a flexible material ("hose") be constructed. In both cases, the pipe or the Hose cross sections as described. "Tubular reactor" in the context of this application an apparatus consisting of pipes and / or Hoses can be constructed.

Tube can be made of natural or synthetic polymer materials, Metals or their combinations exist. For example, you can Metal pipes should be coated on the inside, about for inertness to the reaction mixture and / or to provide the carrier medium. In particular, such serve Coatings to the desired contact angle of Carrier medium and reaction mixture to reach the wall and thus avoid coalescence of the discrete single drops. Also hoses can be used for adjustment of the contact angle can be constructed of layers, so that the inside made of a different material than the outside.

Prefers is a process as described above, wherein the produced Polymer particles are solid. The expert can Parameters of the process (in particular type and amount of monomer and Solvent), adjust so that solid particles are obtained become. The required parameters (conditions) can be applied Hand simple preliminary tests determine.

In In some cases, a method as above is preferred in which the polymer particles produced semisolid or are liquid. If semi-solid or liquid polymer particles can be obtained, it may be advantageous, the resulting polymer particles to merge into a homogeneous phase, then these to subsequent products such as polymer powders or polymer solutions continue to process. Process for obtaining such secondary products, in particular of solid polymer powders, are known to the person skilled in the art.

Prefers is a method as described above, wherein the in step (a) dispersed phase produced one or more free-radical initiators and optionally one or more adjuvants selected from the group consisting of solvents, diluents, Surfactants emulsifiers, cross-linking agents and branching reagents.

The fulfill the inventive method the requirements mentioned and in particular allow the continuous Preparation of Water-Soluble Polymers with High Weight Average "MW". In the interior of the tubular reactor prevail essentially flow conditions which correspond to a plug flow. This ensures that the discrete volumes (drops) from which dispersed the Phase does not or not to a significant extent interact or even coalesce with each other. That's it Volume of the reaction space low and there are polymers with high molecular weights. "Low" means in In this connection, that the reaction volume in the droplets is much smaller than other solution polymerization methods. The volume per droplet is between 0.01 and 50 ml, usually between 0.05 and 10 ml, preferably between 0.1 and 5 ml and especially preferably between 0.1 and 1 ml.

Especially preferred is a method as described above, in which the weight average molecular weight of the produced polymer larger than 500,000, preferably greater than 1,000,000 and more preferably greater than 1500000 is. The weight average molecular weight the polymer produced of the polymer particle is particularly by the initial ratio of initiator to monomer, with a high proportion of initiator too comparatively low molecular weights leads. The specialist is by simple preliminary tests a suitable ratio of Determine initiator to monomer. When using N-vinylpyrrolidone As a monomer, particularly high molecular weights are obtained. All particularly preferred is a method as described above, in which the monomer comprises or consists of N-vinylpyrrolidone and the weight-average molecular weight of the polymer produced greater than 1,000,000, preferably larger than 1500000 and more preferably greater than 2000000 is.

in the Contrary to the methods of microreaction technology arise according to the present invention macroscopic particles with a size in the millimeter range. These are easy to handle and do not tilt for dust formation. It is an advantage of the invention Procedures that also performed highly exothermic reactions without problems can be. Those in industrial processes in all Usually necessary large capacities are going through Received parallel connection of a variety of tubular reactors.

Of the Tubular reactor is in the process of the invention preferably designed as a hose when the process to be carried out only on a small scale. For larger scales (production quantities) Preferably, the use of pipes takes place. A tube reactor can be one, two or more individual hoses or Be built pipes. Preferably, the two or more tubes and / or hoses connected in parallel so that the control technology every single hose and / or pipe to a common Control technology are interconnected and a common monitoring and control of the individual reactions can take place. The expert For this purpose, suitable control devices and methods are known.

The individual or interconnected pipes or hoses can be cooled and heated from the outside. This can be done by hot or cold gases such as air, carbon dioxide, nitrogen, water vapor or other suitable gases. Cooling or heating by means of liquids such as water, oils, liquid salts, liquid metals and alloys and other liquid media such as salt solutions is also possible. The heating can also be done by electrical heating or by radiation such as heat radiation, infrared light, etc. The individual tubes or hoses can be individually surrounded by a jacket, through which the heating or cooling medium is guided around the tubes or hoses. The interconnected pipes or hoses can also be surrounded together with such a jacket. Also, the immersion of the individual or interconnected pipes or hoses in a container in which the heating or cooling medium is and is circulated in a preferred embodiment, is also possible. The person skilled in suitable arrangements are known. The circulation of the heating or cooling mediums can be done mechanically, for example by pumping or self-sufficient, for example by convection.

narrowness Pipe reactors with an inside diameter of less than 0.1 mm tend Increased constipation and therefore less suitable. is the inner diameter of the tubular reactor, however, greater than 5 mm, is the surface-to-volume ratio low, which affects the heat dissipation. In addition, will with increasing inner diameter of the tubular reactor, the laminar flow become increasingly disturbed, resulting in interaction or coalescence the discrete volumes of a dispersed phase lead can. Disturbances of the laminar flow can doing so for example by convection due to temperature differences, caused by heat of reaction and / or cooling, but also due to flow disturbances on the inner wall of the tubular reactor. Preference is given to tubular reactors with a constant Inner diameter or (in the case of a circular cross-section) with a maximum pipe inside diameter in the range of 0.5 to 5 mm. Particularly preferred are tubular reactors with a constant Inner diameter or (in the case of a circular cross-section) with a maximum pipe inside diameter in the range of 0.5 to 3 mm.

In the methods of the invention are size and shape of the cross section of the formed polymer particles perpendicular at least similar to the flow direction in the tubular reactor the size and shape of the cross section of the tubular reactor, but of course a little smaller. The size the discrete volumes of the dispersed ones produced in step (a) Phase is usually about the same size the polymer particles produced in step (b), ie also similar the size and shape of the cross-section of the tubular reactor. This creates flow conditions in the tubular reactor, the coalescence of the discrete volumes obtained in step (a) produced dispersed phase virtually completely suppressed becomes. When the discrete volumes of the dispersed phase are the tube reactor fill almost completely perpendicular to the flow direction, so does the continuous phase between discrete volumes of in a similar manner to the dispersed phase prepared in step (a) like a plug that favors a plug flow or even enforces. The more viscous the continuous phase is, the smaller the diameter of the discrete volumes of the Step (a) produced dispersed phase relative to Pipe internal diameter without causing a coalescence of the discrete Volumes of the dispersed phase occurs.

The Viscosities of the continuous medium are usually such values that flow at reaction temperature guaranteed in the selected inner cross-section, without the droplets of the discontinuous medium coalesce, for example, by excessive pressure due to high viscosity. Suitable viscosities of suitable as continuous media substances usually have Viscosities at reaction temperature of 10 to 10,000 mPas, preferably 100 to 800 and particularly preferably 200 to 5000 mPas.

Of the maximum diameter of a polymer particle perpendicular to the flow direction is the diameter of the circle or the maximum diameter of the circle circle-like extent of the cross section through which the polymer particles can just pass through without touching the circle. The polymer particle has the orientation to the circle that it also during the movement through the tubular reactor to the cross section of the tubular reactor occupies. If a polymer particle is spherical, then that is maximum diameter of the polymer particle its ball diameter. Has a polymer particle the shape of a circular cylinder with round or irregular ends, so is the maximum Diameter of the polymer particle the diameter of the shell of the Circular cylinder. Lenticular polymer particles are one Special case of polymer particles that take the form of a circular cylinder with round or irregular ends, where the length of the jacket of the cylinder is 0. The maximum Diameter of the polymer particle is then the diameter here the mantle of the circular cylinder.

Usually the volume of the droplets at the present results Method from the inner cross section of the pipe or hose used and the length of the droplets. The diameter of the droplets is at least 80% of the inner cross section, preferably 90, more preferably 95, and most preferably at least 98%, and is maximum 99.9999%. The length of the Droplets are usually the one up to 10 times the droplet diameter, preferably the 1 to 5-fold, most preferably 1 to 3-fold.

in the Prior art methods are described in which tubular reactors with other than circular cross-sections perpendicular to the flow direction be used. This allows in principle the production of Polymer particles that have other than circular cross-sections. Usually lead to shapes that are more complicated than the (within normal tolerances) circular tubular reactors but more common to mechanical problems and blockages the tubular reactors.

radical initiators are compounds that under certain conditions form radicals, which are capable of chain initiation of a radical polymerization reaction to effect.

A preferred embodiment of the present invention a method as described above, wherein in step (a) produced continuous phase is a liquid. The Use of a liquid as a continuous phase has (in comparison with a gaseous continuous Phase) the advantage that a better heat dissipation allows is and that the dispersion is more stable, since the also liquid The dispersed phase produced in step (a) has a similar one Density and similar flow behavior as the continuous Phase has.

in the process according to the invention takes place in step (b) regularly consolidate the in step (a) dispersed phase instead, that is it finds a transition from a dispersion of a liquid in the continuous phase to a dispersion of polymer particles held in the continuous phase. Every single one is discrete Volume (droplets) of the liquid dispersed in step (a) Phase solidified as such. This is a sufficiently high Content of monomers and / or a sufficiently low content required of solvent or diluent, what is described in detail elsewhere in this description becomes. The discrete volumes are in the inventive Procedure in step (b) regularly not shared they still coalesce.

In front and after performing step (b) carried out further process steps and reactions These include, for example, pre- and post-polymerizations. For example, polymerizations prior to step (b) may be used serve to prepare block copolymers and graft polymers, for example in be prepared by ionic Po lymerisation part polymers. Block Copolymers Graft polymers can also be obtained if monomers are already used in step (a), which are already oligomers or polymers. Performed after step (b) For example, polymerizations can serve as residual monomer or to crosslink or branch the polymers or to provide the polymer particles with a sheath.

The prominent for size and shape of the cross section the polymer particles in relation to the geometry of the tubular reactor The above applies accordingly to the discrete volumes of in step (a) produced dispersed phase in the liquid Status.

Prefers is a method as described above, wherein the in step (a) continuous phase used an organic liquid is or contains, preferably the continuous Phase is or contains an organic liquid and the dispersion is an inverse dispersion, especially preferably the dispersion is a water-in-oil dispersion.

A Organic liquid is in the sense of this invention Liquid which is at least 70, preferably at least 80 and in particular at least 90 wt .-% of one or more consists of organic compounds. Preference is given to the use of essentially inert organic liquids, d. H. of liquids under the given reaction conditions not or only slightly with the other compounds react in the tubular reactor or with the inner wall of the tubular reactor. Particularly preferred is the use of complete inert liquids. By using (if possible) inert liquids will reduce the frequency of Side reactions affecting the structure of the polymer being formed, z. B. Reactions leading to the formation of branches and side chains lead, such as grafting reactions, decreased. Preference is likewise given to organic liquids which a low solubility in the one produced in step (a) have dispersed phase and in which the components of the dispersed Phase in turn not or only slightly soluble are more detailed, as elsewhere in this description is described. Preferred is a method as described above, wherein the continuous phase produced in step (a) is an organic Liquid is made up of one or more organic Compounds or one or more organic compounds containing at least one, preferably several selected are from the group consisting of unbranched aliphatic hydrocarbons, branched aliphatic hydrocarbons, aromatic hydrocarbons and chlorofluorocarbons. Example of such organic liquids are white oil, Dodecane, iso-octane, ethyl acetate, dioxane, diethyl ether, pentane, cyclohexane, Carbon tetrachloride, toluene, xylene, liquid paraffin, Cyclohexanol and acetone. Preference is given to non-polar liquids such as white oil, dodecane, iso-octane, liquid paraffin, Toluene, xylene and mixtures thereof. It is also preferred if the continuous phase has a boiling point which is at the in tubular reactor operating pressure at least 5, preferably 10, more preferably 15 and in particular at least 20 ° C. is above the selected reaction temperature.

Of the One skilled in the art will be in preferred embodiments of the inventive Procedure to ensure that the liquid or the liquids for use in the continuous Phase is selected so or are that the phase boundary between the continuous phase and that produced in step (a) dispersed phase throughout in step (b) carried out polymerization is maintained.

A Another embodiment of the present invention a method as described above, wherein the continuous Phase is a gas. The use of gases as continuous Phase has the advantage that the separation of continuous and dispersed phase after completion of the reaction very easy is.

each Gas that does not interact with the other components present in the tube reactor reacts to a significant extent or is in considerable extent Releases dimensions, is suitable as a continuous phase. Preference is given to gases that have low problems with corrosion, job security and environmental protection. The continuous phase includes preferably oxygen and / or inert gases, d. H. Gases under Reaction conditions do not interfere with the polymerization. Prefers is a process as described above, wherein the continuous Phase consists of a gas that is selected from the Group consisting of air, oxygen, nitrogen, carbon dioxide, Noble gases, in particular argon, water vapor and mixtures thereof. Preferably used are gases which are the polymers to be prepared do not dissolve or only in very small quantities, such as air, Nitrogen, carbon dioxide and noble gases such as argon. Most notably preferred are inert gases such as carbon dioxide, nitrogen and noble gases such as argon, particularly preferred are nitrogen and argon.

The continuous phase can also be reducing or oxidizing gases contain or consist of which together with constituents the discontinuous phase produced in step (a) is a redox radical initiator system forms. An example of a reducing gas is sulfur dioxide.

In preferred embodiments of the invention Process makes the dispersed phase the exclusive one Reaction space for the polymerization in step (b). The dispersed phase then contains after your production in step (a) all starting materials and any necessary excipients and after the polymerization in step (b) all the reaction products and possibly adjuvants and reaction products remained. Before turn Embodiments of the dispersed ones produced in step (a) Phase are described below.

• (i) Lösungsmittel oder Verdünnungsmittel umfasst oder – alternativ –
• (ii) frei ist von Lösungsmittel oder Verdünnungsmittel und das Polymerisieren im Schritt (b) als Massepolymerisation erfolgt.

The process according to the invention, as described above in various embodiments, is preferably a process in which the dispersed phase

• (i) solvent or diluent comprises or alternatively
• (ii) is free of solvent or diluent and the polymerization in step (b) is carried out as bulk polymerization.

The Designation "bulk polymerization" refers while looking at the discrete particles and the running in it Polymerization reaction.

Preferably, the dispersed phase produced in step (a) according to alternative (i) of the process according to the invention consists to a large majority of (a) monomers and (b) solvent and / or diluent. Solvent or diluent have a high influence on the course of the reaction and the product properties. The weight average (M _w ) of the polymer produced in step (b) depends both on the type of monomers used and on the content of the dispersed phase in solvents or diluents. A dispersed phase produced in step (a) with a high content of solvent and / or diluent and a low content of monomer leads in some polymers to only average values for the weight average (M _w ). Often, the weight average (M _w ) increases with decreasing proportion of solvent or diluent and increasing proportion of monomers, and then decrease again with a very small proportion of solvent or diluent and a very high proportion of monomer.

In the process of the present invention, since the dispersed phase is preferred to be the exclusive reaction space for the polymerization in step (b), it is preferable to use a solvent or diluent having a solvent power for all other components of the dispersed phase produced in step (a). This is especially true for the monomers, but also the polymers are preferably easily or very slightly soluble in the solvent or diluent or miscible therewith without miscibility gap. However, in certain embodiments of the process of the invention, the monomers and / or polymers are less readily soluble in an employed solvent, for example, to precipitate the polymers or to otherwise influence the reaction. The above Definiti Solubility ones are known in the art, such as from Rompps Chemie-Lexikon, 1983, 8th edition, p. 2394 ,

There the polymers prepared in step (b) are water-soluble are polar solvents and diluents for the dispersed phase produced in step (a). Preferred is further a method as described above, wherein the dispersed phase produced in step (a) is one or more Solvent or diluent, which are selected from the group consisting of water, Alcohols having 1 to 4 carbon atoms, preferably methanol, ethanol, n-propanol, Isopropanol, n-butanol, polyols having 2 to 4 carbon atoms, are preferred Ethylene glycol and propylene glycol, diethylene glycol, chloroform, methylene chloride, Triethanolamine, acetic acid, propionic acid, 2-pyrrolidone, Polyethylene glycol and mixtures thereof.

Such Solvents or diluents also intervene in the polymerization and co-determine the molecular weight: Such solvents having a molecular weight-regulating action are, for example, alcohols such as methanol, ethanol, isopropanol, 2-butanol and acetic acid. In particular isopropanol (2-propanol) shows a strong regulatory effect. Such solvents can in particular be used when a low molecular weight desired becomes. The insert can be used as an addition to another solvent or diluents or as an additive to the monomers in the discrete particle. The right choice of quantity The expert can easily determine by suitable preliminary tests.

The most preferred solvents or diluents for the dispersed phase is water. Preferred is a inventive method as described above, wherein the dispersed phase produced in step (a) comprises water, preferably a proportion of water in the range of 0.01 wt .-% to 60 wt .-%, preferably from 1 wt .-% to 60 wt .-% and very particularly preferably from 5 wt .-% to 50 wt .-%, based on the total amount on dispersed phase.

When water is used in the dispersed phase, aqueous polymer particles are regularly obtained in step (b). If the proportion of water in the dispersed phase is less than 0.01% by weight, the influence of the water is only slight. When the proportion of the water is more than 20% by weight, polymer solutions are often obtained instead of solutions or gels of the polymer. With a proportion of water in the range from 1% by weight to 60% by weight, polymer particles with a high weight average (M _w ) can be prepared, this is particularly true when the proportion of water in the range of 5% by weight. to 50 wt .-%, based on the total amount of the dispersed phase.

Of the maximum permissible content of water in the dispersed Phase, which still requires the production of polymer particles instead of Solutions allowed depends, among other things, on the Type of monomers selected and other reaction conditions from. The expert can the maximum allowable share of Determine water by a few simple preliminary tests.

The above for water applies accordingly if other solvents or diluents are used instead of water. Generally, solid polymer particles are obtained when the monomer is soluble, sparingly or sparingly soluble in the solvent or diluent and solutions or gels when the monomer is readily or very readily soluble in the solvent or diluent. The abovementioned definitions of solubilities are known to the person skilled in the art, for example from Rompps Chemie-Lexikon, 1983, 8th edition, p. 2394 , Generally, solid polymer particles will also be obtained rather when the proportion of the monomer in the dispersed phase produced in step (a) is high. Conversely, solutions or gels are obtained when the proportion of the monomer in the dispersed phase produced in step (a) is low. If the monomer is easily or very readily soluble in the solvent or diluent, then, in order to obtain solid polymer particles, it is necessary to use a high proportion of monomers on the dispersed phase produced in step (a). If the monomer in the solvent or diluent has a lower solubility than slightly soluble, a lesser proportion of monomers on the dispersed phase produced in step (a) is sufficient to obtain still solid polymer particles. The person skilled in the art can determine a suitable solvent and the appropriate proportion of monomer in the dispersed phase produced in step (a) by suitable preliminary experiments.

Also preferred is a method according to the invention preferably according to one preferred above designated method wherein the dispersed in step (a) produced Phase a proportion of monomers in the range of 40 wt .-% to 99 Wt .-%, preferably from 40 wt .-% to 95 wt .-% and especially preferably from 50% by weight to 90% by weight, based on the total amount on dispersed phase.

With a proportion of monomers from 40 wt .-% to 99 wt .-% is obtained regularly with polymers a high weight average (M _w ). Particularly high weight average (M _w ) is obtained regularly with a proportion of monomers of 40 wt .-% to 95 wt .-%. With a proportion of monomers of 50 wt .-% to 90 wt .-% is obtained regularly the highest weight average (M _w ). If the proportion of monomers in a process according to the invention according to alternative (i) is less than 40% by weight, polymer particles are frequently obtained with only moderate weight average (M _w ). If the proportion of monomers is greater than 99% by weight, the weight-average molecular weight (M _w ) of the resulting polymer is often lower than that of a proportion of monomers within the ranges given above. In addition, with proportions of monomers greater than 99% by weight, a high degree of crosslinking and undesirable gel formation are frequently observed.

Particular preference is given to a process according to the invention as described above, in which the dispersed phase produced in step (a) has a proportion of water in the range from 0% by weight to 20% by weight and a proportion of monomer in the range of 80% by weight. to 100% by weight. Particularly preferred is a method according to the invention as described above, wherein the dispersed phase produced in step (a) has a content of water in the range of 0 wt .-% to 15 wt .-% and a content of monomer of not less than 85 wt. -% includes. Most preferred is a process according to the invention as described above, wherein the dispersed phase produced in step (a) has a water content in the range 0 wt.% To 10 wt.% And a monomer content of not less than 90 wt. -% includes. Polymers prepared by means of such a dispersed phase regularly give solid, easy-to-handle polymer particles. Such particles have the advantage over commercial polymer powders that they hardly dust, are mechanically strong, easy to handle and are generally not hygroscopic. Compared with the commercially available dilute polymer solutions, the solid polymer particles according to the invention have the advantage that expensive equipment such as tanks, hoses or pumps are not necessary for their handling. At the same time, however, they contain a significantly higher proportion of polymer than dilute solutions and can therefore be transported more cheaply. Solid polymer particles prepared by the process of the invention can be used without expensive purification. They can be freed from the adherent continuous phase by conventional solid-liquid separation techniques, for example by filtration, centrifugation or distillation. If necessary, they are freed by rinsing residues of adhering continuous phase and dried briefly. Polymer particles produced by the process according to the invention can be dried, for example, on belts or by fluidized-bed drying. The resulting particles are directly usable and often do not or only slightly adhere to each other. As far as necessary, you can powders with customarily used (separating) agent, such as hydrophilic and hydrophobically silica (such as Sipernat ^® types and brands Aerosil ^® such as Aerosil ^® 200, Aerosi) ^® R972 Pharma (Degussa)) be separated.

All particularly preferred is an inventive A process as described above, wherein the one produced in step (a) dispersed phase to more than 90%, preferably more than 95% and more preferably more than 98% is monomer and water.

To "rinse residue-adherent continuous phase "usually becomes a solvent used with the continuous Phase is miscible, but a lower boiling temperature than this having. By one or more rinses can thus the continuous phase are separated from the product. The rest of the rinse solvent can then about by evaporation, drying or distillation almost completely or completely separated from the product. As a solvent for rinsing are suitable when using substances such as White oils as continuous phase substances such as pentane, hexane or heptane or others, mild to moderate volatile hydrocarbons.

The inventive method according to the above alternative (ii) as described above, wherein the dispersed phase is free of solvent or diluent and the polymerizing in step (b) is carried out as bulk polymerization, although in some polymers do not lead to the highest weight average (M _w ) produce However, polymer particles with a high solids content, which are usually solids and often incurred in high purity.

Suitable monomers for the use of the process according to the invention are, in particular, the monomers known from the prior art for the preparation of water-soluble polymers. It is preferred if the monomers are homogeneously distributed in the dispersed phase produced in step (a). For the methods described above as preferred wherein the dispersed phase produced in step (a) contains a polar solvent such as water, therefore, monomers having polar functional groups are preferred. Particular preference is given to monomers which are soluble in water, the solubility in water at 23 ° C. preferably being at least 1 g / 100 g of water, preferably at least 5 g / 100 g of water, more preferably at least 25 g / 100 g of water, especially preferably at least 50 g / 100 g What is.

It is particularly preferred in the inventive Method (as described above and preferably as above as preferred) for the polymerization at least one radical polymerizable α, β-ethylenically unsaturated Use monomer. Suitable monomers are for example selected from the group consisting of monoethylenically unsaturated Carboxylic, sulfonic and phosphonic acids, ethylenically unsaturated Nitriles, primary amides α, β-ethylenic unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, N-vinyl lactams, open-chain N-vinyl amide compounds, Esters of α, β-ethylenically unsaturated Mono- and dicarboxylic acids with amino alcohols, amides α, β-ethylenic unsaturated mono- and dicarboxylic acids with diamines, which is at least one primary or secondary Having amino group, vinyl- and allyl-substituted nitrogen heterocycles, Vinyl ethers such as vinyl acetate, vinyl propionate and vinyl butyrate, urea groups having monomers and mixtures thereof.

suitable ethylenically unsaturated carboxylic acids, sulfonic acids and phosphonic acids or their derivatives are, for example selected from the group consisting of acrylic acid, Methacrylic acid, ethacrylic acid, α-chloroacrylic acid, Crotonic acid, maleic acid, maleic anhydride, Itaconic acid, citraconic acid, mesaconic acid, Glutaconic acid, aconitic acid, fumaric acid, the half esters of monoethylenically unsaturated dicarboxylic acids with 4 to 10, preferably 4 to 6 C atoms, for. B. maleic acid monomethyl ester, Vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, Sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropyl sulfonic acid, 2-hydroxy-3-methacryloxy-propylsulfonic acid, styrenesulfonic acids, 2-acrylamido-2-methylpropanesulfonic acid, Vinylphosphonic acid and allylphosphonic acid. The acid group-containing monomers can in the form of free acid or in part or completely neutralized form can be used for polymerization. suitable Bases for neutralization are z. As KOH, NaOH, ammonia, carbonates of alkali and alkaline earth metals or ammonia etc.

Especially preferred monomers are N-vinylpyrrolidone (VP), vinylimidazole, Vinylcaprolactam (Vcap), Quaternized Vinylimidazole, Vinyl Acetate, Vinylformamide, acrylic acid, methacrylic acid and their salts or mixtures thereof.

suitable ethylenically unsaturated nitriles are selected, for example from the group consisting of acrylonitrile, methacrylonitrile and mixtures from that.

Suitable esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ -C ₃₀ alkanediols are, for example, selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl meth acrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate , 3-hydroxy-2-ethylhexyl methacrylate and mixtures thereof.

suitable primary amides α, β-ethylenically unsaturated Monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives are for example selected from the group consisting of Acrylic acid amide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (n-butyl) (meth) acrylamide, N- (tert-butyl) (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (1,1,3,3-tetramethylbutyl) (meth) acrylamide, N-ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide, N- (n-undecyl) (meth) acrylamide, N-tridecyl (meth) acrylamide, N-myristyl (meth) acrylamide, N-pentadecyl (meth) acrylamide, N-palmityl (meth) acrylamide, N-heptadecyl (meth) acrylamide, N-nonadecyl (meth) acrylamide, N-arachinyl (meth) acrylamide, N-behenyl (meth) acrylamide, N-gngnoceryl (meth) acrylamide, N-cerotinyl (meth) acrylamide, N-melissinyl (meth) acrylamide, N-palmitoleinyl (meth) acrylamide, N-oleyl (meth) acrylamide, N-unolyl (meth) acrylamide, N-nonolenyl (meth) acrylamide, N-stearyl (meth) acrylamide, N-lauryl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, morpholinyl (meth) acrylamide and their Mixtures.

suitable N-vinyl lactams and their derivatives are selected, for example from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam and their mixtures.

Suitable open-chain N-vinylamide compounds are, for example, selected from the group consisting of N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-Vi nyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide, N-vinylbutyramide and mixtures thereof.

suitable Amides α, β-ethylenically unsaturated mono- and dicarboxylic acids with diamines containing at least one have primary or secondary amino group for example, selected from the group consisting of N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] methacrylamide and their mixtures.

Suitable monomers are further selected, for example, from the list consisting of N, N-diallylamines and N, N-diallyl-N-alkylamines and their acid addition salts and quaternization. Alkyl is preferably C ₁ -C ₂₄ -alkyl. Preference is given to N, N-diallyl-N-methylamine and N, N-diallyl-N, N-dimethylammonium compounds, such as. As the chlorides and bromides.

suitable Monomers are also vinyl- and allyl-substituted nitrogen heterocycles, for example, selected from the group consisting of N-vinylimidazole, N-vinyl-2-methylimidazole, vinyl- and allyl-substituted heteroaromatic Compounds such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.

The The aforementioned monomers can be used individually, in the form of mixtures within a monomer class or in the form of mixtures of different Monomer classes are used. Amino-containing monomers may be advantageous in the form of their acid addition salts or quaternization products are used; the reference to an amino group-containing monomer is thus within the scope of the present invention Text always also a reference to the acid addition salts and the quaternization products.

The process of the invention is used in a specific embodiment of the preparation of acrylic acid homo- and copolymers. Suitable acrylic acid copolymers preferably comprise at least one comonomer selected from the group consisting of α, β-ethylenically unsaturated dicarboxylic acids, their mono- and diesters and anhydrides; Esters of α, β-ethylenically unsaturated mono- or dicarboxylic acids with C ₁ -C ₂₀ -alkanols; (Meth) acrylamide, esters of vinyl alcohol with C ₁ -C ₃₀ monocarboxylic acids; vinyl-substituted nitrogen heterocycles and mixtures thereof.

In In a preferred embodiment, the comonomer is selected from the group consisting of maleic anhydride, acrylamide, Methacrylamide, vinylformamide, vinylacetamide, N-vinylimidazole and Mixtures thereof.

Very particular preference is given to a process as described above, wherein the monomer used in step (a) or at least one of the monomers used in step (a) is N-vinylpyrrolidone. Most preferred is a process wherein the dispersed phase produced in step (a) contains N-vinylpyrrolidone as the sole monomer. Among the methods as described above, wherein the dispersed phase contains N-vinylpyrrolidone, and especially wherein N-vinylpyrrolidone is the only monomer in the dispersed phase produced in step (a), is more preferably a method (as described above, preferably previously described preferably described method), wherein the dispersed phase produced in step (a) comprises a content of N-vinylpyrrolidone in the range from 40 wt.% to 95 wt.%, preferably from 50 wt.% to 95 wt. and more preferably from 60% to 95% by weight. In these proportions of N-vinylpyrrolidone in the dispersed phase usually high weight average (M _w ) are obtained.

If the proportion of N-vinylpyrrolidone is lower (relative to the dispersed phase) than 40% by weight and no further monomers are present, then the weight average (M _w ) of the polymer is often disadvantageously low. If, on the other hand, the proportion of N-vinylpyrrolidone is greater than 95% by weight, the resulting polymer likewise frequently has an undesirably lower weight average (M _w ). In a proportion of 60 wt .-% to 80 wt .-%, the highest weight average (M _w ) were obtained in own investigations. Are larger, compared with N-vinylpyrrolidone predominant amounts of another monomer present, the N-vinylpyrrolidone units have little effect on the properties of the polymer.

Preferred is a method (as described above, preferably a method described above as preferred) wherein the dispersed phase produced in step (a) has a content of N-vinylpyrrolidone of 80% by weight or more, preferably 85% by weight or more and more preferably 90% by weight or more. If the proportion of N-vinylpyrrolidone is more than 80% by weight, based on the dispersed phase produced in step (a), the process according to the invention is more surprising Way solid polymer particles produce that have a high solids content. This is particularly true when the proportion of N-vinylpyrrolidone is 90% by weight or more.

To the invention described above Processed particles containing or consisting of PVP, have a high solids content and are therefore mechanically strong and easy to handle. Opposite the powdery Surprisingly, they have the commercial PVP Advantage that they can be stored much longer because they do not like molecular weight reduction like powdered PVP subject. You also do not have to be under exclusion of air are stored, are not usually because of their water content hygroscopic and hardly prone to dust formation.

According to the present invention is an inventive Preferred method (as described above, preferably as referred to above as preferred), wherein those used in step (a) Monomers in addition to N-vinylpyrrolidone radically copolymerizable Containing co-monomers. Suitable co-monomers are, for example Acrylic acid and substituted acrylic acids as well Salts, esters and amides thereof, wherein the substituents on the carbon atoms in the two or three position of acrylic acid, and are independently selected from the Group consisting of alkyl groups having 1 to 20 carbon atoms, -CN, COOH particularly preferred are methacrylic acid, ethacrylic acid, Acrylamide, methacrylamide, N, N-dimethylacrylamide and N, N-dimethylmethacrylamide.

Become as comonomers for vinylpyrrolidone or other vinyllactams Acids used and is water or an aqueous Solvents are present in the monomer mixture, so be The acids used in the form of their salts to form an acidic Hydrolysis of vinyl lactams to avoid. The acids can also by suitable bases such as ammonia, caustic soda or sodium hydroxide, Potassium hydroxide or potassium hydroxide are neutralized to the corresponding Salts of acids. As much base is added that the pH in the case of vinylpyrrolidone is not lower than 5.5, preferably not below pH 6, and more preferably not below pH 6.5. Preferably, the pH is in the range of 5 to 10, in particular in the range of 6 to 9. For other vinyl lactams or others acid-sensitive monomers are those for polymerization suitable pH ranges known in the art. These are usually in the range of pH 6 to 10, preferably in the range of pH 7 to 9.

Further suitable co-monomers are amides of acrylic acid and their Derivatives such as ethacrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-t-butylacrylamide, N-octylacrylamide, N-t-octylacrylamide, N octadecylacrylamide, N-phenylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N isopropylmethacrylamide, N-dodecylmethacrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) butyl] methacrylamide, N- [8- (dimethylamino) octyl] methacrylamide, N- [12- (dimethylamino) -dodecyl] methacrylamide, N- [3- (diethylamino) -propyl] methacrylamide, N [3- (diethylamino) propyl] acrylamide, unsaturated sulfonic acids such as acrylamidopropanesulfonic acid; 3-cyanoacrylic.

Also Suitable co-monomers for N-vinylpyrrolidone are esters of acrylic acid and its derivatives, such as methyl acrylate, ethyl acrylate, Propyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, Propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, stearyl (meth) acrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 2 hydroxyethyl acrylate, Hydroxypropyl acrylates, 2-hydroxyethyl methacrylate, 2 hydroxyethyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2 methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-ethoxyethyl methacrylate, hydroxypropyl methacrylate, Glyceryl monoacrylate, glyceryl monomethacrylate, polyalkylene glycol (meth) acrylates, N, N-dimethylaminomethyl (meth) acrylate, N, N-diethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N, N-dimethylaminohexyl (meth) acrylate, N, N-dimethylaminooctyl (meth) acrylate and N, N-dimethylaminododecyl (meth) acrylate.

Other suitable co-monomers are vinyl and allyl esters of carboxylic acids with linear alkyl radicals having 1 to 40 carbon atoms, carboxylic acids with branched alkyl radicals having 3 to 40 carbon atoms and carboxylic acids with carbocyclic alkyl radicals having 3 to 40 carbon atoms, such as vinyl acetate, vinyl propionate and their hydrolysis products such as Vinyl alcohol, vinyl or allyl halides, preferably vinyl chloride and allyl chloride, vinyl ethers, preferably methyl, ethyl, butyl or dodecyl vinyl ether, vinyl formamide, N-vinyl-N-methylacetamide, Vinylamine; methyl vinyl ketone; Vinyl lactams, preferably vinyl pyrrolidone, Vinylcaprolactam and vinylpiperidone, vinyl or allyl substituted heterocyclic compounds, preferably vinylpyridine, vinyloxazoline and allylpyridine, as well as vinylfuran and allyl alcohol.

Furthermore, N-vinylimidazoles according to the following formula (I) are suitable as co-monomers for N-vinylpyrrolidone, in which R ⁹ to R ^11, independently of one another, are hydrogen, alkyl groups having 1 to 4 carbon atoms or phenyl:

preferred Examples are 1-vinylimidazole, 1-vinyl-2-methylvinylimidazole, 3-methyl-1-vinylimidazolium chloride and 3-methyl-1-vinylimidazolium methylsulfate.

mit R¹² = Alkylgruppe mit 1 bis 24 Kohlenstoffatomen. Auch deren Quaternisierungsprodukte sind geeignete Co-Monomere, beispielsweise Diallyldimethylammoniumchlorid.Further suitable co-monomers are diallylamines of the general formula (II)

with R ¹² = alkyl group having 1 to 24 carbon atoms. Also, their quaternization products are suitable co-monomers, for example diallyldimethylammonium chloride.

Further suitable co-monomers for use with N-vinylpyrrolidone (VP) are maleic acid, fumaric acid, maleic anhydride and its half-esters and half-amides and imides, maleimide, crotonic acid, Itaconic acid, vinyl ethers (for example: methyl, ethyl, Butyl or dodecyl vinyl ether), vinylidene chloride, and hydrocarbons with at least one carbon-carbon double bond, preferred Styrene, alpha-methylstyrene, tert-butylstyrene, styrenesulfonic acid and its salts, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutylene, vinyltoluene.

Especially are preferred in the process according to the invention the following co-monomers are used together with N-vinylpyrrolidone: Acrylic acid, methacrylic acid, maleic acid, Fumaric acid, crotonic acid, maleic anhydride and its half esters as well as hemiamides and imides, methyl acrylate, Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isobutyl acrylate, Isobutyl methacrylate, 2-ethylhexyl acrylate, stearyl acrylate, stearyl methacrylate, N-tert-butylacrylamide, N-octylacrylamide, N-t-octylacrylamide, 2-hydroxyethyl acrylate, 2 hydroxypropyl acrylate, 2-2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 3 hydroxypropyl acrylate, alkylene glycol (meth) acrylate, styrene, unsaturated Sulfonic acids and their salts such as acrylamidopropanesulfonic acid and styrenesulfonic acid, vinylpyrrolidone, vinylcaprolactam, Vinyl ethers (for example: methyl, ethyl, butyl or dodecyl vinyl ether), Vinylformamide, N-vinyl-N-methylacetamide, vinylamine, 1-vinylimidazole, 1-vinyl-2-methylimidazole, N, N-dimethylaminomethylmethacrylate and N- [3- (dimethylamino) propyl] methacrylamide; 3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methylsulfate, N, N-dimethylaminoethyl methacrylate, N isopropylmethacrylamide, N- [3- (dimethylamino) propyl] methacrylamide quaternized with methyl chloride, VCAp, VI, 1-vinyl-3-methylimidazolium Salts such as chloride and methyl sulfate (QVI), VAC, (meth) acrylamide, Dimethylaminoethyl (meth) acrylate and dimethylaminoethyl (meth) acrylamide and their quaternized analogs, diallyldimethylammonium chloride, Vinyl alcohol (by hydrolysis from vinyl acetate after polymerization), VFA, vinylamine (by hydrolysis from VFA after polymerization), dimethylaminopropyl (meth) acrylate, Dimethylaminopropyl (meth) acrylamide, (meth) acrylic acid, vinylpiperidone, N, N-dimethyl (meth) acrylamide, tert-butyl (meth) acrylamide, N-tert-octyl (meth) acrylamide, stearyl (meth) acrylamide, Methyl, ethyl, butyl, tert-butyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, N-isopropylacrylamide, Vinyl propionate, 1-vinyl-2-methylimidazole, vinylpyridine, esters of (Meth) acrylic acid or ethers of allyl alcohol and of polyethylene oxide or propylene oxide or poly (ethylene oxide-co-propylene oxide) with a total of 2 to 200 EO or PO units or EO / PO units with methoxy group or hydroxy group at the chain end, methyl vinyl ether, hydroxyethyl (meth) acrylate, Hydroxypropyl (meth) acrylate, vinyllactams, vinyloxazolines such as vinyloxazoline, Vinylmethyloxazoline, vinylethyloxazoline, acrylamidopropanesulfonic acid and allyl alcohol.

Further suitable co-monomers are polyfunctional monomers such as triallylamine, trivinyl ether, divinylethyleneurea, 3-vinyl-N-vinylpyrrolidone, 4-vinyl-N-vinylpyrrolidone, 5-vinyl-N-vinylpyrrolidone, pentaerythritol triallyl ether, methylenebisacrylamide, butanediol diacrylate, hexanediol diacrylate, dipropylene glycol diacrylate, allyl methacrylate , Divinylbenzene, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate and triethylene glycol divinyl ether. Such monomers are usually used in small amounts of 0.01 to 10 wt .-% and lead to the crosslinking of the polymers. Other suitable crosslinking agents are listed elsewhere in the description. The statements made here apply accordingly.

All particularly preferred as comonomers are N-vinylcaprolactam (VCap), N-vinylimidazole (VI), 1-vinyl-3-methylimidazolium salts (QVI), for example Salts by quaternization with methyl chloride or dimethyl sulfate be obtained, vinyl acetate, (meth) acrylamide, dimethylamino-ethyl (meth) acrylate and dimethylaminoethyl (meth) acrylamide and by alkylation resulting products and diallyldimethylammonium chloride.

In In certain cases, preference is given to the preparation of copolymers, which contain, in addition to VP mixtures of said comonomers, for example Ter- or Tetracopolymere. For example, terpolymers from VP / VI / methacrylamide or VP / VCap / VI terpolymers. Preferred copolymers consist of VP and vinyl acetate or of VP and vinylimidazole.

According to the The present invention is a method as described above. preferably, wherein in step (b) copolymers of N-vinylpyrrolidone (VP) with vinyl acetate (VAc) with Fikentscher K values of 20 to 100 are produced. For this purpose, VP and VAc are preferred in one Weight ratio of VP to VAc in a range of 20:80 to 80:20, more preferably in the range of 30:70 to 70:30 and most preferably in a range of 65:35 to 35:65 used. Most preferred is a weight ratio from VP to VAc of 60:40. VP and VAc can also work in one Weight ratio of about or exactly 50:50 used become. Further preferred is an inventive A process wherein in step (b) copolymers of VP and VI are prepared wherein, in step (a), for example, VP and VI have a weight ratio of 1: 1 are used. Also preferred is an inventive Processes, wherein in step (b) copolymers of VP and VCap with K values according to Fikentscher, from 20 to 100, wherein in step (a), VP and VCap, for example, with a weight ratio of 1: 1 are used, Also preferred is an inventive A process wherein in step (b) copolymers of VP and 1-vinyl-3-methylimidazolium chloride (obtained by quaternization of 1-vinylimidazole with methyl chloride) made with Fikentscher K values of 10 to 100, wherein in step (a), VP and QVI are preferably in a weight ratio be used from 5:95 to 95: 5.

Also preferred is a method according to the invention as described above, wherein the one used in step (a) Monomers or at least one of the monomers used in step (a) Acrylic acid is. Particular preference is given to methods wherein the dispersed phase produced in step (a) comprises acrylic acid as contains single monomer. Among the invention Processes in which the dispersed phase produced in step (a) Contains acrylic acid as preferably single monomer, is particularly preferred a method wherein the total content of Mononieren in that produced according to step (a) dispersed phase in the range of 40 wt .-% to 99.99 wt .-%, preferably from 40 wt% to 98 wt%, more preferably from 50 wt% to 90% by weight and most preferably from 50% to 80% by weight is based on the total mass of the dispersed phase.

If the proportion of acrylic acid is less than 40% by weight and no other monomers are present, the weight average (M _w ) of the polymer is often low. If larger amounts of another monomer are present in comparison with acrylic acid, the acrylic acid units have only a slight influence on the properties of the polymer. If, however, the proportion of acrylic acid is greater than 99.99% by weight, the resulting polymer often has an undesirably low weight average (M _w ). When the proportion of acrylic acid is from 40% by weight to 98% by weight, polymers with a high weight average (M _w ) can surprisingly be produced by the process according to the invention. This is especially true when the proportion of acrylic acid is in the range of 50% to 90% by weight. In a proportion of 50 wt .-% to 80 wt .-%, the highest weight average (M _w ) were obtained in own investigations.

In the preferred method of the invention (such as described above) for the preparation of acrylic acid copolymers Comonomers are preferably used as described above and especially preferred as preferred above were designated.

According to the inventive method as described above, the polymer becomes in step (b) by a radical polymerization generated. Preferred is a method as described above, wherein the dispersed phase produced in step (a) (preferably exclusively) Contains monomers containing the vinyl groups.

As a radical initiator, all are basically for the radical polymerization ethylenically unge saturated monomers known initiators, in particular thermally activated free-radical initiators, ionic radical initiators or redox radical initiators. In general, they are initiators based on organic or inorganic peroxides, azo initiators or redox initiator systems. The amount of initiator is usually 0.001 to 5 wt .-%, preferably 0.01 to 2 wt .-% and particularly preferably 0.05 to 1 wt .-%, based on the total amount of the monomers to be polymerized. Particularly preferred are thermally activatable radical initiators, which preferably have a suitable half-life at the polymerization temperature. Thermally activatable free-radical initiators are compounds which upon addition of heat form radicals which are capable of initiating the chain initiation of a free-radical polymerization reaction.

• – Peroxidverbindungen: Hierzu zählen beispielsweise organische Peroxide und Hydroperoxide wie Acetylperoxid, Benzoylperoxid, Lauroylperoxid, tert-Butylperoxy-isobutyrat, Caproylperoxid, Cumolhydroperoxid, Di-tert.-Butylperoxid, tert.-Butylhydroperoxid, tert.-Amylhydroperoxid, tert.-Butylperoxy-acetat, tert.-Butylperoxy-benzoat, tert.-Butylperoxy-octoat, tert.-Butylperoxy-neodecanoat, tert.-Amylperoxy-pivalat, tert.-Butylperoxy-pivalat, Diisopropylperoxy-dicarbonat, Dicyclohexylperoxy-dicarbonat, Dicumylperoxid, Dibenzoylperoxide, Dilauroylperoxid; anorganische Peroxide wie Wasserstoffperoxid, Peroxodischwefelsäure und deren Salze wie Ammonium-, Natrium und Kaliumperoxodisulfat;
• – Azoverbindungen wie 2,2'-Azobis-isobutyronitril (AIBN), 2,2'-Azobis(2-methylbutyronitril), 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamid], 1,1'-Azobis(1-cyclohexancarbonitril), 2,2'-Azobis(2,4-dimethylvaleronitril), 2,2'-Azobis(N,N'-dimethylenisobutyroamidin) 2,2'-Azobis(N,N'-dimethylenisobutyroamidin), 2,2'-Azobis(2-methylpropioamidin), N-(3-Hydroxy-1,1-bis-hydroxymethylpropyl)-2-[1-(3-hydroxy-1,1-bis-hydroxymethyl-propylcarbamoyl)-1-methyl-ethylazo]-2-methyl-propionamid sowie N-(1-Ethyl-3-hydroxypropyl)-2-[1-(1-ethyl-3-hydroxy-propylcarbamoyl)-1-methyl-ethylazo]-2-methyl-propionamid; 2,2'-Azobis(2-cyano-2-butan), Dimethyl-2,2'-azobisdimethylisobutyrat, 4,4'-azobis(4-cyanopentanoic acid), 1,1'-Azobis(cyclohexancarbanitril), 2-(tert.-Butylazo)-2-cyanopropan, 2,2'-Azobis[2-methyl-N-(1,1)-bis(hydoxy-methyl)-2-hydroxyethyl]propionamid, 2,2'-azobis[2-methyl-N-hydroxyethyl)]-propionamid, 2,2'-Azobis(N,N'-dimethylen-isobutyramidin)-dihydrochlorid, 2,2'-Azobis(2-amidinopropan)-dihydro-chlorid, 2,2'-Azobis(N,N'-dimethylen-isobutyramin), 2,2'-Azobis(2-methyl-N-[1,1-bis(hydroxy-methyl)-2-hydroxyethyl]propionamid), 2,2'-Azobis(2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]-propionamid), 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamid], 2,2'-Azobis(isobutyramid)-Anhydrat, 2,2'-Azobis(2,2,4-trimethylpentan), 2,2'-Azobis(2-methylpropan)
• – Redoxinitiatoren, also Initiatorsysteme, die ein Oxidationsmittel, beispielsweise ein Salz der Peroxodischwefelsäure, Wasserstoffperoxid oder ein organisches Peroxid wie tert.-Butylhydroperoxid und ein Reduktionsmittel enthalten. Als Reduktionsmittel enthalten sie vorzugsweise eine Schwefelverbindung, die insbesondere ausgewählt ist unter Natriumhydrogensulfit, Natriumhydroxymethansulfinat und dem Hydrogensulfit-Addukt an Aceton. Weitere geeignete Reduktionsmittel sind stickstoff- und phosphorhaltige Verbindungen wie phosphorige Säure, Hypophosphite und Phosphinate, Di-tert-Butylhyponitrit und Dicumylhyponitrit, sowie Hydrazin bzw. Hydrazinhydrat und Ascorbinsäure. Weiterhin können Redoxinitiatorsysteme einen Zusatz geringer Mengen von Redoxmetallsalzen wie Eisensalze, Vanadiumsalze, Kupfersalze, Chromsalze oder Mangansalze enthalten wie beispielsweise das Redoxinitiatorsystem Ascorbinsäure/Eisen(II)sulfat/Natriumperoxodisulfat.

Examples of suitable polymerization initiators are given below:

• Peroxide compounds: These include, for example, organic peroxides and hydroperoxides such as acetyl peroxide, benzoyl peroxide, lauroyl peroxide, tert-butyl peroxyisobutyrate, caproyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide, tert-butyl peroxy acetate tert-butyl peroxybenzoate, tert-butyl peroxy-octoate, tert-butyl peroxy-neodecanoate, tert-amyl peroxy pivalate, tert-butyl peroxy pivalate, diisopropyl peroxy dicarbonate, dicyclohexyl peroxy dicarbonate, dicumyl peroxide, dibenzoyl peroxides, dilauroyl peroxide; inorganic peroxides such as hydrogen peroxide, peroxodisulfuric acid and their salts such as ammonium, sodium and potassium peroxodisulfate;
• Azo compounds such as 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 1, 1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) 2,2'-azobis (N, N ') dimethyleneisobutyroamidine), 2,2'-azobis (2-methylpropioamidine), N- (3-hydroxy-1,1-bis-hydroxymethylpropyl) -2- [1- (3-hydroxy-1,1-bis-hydroxymethyl-propylcarbamoyl ) -1-methyl-ethylazo] -2-methyl-propionamide and N- (1-ethyl-3-hydroxypropyl) -2- [1- (1-ethyl-3-hydroxy-propylcarbamoyl) -1-methyl-ethylazo] -2-methyl-propionamide; 2,2'-azobis (2-cyano-2-butane), dimethyl 2,2'-azobisdimethyl isobutyrate, 4,4'-azobis (4-cyanopentanoic acid), 1,1'-azobis (cyclohexanecarbanitrile), 2- (tert-butylazo) -2-cyanopropane, 2,2'-azobis [2-methyl-N- (1,1) -bis (hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2'-azobis [ 2-methyl-N-hydroxyethyl)] propionamide, 2,2'-azobis (N, N'-dimethylene-isobutyramidine) dihydrochloride, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2.2 'Azobis (N, N'-dimethyleneisobutyramine), 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxy-methyl) -2-hydroxyethyl] propionamide), 2,2' Azobis (2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] -propionamide), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'- Azobis (isobutyramide) anhydrate, 2,2'-azobis (2,2,4-trimethylpentane), 2,2'-azobis (2-methylpropane)
• - Redox initiators, ie initiator systems containing an oxidizing agent, for example a salt of peroxodisulfuric acid, hydrogen peroxide or an organic peroxide such as tert-butyl hydroperoxide and a reducing agent. As the reducing agent, they preferably contain a sulfur compound, which is particularly selected from sodium hydrogensulfite, sodium hydroxymethanesulfinate and the bisulfite adduct of acetone. Further suitable reducing agents are nitrogen- and phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates, di-tert-butyl hyponitrite and dicumyl hyponitrite, as well as hydrazine or hydrazine hydrate and ascorbic acid. Furthermore, redox initiator systems may contain an addition of small amounts of redox metal salts, such as iron salts, vanadium salts, copper salts, chromium salts or manganese salts, for example the redox initiator system ascorbic acid / iron (II) sulfate / sodium peroxodisulfate.

Especially preferred initiators are azo initiators selected from the list consisting of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2,4-dimethylvaleronitrile), azobis (isobutyronitrile) and 2,2'-azobis (2-amidinopropane) dihydrochloride, and redox initiators, selected from the list consisting of sodium persulfate / hydroxymethylsulfinic acid, Ammonium peroxodisulfate / hydroxymethylsulfinic acid, hydrogen peroxide / hydroxymethylsulfinic acid, Sodium persulfate / ascorbic acid, ammonium peroxodisulfate / ascorbic acid and hydrogen peroxide / ascorbic acid and mixtures thereof.

The The above-mentioned radical initiators can also be used in Any combination can be used.

The Radical initiators may be used as such or in a solvent be used dissolved. The initiators are preferred used dissolved in a suitable solvent. Particularly suitable solvents are those which are others Site of the present text for the production of the dispersed phase in step (a) are indicated as suitable.

A preferred process according to the invention is one in which the dispersed phase produced in step (a) Acrylic acid as monomer and potassium peroxodisulfate (KPS) or ammonium peroxodisulfate (APS) as initiator. Also preferred is a process as described above wherein the dispersed phase produced in step (a) is N-vinylpyrrolidone as (preferably the only) monomer and 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride contains as initiator. In this case, a content of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride of less than or equal to 0.03 mol% based on the total monomer content of the dispersed phase produced in step (a), the best results, in particular one obtains polymers with high weight average (M _w ). With regard to preferred embodiments of processes according to the invention in which acrylic acid or N-vinylpyrrolidone are polymerized, see above

In certain embodiments of the invention Method (as described above and preferably as above referred to as preferred), it is preferred that in step (a) produced dispersed phase and / or the continuous phase Includes surfactants.

suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, Alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoylsarcosinates, alkyl glycol alkoxylates, acyl taurates, acyl isethionates, Alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha olefin sulfonates, in particular the alkali and alkaline earth metal salts, e.g. Sodium, Potassium, magnesium, calcium, as well as ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates may be between 1 to 10 ethylene oxide or propylene oxide units, preferably have 1 to 3 ethylene oxide units in the molecule. Also suitable are, for example, sodium lauryl sulfate, ammonium lauryl sulfate, Sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, Sodium oleyl succinate, ammonium lauryl sulphosuccinate, sodium dodecyl benzene sulphonate, Triethanolamine.

suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidopropyl betaines, Alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or propionates, alkyl amphodiacetates, or dipropionates. For example may also be cocodimethyl sulphopropyl betaine, lauryl betaine, Cocamidopropyl betaine or Natriumcocamphopropionat be used.

When Nonionic surfactants are suitable, for example, the reaction products of aliphatic alcohols or alkylphenols having 6 to 20 C atoms in the alkyl chain, which may be linear or branched, with ethylene oxide and / or propylene oxide. The amount of alkylene oxide is approx. 6 to 60 moles per mole of alcohol. Furthermore, alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, ethoxylated fatty acid amides, alkyl polyglycosides or sorbitan ether esters suitable.

Also suitable are conventional cationic surfactants, such as. B. quaternary Ammonium compounds, for example cetyltrimethylammonium chloride or bromide (INCI Cetrimonium chlorides or bromides), hydroxyethyl cetyldimonium phosphate (INCI Quaternium-44), INCI cocotrimonium methosulfate, INCI Quaternium-52.

Farther suitable for use as surfactants in the invention Method (as described above and preferably as above referred to as preferred), are surface-active substances from linear block copolymers with a hydrophobic moiety a length of more than 5 nm (calculated by the Cosines law), which are preferably defined by the following formula Cw- (B-A-By) x-Dz, where A is a hydrophilic moiety having a solubility in water at 25 ° C of 1% by weight or more, one molecular weight Mw from 200 to 50,000, and is selected to be covalently bound to B; B is a hydrophobic moiety, which has a molecular weight Mw of 300 to 60,000, a solubility in water at 25 ° C of less than 1% by weight and covalent can be bound to A; C and D are end groups which are A or B and may be the same group or different groups; w is 0 or 1; x is an integer greater than or equal to is 1, y is 0 or 1, and z is 0 or 1.

In a further (preferred) embodiment of the process according to the invention (as described above and preferably as preferred above), the dispersed phase and / or the continuous phase produced in step (a) comprises at least one surface-active substance of random comb copolymers which is characterized by the following formula: R1- (Z) m- (Q) n-R2 are defined, wherein R1 and R2 are end groups and may be the same or different and different from Z and Q, Z is a hydrophobic moiety having a solubility in water of 25 ° C of less than 1% by weight, Q is a hydrophilic moiety having a solubility in water of 25 ° C greater than 1% by weight, and m and n are integers greater than or equal to Are 1 and are selected such that the molecular weight Mw is 100 to 250,000. Particularly preferred are 12-hydroxystearic acid block copolymers, more preferably 12-hydroxystearic acid block copolymers with polyethylene oxide. It is particularly preferred the 12-hydroxystearic acid block copolymers are ABA block copolymers. Very particularly preferred surfactants are selected from the group consisting of 1) Hypermer ^® B239: block copolymer of polyhydroxy fatty acid (PFA) and polyethylene oxide (PEO) with Mw of about 3500; 2) Hypermer ^® B246: block copolymer of polyhydroxy fatty acid (PFA) and polyethylene oxide (PEO) with Mw of about 7500; 3) Hypermer ^® B261: block copolymer of polyhydroxy fatty acid (PFA) and polyethylene oxide (PEO) with Mw of about 9600; 4) Hypermer ^® 2234: non-ionic polymeric surface-active compound; 5) Hypermer LP6 ^®: polymeric fatty acid ester with Mw of about 4300; 6) Hypermer IL2296 ^®: nonionic polymeric surface-active compound; 7) Hypermer A-109 ^® block copolymer of a fatty acid or a long-chain alkylene radical with ethylene oxide; 8) Hypermer A-409 ^® block copolymer of a fatty acid or a long-chain alkylene radical with ethylene oxide; 9) Pecosil PS-100 ^® dimethicone copolyol phosphate polymer having 5-12 moles of ethylene oxide per mole of hydrophilic unit; and 10) Pecosil WDS-100 ^® dimethicone copolyol phosphate polymer having 5-12 moles of propylene oxide per mole of hydrophilic unit.

Preference is furthermore given to a process according to the invention (as described above and preferably as preferred above) in which the surface-active substance is selected from the group consisting of - copolymers of polydimethylsiloxanes and organic glycols, - substances with the INCI name Dimethicone PEG-7 phosphates, Polyesters containing polyethylene glycol, polyoxyethylene-glycerol fatty acid esters, polyamide waxes, natural waxes and mixtures thereof. Examples which may be mentioned are commercially available according to the invention suitable copolymers of polydimethylsiloxanes and organic glycols substances having the INCI name PEG / PPG-25/25 dimethicone (z. B. Belsil ^® DMC 6031) and Dimethicone Copolyol Acetate (z. B. Belsil ^® DMC 6032).

As commercially available according to the invention suitable as a surfactant Dimethicone PEG-7 phosphate (INCI) be mentioned, for example Pecosil PS ^® 100th As commercially available are suitable according to the invention polyethylene glycol-containing polyesters, for example, called block copolymers of the Hypermer ^® brand, in particular the type B239, B246, B261, 2234 LP6, A-109, A-409 (described in EP 584771 B1 , P. 10, 2. 25-42). Examples which may be mentioned are commercially available according to the invention suitable polyoxyethylene-glycerol-fatty acid esters Polyglyceryl-2 Dipolyhydroxystearate (INCI) as Dehymuls ^® PGPH (Cognis). Further, according to the invention suitable compounds with the INCI-names PEG-7 Hydrogenated Castor Oil, such as Arlacel ^® 989, Cremophor ^® WO7 (BASF) or Dehymuls ^® HRE 7 (Cognis), PEG-2 Hydrogenated Castor Oil as Arlacel ^® 582, sorbitan monoo- leate / propylglceryl 4/3-ricinoleate as Arlacel ^® 1689 (Croda), sorbitan stearates and sucrose cocoate such. B. Arlartone ^® 2121 (Croda), sorbeth-20 beeswax such. ^Atlas® G-1726 (Croda). As a commercially available polyamide wax suitable according to the invention, mention may be made, for example, of Kahl Wachs 6635 (Kahl & Co).

Examples of commercially available natural waxes which are suitable according to the invention are mixtures of fatty acid esters, fatty acids and fatty alcohols such as, for example, beeswax, berry wax, rice wax (Kahl & Co). Suitable bee waxes are, in particular, those with the CAS numbers 8006-40-4 (White) or 8012-89-3. Suitable bee waxes bear the INCI (EU) designations Cera Alba, Synthetic beeswax, PEG-7 Dimeticone beeswax. Particularly suitable bee waxes are those with the INCI EU name Cera Alba. Suitable soft waxes are for example those with the INCI name Rhus verniciflua Peel Wax (Berry 6290 Wax (Kahl & Co) or Botaniwax OT ^® (Botanigenics, Inc)). Suitable rice waxes are in particular those with CAS number 8016-60-2 or the INCI name Oryza Sativa (Rice) Bran Wax. Such rice waxes are commercially available as Cerewax ^® (Chemyunion Quimica LTDA), ESP ^® Rice Bran Wax (Earth Supplied product, LLC), Florabeads ^® RBW (FLORATECH Americas), Naturebead ^® R20 (Micro Powders, Inc. Personal Care Division), Oryza Soft ^® "COS" (Cosmetochem International Ltd.), ORYZA ^® Wax (Ichimaru Pharcos Company, Ltd.), Ricebran Wax SP 8000 (Ray & Pitsch, Inc.), Rice Wax No.1 (Tri-K industries), Rice Wax 2811 (Kahl ) available.

at the known from the prior art emulsion polymerization of water-soluble polymers are commonly used Emulsifiers used. These serve to stabilize the emulsions and for setting different product parameters. The remainder however, emulsifiers in the product can alter product properties and is therefore generally undesirable. This can be z. B. when used as a thickener. It's special disturbing when using the water-soluble Polymers as auxiliaries in foods, cosmetic agents, Medicines and the like. Emulsifiers cause about it In addition, phase interface phenomena involving the Influence the structure of the polymers. Therefore, an inventive Method (as described above), preferably a method in which no surfactants are added to the dispersion. In such a Process is obtained directly and without further purification the product is a polymer that is free of surfactants and their effects is.

highly crosslinked Polymers are usually not water-soluble, but swell in the presence of water only. Therefore, according to the present invention preferably a method as described above, wherein the dispersion produced in step (a) is not a cross-linker (also known to the skilled person as "branching reagents" or "crosslinkers") contains, so that no highly crosslinked polymers. In alternative embodiments of the invention However, the process comprises the dispersion produced in step (a) at least one "cross-linker" in the sense of the usual Term understanding. This can in particular serve produce long-chain branched polymers. These are "cross-linkers" used in such a low concentration that they only cause such a minor branching that the resulting Polymer is still water soluble. They will be part of the according to the present text also as branching reagents designated. Through their use, the rheological properties of the Polymer dispersions modified. The expert will take care that the resulting polymer is still water-soluble. details Information on the water solubility of the polymer can be found elsewhere in the description and in the claims.

branching reagents (Cross linkers) are, for example, compounds with at least two polymerizable under polymerization conditions, ethylenic unsaturated, nonconjugated double bonds in the molecule. Suitable branching reagents are, for example, esters or ethers of at least dihydric alcohols selected from Group consisting of acrylic ester, methacrylic ester, oleic acid ester, Crotonic acid ester, cinnamic acid ester, 10-undecenoic acid ester, Allyl ethers, vinyl ethers and mixtures thereof. Especially preferred esters or ethers of at least dihydric alcohols are selected from the group consisting of acrylic ester, methacrylic ester, Allyl ethers, vinyl ethers and mixtures thereof. The OH groups of the at least dihydric alcohols can be completely or partially etherified or esterified; the branching reagents but contain at least two ethylenically unsaturated Groups.

When Dihydric alcohols are for example usable diols selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, but-2-ene-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, neopentyl glycol, 3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-bis (hydroxymethyl) cyclohexane, hydroxypivalic neopentyl glycol monoester, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxypropyl) phenyl] propane, Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, Tripropylene glycol, tetrapropylene glycol, 3-thiapentane-1,5-diol, as well as Polyethylene glycols, polypropylene glycols and polytetrahydrofurans with Molecular weights of 200 to 10,000 and mixtures thereof. Except for the homopolymers of ethylene oxide or propylene oxide may also be block copolymers of ethylene oxide or propylene oxide or copolymers incorporating ethylene oxide and propylene oxide groups contained, are used. As alcohols with more than two OH groups For example, alcohols are selected from the Group consisting of trimethylolpropane, glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, cyanuric acid, sorbitan and sugars such as sucrose, glucose, mannose, and mixtures thereof. Of course, the at least bivalent Alcohols also after reaction with ethylene oxide or propylene oxide as the corresponding ethoxylates or propoxylates are used. The at least dihydric alcohols may also initially converted by reaction with epichlorohydrin in the corresponding glycidyl ether become.

Further suitable branching reagents are the vinyl esters and the esters of monohydric, unsaturated alcohols of ethylenically unsaturated C ₃ -C ₆ -carboxylic acids, for example selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and mixtures thereof. Suitable alcohols are, for example, selected from the group consisting of allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl alcohol, 10-undecene 1-ol, cinnamyl alcohol, citronellol, crotyl alcohol, cis-9-octadecen-1-ol and mixtures thereof.

Also suitable as branching reagents are esters of monovalent, unsaturated alcohols with polybasic carboxylic acids, in which at least two of the carboxylic acid groups are monovalent, unsaturated alcohols are esterified. Therefor suitable polybasic carboxylic acids are selected, for example from the group consisting of malonic acid, tartaric acid, Trimellitic acid, phthalic acid, terephthalic acid, citric acid, Succinic acid and mixtures thereof. Suitable for this Monohydric unsaturated alcohols are described above.

Also suitable as branching reagents are the acrylic acid amides, methacrylic acid amides and N-allylamines of at least divalent amines. Such amines are, for example, selected from the group consisting of 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine, diethylenetriamine, isophoronediamine and mixtures thereof. Also suitable net are the amides of allylamine with unsaturated carboxylic acids, for example, selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, polybasic carboxylic acids, as described above and mixtures thereof.

Also suitable is ethenylvinylpyrrolidone (EPP) such as 3-ethenylvinylpyrrolidone, 4-ethenylvinyl pyrrolidone or 5-ethenylvinyl pyrrolidone.

Further are triallylamine and triallyl monoalkylammonium salts, for example selected from the group consisting of triallylmethylammonium chloride and methyl sulfate, and mixtures thereof as branching reagents suitable.

Suitable Branching reagents also include N-vinyl compounds of urea derivatives, at least divalent amides, cyanurates and urethanes, for example urea, ethyleneurea, propyleneurea or tartaramide, for example, selected from the group consisting of N, N'-divinylethyleneurea, N, N'-divinylpropyleneurea and mixtures thereof.

Further suitable branching reagents are for example selected from the group consisting of divinyldioxane, tetraallylsilane or Tetravinylsilane.

Especially Preferred branching reagents (crosslinkers) are, for example Methylenebisacrylamide, triallylamine and triallylalkylammonium salts, Divinylimidazole, pentaerythritol triallyl ether, N, N'-divinylethyleneurea, Reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic acid esters and acrylic esters of polyalkylene oxides or polyhydric alcohols with ethylene oxide and / or propylene oxide and / or epichlorohydrin as well as ethenylvinylpyrrolidones. Very particularly preferred as branching reagents (Crosslinkers) are pentaerythritol triallyl ether, methylenebis-acrylamide, N, N'-divinylethyleneurea, ethenylvinylpyrrolidone, allyl (meth) acrylate, Diallyl tartaric acid, triallylamine and triallyl monoalkylammonium salts and acrylic esters of glycol, butanediol, trimethylolpropane or glycerol or acrylic ester of with ethylene oxide and / or epichlorohydrin reacted glycol, butanediol, trimethylolpropane or glycerin.

Other suitable branching reagents (crosslinkers) are urethane diacrylates and urethane polyacrylates, as described, for. B. under the name Laromer ^{® are} commercially available.

Of course may also be mixtures of the aforementioned compounds as Verzeigungsreagenzien (crosslinker) can be used.

The inventive method (in its various Embodiments) is a production process for polymers, in which a multi-phase system is used. It is from here Advantage, if the product at the end of the reaction only in a single Phase exists. This usually saves a complex workup of the Reaction mixtures such as extractions and the like. It is therefore an inventive method preferred, wherein the process conditions are adjusted so that in step (b), polymer formed remains in the dispersed phase; this applies in particular to those designated as preferred Embodiments of the method according to the invention.

Especially preferred is a method according to the invention preferably as referred to above as preferred, wherein the Solubility of the polymer in the continuous phase at 20 ° C less than 15 g of polymer per 100 g in step (a) continuous phase employed is preferred less than 10 g of polymer per 100 g of continuous used in step (a) Phase, more preferably less than 5 g of polymer per 100 g in Step (a) used continuous phase and especially preferably less than 2 g of polymer per 100 g used in step (a) continuous phase.

Very particular preference is given to a process according to the invention as just described in which the solubility of the polymer at 20 ° C. is less than 5 g of polymer per 100 g of the continuous phase used in step (a) and more than 10 g of polymer per 100 g of a) produced dispersed phase. Even more preferred is a process wherein the solubility of the polymer at 20 ° C is less than 2 grams of polymer per 100 grams of continuous phase used in step (a) and greater than 40 grams of polymer per 100 grams of dispersed one produced in step (a) Phase is. The person skilled in the art will ensure that the abovementioned solubilities by suitably selecting the continuous phase used in step (a) and the dispersed phase produced in step (a), the free-radical initiators, emulsifiers, cross-linkers, any further additives used and the reaction conditions in the continuous and dis pergaged phase can be achieved.

polymerizations lead in multi-phase systems according to the Prior art often leads to polymers whose structure is greatly enhanced by diffusion and similar interfacial phenomena is. This is often desirable to polymers with special To create properties. Such polymerizations can also be combined with perform the procedure as described above. However, it is one of the advantages of the present invention that she also allows a reaction in the interfacial phenomena and in particular diffusion little or no effect on the reaction and the Have reaction products.

• – in Schritt (a) eingesetzten Monomere sowie gegebenenfalls verwendeten Initiatoren und/oder weiteren Hilfsmittel und
• – in Schritt (b) hergestellten Polymere

in der kontinuierlichen Phase unlöslich sind. Bevorzugt ist, wenn bei 20°C nach Gleichgewichtseinstellung weniger als 2 Gew.-% der im Rohrreaktor vorhandenen Gesamtmenge eines jeden Bestandteils in der kontinuierlichen Phase vorliegen.Accordingly, according to the present invention, a process according to the invention (as described above, preferably as described above as being preferred) is correspondingly particularly preferred, in which all

• - used in step (a) monomers and optionally used initiators and / or further auxiliaries and
• - Polymers prepared in step (b)

are insoluble in the continuous phase. It is preferred if, at 20 ° C after equilibration, less than 2% by weight of the total amount of each constituent present in the tubular reactor is present in the continuous phase.

In such a process, the reaction carried out in step (b) proceeds completely in the dispersed phase produced in step (a) and the continuous phase merely serves to delimit the reaction space consisting of the discrete volumes of the dispersed phase produced in step (a) consists. In such a system, interfacial phenomena are minimized and high weight average _molecular weight ( _Mw ) polymers can be obtained.

Under The circumstances are the choice of monomers and other process parameters limited by the nature of the desired polymer and / or by other factors. That's why it may be necessary a certain solubility of the product in the continuous phase as described above. It may also be necessary to use a continuous phase in which the monomers are partially soluble.

Therefore For example, the present invention also includes a method as above wherein the phase dispersed in step (a) and the further process parameters and the continuous phase selected are that by the end of step (b) a maximum of 10 wt .-% of in the dispersed phase initially present monomers into the continuous phase. Also included the present invention a method (as described above), wherein in step (a) the liquid to be dispersed at least 95 wt .-%, preferably all of the used Monomers includes. The remaining maximum 5 wt .-% of monomers are then in the continuous phase.

Becomes in an individual case, the implementation of an inventive Method using phase interface phenomena desired, so can the solubility of the monomers be arbitrarily large in the continuous phase. Also with the continuous phase miscible monomers can then be used. But then it has to worry about that be worn such that the phase interface between dispersed phase and continuous phase is maintained.

For the case that after the polymerization in step (b) parts of Monomers remain in the continuous phase, the process can be guided so that the separated after the reaction continuous phase without removal of the monomers again in one inventive method is used. monomers may also be for reasons other than recycling partly through the continuous phase in the step (a) introduced dispersion are introduced. This is not prefers.

water-soluble Polymers can be either in water or in aqueous Media can be soluble or they can after overpass from nonionic functional groups to ionic functional ones Groups soluble in water or in aqueous media be. Thus, carboxylic acid groups can be carboxylate and amino groups are modified to ammonium groups, as is has already been described above for monomers. water-soluble For the purposes of the present application, polymers are both such Polymers which are soluble in water or in aqueous media are as well as those by protonation or deprotonation solubilized in water or in aqueous media become. For protonation or deprotonation of the polymers can the dispersed phase acids or alkalis are added.

in the Meaning of the above definition for water-soluble Polymers is preferably a process according to the invention, wherein the solubility of the product prepared in step (b) Polymers in water more than 0.1 g per 100 g of water, preferably more than 1 g per 100 g of water, more preferably more than 5 g per 100 g Water, most preferably more than 10 g per 100 g of water and most preferably greater than 50 grams per 100 grams of water.

Prefers is a method according to the invention, wherein the dispersed phase of the dispersion produced in step (a) Introduce the liquid to be dispersed in the continuous Phase or by introducing the continuous phase in the dispersing liquid are generated. Particularly preferred a process according to the invention, wherein the dispersed Phase of the dispersion produced in step (a) by introducing the to be dispersed liquid in the continuous phase is produced.

at the production of solid particles using a method For continuous drop production, a product with a uniform grain size can be obtained without elaborate treatment such as grinding, sieving, sifting or the like directly usable and easy to handle and does not dust.

• – eines statischen Mischers,
• – der Membran-Technik,
• – vibrierender Blenden,
• – der Düsen-Technik,
• – der Kapillar-Technik und/oder
• – durch einen mikrofluidischen Chip mit Flussfokussiereinheit.

Therefore, preference is given to a method according to the invention (as described above, preferably as described above as preferred), wherein in step (a) the dispersed phase is produced by a method for continuous drop formation. Preference is given to a process as described above, preferably a process as referred to above as preferred, wherein in step (a) the dispersed phase is produced by a method for the continuous drop generation, preferably using

• - a static mixer,
• - the membrane technique,
• - vibrating apertures,
• - the nozzle technique,
• - the capillary technique and / or
• Through a microfluidic chip with flux focusing unit.

A preferred embodiment is an inventive A method as described above, wherein the dispersed phase is generated by introducing the dispersed phase into the continuous phase with the help of a cannula, a capillary or a tube.

A Another preferred process variant is a process (as above preferably described as preferred above), wherein the dispersion in step (a) is generated by introducing the dispersed phase into the continuous phase with the help of a Coaxial flow unit, wherein the coaxial flow unit an inner flow tube that contains inside an outer flow tube arranged wherein, in the inner flow tube, the dispersed phase and in the outer flow tube the continuous Phase in the same direction and in what the end of the inner flow tube is arranged so that the dispersed phase is introduced into the continuous phase. Compare to the figures and examples below. It is too possible to perform the procedure so that the dispersed phase in the inner flow tube and the continuous phase in the outer flow tube be introduced.

With the (preferred) method for continuous droplet production can be a method according to the invention so perform that the coefficient of variation of the size the droplets forming the phase dispersed in step (a), less than 5%, preferably less than 3%, more preferably less than 2.5%.

Another parameter which has an influence on the performance of the processes according to the invention and the polymers produced in step (b) is the phase ratio. It is the ratio of the flow rates of continuous phase to dispersed phase in the generation of the dispersion in step (a). With constant supply of the two phases, the phase ratio Ph _{L is} calculated from the quotient of the volume of the continuous phase fed per unit time and the volume of the dispersed phase fed per unit time. If the phase ratio Ph _{L is} too low, the discrete volumes of the dispersed phase produced in step (a) coalesce. If the phase ratio Phi is too high, the weight average (Mw) of the monomer produced is often decreased, and unnecessary amounts of continuous phase may be consumed.

Prefers is a method according to the invention (as above described), wherein the phase ratio is adjusted in that in step (a) discrete volumes of the dispersed phase in the continuous phase, not in step (b) coalesce. Particularly preferred is a method as described above, wherein the phase ratio of 0.3 to 5, preferably 1 to 3 and particularly preferably 1.0 to 2.5.

The nature and form of the tubular reactor can have an influence on the properties of the polymers produced in step (b), in particular the material of the inner wall of the tubular reactor. Preferred is a method (as described above, preferably as referred to above as preferred), wherein the inner wall of the tubular reactor is hydrophobic, that is, the inner wall of the tubular reactor is hardly wetted by the dispersed phase. The occupation behavior of a liquid to a given surface is described by the contact angle. The contact angle is a measure of the wetting behavior of a liquid, in particular water, relative to a surface and can be determined by conventional methods, for example according to ASTM D 5725 , A low contact angle means good wetting and high contact angle means poor wetting.

Prefers is a method (as described above, preferably as referred to above as preferred), wherein the contact angle of the Inner wall of the tubular reactor over the continuous phase at least 60 °, preferably at least 70 °, especially preferably at least 80 °, very particularly preferably at least 90 °. Preferably, a water and Monomer-containing dispersed phase promoted through the tube. The tube inner wall preferably faces in this case Water a contact angle of at least 60 °, preferably at least 70 °, more preferably at least 80 °, most preferably at least 90 °.

The tube can be made entirely of a material which has the above-mentioned contact angle with respect to the monomer phase. But it is also possible that the tube consists essentially of a material forming the inner wall with a lower contact angle with respect to the monomer phase, for example a steel with the material number 1.4571, and in the tube interior with a material forming the inner wall with a larger contact angle with the monomer phase is coated. Suitable coatings include, for example, silicones and fluorine-containing polymers such as perfluoroalkoxyethylene, polytetrafluoroethylene, ethylene-chlorotrifluoroethylene copolymers, ethylene-tetrafluoroethylene copolymers and fluorinated polyethylene. The coating compositions can be applied to the substrate as a dispersion, the solvent then being evaporated off and the residue being tempered. For polytetrafluoroethylene this is for example in US 3,243,321 described. Further coating processes can be found under the keyword "Thin Films" in the electronic version of "Ullmann's Encyclopedia of Industrial Chemistry" (Updated Sixth Edition, 2000 Electronic Release) , Furthermore, the coating compositions can also be incorporated into the nickel layer as part of a chemical nickel plating.

A hydrophobic inner wall of the tubular reactor, as described above, minimizes the interaction between the water-soluble Polymer and the tubular reactor and in the case of a hydrophilic, for example aqueous dispersed phase also minimizes this interaction between the dispersed phase and the tubular reactor. Especially Preferred is a method according to one of the preceding claims, wherein the tubular reactor is an inner wall of polytetrafluoroethylene or silicone possesses.

• (a) Erzeugen einer Dispersion einer flüssigen dispergierten Phase in einer flüssigen oder gasförmigen kontinuierlichen Phase, wobei die dispergierte Phase Monomere umfasst,
• (b) Polymerisieren der Monomeren in der dispergierten Phase unter Verwendung eines thermisch aktivierbaren Radikalinitiators, zu dem wasserlöslichen Polymer, während des Transports der Dispersion in dem Rohrreaktor,

wobei der Rohrreaktor einen kreisförmigen Querschnitt senkrecht zur Fließrichtung besitzt, einen konstanten Innendurchmesser im Bereich von 0,1 bis 5 mm oder einen kreisähnlichen Querschnitt senkrecht zur Fließrichtung mit konstanter Geometrie und einer Rundheit von höchstens 14 mit einem maximalen Innendurchmesser im Bereich von 0,1 bis 5 mm besitzt und wobei der Kontaktwinkel der Innenwandung des Rohrreaktors gegenüber der kontinuierlichen Phase mindestens 60° beträgt,
wobei der maximale Durchmesser eines, mehrerer oder sämtlicher in Schritt (b) hergestellter Polymerpartikel senkrecht zur Fließrichtung mindestens 80% und weniger als 100%, bevorzugt jedoch mindestens 95% und weniger als 100% und besonders bevorzugt mindestens 98% und weniger als 100%, des Rohrinnendurchmessers bzw. des maximalen Rohrinnendurchmessers beträgt und
wobei die in Schritt (a) erzeugte Dispersion eine Wasser-in-Öl-Dispersion ist.The method according to the invention can be configured in various ways, as described above. Preferred embodiments are advantageously combined with each other. For example, a process according to the invention for the continuous preparation of polymer particles of a water-soluble polymer from monomers in a tubular reactor is particularly preferred, with the following steps:

• (a) forming a dispersion of a liquid dispersed phase in a liquid or gaseous continuous phase, the dispersed phase comprising monomers,
• (b) polymerizing the monomers in the dispersed phase using a thermally activatable radical initiator to the water-soluble polymer, during transport of the dispersion in the tubular reactor,

wherein the tubular reactor has a circular cross-section perpendicular to the flow direction, a constant inside diameter in the range of 0.1 to 5 mm, or a circle-like cross section perpendicular to the flow direction with constant geometry and a roundness of at most 14 with a maximum inside diameter in the range of 0.1 to 5 mm and wherein the contact angle of the inner wall of the tubular reactor with respect to the continuous phase is at least 60 °,
wherein the maximum diameter of one, several or all of the polymer particles produced in step (b) perpendicular to the direction of flow at least 80% and less than 100%, but preferably at least 95% and less than 100% and particularly preferably at least 98% and less than 100%, of the inner tube diameter or the maximum inner tube diameter is and
wherein the dispersion produced in step (a) is a water-in-oil dispersion.

The inventive method allows the production of polymer particles, which have different shapes can. Particularly preferred is an inventive Method (as described above), wherein in step (b) lenticular, spherical or rod-shaped particles be generated. Also preferred is an inventive Method (as described above), wherein the coefficient of variation of the Particle sizes smaller than 5%, preferably smaller than 3%, and more preferably less than 2.5%.

Farther preferred is a method according to the invention (as described above), wherein the polymerization in step (b) at a temperature in the range of 0 to 200 ° C, preferred in the range of 15 to 120 ° C and more preferably in Range of 30 to 90 ° C is performed.

by virtue of the use of thermally initiatable polymerization initiators It is advantageous if the reaction temperature is significantly above Room temperature (25 ° C), so that monomer and initiators at Room temperature (25 ° C) can be mixed, without the reaction starting.

To high reaction temperatures require a lot of energy and equipment. At reaction temperatures in the range of boiling temperatures of liquids used for the continuous phase and / or solvents used in the dispersed phase or diluents, may cause more changes the solution properties of the monomers used, auxiliaries and polymers occur. The same applies to the Surface tension. These effects can become but can also be used to control the polymerization reaction can be used.

Farther can pressure fluctuations due to boiling liquids occur. The skilled person will therefore take care the reaction temperature and pressure are selected that the overall process is not affected. The temperature should usually be well below the lowest boiling temperature at the selected pressure of the fluids used and optionally, also azeotropic, mixtures. Is preferred a method as described above, wherein the reaction temperature at the selected pressure at least 5 ° C, preferably 10 ° C and more preferably at least 20 ° C below the boiling point of the substances used and, where appropriate, also azeotropic, mixtures lies.

Another object of the present invention is a single polymer particle or a plurality of polymer particles, preparable according to one of the methods of the invention described above. In this case, a single polymer particle or a plurality of polymer particles is particularly preferred, wherein the polymer then contained is polyvinylpyrrolidone. Most preferred is a single polymer particle or a plurality of polymer particles as described above, wherein the polymer contained therein is polyvinyl pyrrolidone and has a K value of from 10 to 150, preferably from 12 to 120, more preferably from 20 to 100, and most preferably from 70 to 100 has. A discussion of the K values of polyvinylpyrrolidone and the method of its use used in accordance with the present invention can be found, for example, in the publication "Kollidone, Polyvinylpyrrolidone for the Pharmaceutical Industry", BASF, 1998 pp. 20-30 be removed.

A Another preferred embodiment is an inventive single polymer particle or a plurality of polymer particles (as described above), wherein the polymer contained therein (preferably crosslinked) polyacrylic acid or comprises. Also preferred is an inventive single polymer particle or a plurality of polymer particles (as described above), wherein the polymer contained therein crosslinked polyacrylic acid is and properties of a superabsorbent has.

Particular preference is likewise given to a single polymer particle according to the invention or a plurality of polymer particles (as described above), wherein the polymer contained therein (eg PVP, PAS or crosslinked PAS) has a weight average (M _w ) of 3000 to 5500000, preferably of 7000 up to 3,000,000, more preferably from 14,000 to 1,500,000, and most preferably from 500,000 to 1,500,000.

The size and shape of the polymer particles formed are regularly similar to the size and shape of the cross-section of the tubular reactor. The maximum diameter of a polymer particle perpendicular to the flow direction is the maximum diameter of the cross-section of the tubular reactor, through which the polymer particle can barely pass without touching the inner wall of the tubular reactor. Also a preferred off According to the present invention, a plurality of polymer particles (for example PVP, PAS or crosslinked PAS) as described above and in particular as described above are preferred, wherein the average particle size is 0.1 to 5 mm and the proportion of particles with a particle size less than 0.1 mm less than 0.1 wt .-%, preferably less than 0.05 wt .-% and particularly preferably less than 0.01 wt .-%, based on the total mass of the polymer particles.

One Aspect of the present invention is the use of the after According to the invention produced polymer particles for preparing a solution, preferably an aqueous one Solution (the corresponding polymer solutions) or a preparation, these preferably in the following and other applications mentioned in this text becomes.

The Uses of the invention Water-soluble polymer particles are very diverse.

solutions the polymer particles of the invention and / or the polymer particles according to the invention themselves can be used for a variety of applications. solutions the polymer particles according to the invention are preferred used for application in cosmetic products for cleansing the skin. Such For example, cosmetic cleaners are selected from the group consisting of bar soaps, such as toilet soaps, Core soaps, transparent soaps, luxury soaps, de-icing soaps, cream soaps, Baby soaps, skin soaps, abrasive soaps and Syndets, liquid Soaps, such as pasty soaps, soft soaps and washing pastes, and liquid washing, shower and bath preparations, such as washing lotions, shower baths and gels, bubble baths, oil baths and scrub preparations.

The Solutions of the polymer particles according to the invention are also preferred in cosmetic care products and for the protection of the skin, in nail care products and in preparations applied for decorative cosmetics.

Especially preferred is the use of the solutions of the invention Polymer particles in skin care preparations, personal care products, foot care preparations, Deodorants, sunscreens, repellents, shaving preparations, depilatories, Anti-acne products, make-up, mascara, lipsticks, eye shadows, eyeliner pencils, eyeliners, Rouges, powders and eyebrow pencils.

The Skin care products are in particular as W / O or O / W skin creams, Day and night creams, eye creams, face creams, anti-wrinkle creams, Moisturizing creams, bleaching creams, vitamin creams, skin lotions, skin lotions and moisturizing lotions. Depending on the application area can the polymer particles of the invention in one suitable for skin care form, such. B. as a cream, foam, gel, Pen, powder, mousse, milk or lotion can be applied.

• (i) ein Polymer aus nach dem erfindungsgemäßen Verfahren hergestellten Polymerpartikeln und
• (ii) ein Material aus der bei der Herstellung der Polymerpartikeln verwendeten kontinuierlichen Phase.

Another aspect of the present invention is a cosmetic comprising

• (i) a polymer of polymer particles produced by the process according to the invention and
• (ii) a material of the continuous phase used in the preparation of the polymer particles.

to Production of such a cosmetic may be carried out after step (b) obtained dispersion of the process according to the invention can be used directly and without further work-up. Prefers is a cosmetic as described above, wherein the proportion of the material used in the preparation of the polymer particle continuous phase 1 wt .-% or more, preferably 5 wt .-% or more, more preferably 10 wt .-% or more, most preferably 20% by weight or more, and most preferably 50% by weight or more based on the total amount of (i) said polymer and (ii) said material.

Cosmetics, but also other products, often contain materials, especially oils or other low viscosity liquids, which are suitable as a continuous phase in the process of the invention. If such materials are used in the process according to the invention as a continuous phase, the entire dispersion leaving the tube reactor can be used directly without or after very simple workup as a constituent of a cosmetic or of another product. The person skilled in the art will ensure that the reaction conditions in the process according to the invention (in particular the type and amount of continuous phase) are such that the dispersion leaving the tubular reactor is suitable directly or without very simple preparation as a constituent of cosmetics or other products is. Preference is given to a cosmetic according to the invention comprising a liquid searches from the group consisting of organic oils, such. As white oil, and silicone oils, such as. B. Dimethicone. Other oils, fats and / or waxes which are suitable for cosmetic preparations are on page 28, line 39 to page 34, line 22 of WO 2006/106140 and in paragraphs [0029] to [0039] of DE 10257738 A1 described. For the present process are selected such oils, fats and waxes, which are liquid at the chosen reaction temperature and have a viscosity that allows the implementation of the method. Such a selection by individual preliminary tests is readily possible for the person skilled in the art.

Also preferred is the use of the solutions of the invention Polymer particles in hair cosmetic preparations. hair cosmetic Preparations comprise, in particular, styling agents and / or conditioning agents in hair cosmetic preparations such as hair treatments, hair foams (Mousses), (hair) gel or hair sprays, hair lotions, hair conditioners, Hair shampoos, hair emulsions, top fluids, leveling agents for perms, hair dyeing and bleaching products, "hot oil treatment" preparations, Conditioners, setting lotions or hair sprays. Depending on the application can the hair cosmetic preparations as (aerosol) spray, (Aerosol) foam, gel, gel spray, cream, lotion or wax can be applied.

One Another area of application is oral care, ie toothpaste, mouthwash, Adhesive creams and the like.

Also preferred is the use of the solutions of the invention Polymer particles in pharmaceutical applications. They work to one as a thickener, on the other hand as a film former. Specific Applications include the application as a catheter coatings the Use as wet binder, matrix retardant or coating retardant, z. For slow-release dosage forms, gelling agents, Instant Release Coatings and Dragierhilfsmittel and as a binder and solubilizer.

Furthermore, the polymer particles according to the invention and their solutions are suitable for the following applications:
Stripping and leveling agents for textile dyeing, enrichment / separation of (precious) metals and polyvalent cations, brightening agents (textile printing), recording media, concrete admixtures, binders for transfer printing, charge transfer cathodes, polyolefin coating, coatings, disinfectants and preservatives, Diazotypes, Dispersing Aids, Printing Inks, Electrically Conductive Layers, Electrode Gels and Skin Adhesion Gels, Oily Water Oil Recovery, Surface Wettability, Dyeing of Polyolefins, Diffusion Transfer Materials, Ink Transfer Inhibitors, Solid Batteries (eg Lithium Batteries), Solid Electrolytes, Fish Feed Granules, Fixer for perfume oils, flexographic printing plates, flocculants, auxiliaries in the photographic industry (photographic processes, photo papers), precious metal crystallization nuclei for silver precipitation, gas analysis, plaster bandages, glass and fibers (binders, coatings, lubricants), adhesion promoters for dyes, H Aids in the oil and gas production and the oil and gas transport, inhibition of Chlatraten, hydrophilization of surfaces, inkjet, printing inks and ballpoint pen pastes, ion exchangers, isomerization inhibitors, catalysts, Kathedercoating, scale inhibitor or scale remover, ceramics (binder, thickener, solubilizer, dispersing agent ), Adhesive for culture media, adhesive raw materials, adhesives and glue sticks, complexes with organic compounds such as albumin, antioxidants, polyphenols, phenols, tannins, enzymes, proteins and polymers, removal of tannin / phenols and polyphenols from liquids, complexes with inorganic compounds such as halogens, Metals, metal salts and peroxides such as organic peroxides and hydrogen peroxide, preservatives, contact lenses, corrosion protection, plastic additives, paint auxiliaries, photosensitive materials, lithography, solubilization agents, air filters, membrane production such as dialysis membrane for water treatment or blood purification, metal casting and metal hardening, metal colloids and their stabilization, metal complexes for reversible oxygen absorption, metal quench baths, microencapsulation, oil and dye removal from water, oil recovery, paper auxiliaries (special papers, photo papers), paper coating colors, phase transfer Catalysts, photoimaging, pigment dispersions, proton conductors (anhydrous), wastewater cleaners, rust inhibitors or rust removers of metallic surfaces, seed dressing and seed coating, lubricant additives, protective colloid, silver halide emulsions, slow-release fertilizer formulations, solubilizer to increase adsorbability / hydrophobicity, solubilization hydrophobic substances, soil release, synthetic fibers, tertiary petroleum production, textile auxiliaries, ink jet recording media (inkjet papers and films), separation of hydrocarbon mixtures, digestion sparse dyeing of fibers, heat-resistant layers, heat-sensitive layers, heat-sensitive resistors, detergent additives, water-soluble films and cigarette filters.

A further preferred aspect of the present invention is the use of the polymer particles preparable by the process according to the invention for preparing a solution, preferably an aqueous solution of the polymer or a preparation, wherein the polymer preferably acts as (i) thickener, as (ii) flocculant or as (iii) adhesive in pressure-sensitive adhesives. Likewise preferred is the use for cosmetic, pharmaceutical, technical and agro-applications and formulations as a binder, solubilizer and for surface coating.

The The invention will become more apparent by reference to the figures and examples explained. Show it:

1 : A schematic representation of a test setup for carrying out a preferred method according to the invention with a coaxial flow unit.

2 : A schematic side view of a coaxial flow unit for the preparation of a dispersion according to step (a) of the method according to the invention.

1

syringe pumps

2

PTFE tubing (1.0 mm inner diameter)

3

Coaxial flow unit

4

spirally wound PTFE tube reactor

5

frame for the PTFE tube reactor

6

thermostat

7

hose connector made of polyethylene

8th

stainless steel cannula (0.8 mm)

When Coaxial flow unit was a T-tap made of polycarbonate used.

In the 1 The device shown comprises two syringe pumps (for example model "Ismatec KOS 100") ( 1 ) for holding and conveying fluids. The syringe pumps are made with PTFE tubing (polytetrafluoroethylene tubing, outer diameter: 2.5 mm, inner diameter: 1.5 mm) ( 2 ) with coaxial flow unit ( 3 ) connected. The coaxial flow unit ( 3 ) is also equipped with a spirally wound PTFE tube reactor (tube reactor, outer diameter: 2.5 mm, inner diameter: 1 mm, winding radius about 8 cm, length about 9 m) ( 4 in a water-filled transparent thermostat (for example, a "Lauda Compakt Transparent CD 15" thermostat, available from Lauda) ( 6 ) is brought to the desired temperature. The resulting polymer particles are collected for analysis in a reservoir (not shown).

to Preparation of the polymer particles according to the invention For example, the following steps will be performed:

Step (a): First, the syringe or syringes of one of the syringe pumps ( 1 ) with the continuous phase and that of the other syringe pump ( 1 ) filled with the discontinuous phase. Then the pumps are put into operation and the two phases run through the connecting hoses (PTFE hose 2 ) into the coaxial flow unit ( 3 ). The two immiscible fluids meet in the coaxial flow unit ( 3 ), wherein at the outflow of the coaxial flow unit ( 3 ) produces a uniform droplet size dispersion which is introduced into the helically wound PTFE tube reactor ( 4 ) flows.

Step (b): The reactor is preheated to the desired reaction temperature. The reaction temperature is controlled by the thermostat ( 6 ). The dispersion flows into the spirally wound PTFE tube reactor (tubular reactor) ( 4 ) and go through it in length. The dispersion is transported through the reactor and assumes the temperature set therein. Subsequently, the dispersion flows at the outlet of the PTFE tube reactor (tubular reactor) ( 4 ) in a reservoir (not shown). The residence time depends on the length of the reactor and the flow rate of the fluids and is the quotient of reactor volume and volume flow.

In carrying out the method according to the invention, the droplet generation to produce a dispersion can be carried out in many ways. In 2 A device is shown with which a two-phase dispersion of two immiscible fluids can be created by combining two coaxial flows. 2 shows a usable coaxial flow unit ( 3 ). An inner capillary (stainless steel capillary, outer diameter: 1 mm; inner diameter: 0.8 mm), separated from the discontinuous Passing through phase, and a coaxial outer capillary (PTFE tube, outer diameter: 2.5 mm, inner diameter: 1.5 mm) ( 2 ), which is traversed by the continuous phase.

When carrying out the method according to the invention, the continuous phase (eg white oil) flows out of the upper PTFE tube (FIG. 2 ) according to 2 into the coaxial flow unit ( 3 ) and exits the annular gap between the inner capillary and the outer capillary again. The discontinuous phase emerges from the left PTFE tube ( 2 ) into the coaxial flow unit ( 3 ) and inside the inner capillary. At the outlet opening, the discontinuous phase is introduced into the continuous phase, forming droplets within the continuous phase, which are continuously transported by the continuous phase. Since the continuous phase and the discontinuous phase are immiscible, a stable dispersion is formed. The outer capillary, which merges into the actual tubular reactor, should be as hydrophobic as possible in order to avoid phase inversion (in which the discontinuous phase becomes the continuous phase and vice versa). The size and geometry of the droplets of the discontinuous phase or of the polymer particles depends on the size and shape of the outer capillary or tubular reactor, the surface tension of the fluids used and the coefficient of their flow rates.

Examples:

In the examples, an apparatus according to 1 and 2 used.

The following measuring methods were used:
Measurement of the residual monomer content of N-vinylpyrrolidone in polyvinylpyrrolidone (used to determine the conversion in Example 1 below)

Of the Residual monomer content of N-vinylpyrrolidone (NVP) was determined by gas chromatography (GC) determined. The solid polyvinylpyrrolidone (crude product) was washed with n-pentane several times to remove adhering white oil and then briefly (about 5 min) in vacuo dried to remove residues of n-pentane. Approximately 500 mg of the obtained Polyvinylpyrrolidone was dissolved in about 3 ml of ethanol. 20 mg of benzonitrile were added as an internal standard. 0.4 μL of the solution was made using an autosampler (Chrompack CP-9010 Liquid Sampler, available from Varian) in a chromatography column (OP Wax 52 CB, 50 m, 0.32 mm, ID 0.5 μm, from Varian). As a concentration detector became a flame ionization detector (available from Varian) used. The temperature profile of the oven was 140-190 ° C: 4 ° C / min and 190-250 ° C: 20 ° C / min (Injector temp .: 220 ° C, detector temp .: 250 ° C). The gas flows at the flame ionization detector measured at 25 ° C were: nitrogen: 31.6 mL / min, synthetic air: 230 mL / min and hydrogen: 220 mL / min. The hydrogen (30 kPa) was generated by means of a hydrogen generator (Whatman 75-34-220). The calculations for the concentration are based on a Calibration with the pure substances N-vinylpyrrolidone and pyrrolidone was made. The integration of the peaks and the calculation was carried out automatically with an analysis software (MAESTRO Chromatography Data System 2.4, available from Varian Inc.).

Determination of the residual monomer content of acrylic acid (AS) in polyacrylic acid (used to determine the conversion in the following examples 2 and 3)

The residual monomer content of acrylic acid (AS) was investigated by means of gradient high pressure liquid chromatography (HPLC). To this was mixed 75 mg of the sample solution with 10 g of potassium dihydrogen phosphate solution (prepared by dissolving 5.44 g of potassium dihydrogenphosphate in 2 L bidistilled water and then adjusting the pH to 85 with 2% ortho-phosphoric acid), and with Using an autosampler (Smartline Autosampler 3800, available from Knauer GmbH), 60 μL was injected onto the chromatography column (BetaMax Acid 95205-123030, 125 x 3 mm, particle size 5 μ, manufacturer: Thermo Fischer Scientific Inc.). The column was tempered to 34 ° C (Haake NB22, manufacturer: Thermo Fischer Scientific Inc.). As a second solvent, methanol was gradually added to the eluent via a dynamic mixing chamber (Knauer GmbH) (start: 0.1 mL / min, from the first minute: 0.089 mL / min ² , from the 9th minute: 0.9 mL / min; Minute: 0.8 mL / min ² , from the 12th minute: 0.1 mL / min). The total eluent flow rate was 1 mL / min.

The Detection of the acrylic acid is carried out by means of a UV detector (WellChrom UV Detector K-2600, available from Knauer GmbH) in a wavelength range of 195-219 nm. The Residual monomer content was determined by means of a previously determined calibration line calculated. The evaluation of the results took place with the help of a Process software (EuroChrom for Windows 3.05, Knauer GmbH).

Viscosimetry and K value of polyvinylpyrrolidone (PVP) (used to determine the K value in the following example 1)

Preamble:

The viscosity of an aqueous solution of water-soluble PVP depends on the molecular weight. From the viscosity, the viscosity average molecular weight (M _v ) can be calculated accordingly. The K value is an empirical data for the viscosity-average molecular mass, which results from the Fikent equation for dilute solutions.

Determination of the K value

A 5% by weight aqueous polymer solution was prepared when the expected K value was below 20, a 1% by weight solution when the expected value exceeded 20 and a 0.1% by weight. -solution if a K-value above 100 was expected. The solid polyvinylpyrrolidone (PVP) (crude product) was washed with n-pentane several times to remove adhering white oil. Subsequently, the PVP was briefly dried (about 5 minutes) in vacuo to remove residues of n-pentane. For the measurement, the PVP thus obtained was weighed into a 50 ml volumetric flask. The sample balance of the undried polymer was corrected by the previously determined conversion in% (determined from the residual monomer content, measuring method see above) and the monomer content in% of the dispersed phase used according to the following equation (1): m poly = m · M · U 10000 (1)

Where: m = _poly corrected sample weight in [g], m = sample of the non-dried polymer in [g], M = monomer content of the dispersed phase used [wt .-%] in, U = conversion in [%] (Calculated from the residual monomer content).

The weighed polymer was shaken in a little demineralized water at room temperature until everything dissolved. The volumetric flask was then filled to the mark with demineralized water and the solution was added according to the specifications in a micro Ubbelohde capillary viscometer (Schott & Gen, No. 1c, available from Schott). The viscometer was tempered in a thermostat for at least 30 min at 25.0 + 0.1 ° C. Subsequently, the flow time of the polymer solution t _poly between the calibrated markings was measured several times with an optical detector (bulkhead) and the arithmetic mean was determined therefrom. To obtain the relative viscosity, it is necessary to determine the flow time of water t _H2O before each measurement series.

The Hagenbach-Couette correction (see Table 1), which is indicated by the manufacturer of the Ubbelohde viscometer, was subtracted from the respective flow time t _poly or t _H2O . The relative viscosity is calculated by the following equation (1).

The K value was calculated from the relative viscosity η _rel using Equation 2:

mit m_Poly = Masse (Polymer) in [g], V = Volumen in [ml] Tabelle 1: Hagenbach-Couette-Korrektur für Mikro-Ubbelohde Viskosimeter DIN 51562 Teil 2, Typen-Nr. 536, 537 und 538 Durchflusszeit t [s] Korrektursekunden für die Hagenbach-Couette-Korrektur [s] 30 0,08 40 0,04 50 0,03 60 0,02 70 0,01 80 0,01 90 0,01 100 0,01 Where:

with m _poly = mass (polymer) in [g], V = volume in [ml] Table 1: Hagenbach Couette correction for micro Ubbelohde viscometer DIN 51562 part 2, type no. 536, 537 and 538 Flow time t [s] Correction seconds for the Hagenbach-Couette correction [s] 30 0.08 40 0.04 50 0.03 60 0.02 70 0.01 80 0.01 90 0.01 100 0.01

The specified correction seconds refer to the respective nominal constant. The term micro-Ubbelohde type 1c or Ic means that capillary viscometer of this type from Schott according to the manufacturer have a device constant ("nominal constant") of about 0.03 mm ² / s ² . The exact capillary constant is usually listed in the manufacturer's certificate for each device. For the calculation of the Hagenbach Couette correction, the deviation of the certificate value from the setpoint constant is insignificant, which is why the corresponding setpoint constant is calculated. See also Kollidon, Polyvinylpyrrolidone for the pharmaceutical industry ", BASF, March 2008, Edition 9, pp. 56-57

Determination of the Weight-Average Molar Mass of the Polyacrylic Acid (Used to Determine the Weight-Average Molar Mass (M _w ) in Examples 2 and 3 below)

The weight average molecular weight (M _w ) of polyacrylic acid (PAS) was determined by gel permeation chromatography (GPC). To this was dissolved about 1 g of the solution or mixture containing product and stopper (see Example 2) in about 1 g of GPC eluent (prepared by dissolving 7.87 g of ammonium formate in 2 L of bidistilled water and 500 ml of acetonitrile). 20 μL of the solution was transferred by means of an autosampler to the chromatography columns (Shodex OH pak SB-G No. L302073, 6 × 50 mm, particle size: 10 μm, Shodex OH pak SB-804 HQ No. L301001, 8 × 300 mm, Particle size: 10 μm, Shodex OH pak SB-802.5 HQ No. L303073, 8 × 300 mm, particle size: 10 μm, Shodex OH pak SB-805 HQ No. L310080, 8 × 300 mm, particle size: 10 μm, Shodex OH pak SB-802 HQ No. L403058, 8 × 300 mm, particle size: 10 μm, manufacturer of all columns: Shows Denko Europe GmbH) injected. The system operates at 50 ° C with an eluent flow rate of 0.5 mL / min. The polymer was detected using a refractive index detector (RID detector K-2300 / A2010 manufacturer: Knauer GmbH). The weight average molecular weight (M _w ) was calculated from a calibration with narrowly distributed polyethylene glycol standards (molecular weight range 21400-1410000 g / mol, available from PSS). The evaluation was done with a data processing software (Mathematica 5.2, by Wolfram Research).

Example 1: Preparation of polyvinylpyrrolidone (PVP)

In Tables 2.1 and 2.2 below are examples given listed. Not listed in the tables Parameters are identical to those of Example 1.4, see immediately. The sum of monomer content and water content of the dispersed Phase is always 100 wt .-%.

Example 1.4:

• * Bezogen auf die Summe aus Monomer und Wasser.
• ** 2,2'-Azobis[2-(2-imidazolin-2-yl)propan] Dihydrochlorid in Molprozent bezogen auf das Monomer.
• *** Es wurde Weißöl eingesetzt, dass vor Einsatz zweimal mit gleichen Teilen Wasser ausgeschüttelt wurde.

A mixture of 10,500 g of ice-cooled N-vinylpyrrolidone (VP), 4.485 g of ice-cold distilled water and 0.0153 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (VA-044, Wako ) were weighed together, mixed to complete dissolution and transferred to an ice-cold syringe (20 ml). The template was cooled to about 0 ° C throughout the experiment. The flow rate of the monomer phase was 3.3 ml / h. White oil (Exxon Mobil) with a flow rate of 6.6 ml / h was used as the continuous phase (phase ratio: 2). The average residence time in the tube reactor was 60 minutes and the reaction temperature 60 ° C. The product was collected in a chilled vessel for later analysis, washed with small amounts of n-pentane and then vacuum dried briefly (about 2 minutes) at 100 mbar. Table 2.1: Continuous suspension polymerization of VP with different continuous phases and phase ratios Example no. Monomer content [weight percent] * Initiator ** [mol%] continuous phase Sales [%] K value phase relationship 1.1 70 0.05 dodecane 91 111 2 1.2 70 0.05 iso-octane 87 119 2 1.3 70 0.05 White oil-water extraction *** 94 118 2 1.4 70 0.05 White oil 94 116 2 1.5 70 0.05 White oil 94 118 2.5

• * Based on the sum of monomer and water.
• ** 2,2'-Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in mole percent based on the monomer.
• *** White oil was used, which was shaken out twice with equal parts of water before use.

The in the examples 1.1 to 1.4 used continuous phases differ essentially by boiling point and viscosity. It turns out that the type of continuous phase here is none or has little effect on sales and K value of the PVP. Only the conversion of 87% in the case of the use of iso-octane gives way slightly different from the other values.

One Comparison between Examples 1.4 and 1.5 of Table 2.1 shows that the change of the phase ratio of 2 to 2.5 also no or no appreciable influence Sales and K value has.

• * Bezogen auf die Summe aus Monomer und Wasser.
• ** 2,2'-Azobis [2-(2-imidazolin-2-yl)propan] Dihydrochlorid in Molprozent bezogen auf das Monomer

The experiments disclosed in Table 2.2 were carried out as described above. The weighings of the monomer and of the water were adjusted according to the monomer proportions given in Table 2.2. The sum of monomer content and water content of the dispersed phase is always 100% by weight. Table 2.2: Influence of the monomer content of the dispersed phase on the conversion of the monomer and the K value of the PVP example Monomer content [weight percent] * Initiator ** [mol%] continuous phase Sales [%] K value phase relationship 1.6 30 0.05 White oil 89 99 2 1.7 50 0.05 White oil 93 111 2 1.4 70 0.05 White oil 94 118 2 1.8 80 0.05 White oil 99 96 2

• * Based on the sum of monomer and water.
• ** 2,2'-Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in mole percent based on the monomer

Examples 1.6, 1.7, 1.4 and 1.8 of Table 2.2 show that sales with increasing monomer content in the dispersed phase increases. Of the By contrast, K value goes through a maximum at a monomer content of 70 percent by mass.

The prepared according to Example 1.8 polymer particles are firm.

Example 2: Preparation of polyacrylic acid (PAS)

In The following Table 3 lists examples given. Unlisted parameters are identical to those of Example 2.4, see below. The sum of monomer content and Water content of the dispersed phase is always 100% by weight. The weights of the monomer and the water were corresponding adapted to the monomer proportions shown in Table 3.

A Mixture of 6.00 g of acrylic acid (AS), 4.00 g of distilled Water and 0.03 g of potassium peroxodisulfate (KPS) as initiator weighed together until completely detached mixed and the generated liquid was made with the help of a Syringe pump at a flow rate of 1.5 ml / h in the tube reactor injected. The continuous phase was white oil (Exxon Mobil) at a flow rate of 8 ml / min.

• * Bezogen auf die Summe aus Monomer und Wasser.
• ** Molprozent bezogen auf das Monomer

The reaction time was 7 minutes and 30 seconds, and the reaction temperature was 80 ° C. The reaction was stopped at a 1: 1 ratio using a 4-methoxyphenol solution (5 g 4-methoxyphenol per 250 g bidistilled water). Table 3: Influence of the monomer content of the dispersed phase on the conversion of the monomer and the weight average molecular weight (M _w ) of the PAS example AS [weight percent] * KPS [mol%] ** Sales [%] M _w [g / mol] 2.1 30 0.1 49.28 245627 2.2 40 0.1 68,30 726914 2.3 50 0.1 87.12 884228 2.4 60 0.1 89,00 1230240 2.5 70 0.1 88.28 954067

• * Based on the sum of monomer and water.
• ** mole percent based on the monomer

As shown in Table 3, the conversion initially increases with the monomer content, but is essentially constant between 50% by weight and 70% by weight monomer content. As in the preparation of PVP in Example 1, the mass-average molecular weight (M _w ) also goes through a maximum in the production of PAS. It is under the experimental conditions at a monomer content of about 60 wt .-%.

Example 3: Preparation of polyacrylic acid (PAS) with argon as the continuous phase

It were experiments with different monomer proportions of 30 and 40 percent by mass as described under Example 2 performed. However, instead of white oil, argon was considered continuous Phase used. The argon was used instead in a syringe pump presented in a gas bomb. The gas flow was with the help of a Pressure reducer set. The on the coaxial flow unit applied argon gas pressure was 1.8 bar. The reaction time was 2 minutes and 30 seconds.

The parameters and results of these experiments are listed in Table 4. Table 4: example AS [mass percentage] KPS [mol%] Sales [%] M _w [g / mol] 3.1 30 0.1 57.4 480750 3.2 40 0.1 51.7 503401

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• DE 102004049730 B4 [0005]
• WO 01/64332 A1 [0005]
• - EP 584771 [0106]
• US 3243321 [0144]
• - WO 2006/106140 [0164]
• - DE 10257738 A1 [0164]

Cited non-patent literature

• - "Polymerizations in Microstructured Reactors: An Overview", Chemie Ingenieur Technik, 2005, 77, No. II, pp. 1693-1714 [0005]
• - Int. J. Multiphase Flow 2003, 29, 813-840 [0006]
• Macromolecules 2004, 37, 2954-2964 [0006]
• - Colloids Interface Sci. 1985, 105, 560-569 [0006]
• - Chem. Eng. Sci. 2004, 59, 3045-3058 [0006]
• Science 2002, 295, 1695-1698 [0006]
• - Phys. Rev. Lett. 2001, 87, 274-501 [0006]
• - J. Am. Chem Soc. 2005, 127, 8058-8063 [0006]
• - Angew. Chem. Int. Ed. 2005, 44, 724-728 [0006]
• Macromolecules 2005, 38, 4536-4538 [0006]
• Langmuir 2005, 21, 11614-11622 [0006]
• - Rompps Chemie-Lexikon, 1983, 8th Edition, p. 2394 [0042]
• - Rompps Chemie-Lexikon, 1983, 8th edition, p. 2394 [0048]
• ASTM D 5725 [0142]
• - "Ullmann's Encyclopedia of Industrial Chemistry" (Updated Sixth Edition, 2000 Electronic Release) [0144]
• - "Kollidone, Polyvinylpyrrolidone for the Pharmaceutical Industry", BASF, 1998, pp. 20-30 [0152]
• - Polyvinylpyrrolidone for the pharmaceutical industry ", BASF, March 2008, edition 9, pp. 56-57 [0192]

Claims (15)

Process for the continuous production of Polymer particles of a water-soluble polymer of monomers in a tube reactor, with the following steps: (a) Create a dispersion of a liquid dispersed phase in a liquid or gaseous continuous Phase, wherein the dispersed phase comprises monomers, (b) polymerizing the monomers in the dispersed phase using a or more radical initiators, to the water-soluble Polymer, during the transport of the dispersion in the tubular reactor in which the tubular reactor has a circular cross-section perpendicular to the flow direction and a constant inner diameter in the range of 0.1 to 5 mm or a circular cross-section perpendicular to the flow direction with constant geometry and a roundness of not more than 14 with a maximum inner diameter in the Range of 0.1 to 5 mm and the maximum diameter of one, more or all of the polymer particles prepared in step (b) perpendicular to the flow direction at least 80% and less as 100% of the inner tube diameter or the maximum inner tube diameter is. The method of claim 1, wherein in step (a) produced dispersed phase one or more radical initiators and optionally selected one or more excipients from the group consisting of solvents, diluents, Surfactants, emulsifiers, crosslinkers and branching reagents contains Method according to one of claims 1 or 2, wherein the continuous phase used in step (a) is a Is fluid, preferably the continuous Phase is or contains an organic liquid, in which more preferably, the continuous phase is an organic liquid is or contains and the dispersion is an inverse Dispersion is, wherein particularly preferably the dispersion is a water-in-oil dispersion. Method according to one of the preceding claims, wherein the dispersed phase produced in step (a) comprises water, preferably a proportion of water in the range of 0.01 wt .-% to 60 wt .-%, preferably from 1 wt .-% to 60 wt .-% and very particularly preferably from 5 wt .-% to 50 wt .-%, based on the total amount on dispersed phase. Method according to one of the preceding claims, wherein the dispersed phase produced in step (a) comprises a portion to monomers in the range of 40% to 99% by weight, preferably from 40% by weight to 95% by weight and more preferably from 50% by weight to 90 wt .-%, based on the total amount of dispersed phase. Method according to one of the preceding claims, wherein the dispersed phase produced in step (a) comprises a portion to N-vinylpyrrolidone in the range of 40% to 95% by weight, preferably from 50 wt .-% to 95 wt .-% and particularly preferably from 60 wt .-% to 95 wt .-%. Method according to one of the preceding claims, wherein the contact angle of the inner wall of the tubular reactor opposite the continuous phase at least 60 °, preferably at least 70 °, more preferably at least 80 °, completely more preferably at least 90 °. Method according to one of the preceding claims, wherein the polymerization in step (b) at a temperature in Range from 0 to 200 ° C, preferably in the range of 15 to 120 ° C and more preferably in the range of 30 to 9000 is carried out. Single polymer particle or plurality of polymer particles, preparable by a method according to one of preceding claims. Single polymer particle or plurality of polymer particles according to claim 12, wherein the polymer contained therein is selected is from the group consisting of polyvinylpyrrolidone, polyacrylic acid and crosslinked polyacrylic acid. A single polymer particle or plurality of polymer particles according to any one of claims 9 or 10, wherein the polymer contained therein has a weight average (M _w ) of 3,000 to 5,500,000, preferably 7,000 to 3,000,000, more preferably 14,000 to 1,500,000 and most preferably 500,000 to 1,500,000 having. Single polymer particle or a plurality of Polymer particles according to claim 10, wherein the polymer contained therein Polyvinylpyrrolidone is and a K value of 10 to 150, preferred from 12 to 120, more preferably from 20 to 100 and most especially preferably from 70 to 100 has. A plurality of polymer particles according to any one of claims 9 to 12, wherein the average particle size is 0.1 to 5 mm and the proportion of particles with a Particle size less than 0.1 mm less than 1 wt .-% is preferred less than 0.5% by weight, and more preferably less than 0.1 Wt .-%, based on the total mass of the polymer particles. Use of polymer particles according to one of the claims 9 to 13 for the preparation of a solution, preferably one aqueous solution, or a preparation of the polymer. Use according to claim 13, wherein the polymer is as (i) thickeners, as (ii) flocculants or (iii) adhesives acting in pressure-sensitive adhesives.