MXPA06003200A - Microgels in non-crosslinkable organic media - Google Patents

Abstract

The invention relates to a composition containing a specific non-crosslinkable medium and at least one microgel. The invention also relates to methods for producing said composition, to uses of the same, and to microgel-containing polymers, rubber, lubricants, coatings etc. produced therefrom.

Description

MICROGELS IN NON-RETICULABLE ORGANIC MEDIA DESCRIPTION OF THE INVENTION The invention relates to a composition which comprises at least one specific non-crosslinkable medium and at least one microgel, processes for its preparation, uses of the compositions, and polymers containing microgel, rubbers, lubricants, coatings etc, preparations of it. It is known to use rubber gels, including modified rubber gels, in mixtures with the most diverse rubbers, for example to improve the rolling resistance in the production of vehicle tires (see for example, DE 42 20 563, GB-PS 10 78 400, EP 405 216 and EP 854 171). In this case, rubber gels are always incorporated in solid matrices. It is also known to incorporate printing ink pigments in finely distributed form in liquid media suitable for them, in order to finally prepare printing inks (see for example EP 0 953 615 A2, EP 0 953 615 A3). In this case, particle sizes below 100 • nm are achieved. Various dispersion apparatuses, such as kneader, glass mill, homogenizer or triple roller mill, dissolution vessel and / or single or multiple screw extruder, are used for the dispersion. The use of Ref. 170199 homogenizers and their mode of operation is described in the Marketing Bulletin of APV Homogeniser Group - "High-pressure homogenisers processes, product and applications" of William D. Pandolfe and Peder Baekgaard, mainly for the homogenization of emulsions. The use of rubber gels as a solid component in mixtures with liquid organic media with the aid of the preparation of very finely distributed rubber gel dispersions having particle diameters significantly below one μm and homogenization thereof by means of A homogenizer is not described in the aforementioned documents. The Journal Chínese of Science Polymer, volume 20, no. 2, (2002), 93-98 describes microgels which are completely crosslinked by high energy radiation and their use to increase the impact resistance of plastics. In the preparation of specific epoxy resin compositions, a mixture of a nitrile / butadiene microgel crosslinked by carboxyl terminated radiation and the diglycidyl ether of bisphenol A, an organic, crosslinkable medium, indirectly occurs. Additionally, compositions containing liquid microgel are not described. US 20030088036 A1 discloses similarly reinforced thermosetting resin compositions, for the preparation of which the microgel particles crosslinked by radiation are likewise mixed with thermosettable prepolymers (also see EP 1262510 Al). DE 2910154 discloses dispersions of rubber particles with organic solvent. These are prepared by adding the solvents to an aqueous rubber latex, with the addition of a dispersing agent. This specification effectively also mentions the possibility of removing the water resulting from the latex. However, anhydrous dispersions are not described. Dispersions which are substantially anhydrous are practically not obtainable by this process (see also the recognition in DE-A-3742180, page 2, line 10, of the same Applicant). However, there is a disadvantage in many uses. The dispersions described in the aforementioned patents also necessarily comprise additional dispersing agents or emulsifiers to achieve a homogeneous distribution of the aqueous and organic phases. The presence of such emulsifiers or dispersing agents, however, is very importunate in many uses. The rubber particles described herein are also relatively thick. D-A-3742180 describes dispersions of graft polymers containing silicone in liquid amides, which are likewise prepared from aqueous latexes. In the dispersions described therein, however, water is only greatly separated and complete separation is difficult. The graft polymers containing silicone are in addition to very thick particles (240 nm). The dispersions described herein can be used to improve the fibrillation properties of PAN film. Due to its specific structure with a silicone core and acrylate cover, however, the graft polymers are unsuitable in particular for use in lubricants due to their incompatibility. The inventors of the present invention have now found that it is possible for microgels to be finely distributed in liquid organic media of a certain viscosity, for example using a homogenizer. The division of the microgels in the organic medium down into the range of primary particles is a prerequisite, for example, for rendering the nanoproperties of the microgels usable, in particular the reproducibility, in some uses, for example in the case of incorporation into plastics The liquid compositions according to the invention comprising the specific microgels can disclose a large number of new uses of microgels which to date were not accessible with the microgels per se. Accordingly, for example, in one embodiment of the invention, at the base of the fine distributions which the compositions according to the invention can be achieved are incorporated, for example, into plastics and lubricants, as a result of which they get completely new properties. The compositions according to the invention consequently show, surprisingly, properties comparable with those of commercial fats (stability towards settlement, low oil separation, consistency, etc.).; however, they have more favorable properties with respect to eg shear stability (i.e., almost no change in penetration values after grinding with 60,000 shocks) and exceptionally high drip points as otherwise only achieved by fats heat resistant, such as for example PU fats or complex Ca fats. In addition, the compositions according to the invention exhibit a positive action on the coefficients of friction, which is completely not typical of standard fats. The microgel-containing compositions according to the invention can be used in a large number of fields, such as for example in elastomeric PU systems (cold-melt systems and hot-melt systems), in coating compositions or as additives to lubricants In the compositions containing microgel according to the invention, the materials which are incompatible per se form a homogeneous distribution which remains stable even during relatively large storage (6 months).

P. Potschke et al., Kautschuk Gummi Kunststoffe, 50 (11) (1997) 787 shows that in the case of incompatible materials, such as for example a derivative of p-phenylenediamine as the dispersed phase and TPU as the surrounding phase, no domains smaller than 1.5 μm can be made. It is surprising that such small dispersed phases are achieved with the microgel compositions of the present invention. Compositions containing microgel have been found. for which the most diverse rheological properties have been determined. In compositions containing suitable microgel, surprisingly, a very high viscosity or thixotropy structure has been found, but also flow properties similar to those of Newtonian fluids. This can be used to control, in addition to other properties, the flow properties of any of the liquid compositions desired by microgels. The present invention therefore provides a composition comprising at least one non-crosslinkable organic medium (A) which has a viscosity of less than ,000 mPas at a temperature of 120 ° C and at least one microgel (B) Preferably, the viscosity of the organic medium is less than 1,000 mPas, more preferably less than 200 mPas, even more preferably less than 100 mPas at 120 ° C, still more preferably less than 20 mPas at 120 ° C. The viscosity of the non-crosslinkable organic medium (A) is determined at a speed of Bs'1 with a cone and plate measuring system in accordance with DIN 53018 at 120 ° C.

Microgels (B) The microgel (B) used in the composition according to the invention is a cross-linked microgel. In a preferred embodiment, it is not a microgel which is crosslinked by high energy radiation. The high energy radiation conveniently means at this point electromagnetic radiation having a wavelength of less than 0.1 μm. The use of microgels which are crosslinked by high energy radiation, as described for example, in Chínese Journal of Polymer Science, volume 20, no. 2, (2002), 93-98, is disadvantageous since microgels which are crosslinked by high energy radiation can practically not be prepared on an industrial scale. The use of high-energy radiation from radioactive sources of radiation, such as radioactive cobalt, is also accompanied by serious safety problems. Since the microgels crosslinked by radiation and also as a rule are completely microgels crosslinked by radiation completely, the change in the modulus from the matrix phase to the dispersed phase in the incorporation of the composition according to the invention, for example in plastics, it's direct. As a result, tearing effects can occur under sudden tension between the matrix and the dispersed phase, whereby the mechanical properties, the swelling properties and the cracking by stress corrosion etc. of plastics containing microgels prepared using the compositions according to the invention are damaged. In a preferred embodiment of the invention, the primary microgel particles (B) have an approximately spherical geometry. According to DIN 53206: 1992-08, the primary particles are microgel particles dispersed in the coherent phase which can be detected as individual by suitable physical methods (electron microscope) (quote, for example, Ropp Lexikon, Lacke und Druckfarben, Georg Thie and Verlag, 1998).

An "approximately spherical" geometry means that the dispersed primary particles of the microgels substantially produce the image of a detectable circular area when the composition is viewed, for example with an electron microscope. Since the microgels substantially do not change their shape or morphology during further processing of the compositions according to the invention, the above and below statements are also applied in the same manner to the microgel-containing compositions obtained with the composition according to the invention, such as, for example, plastics, coating compositions, lubricants or the like. In the primary particles of the microgel (B) which are contained in the composition according to the invention, the deviation of the diameters of a single primary particle is defined as [(di-d2) / d2] x 100, where di and d2 are either of the two desired diameters of the primary particle and di es >; d2, is preferably less than 250%, more preferably less than 100%, even more preferably less than 80%, even more preferably less than 50%. Preferably, at least 80%, more preferably at least 90%, still more preferably at least 95% of the primary particles of the microgel have a deviation from the diameters, defined as [(di-d2) / d2] x 100, where di and d2 are any of the two desired diameters of the primary particle and di es > d2, less than 250%, preferably less than 100%, even more preferably less than 80%, even more preferably less than 50%. The aforementioned deviation of the diameters of the individual particles can be determined by the following method. A thin section of the solidified composition according to the invention first occurs. A transmission electron microscopy photograph is then produced at an extension of, say, 10,000 times or 200,000 times. In an area of 833.7 x 828.8 nm, the largest and smallest diameters are determined as di and d2 in 10 primary microgel particles. If the deviation defined above by at least 80%, more preferably at least 90%, even more preferably at least 95% of the measured primary microgel particles is in each case below 250%, more preferably below 100%, even more preferably less than 80%, still more preferably below 50%, the primary microgel particles have the deflection characteristic defined above. If the concentration of the microgels in the composition is too high that the visible primary microgel particles substantially overlap, the evaluation capacity can be improved by proper pre-dilution of the measurement sample. In the composition according to the invention, the primary particles of the microgel (B) preferably have an average particle diameter of 5 to 500 nm, more preferably 20 to 400 nm, more preferably 20 to 300 nm, more preferably 20 to 250 nm , still more preferably 20 to 99, even more preferably 40 to 80 nm (diameter values in accordance with DIN 53206). The preparation of particularly finely divided microgels by emulsion polymerization is carried out by controlling the reaction parameters in a manner known per se (see, for example, HG Elias, Makromoleküle, volume 2, Technologie, 5th edition, 1992, page 99 and sec.) . Since the morphology of the microgels substantially does not change during the further processing of the composition according to the invention, the average particle diameter of the dispersed primary particles substantially corresponds to the average particle diameter of the primary particles dispersed in the processing products. additional obtained with the composition according to the invention, such as plastics, lubricants, coatings etc. that contain microgel. This is a particular advantage of the composition according to the invention. To a certain degree the formulations of. microgel stable in storage, made to order which have a defined morphology of the microgels and which the customer can easily process additionally in the desired uses can be made available to customers. The dispersion, homogenization or even expensive preparatory preparation of the microgels is no longer necessary, and for this reason it is expected that such microgels will also find use in fields where their use to date seemed to be too expensive. In the composition according to the invention, the microgels (B) conveniently have contents which are insoluble in toluene at 23 ° C (gel content) of at least about 70% by weight, more preferably at least about 80% by weight , still more preferably at least about 90% by weight. The content which is insoluble in toluene is determined here in toluene at 23 °. In this method, 250 mg of the microgel was swollen in 20 ml of toluene for 24 hours at 23 ° C, while shaking. After centrifugation at 20,000 rpm, the insoluble content was separated and dried. The gel content is produced by the quotient of the dry residue and the weighed amount and is set in percent by weight. In the composition according to the invention, the microgels (B) conveniently have a swelling index in toluene at 23 ° C of less than about 80, more preferably less than 60, still more preferably less than 40. Swelling rates of the microgels (Qi) therefore in particular they can preferably be between 1-15 and 1-10. The swelling index is calculated from the weight of the solvent-containing microgel (after centrifugation at 20,000 rpm) which has been swollen in toluene 23 ° C for 24 hours and the weight of the dry microgel. Qi = wet weight of the microgel / dry weight of the microgel. To determine the swelling index, 250 mg of the microgel was swollen in 25 ml of toluene for 24 h, while shaking. The gel was centrifuged and weighed, and then dried to constant weight at 70 ° C and weighed again. In the composition according to the invention, the microgels (B) conveniently have glass transition temperatures Tg of -100 ° C to + 120 ° C, more preferably -100 ° C to + 100 ° C, even more preferably -80 ° C to + 80 ° C. In rare cases, microgels which have no glass transition temperature due to their high degree of crosslinking can also be used. In addition, the microgels (B) used in the composition according to the invention preferably have a vitreous transition range greater than 5 ° C, preferably greater than 10 ° C, more preferably greater than 20 ° C. The microgels which have such a vitreous transition interval are as a rule not completely homogenously crosslinked - in contrast to the microgels completely homogeneously crosslinked by radiation. This means that the change of modulus from the matrix phase to the dispersed phase in the microgel-containing plastic compositions which are prepared, for example, from the compositions according to the invention is not straightforward. As a result, under sudden tension in this compositions the tearing effects between the matrix and the dispersed phase do not occur, whereby the mechanical properties, the swelling properties and the cracking by stress corrosion etc. they are advantageously influenced. The vitreous transition temperatures (Tg) and the vitreous transition interval (? Tg) of the microgels are determined by means of differential thermal analysis (DTA, also differential scanning calorimetry (CED)) under the following conditions: Two cooling cycles / heating are performed for the determination of Tg and? Tg. The Tg and? Tg are determined in the second heating cycle. For determinations, 10-12 mg of the selected microgel are placed in a CED sample container (standard aluminum tray) from Perkin-Elmer. The first cycle of CED is performed first by cooling the sample below -100 ° C with liquid nitrogen and then heating to + 150 ° C at a rate of 20 k / min. The second cycle of CED is initiated by immediate cooling of the sample provided that a sample temperature of +150 ° C is reached. The cooling is carried out at a speed of approximately 320 k / min. In the second heating cycle, the sample is heated to +150 ° C once again as in the first cycle. The heating rate in the second cycle is again 20 k / min. The Tg and? Tg are determined in a graph in the curve of the second heating operation. For this purpose, three straight lines are plotted on the CED curve. The 1st straight line is plotted on the curve section of the CED curve below Tg, the 2nd straight line is plotted on the branch of the curve running through the Tg which has the inflection point and the 3rd Straight line is plotted on the branch of the curve of the CED curve above Tg. Three straight lines with two points of intersection are obtained in this way. The two points of intersection are each characterized by a characteristic temperature. The glass transition temperature Tg is obtained as the midpoint of these two temperatures and the glass transition interval? Tg is obtained from the difference between the two temperatures. The microgels which are contained in the composition according to the invention and are preferably or crosslinked by high energy radiation can be prepared in a manner known per se (see, for example, EP-A-405 216, EP-A-854171, DE-A 4220563, GB-PS 1078400, DE 197 01 489.5 , DE 197 01 488.7, DE 198 34 804.5, DE 198 34 803.7, DE 198 34 802.9, DE 199 29 347.3, DE 199 39 865.8, DE 199 42 620.1, DE 199 42 614.7, DE 100 21 070.8, DE 100 38 488.9 , DE 100 39 749.2, DE 100 52 287.4, DE 100 56 311.2 and DE 100 61 174.5). The use of CR, BR and NBR microgels in mixtures with rubbers containing double bonds is claimed in patent applications / EP-A 405 216, DE-A 4220563 and in GB-PS 1078400. DE 197 01 489.5 describes the use of microgels subsequently modified in mixtures with rubbers containing double bonds, such as NR, SBR and BR. The microgels are conveniently understood as meaning rubber particles which are obtained, in particular, by cross-linking the following rubbers: BR: polybutadiene, ABR: butadiene copolymers / C1-4 alkyl ester of acrylic acid SBR styrene copolymers / butadiene having styrene contents of 1-60, preferably 5-50 weight percent, X-SBR: carboxylated styrene / butadiene copolymers, FM: fluorinated rubber, ACM: acrylate rubber, NBR: polybutadiene / acrylonitrile copolymers having acrylonitrile contents of 5-60, preferably 10-50 weight percent, X-NBR: carboxylated nitrile rubbers, CR: polychloroprene, IIR: isobutylene / isoprene copolymers having isoprene contents of 0.5-10 percent by weight, BIIR: brominated isobutylene / isoprene copolymers having bromine contents of 0.1-10 weight percent, CIIR: chlorinated isobutylene / isoprene copolymers having bromine contents of 0.1-10 weight percent, HNBR: partially or fully hydrogenated nitrile rubbers, EPDM: ethylene / propylene / diene copolymers, EAM: ethylene / acrylate copolymers, EVM: ethylene / vinyl acetate copolymers, CO and ECO: epichlorohydrin rubbers, Q: silicone rubbers, excluding silicone graft polymers, AU: polyester-urethane polymers, EU: polyether-urethane polymers, ENR: epoxidized natural rubber or mixtures thereof. The non-crosslinked microgel starting materials are conveniently prepared by the following methods: 1. Emulsion polymerization 2. Solution polymerization of rubbers which are not accessible via variant 1 3. Naturally occurring latex, such as for example latex of natural rubber, can also be used. In the composition according to the invention, the microgels (B) used are preferably those which are obtainable by emulsion polymerization and crosslinking. The following monomers which can undergo free-radical polymerization are used, for example, in the preparation, by emulsion polymerization, of the microgels used according to the invention: butadiene, styrene, acrylonitrile, isoprene, acrylic acid esters and methacrylic, tetrafluoroethylene, vinylidene fluoride, hexafluoropropene, 2-chlorobutadiene, 2,3-dichlorobutadiene and carboxylic acids containing double bonds, such as for example acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc., hydroxy compounds containing double bonds, such as, for example, hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxybutyl methacrylate, functionalized amine (meth) acrylates, acrolein, N-vinyl-2-pyrrolidone, N-allylurea and N-allyl thiourea as well as esters of amino- (meth) acrylic acid, such as 2-tert-butylaminoethyl methacrylate, and 2-tert-butylaminoethylmethacrylamide, etc. The crosslinking of the rubber gel can be achieved directly during the emulsion polymerization, such as by copolymerization with multifunctional compounds having a crosslinking action, or by subsequent crosslinking as described below. Direct crosslinking is a preferred embodiment of the invention. Preferred multifunctional comonomers are compounds having at least two, preferably 2 to 4 copolymerizable C = C double bonds, such as diisopropenylbenzene, divinylbenzene, divinyl ether, di-inyl sulfone, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, 1,2-polybutadiene, N, N'-m phenylenemaleimide, 2,4-toluylenebis (maleimide) and / or triallyl trimellitate. The compounds which are also possible are the acrylates and methacrylates of polyhydric, preferably 2 to 4-hydroxy C2 to CIO alcohols, such as ethylene glycol, propane-1,2-diol, butanediol, hexanediol, polyethylene glycol having 2 to 20, preferably 2 to 8 units of oxyethylene, neopentyl glycol, bisphenol A, glycerol, trimethylolpropane, pentaerythritol and sorbitol, with unsaturated polyesters of aliphatic acid di- and polyols and maleic acid, fumaric acid and / or itaconic acid. Cross-linking to produce rubber microgels during emulsion polymerization can also be carried out by continuing the polymerization to high conversions, or in the monomer feed process by polymerization with high internal conversions. Performing emulsion polymerization in the absence of regulators is also another possibility. For the crosslinking of the non-crosslinked or weakly crosslinked microgel starting substances after the emulsion polymerization, the latexes which are obtained in the emulsion polymerization are very preferably used. In principle, this method can also be used in non-aqueous polymer dispersions which are otherwise accessible, such as, for example, by redissolution. Natural rubber latexes can also be crosslinked in this way. Suitable chemistries having a crosslinking action are, for example, organic peroxides, such as dicumyl peroxide, t-butyl cumyl peroxide, bis- (t-butylperoxyisopropyl) benzene, di-t-butyl peroxide, 2,5- 2,5-dimethylhexane dihydroperoxide, 2,5-dimethylperoxide 2,5-dimethylhexine, dibenzoyl peroxide, bis- (2,4-dichlorobenzoyl) peroxide and t-butyl perbenzoate, and organic azo compounds, as azo-bis-isobutyronitrile and azo-bis-cyclohexannitrile, as well as di- and polimercapto compounds, such as dimercaptoethane, 1,6-dimercaptohexane, 1, 3, 5-trimercaptotriazine and mercapto termination polysulfide rubbers, such as mercapto termination reaction of bis-chloroethylformal with sodium polysulfide. The optimal temperature for post-cross-linking will of course depend on the reactivity of the cross-linking agent, and the post-cross-linking can be carried out at temperatures from room temperature to about 180 ° C, optionally under increased pressure (in this context see Houben-Weyl, Methoden der organischen Chemie, 4th edition, volume 14/2, page 848). Peroxides are particularly preferred crosslinking agents. The crosslinking of rubbers containing C = C double bonds to produce microgels can also be carried out in dispersion or emulsion with partial, optionally complete, simultaneous hydrogenation of the C = C double bond by hydrazine, as described in US 5,302,696 or US 5,442,009, optionally other hydrogenation agents, for example organometallic hydride complexes. An increase in particle size by agglomeration can optionally be carried out before, during or after the post-crosslinking. In the preparation process without the use of high energy radiation preferably used according to the invention, incompletely homogeneously crosslinked microgels which can have the advantages described above are always obtained. The rubbers which are prepared by solution polymerization can also serve as starting materials for the preparation of the microgels. In these cases the solutions of these rubbers in suitable organic solvents are used as the starting substances. The desired sizes of the microgels are established by mixing the rubber solution in a liquid medium, preferably in water, optionally with the addition of suitable surface active auxiliaries, such as, for example, surfactants, by means of suitable units so that a dispersion of the rubber in the range of suitable particle size is obtained. The process for crosslinking the dispersed solution rubbers is as previously described for the subsequent crosslinking of emulsion polymers. Suitable crosslinking agents are the aforementioned compounds, it being possible for the solvent used for the preparation of the dispersion to be optionally removed, for example by distillation, before crosslinking. The microgels which can be used for the preparation of the composition according to the invention are both unmodified microgels, which substantially do not contain reactive groups, in particular on the surface, as modified microgels modified with functional groups, in particular in the surface. The last microgels can be prepared by chemical reaction of microgels already crosslinked with chemicals which are reactive towards double C = C bonds. These reactive chemicals are, in particular, those compounds with the aid of which polar groups, such as for example aldehyde, hydroxyl, carboxyl, nitrile, etc. and groups containing sulfur, such as for example mercapto, dithiocarbamate, polysulfide, xanthogenate, thiobenzothiazole and / or dithiophosphoric acid and / or unsaturated dicarboxylic acid groups, can be chemically bound to the microgels. This also applies to N, N'-phenylenediamine. The proposed modification of the microgel is the improvement of the compatibility of the microgel if the composition according to the invention is used for the preparation of the last matrix in which the microgel is incorporated or the composition according to the invention is used for the incorporation in a matrix, to achieve a good distribution capacity during the preparation and a good coupling. Particularly preferred modification methods are the grafting of the microgels with functional monomers and reaction with low molecular weight agents. For the grafting of the microgels with functional monomers, the aqueous microgel dispersion is conveniently used as the starting material, which is reacted with polar monomers, such as acrylic acid, methacrylic acid, itaconic acid, hydroxyethyl (meth) acrylate , (meth) hydroxypropyl acrylate,(me) hydroxybutyl acrylate, acrylamide, methacrylamide, acrylonitrile, acrolein, N-vinyl-2-pyrrolidone, N-allylurea and N-allyl thiourea, and secondary amino- (me) acrylic acid esters, such as methacrylate of 2-tert-butylaminoethyl, and 2-tert-butylaminoethylmethacrylamide, under the conditions of a free radical emulsion polymerization. Microgels that have a core / shell morphology, where the shell has a high compatibility with the matrix, are obtained in this way. It is desirable that the monomer used in the modification step be grafted as quantitatively as possible into the unmodified microgel. The functional monomers are conveniently measured before complete cross-linking of the microgels. The grafting of the microgels in non-aqueous systems is a principle also conceivable, a modification with monomers by ionic polymerization methods also become possible in this way. The following reagents are possible in particular for the surface modification of the microgels with low molecular weight agents: elemental sulfur, hydrogen sulfide and / or alkylpolymercaptans, such as 1,2-dimercaptoethane or 1,6-dimercaptohexane, further dialkyl- and dialkylaryl dithiocarbamate, such as the alkali metal salts of dimethyldithiocarbamate and / or dibenzyldithiocarbamate, further alkyl and aryl xanthogenates, such as potassium methyl xanthogenate and sodium isopropyl xanthogenate, as well as the reaction with the alkaline earth metal or alkali metal salts of dibutyldithiophosphoric acid and dioctyl thiophosphoric acid as well as dodecyldithiophosphoric acid.

The mentioned reactions can also be advantageously carried out in the presence of sulfur, the sulfur is coincident with the formation of polysulfide bonds. Free radical initiators, such as azo initiators and / or organic or inorganic peroxides, can be added for the addition of this compound. A modification of microgels containing double bonds, such as for example by ozonolysis or by halogenation with chlorine, bromine and iodine, is also possible. An additional reaction of modified microgels, such as for example the preparation of microgels modified by hydroxyl groups from epoxidized microgels, is also understood as chemical modification of microgels. In a preferred embodiment, the microgels are modified by hydroxyl groups, in particular also on the surface thereof. The hydroxyl group content of the microgels is determined as the hydroxyl number with the mg dimension of K0H // g of polymer by reaction with acetic anhydride and acetic acid titration whereby it is released with KOH in accordance with DIN 53240. The The hydroxyl number of the microgels is preferably between 0.1-100, even more preferably between 0.5-50 mg of KOH / g of polymer. The amount of modifying agent employed depends on the activity of the same and the requirements imposed in the individual case and is in the range of 0.05 to 30 weight percent, based on the total amount of rubber microgel employed, and 0.5-10 percent by weight, based on the total amount of rubber gel, is particularly preferred. The modification reactions can be carried out at temperatures of 0-180 ° C, preferably 20-95 ° C, optionally under a pressure of 1-30 bar. The modifications can be made in rubber microgels in substance or in the form of their dispersion, it being possible to use organic solvents or also water as the reaction medium in the latter case. The modification is particularly preferably carried out in an aqueous dispersion of the crosslinked rubber. The use of unmodified microgels is particularly preferred in the case of compositions according to the invention which are used for incorporation into non-polar rubbers or non-polar thermoplastics, such as, for example, polypropylene, polyethylene and block copolymers based on styrene, butadiene and isoprene (SBR, SIR) and hydrogenated isoprene / styrene block copolymers (SEBS) and conventional TPE-Os and TPE-Vs, etc. The use of modified microgels is preferred in particular in the case of compositions according to the invention which are used for incorporation into polar rubbers or polar thermoplastics (A), such as, for example, PA, TPE-A, PU , TPE-U, PC, PET, PBT, POM, PMMA, PVC, ABS, PTFE, PVDF, etc. The average diameter of the prepared microgels can be adjusted with a high degree of accuracy, for example to 0.1 micrometers (100 nm) + 0.01 micrometers (10 nm), so that, for example, a particle size distribution is achieved in which at least 75% of all microgel particles are between 0.095 micrometers and 0.105 micrometers in size. Other average diameters of the microgels, in particular in the range between 5 to 500 nm, can be established with the same accuracy (at least 75% by weight of all the particles are placed around the maximum of the size distribution curve of integrated particle (determined by light scattering) in a range of ± 10% above and below the maximum) and used. As a result, the morphology of the dispersed microgels in the composition according to the invention can be adjusted practically with "high precision" and the properties of the composition according to the invention and of the plastics prepared therefrom, for example, are they can adjust. Microgels prepared in this way, preferably based on BR, SBR, NBR, SNBR or acrylonitrile or ABR, can be prepared, for example, by evaporation, coagulation, by co-coagulation with an additional latex polymer, by freeze-coagulation (compare US-PS 2187146) or by spray drying. Commercially available flow aids, such as, for example, CaCO3 or silica, can also be added in the case of spray-drying processing. In a preferred embodiment of the composition according to the invention, the microgel (B) is based on rubber. In a preferred embodiment of the composition according to the invention, the microgel (B) is modified by functional groups which are reactive toward C = C double bonds. In a preferred embodiment, the microgel (B) has a swelling index in toluene at 23 ° C from 1 to 15. The composition according to the invention preferably has a viscosity of 2 mPas up to 50,000,000 mPas, more preferably 50 mPas up to 3,000,000 mPas at a speed of 5 s_1, measured with a cone-plate viscometer in accordance with DIN 53018, at 20 ° C.

Non-crosslinkable organic medium (A) The composition according to the invention comprises at least one organic medium (A) which has a viscosity at a temperature of 120 ° C of less than 30,000 mPas, more preferably less than 1,000 mPas, more preferably less than 200 mPas, more preferably less than 100 mPas, even more preferably less than 20 mPas at 120 ° C. Such a medium is liquid to solid, preferably liquid or flowable, at room temperature (20 ° C). The organic medium in the context of the invention means that the medium contains at least one carbon atom. The non-crosslinkable media in the context of the invention is understood to mean, in particular, those media which do not contain groups which can be crosslinked via functional groups containing heteroatoms or C = C groups, such as, in particular, monomers or conventional prepolymers which are crosslinked or polymerized in a conventional manner by means of free radicals, with UV rays, by heat and / or by polyaddition or polycondensation with the addition crosslinking agents (for example, polyisocyanates, polyamines, acid anhydrides) etc., with the formation of oligomers in the conventional manner. According to the invention, the organic non-crosslinkable media which can also be used are those means which effectively contain, for example, certain unsaturated link contents (certain polyester oils, rapeseed oil, etc.) or groups hydroxyl (polyethers), but are not crosslinked or polymerized to form oligomers or polymers in the conventional manner. The non-crosslinkable media are, in particular, also solvents, in particular those according to DIN 55 945. The non-crosslinkable media (A) are preferably non-crosslinkable media which are liquid at room temperature (20 ° C), in particular hydrocarbons (straight chain, branched, cyclic, saturated, unsaturated and / or aromatic hydrocarbons having 1 to 200 carbon atoms, which optionally can be substituted by one or more substituents chosen from halogens, such as chlorine, fluoro, hydroxyl, oxo , amino, carboxyl, carbonyl, aceto or amido), synthetic hydrocarbons, polyether oils, ester oils, phosphoric acid esters, oils containing silicon and halohydrocarbons or halocarbons (see, for example, Ullmanns Enzyklop die der technischen Chemie, Verlag Chemie Weinheim, volume 20, (1981) 457 and sec., 504, 507 and sec, 517/518, 524). These non-crosslinkable media (A) are distinguished in particular by viscosities of 2 to 1,500 mm2 / s (cSt) at 40 ° C. The non-crosslinkable media (A) are preferably non-crosslinkable media which are liquid at room temperature (20 ° C), in particular solvents according to DIN 55 945, such as xylene, naphtha solvent, methyl ethyl ketone, methoxypropyl acetate , N-methylpyrrolidone and dimethylsulfoxide. Synthetic hydrocarbons are obtained by polymerization of olefins, condensation of olefins or chloroparaffins with aromatics or condensation by dechlorination of chloroparaffins. Examples of polymer oils are polymers of ethylene, polymers of propylene, polybutenes, polymers of major olefins and alkylaromatics. The ethylene polymers have molecular weights of between 400 and 2000 g / mol. The polybutenes have molecular weights between 300 and 1500 g / mol. In the case of polyether oils, a distribution is made between aliphatic polyether oils, polyalkylene glycols, in particular polyethylene and propylene glycols, copolymers thereof, their mono- and di-ethers and ester-ethers and diesters, tetrahydrofuran polymer oils , perfluoroalkyl ethers and polyphenyl ethers. The perfluoropolyalkyl ethers have viscosities of 8 to 19500 mm2 / s at 38 ° C. The polyphenyl ethers are prepared by condensation of alkali metal phenolates with halobenzenes. Diphenyl ether and its alkyl derivatives are also used. Examples of the ester oils are the alkyl esters of aliphatic acid, bis- (2-ethylhexyl) sebacate and bis- (3,5,5,5-trimethylhexyl) sebacate or adipate as well as the esters of fatty acids occurring naturally with mono- or polyfunctional alcohols, such as TMP oleate. The ester oils containing fluoro form an additional class. In the case of phosphoric acid esters, a distinction is made between triaryl, trialkyl and alkyl aryl phosphates. Examples are tri- (2-ethylhexyl) phosphate and bis- (2-ethylhexyl) phenyl phosphate. The oils containing silicon are silicone oils (polymers of the alkyl- and arylsiloxane series) and silicates. Examples of renewable non-crosslinkable organic media are rapeseed oil and sunflower oil. Halohydrocarbons and halocarbons include chlorinated paraffins, such as chlorotrifluoroethylene polymer oils, and hexafluorobenzene. Solvents (non-reactive) according to DIN 945 are hexane, benzines, specified boiling range, mineral benzene, xylene, naphtha solvent, balsam turpentine, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, isophorone, acetate of butyl, 1-methoxypropyl acetate, butyl glycol acetate, ethyl diglycol acetate and N-methylpyrrolidone (Brock, Thomas, Gorteklaes, Michael, Mischke, Peter, Lehrbuch der Lacktechnologie, Curt R. Vincentz Verlag Hannover, (1998) 93 and sec. ). Particularly preferred non-crosslinkable media include: polyethers, for example Baylube 68CL, naphthenic oils, for example Nynas T 110, highly refined paraffinic mineral oils, for example Shell Catenex S 932, ester oils, for example Methyl Ester SU, and oils a base of renewable raw materials, for example refined rapeseed oil. The particularly preferred non-crosslinkable media (A) are the large class of hydrocarbons, the polyether oils and the solvents according to DIN 55 945. The composition according to the invention preferably contains 0.5 to 90% by weight, more preferably 1- 40% by weight, even more preferably 2-3% by weight of the microgel (B), based on the total amount of the composition. The composition according to the invention further preferably contains 10 to 99.5% by weight, more preferably 40-97% by weight, even more preferably 50 to 95% by weight, more preferably more than 60 to 95% by weight of the organic medium (A ). The composition according to the invention preferably comprises the non-crosslinkable organic medium (A) and the microgel (B) and optionally the additional components mentioned later. The presence of water is not preferred, and the compositions according to the invention preferably contain less than 0.8% by weight, even more preferably less than 0.5% by weight of water. The presence of water is most preferably excluded (< 0.1% by weight). The latter in general is the case in the compositions according to the invention due to the preparation. The composition according to the invention can additionally comprise fillers, pigments and additives, such as dispersion aids, deaerators, flow agents, flow promoters, auxiliary substances for wetting the substrate, adhesion promoters, anti-sedimentation agents, auxiliary substances to control the humidity of the substrate or to control the conductivity, auxiliary substances to control the color tone stability, gloss and plaster, oxidation inhibitors, pour point depressants, high pressure additives, foam prevention agents, demulsifiers , wear protection additives, corrosion protection additives, non-ferrous metal deactivators, coefficient of friction modifiers, etc. The additives mentioned in particular can be incorporated at this point particularly uniformly in the compositions according to the invention, which in turn leads to the improvement in the product prepared thereof, such as polymeric compositions, lubricants, etc. Pigments and fillers particularly suitable for the preparation of the compositions according to the invention which comprise the non-crosslinkable medium (A), and microgel-containing plastics prepared therefrom are, for example: inorganic and organic pigments, silicone fillers, such as kaolin, talcum, carbonates, such as calcium carbonate and dolomite, barium sulfate, metal oxides, such as zinc oxide, calcium oxide, magnesium oxide and aluminum oxide, highly dispersed silicas (precipitated and thermally prepared silicas) ), metal hydroxides, such as aluminum hydroxide and magnesium hydroxide, glass fibers and glass fiber product (strips, strands or glass microbeads), carbon fibers, thermoplastic fibers (polyamide, polyester or aramid), gels rubber based on polychloroprene and / or polybutadiene or also all the other gel particles previously described which have n a high degree of crosslinking and a particle size of 5 to 1,000 nm. The aforementioned fillers can be used by themselves or in a mixture. In a particularly preferred embodiment of the process, 0.5-3.0 parts by weight of rubber gel (B), optionally together with 0.1 to 40 parts by weight of fillers, and 30-99.5 parts by weight of the liquid non-crosslinkable medium (A) are used for the preparation of the compositions according to the invention. The compositions according to the invention may additionally comprise auxiliary substances, such as anti-aging agents, heat stabilizers, light stabilizers, ozone protection agents, processing aids, plasticizers, tackifiers, blowing agents, dyes, waxes. , extenders, organic acids and filler activators, such as, for example trimethoxysilane, polyethylene glycol or others which are known in the industries described. The auxiliary substances are used in conventional quantities, which depend, inter alia, on the proposed use. Conventional amounts are, for example, amounts of 0.1 to 50% by weight, based on the amounts of liquid medium (A) used and rubber gel (B) used. In a preferred embodiment, the composition according to the invention is prepared by mixing at least one non-crosslinkable organic medium (A) which has a viscosity of less than 30,000 mPas at a temperature of 120 ° C and at least one dry microgel powder (B) preferably less than 1% by weight, even more preferably less than 0.5% by weight of volatile contents (no microgel latex is used during the mixing of components (A) and (B)) which is not crosslinked by high energy radiation, by means of a homogenizer, a bead mill, a triple roller mill, a single or multiple screw extruder, a kneader and / or dissolution vessel, preferably by means of a homogenizer, a pearl mill or a triple roller mill. With regard to the viscosity of the composition to be prepared, the kneader, in which preferably only very highly viscous compositions (almost solid to solid) can be employed, is the most limited, ie it can be used only in special cases. The disadvantages of the bead mill are the comparatively limited viscosity range (tending towards light compositions), high cleaning expense, expensive product change of the compositions which can be used as well as abrasion of the balls and grinding apparatus. The homogenization of the compositions according to the invention is particularly preferably carried out by means of a homogenizer or a triple roller mill. The disadvantages of the triple roller mill are the comparatively limited viscosity range (tending towards very thick compositions), low yield and non-closed processing procedure (poor work safety). The homogenization of the compositions according to the invention is therefore most preferably carried out by means of a homogenizer. The homogenizer allows light and thick compositions to be processed at high performance (high flexibility). Product changes can be made comparatively quickly and without problems. It is surprising and new that microgels (B) can be dispersed in non-crosslinkable organic media; the dispersion which has been successful under the primary particles is particularly surprising (see examples). The dispersion of the microgels (B) in the liquid medium (A) is carried out in the homogenizer in the homogenization valve (see figure 1). In the process which is preferably employed according to the invention, the agglomerates are divided into aggregates and / or primary particles. Agglomerates are units which can be physically separated, during dispersion of which no change in the primary particle size takes place. The product to be homogenized enters the homogenization valve at a slow speed and accelerates at high speeds in the homogenization opening. The dispersion takes place after the opening, mainly at the base of turbulence and cavitation (William D. Pandolfe, Peder Baekgaard, Marketing Bulletin of APV Homogeniser Group - "High-pressure homogenisers processes, product and applications"). The temperature of the composition according to the invention on introduction into the homogenizer is conveniently -40-149 ° C, preferably 20-80 ° C. The composition according to the invention to be homogenized is conveniently homogenized in the apparatus under a pressure of 20 to 4,000 bar, preferably 100 to 4,000 bar, preferably 200 to 4,000 bar, preferably 200-2000 bar, most preferably 500-1,500 bar. The number of steps depends on the desired dispersion quality and can vary between one and 20, preferably one to 10, more preferably one to four steps. The compositions prepared according to the invention have a particularly fine particle distribution, which is achieved in particular with the homogenizer, which is also extremely advantageous with respect to the flexibility of the process with respect to the varied viscosities of the liquid media and of the resulting compositions and the necessary temperatures as well as the dispersion quality. The invention also relates to the use of the composition according to the invention for the preparation of plastics and polymers containing microgel, as explained above. If the compositions according to the invention are incorporated into thermoplastic polymers, it was found, quite surprisingly, that polymers containing microgel are obtained which behave similar to thermoplastic elastomers. The invention furthermore also relates to shaped articles and coatings produced therefrom by conventional processes. The invention is explained in more detail with reference to the following examples. The invention is of course not limited to these examples.

EXAMPLES Example 1: SBR gel in Nynas T110 In example 1 described in the following, it is shown that the compositions according to the invention which exhibit particular rheological characteristics, such as flow properties of structural viscosity, thixotropic and approximately Newtonian, they are obtained using microgels based on SBR. The use of the composition according to the invention as a functional and / or rheological additive, inter alia, arises from this. The microgels which have little influence on the viscosity, ie in a first approximation, show Newtonian flow properties, have favorable prerequisites for the use of the mixtures according to the invention in rubber or plastic. The microgels which greatly influence the viscosity, ie show thixotropic flow properties or structural viscosity, are suitable in particular for the use of the mixtures according to the invention in fats. The composition is shown in the following table: 1. Nynas T 110 80% 2. Micromorph 1P or 5P 20% Total 100 Nynas T 110 is a hydrogenated naphthenic oil from Nynas Naphthenics AB. Micromorph 5P is a crosslinked rubber gel having an OH number of 4 based on SBR from RheinChemie Rheinau GmbH. Micromorph 5P comprises 40% by weight of styrene, 57.5% by weight of butadiene and 2.5% by weight of dicumyl peroxide. Micromorph 1P is a surface-modified, cross-linked rubber gel based on SBR from RheinChemie Rheinau GmbH. Micromorph 1P comprises 80% by weight of styrene, 12% by weight of butadiene, 5% by weight of ethylene glycol dimethacrylate (? GDMA) and 3% by weight of hydroxymethyl methacrylate (HEMA). The characteristic data of the SBR gels are summarized in Table 1.

Table 1. Properties of Micromorph 1P and 5P of microgels, The abbreviations in the table have the following meanings: DCP: dicumyl peroxide D50: The ugly diameter is defined according to DIN 53 306 as the average. In this case it is the average particle diameter of the particles in the latex. The particle diameter of the latex particles was determined at this point by means of ultracentrifugation (W. Scholtan, H. Lange, "Bestimmung der Teilchengroßenverteilung von Latices mit der Ultrazentrifuge", Kolloid-Zeitschrift • und Zeitschrift für Polymere (1972) voluman 250, emission 8). The diameter values in the latex and for the primary particles in the compositions according to the invention are practically the same, since the particle size of the microgel particles does not change during the preparation of the composition according to the invention.

Tg: glass transition temperature For the determination of Tg and? Tg, the DSC-2 apparatus of Perkin-Elmer was used. swelling index QI The swelling index QI was determined as follows: The swelling index was calculated from the weight of the solvent-swollen microgel in toluene at 23 ° C for 24 hours and the weight of the dry microgel: Qi = wet weight of the microgel / dry weight of the microgel To determine the swelling index, 250 mg of the microgel was swollen in 25 ml of toluene for 24 h, while shaking. The (wet) gel swelled with toluene was weighed, after centrifugation at 20,000 rpm, and then dried to constant weight at 70 ° C and weighed again.

OH number (hydroxyl number) The OH number (hydroxyl number) was determined in accordance with DIN 53240 and corresponds to the quantity of KOH in mg which is equivalent to the amount of acetic acid which is released during the acetylation of 1 g of substance with acetic anhydride.

Acid number The acid number was determined in accordance with DIN 53402 as already mentioned above and corresponds to the amount of KOH in mg which is necessary to neutralize one g of the polymer.

Gel content The gel content corresponds to the content which is insoluble in toluene at 23 ° C. The gel content is given by the quotient of the dry residue and the weighed amount and is set in percent by weight.

Example of Preparation 1 for Micromorph 1P Micromorph 1P is a hydroxyl-modified SBR-based microgel, prepared by direct emulsion polymerization using the ethylene glycol dimethacrylate crosslinking comonomer. 325 g of the Na salt of a long chain alkylsulfonic acid (330 g of Mersolat K30 / 95 from Bayer AG) and 235 g of the Na salt of methylene bridged naphthalenesulfonic acid (Baykanol PQ from Bayer AG) were dissolved in 18.71 kg of water and the solution was initially introduced in an autoclave of 40 1. The autoclave was evacuated and charged with nitrogen 3 times. Then, 8.82 kg of styrene, 1.32 kg of butadiene, 503 g of ethylene glycol dimethacrylate (90% pure), 314 g of hydroxyethyl methacrylate (96%) and 0.75 g of hydroquinone onomethyl ether were added. The reaction mixture was heated to 30 ° C, while stirring. Then an aqueous solution consisting of 170 g of water, 1.69 g of ethylenediaminetetraacetic acid (Merck-Schuchardt), 1.35 g of iron (II) * 7H20 sulphate, 3.47 g of Rongalit C (Merck-Schuchardt) and 5.24 g was measured. of trisodium phosphate * 12H20. The reaction was started by adding an aqueous solution of 2.8 g of p-menthane hydroperoxide (Trigonox NT 50 of Akzo-Degussa) and 10.53 g of Mersolat K 30/95, dissolved in 250 g of water. After a reaction time of 5 hours, the mixture was post-activated with an aqueous solution consisting of 250 g of water, in which 10.53 g of Mersolat K30 / 95 and 2.8 g of p-menthane hydroperoxide (Trigonox NT 50) were dissolved. When a polymerization conversion of 95-99% was reached, the polymerization was stopped by the addition of an aqueous solution of 25.53 g of diethylhydroxylamine, dissolved in 500 g of water. Then, the unreacted monomers were removed from the latex by steam stripping. The latex was filtered and, as in example 2 of US 6399706, stabilizer was added and the product coagulated and dried. The Micromorph 5P was prepared analogously. The dried microgel powders of Micromorph 1P and Micromorph 5P further processed according to the invention were obtained from the latex by spray drying. For the preparation of the composition according to the invention, Nynas T 110 was initially introduced into the preparation vessel and the Micromorph 5P was added, while being stirred by means of a dissolution vessel. The composition was passed through the homogenizer four times under 950 bar. The laboratory high pressure homogenizer APV1000 from Invensys was used as the homogenizer. The rheological properties of the composition were determined with a rheometer, MCR300, from Physica. A plate and cone system, CP25-1, was used as the measuring body. The measurements were made at 20 ° C. Some measurement results for the 80% composition of Nynas T 110 and 20% of Micromorph 1P and Micromorph 5P are shown in the following table 2. The fats of LÍ-120H, a semi-finished product, and E301 (15%) , a laboratory product from RheinChemie Rheinau GmbH, were also measured as a comparison. The viscosities?, Which were measured at shear rates v 'of 5 s "1, 100 s" 1, 1,000 s "1, 3,000 s" 1 and 0.1 s "1, are shown in the table. with a measurement program in which the measurement values (dynamic viscosities? etc.) were recorded in the sequence given above.The quotient? (v '= 0.1 s "1) / (v' = 3,000 s_1) was defined as an arbitrary measure of the viscosity increase action of the microgel. The composition of 80% of Nynas T 110 and 20% of Micromorph 5P, which was passed through the homogenizer four times under 950 bar, shows rheological properties comparable with those of LÍ-120H AK33 or E301, ie the Micromorph 5P is suitable as a raw material for the preparation of fats. The values in Table 2 show very clearly that various rheological properties can be achieved with the microgels.

Table 2. Rheological characterization of Micromorph 1P and 5P (in each case 20% by weight) in Nynas T 110; 20 ° C, cone-plate: CP 25-1. Name characteristics? ? ? 1 x (v '- .la "omentarlos v' = 5 s" 1 v '= 100 s "1 v' = 1000 s" 1 • 3000 s "1 V'aO.l S" 1 11 < V = 3000 a VC [Pas] [Pas] [Pas] [PasJ (Pas] [1 Example fat without additive (product sep? -teiriBinaio), 0.0935 s "1 viscosity e place of structural, not very Ü120H 0.1 < Tl 375 23.3 3.9 _ 7950 20233) tixo rópico Example fat without 0.015 s_1 additive, viscosity instead of structural in E301 (15%) 0.1 s "1 83 14.6 6.6 - 2420 3683> mineral oil M. lP / 0x950 AE2564S / 5" bar 23.4 5.1 3.45 2.3 1350 391 M. lP / lx950 flow properties AE25648 / 5"Bar 1.81 1.42 1.24 1.11 5.9 5 almost Newtonian 10 ^ 1 M. 1P / 2X950 flow properties AB25648 / 51 'bar 2.3 1.77 1.34 1.20 1.99 1.5 almost Sewtonian M. 1P / 3x950 slightly AE25648 / 51) bar 3.9 2.01 1.42 1.25 1.72 1.2 tixo rópico M. 1P / 4X950 AE25648 / 51- »bar 9.3 2.80 1.71 1.46 3.3 2 Tixo rópico M. 5P / 0x950 AE25648 / 62 'bar. 6.8 1.94 1.56 1.38 2.02 1.3 M. 5P / lx950 viscosity AE2S648 / 62 'bar 11.9 5.4 3.8 2.44 2150 563 structure ral 15 M. 5P / 2x950 viscosity AE25648 / 621 bar 19.6 6.0 3.6 2.34 1750 489 structural M. 5P / 3X950 viscosity AE25648 / 62 'bar 33 6.8 3.6 2.36 1580 444 structural structural viscosity M. 5P / 4x950, not very AB256 8 / '6:!, Bar 57 7.7 3.6 2.40 1720 475 tixo rópico 1) 20% by weight of Micromorph 5P in Nynas T 110 2) 20% by weight of Micromorph 5P in Nynas T 110 3)? (V '= 0.1 s "1) /? (V = 1000 s" 1) The values measured show a thickening which, with suitable choice of microgel / lubricant combination from the rheology point of view, surprisingly allows the preparation of lubricating greases. In addition, the rheological properties can be controlled with microgels in the described liquid media. The compositions according to the invention are of particular interest as thickeners, as agents for preventing runoff and settling and as a rheological additive. The described compositions or similar compositions can be used advantageously in lubricating greases, lacquers and paints, adhesives, rubber, plastics and gel coatings or thermoplastic elastomers. The compositions prepared in Example 1 can be used particularly advantageously in lubricating greases. In these, they lead to particularly favorable properties, such as high thixotropy and structural viscosity. Additionally, very advantageous properties which are co-introduced into the particular systems via the microgels can be seen from the following examples.

Example 2: Transparency and separation of phases as well as rheological and tribological properties of the lubricants of the combination of 2% microgel - lubricating oil In the example 2 described in the following, it is shown that the compositions according to the invention which exhibit characteristics Particular with respect to transparency and stability towards separation are obtained using microgels based on SBR and NBR. The composition is shown in the following table: 1. Lubricating oil 98% 2. Microgel 2% Total 100% Shell Catenex S 932 is a highly refined, paraffinic mineral oil from Deutsche Shell GmbH. Shell Gravex 921 is a manufactured oil based on naphthene, hydrogenated from Shell &DEA Oil GmbH. Methyl Ester SU is a methyl ester (Radia 7961) from Oleon NV. Silicone Oil M350 is a polydimethylsiloxane from Bayer MaterialScience AG. Baylube 68CL is a polyether from RheinChemie Rheinau GmbH. OBR 1210 and OBR 1212 microgels are surface-modified, crosslinked rubber gels based on SBR from RheinChemie Rheinau GmbH. Micromorph 4P is crosslinked rubber gel which is not surface modified and is based on SBR, from RheinChemie Rheinau GmbH.

OBR 1310D is a cross-surface modified rubber gel based on NBR (table 3). The microgels are prepared by a procedure analogous to that described in Example 1 for Micromorph 1P.

Table 3. Composition of the microgels OBR 1210, OBR 1212, OBR 1310D and Micromorph 4P.

The characteristic data of the SBR gels and the NBR gel are summarized in table 4.

Table 4. Properties of OBR 1210, PBR 1212, OBR 1310D and Micromorph 4P.

The abbreviations in the table have the following meanings: SAespec. : specific surface area in m2 / g Vitreous transition interval: The vitreous transition interval was determined as described above. Otherwise see example 1.

Control of homogeneity: Samples were visually tested for separation one week after preparation.

Transparency control: The transparency of the samples was verified visually. The samples which showed separation or flocculation were shaken before evaluation.

Preparation of the compositions according to the invention For the preparation of the composition according to the invention, the particular lubricating oils were initially introduced into the preparation vessel and the particular microgel was added, while being stirred by means of a dissolving vessel. . The mixture was allowed to stand for at least one day, and then it was processed with the homogenizer. The composition according to the invention was introduced into the homogenizer at room temperature and passed through the homogenizer six times in batch operation under 900 to 1, 000 bar. During the first step the microgel paste was heated to about 40 ° C, and during the second step to about 70 ° C. Then, the microgel paste was cooled to room temperature by letting it stand, and the operation was repeated until six steps were achieved. The rheological properties of the composition were determined with a rheometer, MCR300, from Physica. A plate and cone system, CP 50-2, was used as the measuring body. The measurements were made at 40 ° C. Some measurement results for the microgels described above are shown in the following tables 5 to 7.

Table 5. Blotting and separation of lubricating oils containing microgel (2% microgel): room temperature Oil Microgel Dispersion Turbidity Separation of lubricant phases Shell satenex OBR 1212 6x milky turbid without S932 settlement OBR 1310D 6x moderately severe settlement severe Micromorph 4P 6x turbid milky settlement severe Shell Gravex OBR 1210 6x cloudy milky settlement 921 severe OBR 1310D 6x cloudy / moderately severe clear settlement Micromorph 4P 6x milky turbid without settlement Methyl Ester OBR 1210 6x very weakly without SU transparent settlement OBR 1212 6x cloudy milky without settlement turbid milky settlement moderate Micromorph 4P 6x milky turbid without settlement Oil of OBR 1210 6x turbid milky without silicone M350 settlement OBR 1310D 6x turbid milky settlement severe Micromorph 4P 6x turbid milky without settlement From table 5 it can be seen that there are many compositions according to the invention which on the one hand are based on different lubricating oils and on the other hand do not settle. In particular, the Micromorph 4P does not show settlement in any combination. This is surprising, since only 2% by weight of microgel is added. In addition, a composition was found which is largely transparent and does not separate, mainly OBR 1210 in Methyl Ester SU.

Table 6. Rheological characterization of lubricating oils containing microgel; 40 ° C; cone-plate: CP 50-2 measuring system.

From the values in Table 6, the rheological action of the microgels even at a concentration of two percent can be clearly seen; however, there is a clear differentiation in properties of Newtonian flow, structural viscosity and thixotropic. OBR 1210 has Newtonian flow properties in M350 Silicone Oil. The SRV tests were also performed to determine the coefficient of friction (Tab 7, figures 2a and 2b). The SRV tests were performed by the method of ASTM 5706-97, a ring-plate geometry was chosen instead of a ball-plate geometry: steel ring 100 CR 6 coated on steel plate 100 CR 6 Frequency: 50 Hz Load: 300 N (varies as required) Temperature: 100 ° C Amplitude: 1,500 mm Duration: 60 minutes Table 7. SRV test in the 2% by weight combinations of microgel (OBR 1210) - lubricating oil (Baylube 68CL) and Baylube 68CL for comparison; ring-plate.

Load: 300N Coefficient Coefficient Wear Appearance steel ring 100C 6 / friction friction plate site steel plate 100CR6, min max de r covered friction 68CX-1210 0.025 μ 0.087 μ can not be white measure metallic Baylube 68C as a reference 0. 044 μ 0. 081 duplicate duplicate It can be seen from table 7 that for the composition according to the invention, OBR 1210 / Baylube 68CL, a clearly low coefficient of friction was found compared to Baylube 68CL pure lubricating oil. Furthermore, it was found that the course of the curve during the measurement is smoother, which indicates that the microgels lead to less wear on the surface of the test plate. The microgel, similar to many other microgels, also surprisingly has properties which reduce the coefficient of friction and can therefore be used as a coefficient of friction modifier.

Example 3: Separation of phases and rheological and tribological properties of the lubricants of the combination of 10%, 15%, 20% and 30% of microgel - lubricating oil In the example 3 described in the following, it is shown that the compositions according to with the invention which exhibit particular characteristics with respect to transparency and stability with respect to separation can be obtained using microgels based on SBR and NBR. It was also found that lubricating greases can be obtained. The composition of the microgel paste is shown in the following table: 1. Lubricating oil 90%, 85%, 80%, 70% 2. Microgel 10%, 15%, 20%, 30% Total 100% Shell Catenex S 932 is a highly refined, paraffinic mineral oil from Deutsche Shell GmbH. Methyl Ester SU is a methyl ester (Radia 7961) from Oleon NV. The refined rape seed oil is an oil of Cereol Deutschland GmbH, which is obtained from renewable raw materials. Baylube 68CL is a polyether from RheinChemie Rheinau GmbH. Nynas T 110 is a hydrogenated naphthenic oil from Nynas Naphthenics AB. The OBR 1210 and OBR 1212 microgels are surface modified rubber gels, cross-linked with SBR-based RheinChemie Rheinau GmbH. OBR 1135 and Micromorph 5P are cross-linked rubber gels which are not surface modified and are based on BR and SBR respectively, RheinChemie Rheinau GmbH. The Micromorph 5P is described in Example 1. The compositions of the OBR 1210 and OBR 1212 microgels are described in Example 2. OBR 1135 is a BR gel; It comprises 97.5% and 2.5% dicumyl peroxide. The microgels are prepared as described in Example 1 for Micromorph 1P.

The fats LÍ-120H, a semi-finished product, and E301 (15%) and M10411, laboratory products from RheinChemie Rheinau GmbH, were also measured as a comparison. The characteristic data of the microgels are summarized in examples 1 and 2.

Preparation of the compositions according to the invention The composition according to the invention was prepared as already described above. In deviation from this, an air pressure of 1 to 5 bar is required in certain cases to transport the material in the homogenizer. The number of steps is established in the following. The rheological properties of the composition were determined with a rheometer, MCR300, from Physica. A plate and cone system, CP 25-1, was used as the measuring body. The measurements were made at 20 ° C. Some measurement results for the microgels described above are shown in the following (Tables 8-10): 20 and 30% of Micromorph 5P / Nynas T110 exuded little lubricating oil and are solid. Only 30% of OBR 1135 and 'OBR 1210 / Nynas T110 exuded little lubricating oil and are solid. 20% of OBR 1135 / rape seed oil and 20% of Micromorph 5P / rape seed oil also show no separation on the surface, even after 1.5 years.

Hardly any separation is also shown with 10% of the same gels in rapeseed oil.

Table 8. Rheological characterization of lubricating greases containing microgel; 20 ° C; cone-plate: measuring system CP 25-1.

The pour point, oil separation capacity and penetration were measured by the method or in accordance with the particular standards: DIN 51801: Pour point: Pour point describes the temperature at which the first drop emerges from the material to be determined and touches the base of the drip container.

DIN 51580: Penetration: Penetration is understood to mean the measurement of the consistency of paste-like materials or waxy solids by penetration of a conical cone cover into the sample. The penetration depth in 1/10 mm is established as the penetration value P. In an untreated sample: Pu In a ground sample: Pm, 60 (after 60 strokes) or PM, 100,000 (after 100,000 strokes).

DIN 51817: Oil separation: Oil separation is a measure of the stability of the grease matrix of base liquid and thickener. The sample was weighed with a weight, for example, at 40 ° C for a certain time. By this means, the base liquid emerges from the fat matrix during loading. The percentage content of base liquid after the charging time at the given temperature was determined.

Table 9. Physical properties of the 30% microgel combinations (Micromorph 5P, OBR 1135, OBR 1210) - lubricating oil (Baylube 68CL, Methyl Ester SU, Nynas T 110, Shell Catenex S932) and M10411 PU grease and Lithium grease 120H for comparison. Point of fluidity, penetration at rest and grinding. Pour point Penetration Penetration Pu / Pm 60 Pm, 60,000 grease LI-120H Methyl Ester SU-177 215/214 249 Micromorph 5P (30%) Baylube 68CL - OBR1210 174/137 238/247 238 (30%) Nynas T110 - OBR 1135 > 280 180/191 196 (30%) Nynas T110 - grease M10411 190/213 320 PU (12%) The oil separation capacity (18h / 40 ° C) is the same for the composition according to the invention of Nynas T110 - OBR 1135 (30%) and fat lithium grease L-120H: 0.29%. The values of Pu low and Pm, 60,000 are typical of fats. This is conformed by the measurements in lithium fat 12 and Pu fat, as can be seen from table 9. The microgel-lubricating oil combinations show little or no difference in the values for the Pu Penetration and the Grinding penetration P, 6o, ooo- Accordingly, the combination of OBR 1210-Baylube 68CL in particular is stable to shear forces.

Table 10. SRV test in 30% microgel combinations (Micromorph 5P, OBR 1210) - lubricating oil (Baylube 68CL, Methyl Ester SU, Shell Catenex S932) and M10411 PU grease and 12 lithium grease for comparison.

The course of the SRV curves shows the following: In contrast to comparison fats, the OBR 1210 grease shows a smooth course of the curve, which ends at the lower level of the coefficient of friction, and a white friction site metal.

Table 11. Wear tests in the 30% microgel combinations (Micromorph 5P, OBR 1210) - lubricating oil (Baylube 68CL, Methyl Ester SU, Shell Catenex S932) and M10411 PU grease and 12 lithium grease for comparison. FBA shock load FBA / load items (by DIN welding method (DIN 51350; DIN balls) 51350, part 4) 1,000 N 1, 420 rpm, 1 min 1, 420 rpm, 1 min grease LÍ-120H without Fuchs 2.60 mm + 1,400 / -1,500 N (P 1031) aggregate Methyl Ester SU - 1.75 mm + 1,800 / -1,900 N Micromorph 5P (303 Baylube 68C - OBR 1210 0.78 mm + 1,800 / -1,900 N (30%) M grease 10411 PU (12%) 3.50 mm <1,400 N in Nynas T110 Table 11 shows that the shock load and FBA articles / solder charge are significantly improved according to the invention. Example 3 shows that the compositions according to the invention having a relatively high content of microgel (15-30%) surprisingly show properties comparable to those of commercial fats (stability towards settling, low oil separation, consistency, etc.). ) but more favorable properties (high shear stability), ie almost no change in penetration values after milling with 60,000 strokes) and exceptionally high pour points as otherwise only achieved by heat-resistant greases, such as such as PU fats or complex Ca fats. Furthermore, these compositions exhibit a positive action on friction coefficients, which is completely not typical of standard fats.

Example 4: SBR OBR 1312B gel, modified by hydroxyl groups, in Baylube 68CL In Example 4 described below, it is shown that, using SBR-based microgels which are modified by hydroxyl groups, the compositions according to the invention which mainly contain primary particles having an average particle diameter of about 43 nm can be prepared in a homogenizer by applying 900 to 1000 bar with 2 to 6 steps. The composition is shown in the following table: 1. Baylube 68CL 97.8 2. OBR 1312B 2.0 3. Dispersion aid 0.2 Total 100.0 Baylube 68CL is a polyether from RheinChemie Rheinau GmbH. The OBR 1312B microgel is a cross-surface modified rubber gel based on SBR from RheinChemie Rheinau GmbH (Table 12). The microgel was prepared analogously to Example 1 for Micromorph 1P.

Table 12. Composition of OBR 1312B microgel.

The characteristic data of OBR 1312B are summarized in Table 13.

Table 13. OBR 1312B properties.

For the preparation of the composition according to the invention, Baylube 68CL was initially introduced into the preparation vessel and OBR 1312B was added, while being stirred by means of a dissolution vessel. The mixture was allowed to stand for at least one day, and then further processed with the homogenizer. The composition according to the invention was introduced into the homogenizer at room temperature and passed through the homogenizer 6 times under 960 bar in batch operation. During the first step the microgel paste was heated to about 40 ° C, and during the second step to about 70 ° C. Then, the microgel paste was cooled to room temperature and dispersed a third and fourth time. This was repeated until six steps were achieved. The particle diameter of the latex particles was determined by means of ultracentrifugation (W. Scholtan, H. Lange, "Bestimmung der Teilchengroßenverteilung von Latices mit der Ultrazentrifuge", Kolloid-Zeitschrift und Zeitschrift für Polymere (1972) volume 250, issue 8). The particle size distributions of the original latex, not yet dried, of the OBR 1312B microgel and the OBR 1312B redispersed in Baylube 68CL (TZE 122) can be seen in the following figures. It can be seen that, surprisingly, almost the entire amount of the powder dried and thus of agglomerated OBR has successfully redispersed below the primary particles, the average particle diameter of the redispersed mixture is still below the average particle diameter of the original latex. It will also be noted that the measurement was made in a redispersed sample which has been stored for 6 months at room temperature, that is, the dispersion surprisingly remained stable for 6 months.

Due to its low content of re-agglomerated particles, the redispersed composition is also highly transparent. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (39)

CLAIMS Having described the invention as above, the contents of the following claims are claimed as property:

1. Composition, characterized in that it comprises at least one non-crosslinkable organic medium which has a viscosity of less than 30,000 mPas at a temperature of 120 ° C and at least one microgel.

2. Composition in accordance with the claim 1, characterized in that the non-crosslinkable organic medium has a viscosity of less than 1,000 mPas at a temperature of 120 ° C.

Composition according to claim 1, characterized in that the non-crosslinkable organic medium has a viscosity of less than 200 mPas at a temperature of 120 ° C.

4. Composition according to claim 1 to 3, characterized in that the primary particles of the microgel have an approximately spherical geometry.

Composition according to claims 1 or 4, characterized in that the deviation of the diameters of a single primary particle of the microgel, defined as [(di-d2) / d2] x 100, where di and d2 are any of the two desired diameters of the primary particle and di es > d2, is less than 250%.

6. Composition according to claim 5, characterized in that the deviation is less than 50%.

Composition according to one of claims 1 to 6, characterized in that the primary particles of the microgel have an average particle size of 5 to 500 nm.

Composition according to one of claims 1 to 6, characterized in that the primary particles of the microgel have an average particle size of less than 99 nm.

Composition according to one of claims 1 to 8, characterized in that the microgels have contents which are insoluble in toluene at 23 ° C of at least about 70% by weight.

Composition according to one of claims 1 to 9, characterized in that the microgels have a swelling index in toluene at 23 ° C of less than about 80.

11. Composition according to one of claims 1 to 10, characterized because the microgels have glass transition temperatures of -100 ° C to +120 ° C.

Composition according to one of claims 1 to 11, characterized in that the microgel is a cross-linked microgel which is not cross-linked by high energy radiation.

Composition according to one of claims 1 to 12, characterized in that the microgels have a vitreous transition interval width greater than about 5 ° C.

Composition according to one of Claims 1 to 13, characterized in that the microgels are obtainable by emulsion polymerization.

15. Composition according to one of claims 1 to 14, characterized in that the microgel is rubber-based.

Composition according to one of claims 1 to 15, characterized in that the microgel is based on random homopolymers or copolymers.

Composition according to one of Claims 1 to 16, characterized in that the microgel is modified by functional groups which are reactive towards C = C double bonds.

Composition according to one of claims 1 to 17, characterized in that the non-crosslinkable medium is at least one compound which is selected from the group consisting of solvents, saturated or aromatic hydrocarbons, polyether oils, synthetic ester oils and that occur naturally, polyether-ester oils, phosphoric acid esters, silicon-containing oils, halohydrocarbons and liquid renewable raw materials.

Composition according to one of claims 1 to 18, characterized in that it comprises 0.1 a 90% by weight of the microgel, based on the total amount of the composition.

Composition according to one of claims 1 to 19, characterized in that it comprises 10 to 99.9% by weight of the non-crosslinkable organic medium.

21. Composition according to one of claims 1 to 20, characterized in that it additionally comprises fillers and / or additives.

Composition according to one of Claims 1 to 21, characterized in that it has been prepared by mixing the non-crosslinkable medium and the microgel by means of a homogenizer, a bead mill (stirred ball mill), a triple roller mill, a single or multiple screw extruder, a kneader, an Ultra-Turrax apparatus and / or a dissolution vessel.

23. Composition according to claim 22, characterized in that it has been prepared by means of a homogenizer, a bead mill (stirred ball mill), a triple roller mill or a dissolving vessel.

24. Composition according to one of claims 1 to 23, characterized in that it has a viscosity of 2 mPas up to 50,000,000 mPas at a speed of 5 s-1, determined with a cone and plate measuring system in accordance with DIN 53018 at 20 ° C.

Composition according to one of claims 1 to 24, characterized in that the microgel has a swelling index in toluene at 23 ° C from 1 to 15.

Composition according to one of claims 1 to 25, characterized in that the microgels have contents which are insoluble in toluene at 23 ° C of at least 95% by weight.

Composition according to one of Claims 1 to 26, characterized in that the microgel is not modified with hydroxyl groups.

28. Composition according to one of claims 1 to 27, characterized in that the microgel is not modified.

29. Use of the composition according to one of claims 1 to 28 for incorporation into thermoplastics, rubbers or thermoplastic elastomers.

30. Use of the composition according to one of claims 1 to 28 for the preparation of polymers containing microgel.

31. Use according to claim 30 for the preparation of rubbers containing microgel.

32. Use according to claim 30 for the preparation of thermoplastic elastomers containing microgel.

33. Use of the composition according to one of claims 1 to 28 for the preparation of lubricants, shaped articles or coatings.

34. Use of the compliant composition of claim 33 for the preparation of lubricating greases and modified lubricating oils.

35. Use of the composition according to one of claims 1 to 28 as an additive for plastics, rubbers, coating compositions or lubricants.

36. Use of microgels as a rheological additive, in particular as a thickener or thixotropic agent, in non-crosslinkable organic media which have a viscosity of less than 30,000 mPas at a temperature of 120 ° C.

37. Plastics, rubbers, thermoplastic elastomers, coating compositions or lubricants, characterized in that they comprise the compositions according to one of claims 1 to 28.

38. Process for the preparation of the composition according to one of claims 1 to 28 , characterized in that the components (A) and (B) are jointly subjected to treatment with a homogenizer, bead mill, triple roller mill, a single or multiple screw extruder, a kneader and / or a dissolution vessel.

39. Process for the preparation of the composition according to one of claims 1 to 28, characterized in that the components (A) and (B) are jointly subjected to treatment with a homogenizer, a bead mill, a triple roller mill and / or a dissolution container.