MX2008010375A - Nanoscale superparamagnetic poly(meth)acrylate polymers - Google Patents

Abstract

The invention relates to hybrid materials comprising polymers which envelop nanoscale, superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic powders, to a process for producing these materials and to their use.

Description

POLYMERS OF POLYMER (MET) SUPERPARAMAGNETIC ACRILATE TO NANOESCALA Description The invention relates to hybrid materials comprising polymers that involve superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic nanoscale powders, a method for producing said materials, and their use. Prior art In DE 100 37 883 (Henkel) 0.1% by weight - 70% by weight of magnetic particles are used to be able to heat a substrate by microwave radiation. The substrate used is an adhesive, which sets as a result of heating. Heating of the adhesive can also be used to soften the adhesive. The interaction between the particles and the polymer are not described. DE 100 40 325 (Henkel) describes a method involving the application of an activatable microwave detonator and a thermoimpregnating adhesive to substrates and the use of microwaves to carry out heating and bonding. DE 102 58 951 (Sus Tech GmbH) describes an adhesive layer comprising a composite of ferrite particles (surface modified with oleic acid) and PE, PP, EVA and copolymers. The ferrite particles could also have been modified with silanes, quaternary ammonium compounds and saturated / unsaturated fatty acids and salts of strong inorganic acids. DE 199 24 138 (Henkel) describes an adhesive composition with nanoscale particles. EP 498 998 describes a method for heating a polymer by microwaves, where the ferromagnetic particles are dispersed in the polymeric matrix and the microwaves are scattered. The ferromagnetic particles are dispersed only in the polymeric matrix. WO 01/28 771 (Loctite) describes a curable mixture comprising 10% by weight - 40% by weight of particles that can absorb microwaves, a curable component, and a polymerization agent. The components are only mixed. WO 03/04 2315 (Degussa) discloses an adhesive compound for producing thermosetting plastic, comprising a polymer mixture and degrading particles, the degrading particles are composed of fillers, which are ferromagnetic, ferrimagnetic, superparamagnetic or paramagnetic, and degrading units joined together. chemical way to the filler particles. The filler particles could also have been modified in the surface. The filler particles could have a core / shell structure. The adhesive association obtained can be divided again by heating it to a temperature higher than the maximum temperature or at a temperature sufficient to break the chemical bonds of the thermally unstable groups of the modified filler particles on its surface. DE-A-101 63 399 discloses a nanoparticulate preparation having a bound phase and, dispersed therein, at least one particle phase of nano-scale superparamagnetic particles. The particles have a volume average particle diameter in a range of 2 to 100 nm and contain at least one mixed metal oxide of the general formula MII III04, where Mil refers to a first metal component which comprises at least two different, divalent metals, and MUI means a major metal component comprising at least one trivalent metal. The ligated phase can be composed of water, an organic solvent, a polymerizable monomer, a polymerizable monomer mixture, a polymer and mixtures. The preparations are preferred in the form of an adhesive compound. It is an object of the invention to provide a material composed of superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic nanoscale particles.

The objective is achieved by the provision of a hybrid material comprising superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic nanoscale particles enveloped by polymers, in particular by poly (meth) acrylates. The objective is also achieved by a miniemulsion polymerization method. Said method, in contrast to conventional methods of emulsion polymerization, allows the preparation of the core particles (inorganic particle) / shell (polymer). The objective is achieved by a method of Claim 16. The cores may be wrapped by a shell, but may also be two or more shells, or by a shell with gradients. The wrappers may have similar or different polymer compositions, or in a single wrap the polymer composition may vary (gradients). Through the coating of the superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic particles at the nanoscale with the polymer, a better interaction of the particle with the polymer envelope is achieved and therefore it is possible to achieve the heating of the adhesive with fewer superparamagnetic, ferromagnetic particles. , ferrimagnetic or paramagnetic at the nanoscale of those that were needed in the prior art. The heating can be carried out by means of conventional forms of energy, but it is preferred that it be through inductive energy. With the hybrid materials of the invention it is possible to prepare adhesives from the stage and the 2nd stage. The 2nd stage adhesives with the hybrid material of the invention are distinguished by an adhesive bonding effect (preliminary adhesive bond, positioning) and a final adhesive bond through the introduction of high energy, into a material. The superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic nanoscale particles are emulsified, without previous activation or preliminary coating, in a system formed of one or more monomers, water and an inert solvent, where when considered appropriate with the help of an emulsifier and / o of a hydrophobic agent, and the polymerization starts later by the usual techniques. The superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic nanoscale particles may be enclosed in a core / shell structure with one or more polymer shells or polymer blends. In a first step, a first shell of the core / shell system is applied by mini-emulsion polymerization. Any subsequent wrapping is formed in situ by measured addition of the monomeric current.

The monomers used are preferably mixtures of (meth) acrylates. Polymeric methacrylates are generally obtained by free radical polymerization of mixtures which are composed of methyl methacrylate. In general these mixtures contain at least 40% by weight, preferably at least 60% by weight and with particular preference at least 80% by weight, based on the weight of the monomers, of methyl methacrylate. Furthermore, these mixtures for the preparation of polymethyl methacrylates can be composed of more (meth) acrylates which are copolymerizable with methyl methacrylate. The term (meth) acrylates herein refers not only to methacrylate, etc., for example, but also to acrylate, such as methyl acrylate, ethyl acrylate, etc., for example, and additional mixtures of both. These monomers are well known. They include, among others, (meth) acrylates which are derived from saturated alcohols, such as methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, for example; (meth) -acrylates which are derived from unsaturated alcohols, such as oleyl (meth) acrylate, 2-propynyl (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, for example; aril (meth) acrylate, such as benzyl (meth) acrylate or phenyl (meth) acrylate, with the possibility that the aryl radicals in each case are irreplaceable or replaceable up to four times; cycloalkyl (meth) acrylates, such as 3-vinylcyclohexyl (meth) acrylate, bornyl (meth) acrylate; hydroxylalkyl (meth) acrylate, such as 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxy-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; glycol di (meth) acrylates, such as 1,4-butanediol (meth) acrylate, ether (meth) acrylates of ether alcohols, such as tetra-hydrofurfuryl (meth) acrylate, vinyloxyethoxyethyl (meth) acrylate; amides and nitriles of (meth) acrylic acid, such as N- (3-dimethylaminopropyl) (meth) acryl-amide, N- (diethylphosphono) (meth) acrylamide, l-met-acryloylamido-2-methyl-2-propanol; methacrylates containing sulfur, such as ethylsulfinyl ethyl (meth) acrylate, 4-thiocyanatobutyl (meth) acrylate, ethyl-sulfonylethyl (meth) acrylate, thiocyanatomethyl (meth) acrylate, methylsulfinylmethyl (meth) acrylate, bis ((meth) acryloyloxyethyl sulfide); polyfunctional (meth) acrylates, such as trimethyloylpropane tri (meth) acrylate. In addition to the (meth) acrylates listed above, the polymerization compositions may also contain more unsaturated monomers which are copolymerizable with methyl methacrylate and with the (met) acrylates mentioned above. Such monorails include, among others, 1-alkenes, such as hex-l-ene, hept-l-ene; branched alkenes, such as vinylcyclohexane, 3, 3-dimethyl-1-propene, 3-methyl-1-diisobutylene, 4-methylpent-1-ene, for example; acrylonitrile; vinyl esters, such as vinyl acetate; styrene, substituted styrenes having an alkyl substituent in the side, such as [alpha] -methylstyrene chain [alpha] ethylstyrene, for example, substituted styrenes with an alkyl substituent on the ring such as vinyltoluene and p-methylstyrene, halogenated styrene such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes, for example; vinyl heterocyclic compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl - 5-vinylpyridine, 3-ethyl -4-vinylpyridine, 2, 3 -dimietil-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3 -vinilcarbazol, 4 -vinilcarbazol, 1-vinylimidazole, 2-methyl-l-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3 -vinilpirrolidina, N-vinylcaprolactam, N-vinilbutirolactam, vinyloxolane, vinylfuran, vinylthiophene , vinyl thiolane, vinyl thiazoles and hydrogenated vinyl thiazoles, vinyl oxazoles and vinyl -oxazoles hydrogenated; vinyl and isopropyl ethers; maleic acid derivatives, such as maleic anhydride, methylmaleic anhydride, maleimide, methylmaleimide, for example; and diens, as is the divinylbenzene, for example. In general these comonomers are used in an amount of 0% to 60% by weight, preferably 0% to 40% by weight and particularly preferably from 0% to 20% by weight, based on the weight of the monomers, with the possibility that the compounds are used individually or as a mixture. Polymerization usually starts by the use of known free radical catalysts. Preferred catalysts include, among others, well known azo catalysts in the art, such as AIBN and 1, 1-azobisciclohexan-carbonitrile, catalysts soluble free radical water such as peroxysulfates or hydrogen peroxide, for example, and also peroxy such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, methyl isobutyl ketone peroxide, peroxide cilcohexanona, dibenzoyl peroxide, tert-butyl proximal compounds benzoate, tert-butyl peroxyisopropyl carbonate, 2, 5-bis (2-ethylhexanoylperoxy) -2, 5-dimethylhexane, tert-butylperoxy -2-ethylhexanoate, tert-butylperoxy-3, 5, 5-trimethylhexanoate, dicumyl peroxide , 1,1-bis- (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butyl peroxy) -3,3,5-trimethylcyclohexane, cumyl hydroperoxide, tert-butyl hydroperoxide, bis (4-tert-butylcyclo) -hexyl) peroxydicarbonate, mixtures between two or more above-mentioned compounds, and also mixtures of the aforementioned compounds with not mentioned compounds which can form free radicals in the same way. These compounds are often used in an amount of 0.01% to 10% by weight, preferably from 0.1% to 3% by weight, based on the weight of the monomers. In this context it is possible to use different poly (meth) acrylates which differ for example in molecular weight or in monomeric composition. The hydrophobic agents can also be added to a hybrid material. Some suitable examples include hydrophobes from the group of hexadecanes, tetraethylsilanes, oligostyrenes, polystyrenes or hexafluorobenzenes. Particular preference is given to copolymerizable hydrophobes, since they do not exude in the course of subsequent use. Particular preference is given to (meth) acrylates derived from saturated alcohols with C 6-24 atoms, with the possibility that the alcohol residue is linear or branched. Thus, for example, a monomeric composition comprises ethylenically unsaturated monomers of the formula (I) (Figure) (I), wherein R is hydrogen or methyl, Rl is a linear or branched alkyl radical with 6 to 40 carbon atoms. carbon, preferably from 6 to 24 carbon atoms, R2 and R3 are independently hydrogen or a group of the formula -COOR ', where R' represents a hydrogen or a linear or branched alkyl radical with 6 to 40 carbon atoms. carbon. The ester compounds with long-chain alcohol residue can be obtained, for example, by the reaction of (meth) acrylates, fumarates, maleates and / or the corresponding acids with long-chain fatty alcohols, the product usually comprising a mixture of esters , such as, for example, (meth) acrylates with alcohol residues whose chains differ in length. These fatty alcohols include, among others, Oxo Alcohol- * 7911 and Oxo Alcohol "* 7900, Oxo Alcohol- * 1100 from Monsanto, Alphanol? 79 from ICI, Nafol? 1620, Alfol- * 610 and Alfol? 810 from Condea; Epal; ? 610 and Epal? 810 from the Ethyl Corporation, Linevol? 79, Linevol? 911 and Dobanol? 25L from Shell AG; Lial 125 from Augusta "* Milan; Dehydad- * and Lorol- * by Henkel KGaA, and Linopol- * 7-11 and Acropol? 91 Ugine Kuhlmann. The aforementioned ethylenically unsaturated monomers can be used individually or as mixtures. In preferred embodiments of the method of the invention at least 50 percent by weight of the monomers, preferably at least 60 percent by weight of monomers, particularly preferably more than 80% by weight of the monomers, based on the total weight of the ethylenically unsaturated monomers, are (meth) acrylates. Further preference is given to monomer compositions containing at least 60 percent by weight, particularly preferably more than 80% by weight, of (meth) acrylates having alkyl or heteroalkyl chains containing at least 6 carbon atoms , based on the total weight of the ethylenically unsaturated monomers. In addition to (meth) acrylates, preference is also given to maleates and fumarates which additionally have long chain alcohol residues. As an example it is possible to use hydrophobes which derive from the group of alkyl (meth) acrylates having from 10 to 30 carbon atoms in the alcohol group, especially undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, 2-methylhexadecyl ( met) acrylate, heptadecyl (meth) acrylate, 5-isopropylheptadecyl (meth) acrylate, 4-tert-butyloctadecyl (meth) acrylate, 5-ethylctadecyl (meth) acrylate, 3-isopropyloctadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, cetyleicosyl (meth) acrylate, stearylenyl (meth) acrylate, docosil (meth) acrylate, eicosyltetratriacontyl (meth) acrylate, lauryl (meth) acrylates, stearyl (meth) acrylates, behenyl (meth) acrylates and / or methacrylic esters and mixtures thereof. In order to control the molecular weight of the polymers it is possible to carry out the polymerization in the presence of regulators, if desired. Examples of regulators include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, hydroxylammonium sulfate and hydroxylammonium phosphate. It is also possible to use regulators which contain sulfur in an organically bound form, such as organic compounds containing SH groups, such as thioglycolaacetic acid, mercaptopropionic acid, mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptohexanol, dodecyl mercaptan and tert-dodecyl mercaptan. As regulators it is also possible to use hydrazine salts such as hydrazinium sulfate. The regulator amounts, based on the monomers to be polymerized, are 0% to 5%, preferably 0.05% to 0.3% by weight. The nuclei of the invention, the superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic particles at the nanoscale, are composed of a matrix and a domain. The particles are composed of magnetic metal oxide domains having a diameter of 2 to 100 nm in a non-magnetic metal oxide matrix or a metal dioxide matrix. The magnetic metal oxide domains can be selected from a group of ferrites, with particular preference in the group of iron oxides. They may be surrounded in turn, totally or partially, by a non-magnetic matrix, for example, of the group of silicon oxides. The superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic particles at the nanoscale are in the form of powder. The powder may be composed of added primary particles. They are said to be added in the sense of the invention with reference to three-dimensional structures of combined primary particles. The union of two or more aggregates can form agglomerates. Said agglomerates can be easily separated again. In contrast, it is not possible in a general way to decompose the aggregates into primary particles. The aggregate diameter of the superparamagnetic powder may preferably be greater than 100 nm and less than 1 pm. Preferably, the superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic powder can have a diameter at least in a spatial direction of no more than 250 nm. With respect to the domains, reference is made to regions within the matrix that are spatially separated one from the other. The domains of superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic powder have a diameter between 2 and lOOnm. The domains may also contain non-magnetic regions which does not contribute to the magnetic properties of the powder. In addition it is also possible that there are magnetic domains which by virtue of their size do not show superparamagnetism, and which causes a remanence. This leads to an increase in volume-specific saturation magnetization. The proportion of these domains compared to the number of superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic domains is, however, low. According to the present invention the number of superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic domains present in the superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic powder is such that it allows the preparation of the invention to be heated by means of an alternating magnetic or electromagnetic field. The domains of the superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic powder may be surrounded in whole or in part by the surrounding inorganic matrix. The fact that they are surrounded in a partial way means that the Individual domains can protrude from the surface of an aggregate. The domains may contain one or more metal oxides. The magnetic domains may preferably contain the oxides of iron, cobalt, nickel, chromium, europium, yttrium, samarium or gadolinium. In these domains the metal oxides may be present in a uniform modification or in different modifications. A magnetic domain that is particularly preferred is iron oxide in the form of gamma-Fe203 (y-Fe203), Fe304, gamma-Fe203 (y-Fe203) and / or Fe30 mixtures. The magnetic domains can then be present in the form of a mixed oxide of at least two metals, with the metallic components iron, cobalt, nickel, tin, zinc, cadmium, magnesium, manganese, copper, barium, magnesium, lithium or yttrium. The magnetic domains can additionally be substances with the general formula MIIFe204, where Mil is a metallic component comprising at least two different divalent metals. Preferably one of the divalent metals can be manganese, zinc, magnesium, cobalt, copper, cadmium or nickel. It is also possible that the magnetic domains are composed of ternary systems of the general formula (Mal- x-y MbxFey) IIFe2III04, where Ma and Mb, respectively, are the metals manganese, cobalt, nickel, zinc, copper, magnesium, barium, yttrium, tin, lithium, cadmium, magnesium, calcium, strontium, titanium, chromium, vanadium, niobium, molybdenum, with x = 0.05 to 0.95, y = 0 to 0.95 and x + y = l. Particular preference can be given to ZnFe204, MnFe20", Mn0.6Feo.4 e204, n0.5Zno.5Fe204, Zn0.iFei.9O4, Zn0.2Fei.8O4, Zn0.3Fei. O4, Zn0.4Fei.6O4 or Mn0.39Zno.27Fe2.3404, MgFe203, gi.2Mn0.2Fei.6O4, Mg1.4Mn0.4Fei.2O4, Mgi.6Mno.6Feo.804, Mgx.eMno.eFeo ^ O, ,. The metal oxide option of the non-magnetic matrix is not further restricted. Preference may be given to oxides of titanium, zirconium, zinc, aluminum, silicon, cerium or tin. For the purposes of the invention the metal oxides also include carbon dioxides, such as silicon dioxide, for example. It is also possible that the matrix and / or the domains are in amorphous and / or crystalline form. The proportion of the magnetic domains in the powder is not restricted because there is a spatial separation of the matrix and domains. The fraction of the magnetic domains in the superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic powder can be preferably 10% to 100% by weight. Suitable superparamagnetic powders are described for example in EP-A-1284485 and also in DE 10317067, hereby incorporated by reference in their entirety. The preparation of the invention may preferably have a superparamagnetic powder fraction in a range of 0.01% to 60% by weight, preferably in a range of 0.05% to 50% by weight and with a very particular preference in a range of 0.1% to 10% by weight. The powder can be prepared by means of different preparation methods. For example, a silicon chloride can be evaporated at an elevated temperature and is carried along with a carrier gas to the mixing zone of a combustion furnace. In addition, an aerosol, obtained from an aqueous solution of iron chloride in the mixing zone with the combustion furnace is introduced by a carrier gas. There, the homogenously mixed gas / aerosol mixture is burned at an adiabatic combustion temperature. After the reaction, in a known manner, the reaction gases and the resulting powder are cooled and separated by means of a filter from the waste gas stream. In a subsequent step, by treatment with nitrogen containing steam, the remaining hydrochloric acid residues are removed from the powder. Next, the table gathers, as an example, some physicochemical information for superparamagnetic powders.

Table 1: Physicochemical values of superparamagnetic powders Calculated in Fe203; the domains contain Fe203 and Fe304; Fe203 33% by weight The resulting superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic powder is then processed with a mini-emulsion polymerization process to result in the hybrid materials of the invention. The polymerization by miniemulsion can be carried out in the following manner: a) In a first step the nanoscale powder is dispersed in the monomers or in the monomer mixture or in water, b) In the second step a monomer or monomer mixture is dispersed with hydrophobic agents and emulsifier in water. c) In the third step, the dispersions of a) and b) are dispersed with the help of an emulsifier by means of ultrasound, membrane, rotor / stator system, stirrer and / or high pressure, d) polymerization of the dispersion of c is initiated. ) thermally. The fraction of superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic powder in the polymers can be between 1-99% by weight. The hybrid materials produced in this manner are preferably used in adhesives. Preference is given to a core construction (hybrid material) / sheath (s) (polymers). Preferably a first (inner) shell comprises polymers or polymer blends having gel consistency at room temperature in plasticizers or adhesives containing plasticizers or in epoxy adhesives. At higher temperatures, on the other hand, these polymers enter into degradative reactions with the plasticizers. The monomers of the group of the (meth) acrylates and imidazoles are particularly suitable for this purpose, preferably the vinylimidazoles. There may also be presence of auxiliaries and additives, such as emulsifiers and hydrophobic agents, for example. In the case of a multiple casing construction, the outer casing preferably consists of a polymer or polymer mixture which does not have a gel consistency at room temperature in the matrix (an adhesive, for example) but if it has gel consistency in the matrix at an elevated temperature. An outer shell composed of polymethyl methacrylate or mixtures with vinylimidazole is preferred. These adhesives are used in automotive construction, aircraft construction, shipbuilding, railway vehicle construction and space travel technology. The following examples are provided to better illustrate the present invention, but do not serve as a restriction of the invention to the features disclosed herein. Examples Implementation of the polymerization, by miniemulsion to apply a coating Example 1: 7.13 g of methyl methacrylate, 7.13 g of butyl methacrylate, 0.75 g of 2-dimethylaminoethyl methacrylate, 0.6 g of hexadecane and 1.5 g of hexadecane are homogenized in a beaker. MagSilicon (Si02 / Fe203) by using an Ultraturrax for 1 minute and then homogenized with ultrasound for 1 minute. In a second beaker, 5.0 g of Texapon are mixed in 15% form (Cognis, Germany) and 80 g of water by stirring. The solution of the first beaker is introduced into that of the second beaker and the combined solution is subjected to ultrasound with ice cooling for 4 minutes. As an initiator, 0.22 g of tert-butyl per-2-ethylhexanoate is introduced, and the solution is poured into a ball flask and heated to 80 ° C. The polymerization time is 3 hours. The ultrasonic processor UP 200 S (Dr. Hielscher GmbH, Teltow) used in the experiments has an effective power of 150 W, which can be regulated continuously from 20% to 100%, a frequency of 24 kHz and an energy density maximum of 12 to 600 W / cm2 in accordance with Sonotrode (here, Sonotrode S14D, diameter 14 mm, length 100 mm). For the experiments, the effective potency was established at 100%. Example 2: 7.43 g of methyl methacrylate, 7.13 g of butyl methacrylate, 0.45 g of 2-methacryloyloxyethyl phosphate, 0.6 g of hexadecane and 1.5 g of MagSilicon (SiO2 / Fe203) are homogenized in a beaker using an Ultraturrax. for 1 minute and then homogenized with ultrasound for 1 minute. In a second beaker is they mix 1.0 g of Texapon in 15% form (Cognis, Germany) and 80 g of water by stirring. The solution of the first beaker is introduced into that of the second beaker and the combined solution is subjected to ultrasound with ice cooling for 7 minutes. As an initiator, 0.22 g of tert-butyl per-2-ethylhexanoate is introduced, and the solution is poured into a ball flask and heated to 80 ° C. The polymerization time is 3 hours. Example 3: 7.49 g of methyl methacrylate, 7.43 g of butyl methacrylate, 0.09 g of 2-methacryloyloxyethyl phosphate, 0.6 g of hexadecane and 1.5 g of MagSilicon (SiO2 / Fe203) are homogenized in a beaker through the use of a Ultraturrax for 1 minute and then homogenized with ultrasound for 1 minute. In a second beaker, 5.0 g of Texapon are mixed in 15% form (Cognis, Germany) and 80 g of water by stirring. The solution of the first beaker is introduced into that of the second beaker and the combined solution is subjected to ultrasound with ice cooling for 7 minutes. As an initiator, 0.22 g of tert-butyl per-2-ethylhexanoate is introduced, and the solution is poured into a ball flask and heated to 80 ° C. The polymerization time is 3 hours. Example 4: In a beaker, 7.43 g of methyl methacrylate, 7.13 g of butyl methacrylate, 0.45 g of 2-methacryloyloxyethyl phosphate, 0.6 g of hexadecane and 1.5 g of MagSilicon (SiO / Fe203) by using an Ultraturrax for 1 minute and then homogenizing with ultrasound for 1 minute. In a second beaker, 5.0 g of Texapon are mixed in 15% form (Cognis, Germany) and 80 g of water by stirring. The solution of the first beaker is introduced into that of the second beaker and the combined solution is subjected to ultrasound with ice cooling for 7 minutes. As an initiator, 0.22 g of tert-butyl per-2-ethylhexanoate is introduced, and the solution is poured into a ball flask and heated to 80 ° C. The polymerization time is 3 hours. Example 5: 7.5 g of methyl methacrylate, 7.5 g of butyl methacrylate, 0.6 g of hexadecane and 1.5 g of MagSilicon (Si02 / Fe203) are homogenized in a beaker using an Ultraturrax for 1 minute and then homogenized with Ultrasound for 1 minute. In a second beaker, 5.0 g of Texapon are mixed in 15% form (Cognis, Germany) and 80 g of water by stirring. The solution of the first beaker is introduced into that of the second beaker and the combined solution is subjected to ultrasound with ice cooling for 7 minutes. As an initiator, 0.22 g of tert-butyl per-2-ethylhexanoate is introduced, and the The solution is poured into a ball flask and heated to 80 ° C. The polymerization time is 3 hours. Example 6: 7.13 g of methyl methacrylate, 7.13 g of butyl methacrylate, 0.75 g of 2-dimethylaminoethyl methacrylate, 0.6 g of hexadecane and 1.5 g of MagSilicon (SiO2 / Fe203) are homogenized using a Ultraturrax in a beaker. for 1 minute and then homogenized with ultrasound for 1 minute. In a second beaker, 5.0 g of Texapon are mixed in 15% form (Cognis, Germany) and 80 g of water by stirring. The solution of the first beaker is introduced into that of the second beaker and the combined solution is subjected to ultrasound with ice cooling for 7 minutes. As an initiator, 0.22 g of tert-butyl per-2-ethylhexanoate is introduced, and the solution is poured into a ball flask and heated to 80 ° C. The polymerization time is 3 hours.

Claims (23)

1. CLAIMS 1. Hybrid material comprising superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic nanoscale particles surrounded by polymers.
2. 2. Hybrid material according to claim 1, characterized in that the superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic particles at the nanoscale are surrounded by poly (meth) acrylates.
3. 3. Hybrid material according to claim 1, characterized in that the wrapping polymers have a single layer or a multi-layer construction.
4. 4. Hybrid material according to claim 1, characterized in that the core is composed of superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic particles at the nanoscale of the group of ferrites.
5. 5. Hybrid material according to claim 4, characterized in that the core is composed of superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic nanoscale particles of the group of ferrites wrapped in silicon oxides.
6. 6. Hybrid material according to claim 4, characterized in that the core is composed of superparamagnetic, ferromagnetic, ferrimagnetic or paramagnetic nanoscale particles of the group of iron oxides enveloped by silicon oxides.
7. 7. Hybrid material according to claim 1, characterized in that the first shell comprises polymers which have a gel consistency in plasticizers or in adhesives containing plasticizers or in epoxy adhesives.
8. 8. Hybrid material according to claim 1, characterized in that the first shell comprises polymers or polymer blends that at high temperatures enter into plasticizing degrading reactions.
9. 9. Hybrid material according to claim 1, characterized in that the polymers in the first shell are composed of one or more monomers of the group of the (meth) acrylates and imidazoles.
10. 10. Hybrid material according to claim 9, characterized in that the polymers in the first shell are vinylimidazole compounds.
11. 11. Hybrid material according to claim 1, characterized in that the auxiliaries and subsequent additives are present.
12. 12. Hybrid material according to claim 1, characterized in that emulsifiers and hydrophobic agents are present.
13. 13. Hybrid material according to claim 1, characterized in that the outer shell or the shells are / are composed of polymers or polymer blends that do not have gel consistency in the matrix at temperature environment and polymer or polymer blends that have gel consistency in the matrix at elevated temperature.
14. 14. Hybrid material according to claim 13, characterized in that the outer casing or casings are / are composed of mixtures of polymethyl methacrylate and vinyl imidazole.
15. 15. Hybrid material according to claim 13, characterized in that the outer casing or casings are / are composed of polymethyl methacrylate.
16. 16. Method for producing hybrid materials according to Claim 1 by mini-emulsion polymerization.
17. 17. A method for producing hybrid materials according to claim 1, characterized in that a) the nanoscale powder is dispersed in the monomers or monomer mixtures or in water, b) the monomers or monomer mixtures are dispersed with hydrophobic agents, emulsifiers and water, c) the dispersions of a) and b) are dispersed and d) are subsequently polymerized.
18. 18. Method for producing hybrid materials according to claim 17, characterized in that c), the dispersions of a) and b) are dispersed by means of ultrasound, membrane, high pressure, rotor / stator system and / or agitated.
19. 19. The use of the hybrid materials according to claim 1 in adhesives.
20. 20. The use of the hybrid materials according to Claim 1 as a one component adhesive.
21. 21. The use of the hybrid materials according to Claim 1 in an adhesive matrix as a 2nd stage adhesive.
22. 22. The use of the hybrid materials according to Claim 21 in an epoxy matrix as a 2nd stage adhesive.
23. 23. The use of the adhesives according to claim 19 and 22 in automotive construction, construction of aircraft, construction of ships, construction of railway vehicles and technology for space travel.