DE102008001583A1 - Emulsion polymer, is obtained by polymerizing mixture, where mixture comprises one or multiple monomers from mono-functional methacrylate monomers, styrene or vinyl, and copolymerizable monomer - Google Patents

Abstract

The emulsion polymer is obtained by polymerizing a mixture. The mixture comprises 5-99.9 wt.% of one or multiple monomers from mono-functional methacrylate monomers, styrene or vinyl, and 0-70 wt.% of one or multiple copolymerizable monomers. 0-20 wt.% of one or multiple unsaturated vinyl compounds, 0-20 wt.% of one or multiple polar monomers, and 0.1-95 wt.%, preferably 10-60 wt.%, particularly 20-50 wt.% of an activator. The activator having general formula (I). R 1>H or methyl, preferably methyl; X : linear or branched alkanediyl with 1-18C atoms, ethylene or hydroxy propylene group, which are substituted single or multiple times with hydroxyl or 1-4C alkoxy; R 2>H or linear or branched alkyl residue with 1-12C, methyl, ethyl or 2-hydroxy ethyl, which are substituted single or multiple times with hydroxyl or 1-4C alkoxy, where the hydroxyl group is esterified with methacrylic acid; and R 3>, R 4>, R 5>, R 6> and R 7>H or linear or branched alkyl or alkoxy with 1-8C, which are substituted single or multiple times with hydroxyl, and if necessary two of the residue R 3>-R 7> are connected with each other to 5-7 membered ring and form a condensed aromatic ring system with phenyl residue. An independent claim is also included for a redox initiator system for hardening two or multi-component systems for use in adhesives, casting resins, floor coatings and other reactive coatings, sealant materials, impregnation materials, embedding materials, materials for the production of synthetic marble and other synthetic rocks, materials for reactive plugs, dental materials, porous plastics molds for ceramic objects, or in unsaturated polyester resins and vinyl ester resins with a controllable pot life, which contains 0.8-69.94 wt.% of an emulsion, 30-99.14 wt.% of two or multiple ethylenic unsaturated monomers, 0.05-10 wt.% peroxide, 0-60 wt.% unsaturated oligomers, 0.01-2 wt.% of a polymerization inhibitors, and 0-800 weight parts of support and additives. [Image].

Description

The Invention describes a novel emulsion polymer containing Activator compounds, a cure by a redox initiator system Two- or multi-component system with controllable pot life, which the novel emulsion polymer comprises, as well as the application of the two-component or multi-component system.

Especially The invention relates to emulsion polymers with covalent bound activators as well as two- or multi-component systems, in which, in addition to the emulsion polymer containing the activator component also two monomers with different swelling capacity for the emulsion polymer used. expedient the swelling capacity of a first monomer component is sufficient not sufficient to the polymerization of the two- or multi-component system trigger while swelling a second monomer component for the emulsion polymer is sufficiently high to initiate polymerization of the system. The polymerization is only by addition of this monomer triggered with sufficiently high swelling capacity. Finally, the invention also relates to the various Applications of two- or multi-component systems.

By Redox initiation curing two-component systems based on Free-radically polymerizable monomers have long been known. As a rule, one proceeds in such a way that a liquid monomer or monomer mixture which may contain a redox component the application the missing redox system components or all redox system components be added.

Besides systems are described, which additionally in the monomer or monomer mixture dissolved polymer. Especially In dental applications, systems are still known in which liquid monomer, a bead polymer and a redox initiator system mixed before use to a high-viscosity mass.

Exemplary for a multiplicity of publications on the topic are the DE 43 15 788 . DE OS 1 544 924 and the DE 27 10 548 called. All these systems have the disadvantage that, after the components have been mixed together, the time available for processing (pot life) is limited or that energy must be introduced during the application, for example in the form of grinding and friction forces. Although the pot life can be prolonged by reducing the redox component concentration, there are limits to this, since hardening is impaired as the redox component concentration decreases. A further disadvantage of the formulations of the prior art is that the maximum concentrations in the workplace (MAK values) of readily volatile monomers, such as, for example, methyl methacrylate, can be exceeded. This application disadvantage can be counteracted only to a limited extent by the use of less volatile monomers, since the bead polymers which are frequently used, for example, are not swelled up with sufficient speed by less volatile monomers. Furthermore, the oxygen inhibition of the polymerization is more pronounced when using the less volatile monomers than when using methyl methacrylate.

DE 100 51 762 provides monomeric polymer systems based on aqueous dispersions which, in addition to good mechanical properties, offer the advantage of emitting no or only very few monomers and, moreover, being easy to handle and having a high storage stability. For this purpose, mixtures of aqueous dispersions are used whose particles have been swollen with an ethylenically unsaturated monomer, each containing one of the redox components. These swollen aqueous systems are virtually unlimited shelf life and cure only after evaporation of the water and the subsequent film formation. The disadvantage of these systems is that curing by the required evaporation of the water, especially with thicker layers, takes a long time and disturbs larger amounts of water in a number of applications, such as reactive adhesives.

WO 99/15592 describes reactive plastisols which, after thermal gelation and curing, lead to films with good mechanical properties. These plastisols consist of a known base polymer, preferably in the form of a spray-dried emulsion polymer, a reactive monomer content consisting of at least one monofunctional (meth) acrylate monomer, a plasticizer and optionally further crosslinking monomers, fillers, pigments and excipients. The base polymer may have a core / shell structure and contain from 0-20% of polar comonomers. The plastisols are storage stable for weeks and must be heated to high temperatures (eg 130 ° C) for filming.

The DE 103 39 329 A1 describes a two-component system with controllable pot life curing by a redox initiator system consisting of one or more emulsion polymers and an ethylenically unsaturated monomer or a monomer mixture of ethylenically unsaturated monomers wherein both the emulsion polymer and the monomer or monomer mixture contain one of the components of a redox initiator system can. The control of the pot life is achieved by absorption of at least one component of the redox initiator system on the polymer. In this case, the low molecular weight initiator component is physically encapsulated in polymer particles which are prepared by emulsion polymerization. If the encapsulated polymer together with monomer in the application of the two-component system swells the polymer, the former encapsulated and / or absorbed initiator component is released and can exert their effect. Although this "encapsulation" of a component of the initiator system in the polymer already allows a very favorable and variable control of the pot life, such a regulation is still in some ways in need of improvement.

in this connection On the one hand, it concerns the safety of the application. By overlay, that is too long storage, for example, the concentration the encapsulated in the polymer component, such as by migration. As a consequence, the reactivity of the system may be increased deviate from the nominal values.

On the other hand, it is already difficult in itself, in which in the DE 103 39 329 A1 described system to achieve a high loading of the polymer with the encapsulated component. In practice, at higher loads, z. 5% or above, effects suggesting incomplete inclusion of the activator. However, it may well be that you need particularly reactive systems, so that a very high degree of loading of up to 40% (w / w) or even more (> 40% [w / w]) is desired.

After all also has a high degree of loading and just then the long-term safety the degree of loading can be guaranteed.

Besides In many systems of application security is getting bigger becoming increasingly important. The components of the redox initiator system, essentially the activator component and the peroxidic Component are essential to the speed of the Curing of the entire system. As far as the two mentioned special components until hardened separately from each other be stored, there is always the danger that failing to dose one of the two components desired too slow or too fast curing reaction comes.

In In view of the prior art mentioned and discussed above It was an object of the invention to provide novel emulsion polymers create their use in two-component or multi-component systems ensures high shelf life of the systems. The emulsion polymers are intended to safely control the pot life paired with the greatest possible variability allow the components to be stored together. The Emulsion polymers are also intended to use a peroxide component in an organic, non-aqueous system.

Regarding of the system should be curing at room temperature two- or Multi-component systems are provided, whose pot life is adjustable within wide limits and which nevertheless at a defined time without energy or external curing mechanical impulse quickly and completely.

Further the task consisted in, even in thin layers without Exclusion of air requires complete curing to reach.

A further problem to be solved according to the invention is to minimize odor nuisance and in use the concentration of monomer in the air below the applicable limit for each monomer to keep.

A Another task was a wide range of variation allow the activator concentration.

Farther the pot life should be independent of the storage life of the or multi-component system. So are pot lives often by a certain concentration of inhibitors set. After prolonged storage under unfavorable Conditions, the inhibitors may be partially consumed, so that the pot life is shorter than desired.

Under Another object of the invention was to specify a system that the above-mentioned spectrum of properties is sufficient in total can and yet is easy and safe to handle.

Also the indication of uses for the invention System was to be done.

Further The object of the invention was also the number of components of the multicomponent system as much as possible, if possible, three or more multi-component systems to avoid and possibly two-component systems use.

After all It was also an object of the invention to provide a system that the Metering safety of the two components with regard to mixing guaranteed by activator and peroxide. The ratio should be from activator to peroxide by the user if possible can not be changed to difficulties exclude when initiating the cure of the entire system to be able to.

• a) 5 bis 99,9 Gew.-% eines oder einer Mehrzahl von Monomeren mit einer Wasserlöslichkeit < 2 Gew.-% bei 20°C ausgewählt aus der Gruppe bestehend aus monofunktionellen (Meth)acrylatmonomeren, Styrol und Vinylestern;
• b) 0 bis 70 Gew.-% eines oder einer Mehrzahl mit den Monomeren a) copolymerisierbaren Monomeren;
• c) 0 bis 20 Gew.-% einer oder einer Mehrzahl zweifach oder mehrfach vinylisch ungesättigter Verbindungen;
• d) 0 bis 20 Gew.-% eines oder einer Mehrzahl polarer Monomere mit einer Wasserlöslichkeit > 2 Gew.-% bei 20°C; und
• e) 0,1–95 Gew.-% wenigstens eines Aktivators der Formel I,
  
  worin – R¹ Wasserstoff oder Methyl ist; – X eine lineare oder verzweigte Alkandiylgruppe mit 1 bis 18 Kohlenstoffatomen ist, die ein oder mehrfach mit Hydroxylgruppen und/oder mit C1-C4 Alkoxygruppen substituiert sein kann; – R² Wasserstoff oder einen linearen oder verzweigten Alkylrest mit 1 bis 12 Kohlenstoffatomen bedeutet, der gegebenenfalls ein oder mehrfach mit Hydroxylgruppen oder C1-C4-Alkoxygruppen substituiert ist, wobei die Hydroxylgruppen partiell mit (Meth)acrylsäure verestert sein können; – R³, R⁴, R⁵, R⁶ und R⁷ unabhängig voneinander Wasserstoff oder eine lineare oder verzweigte Alkyl- oder Alkoxygruppe mit 1 bis 8 Kohlenstoffatomen bedeuten, die ein oder mehrfach mit Hydroxylgruppen substituiert sein können; und wobei gegebenenfalls zwei der Reste R³ bis R⁷ miteinander zu einem fünf- bis siebengliedrigen Ring verbunden sind und gegebenenfalls ein kondensiertes aromatisches Ringsystem mit dem Phenylrest bilden; wobei der Aktivator e) über kovalente Bindungen in das Emulsionspolymerisat eingebaut ist; wobei das Emulsionspolymerisat dadurch erhältlich ist, dass man nach Art einer Kern-Schale-Polymerisation die Bestandteile a) bis e) in einer ersten Stufe als Kern polymerisiert und daran anschließend in wenigstens einer weiteren Stufe als Schale eine Mischung der Bestandteile a) bis d); und wobei die Komponenten a) bis e) zusammen 100 Gew.-% der polymerisierbaren Bestandteile des Emulsionspolymerisats ergeben;

Das genannte Emulsionspolymerisat wird im Zusammenhang mit dem Zwei- oder Mehrkomponentensystem nachfolgend auch als Komponente A) bezeichnet.The objects according to the invention or partial aspects of the objects according to the invention are achieved by a novel emulsion polymer obtainable by polymerization of a mixture

• a) 5 to 99.9 wt .-% of one or a plurality of monomers having a water solubility <2 wt .-% at 20 ° C selected from the group consisting of monofunctional (meth) acrylate monomers, styrene and vinyl esters;
• b) 0 to 70 wt .-% of one or a plurality of monomers copolymerizable with the monomers a) monomers;
• c) 0 to 20 wt .-% of one or a plurality of di- or polyunsaturated vinyl compounds;
• d) 0 to 20 wt .-% of one or a plurality of polar monomers having a water solubility> 2 wt .-% at 20 ° C; and
• e) 0.1-95% by weight of at least one activator of the formula I,
  
  wherein - R ^{1 is} hydrogen or methyl; X is a linear or branched alkanediyl group having 1 to 18 carbon atoms which may be monosubstituted or polysubstituted by hydroxyl groups and / or by C1-C4 alkoxy groups; - R ^{2 is} hydrogen or a linear or branched alkyl radical having 1 to 12 carbon atoms, which is optionally substituted one or more times with hydroxyl groups or C 1 -C 4 -alkoxy groups, wherein the hydroxyl groups may be partially esterified with (meth) acrylic acid; - R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} independently hydrogen or a linear or branched alkyl or alkoxy group having 1 to 8 carbon atoms, which may be monosubstituted or polysubstituted by hydroxyl groups; and where appropriate, two of the radicals R ³ to R ⁷ are joined together to form a five- to seven-membered ring and optionally form a fused aromatic ring system with the phenyl radical; wherein the activator e) is incorporated into the emulsion polymer via covalent bonds; wherein the emulsion polymer is obtainable by polymerizing the constituents a) to e) in a first stage as a core in the manner of a core-shell polymerization and then, in at least one further stage as shell, mixing the components a) to d) ; and wherein components a) to e) together give 100% by weight of the polymerizable constituents of the emulsion polymer;

The said emulsion polymer is also referred to below as component A) in connection with the two-component or multicomponent system.

The notation (meth) acrylate here as well as in the entire context of the invention comprises both Me thacrylate, such as. As methyl methacrylate, ethyl methacrylate, etc., as well as acrylate, such as. As methyl acrylate, ethyl acrylate, etc., as well as mixtures of the two.

The Emulsion polymer = component A) is preferably substantially from (meth) acrylate monomers and styrene and / or styrene derivatives and / or vinyl esters.

Especially the structure is preferably composed of at least 80% methacrylate and acrylate monomers, most preferably, the structure is made exclusively Methacrylate and acrylate monomers.

Examples for monofunctional methacrylate and acrylate monomers with a water solubility <2% by weight at 20 ° C (component Aa)) are in an incomplete Listing of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, Hexyl (meth) acrylate, ethylhexyl (meth) acrylate, isodecyl methacrylate, Lauryl methacrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, Phenylethyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate. Methods for determining the water solubility of organic Compounds are familiar to the person skilled in the art.

Under Styrene derivatives are understood as meaning, for example, α-methylstyrene, Chlorostyrene or p-methylstyrene. Examples of vinyl esters are vinyl acetate and longer chain derivatives such as vinyl versatate.

Methacrylate monomers, in particular methyl methacrylate, are preferably incorporated in order to achieve a higher glass transition temperature, methacrylates having a C number> 4 in the side chain and acrylates in order to lower the glass transition temperature. Advantageously, the monomers are combined so that a glass transition temperature above 60 ° C results, preferably above 80 ° C and especially above 100 ° C, when the emulsion polymer A) is to be isolated by drying. The glass transition temperatures are measured after EN ISO 11357 , If the emulsion polymer A) is to be added to the two-component or multi-component system as an aqueous dispersion, the glass transition temperature may be lower. In order to oppose a sufficiently high swelling resistance to the monomers present later in the two-component or multicomponent system, a glass transition temperature above room temperature is advantageous in some cases. It is preferably above 30 ° C., more preferably above 40 ° C., in particular above 60 ° C.

In order to is not excluded that in certain cases glass transition temperatures below room temperature may be advantageous. That can For example, be the case when the solvent power or Swelling capacity of the two- or multi-component system used monomers is low, so that the swelling too long would take.

At a known glass transition temperature of homopolymers, the glass transition temperatures of the copolymers can be calculated in a first approximation according to the following formula from Fox:

T _{g is} the glass transition temperature of the copolymer (in K), T _gA , T _gB , T _gc , etc., the glass transition temperatures of the homopolymers of monomers A, B, C, etc. (in K). w _A , w _B , w _C , etc. represent the mass fractions of the monomers A, B, C, etc. in the polymer.

ever higher the glass transition temperature of the polymer, the larger is the swelling resistance compared to the before application the system added monomers and thus the pot life. As well causes an increasing molecular weight / molecular weight of the polymer generally an increase in the swelling resistance.

insofar particularly preferred emulsion polymers A) are characterized in that in that a) one or more methacrylate monomers and / or acrylate monomers consists. Especially useful is a) methyl methacrylate.

To Examples of the component A b) belong to other maleic anhydride, itaconic anhydride and esters of itaconic and maleic acid. Your share of Emulsion polymer may be up to 70 wt .-%, preferably are from 0-30% by weight, in particular 0-10% by weight contain. Most preferably, component A b) is omitted.

The incorporation of higher proportions of di- and / or polyunsaturated monomers (crosslinker = Component A c)) limits the achievable degree of swelling in the formulation and can lead to an inhomogeneous polymer at the nanoscale level. This need not be detrimental in any case, but is preferably not sought. Therefore, the content of polyunsaturated monomers is preferably limited to 20% by weight, based on component A), more preferably less than 10% by weight, more preferably less than 2% by weight, especially less than 0.5 Wt .-% or it is completely dispensed polyunsaturated monomers.

To in the context of the invention can be used with success polyunsaturated Monomers (crosslinkers) include, but are not limited to, ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate and their higher homologues, 1,3- and 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate or (Meth) acrylates of ethoxylated trimethylolpropane, triallyl cyanurate and / or allyl (meth) acrylate.

Of the Swelling resistance of the emulsion polymer for swelling acting compounds can also by the incorporation of polar monomers (Component A d)), such as methacrylamide or methacrylic acid be controlled in the emulsion polymer. This one comes along increasing amount of methacrylamide or methacrylic acid.

Examples for further polar monomers are acrylic acid, acrylamide, Acrylonitrile, methacrylonitrile, itaconic acid, maleic acid or N-methacryloyloxyethylethyleneurea and N-methacryloylamidoethylethyleneurea. Also N-methylolacrylamide or N-methylolmethacrylamide and their Ethers are conceivable, if their proportion is so limited that despite crosslinking of the dispersion particles whose swelling sufficient is possible and the initiation of the polymerization is not affected.

Of the Proportion of N-methylolacrylamide or -methacrylamide should be 10% by weight, as far as possible in relation to component A). Preferably, a content below 5 wt .-%, more preferably below 2 wt .-%, in particular 0 wt .-%.

Further polar monomers include, among others, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Homologs of the alkoxypolyethylene glycol methacrylate, the alkoxypolypropylene glycol methacrylate, of methacryloyloxypolyethylene and polypropylene glycol and of vinyloxypolyethylene and polypropylene glycol. All monomers mentioned can also as a mixed form of ethylene and propylene glycol repeating units available. The degree of polymerization may be 2 to 150, preferably 2 to 25. Alkoxy is primarily methyl, ethyl and butyl radicals. Longer alkyl chains, such as. B. C18, are also possible, but not preferred. Especially preferred is a methyl radical.

Of the Proportion of polar monomers depends primarily on the desired pot life of the formulation, but it is also linked to the glass transition temperature of the polymer. The lower the glass transition temperature is higher, the higher the required Proportion of polar monomers to a certain swelling resistance to reach. Furthermore, the proportion of polar monomers the dissolving power of the monomers used in the formulation B to vote.

In As a rule, the proportion of polar monomers is in the range of 0 and 20% by weight, preferably from 1 to 10% by weight, more preferably from 2 to 5 wt .-%, in particular from 3 to 5 wt .-%, based on the component A). Are short pot lives desired, for example a few Minutes, or is the dissolving power of the monomers in component B) low, it may be advantageous to reduce the content to below 2%. to restrict or completely abstain from polar monomers.

methacrylamide and acrylamide and methacrylic acid and acrylic acid are particularly effective and are therefore preferred when long Pot lives are desired. Particularly preferred is a combination of Methacrylamide or acrylamide with methacrylic acid or acrylic acid in the weight ratios of 3 to 1 to 1 to 3.

The in the context of the invention successfully to be used component A e) obeys the general formula I.

For the disclosure of the invention is meant a linear or branched alkanediyl group having 1 to 18 carbon atoms, an unbranched or branched hydrocarbon radical having 1 to 18 carbon atoms, such as. The methanediyl (= methylene group), ethanediyl, propanediyl, 1-methylethanediyl, 2-methylpropanediyl, 1,1-dimethylethanediyl, pentanediyl, 2-methylbutanediyl, 1,1-dimethylpropanediyl, hexane diyl, heptanediyl, octanediyl, 1,1,3,3-tetramethylbutanediyl, nonanediyl, isononanediyl, decanediyl, undecanediyl, dodecanediyl or hexadecanediyl.

Under the term linear or branched alkyl radical having 1 to 8 carbon atoms is meant for the invention radicals such. The methyl, Ethyl, propyl, 1-methylethyl, 2-methylpropyl, 1,1-dimethylethyl, Pentyl, 2-methylbutyl, 1,1-dimethylpropyl, hexyl, heptyl, octyl, or the 1,1,3,3-tetramethylbutyl radical.

Under the term linear or branched alkyl radical having 1 to 12 carbon atoms For the invention, radicals with 1 to 8 carbon atoms are understood as described above and z. The nonyl, isononyl, decyl, Undecy- or the dodecyl radical.

The term C ₁ -C ₄ alkoxy groups for the invention are understood to mean alkoxy groups in which the hydrocarbon radical is a branched or unbranched hydrocarbon radical having 1 to 4 carbon atoms, such as. As the methyl, ethyl, propyl, 1-methylethyl, 2-methylpropyl or 1,1-dimethylethyl.

Under the term linear or branched alkoxy group having 1 to 8 carbon atoms are understood for the invention alkoxy groups, in the hydrocarbon radical is a branched or unbranched Hydrocarbon radical having 1 to 8 carbon atoms, such as. Methyl, ethyl, propyl, 1-methylethyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 2-methylbutyl, 1,1-dimethylpropyl, Hexyl, heptyl, octyl, or 1,1,3,3-tetramethylbutyl.

As the formula (I) shows the possible Activator components A e) generally (meth) acryloyl-functionalized Aminabkömmlinge. This is generally done with the activator or accelerator components of modified amines such as 2-N- (ethylanilino) ethanol or 2-N- (ethylanilino) propanol, and makes these amines polymerizable Accelerator / activator components, preferably by introduction of (meth) acrylate groups. Accordingly, for example also m-toluidine and xylidine derivatives or other derivatives as Starting point for obtaining the activator or accelerator component be used.

To preferably usable activator / accelerator components A e) Inter alia, the following classes of compounds include: N - ((meth) acryloyl (poly) oxyalkyl) -N-alkyl- (o, m, p) - (mono, di, tri, tetra, penta) alkylaniline, N - ((meth) acryloyl (poly) oxyalkyl) -N- (arylalkyl) - (o, m, p) - (mono, di, tri, tetra, penta) alkylaniline, N - ((meth) acryloyl (poly) oxyalkyl) -N-alkyl- (o, m, p) - (mono, di, tri, tetra, penta etc.) alkylnaphthylamine, N - ((meth) acrylamidoalkyl) -N-alkyl- (o, m, p) - (mono, di, tri, tetra, penta) alkylaniline. Examples of further amines are N, N-dimethylaminoethyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, 3-dimethylamino-2,2-dimethylpropyl (meth) acrylate, tert-butylaminoethyl (meth) acrylate, N-vinylimidazole and dimethylaminopropyl (meth) acrylamide. Preference is given to N - ((meth) acryloyloxyethyl) -N-methylaniline, N - ((meth) acryloyloxypropyl) -N-methylaniline, N - ((meth) acryloyloxypropyl) -N-methyl- (o, m, p) -toluidine, N - ((meth) acryloyloxyethyl) -N-methyl- (o, m, p) -toluidine, N - ((meth) acryloylpolyoxyethyl) -N-methyl- (o, m, p) -toluidin. These Substances are used singly or in mixture of two or more.

Particularly advantageous emulsion polymers for the purposes of the invention are methacryloyl-functionalized substances, ie those compounds of the formula (I) in which R ^{1 is} methyl.

In a further preferred embodiment, the polymers are characterized in that in the formula (I) X is an ethanediyl, ie an ethylene group -CH ₂ -CH ₂ -.

In another particularly preferred embodiment, the emulsion polymer is characterized in that X in the formula (I) is a hydroxyl-substituted propanediyl group, namely a 2-hydroxypropylene group -CH ₂ -CH (OH) -CH ₂ -.

Further preferred activators result from the fact that the radical R ² in the formula (I) is selected from the group consisting of methyl, ethyl and 2-hydroxyethyl.

Preferably, e1) contains only one (meth) acryloyl group. Possible, although not preferred, is a multiple unsaturation by partial esterification of the hydroxyl groups in R ² with (meth) acrylic acid, which can not always be completely avoided in the synthesis. A content of such crosslinking structures is not critical, as long as he the usability of the emulsion polymers A) in the two- or Mehrkom Component systems not impaired, for example, by no longer sufficient swellability of the emulsion in monomers due to a high degree of crosslinking. Typically, a proportion of polyunsaturated activator monomer below 5% by weight, based on the polymer composition, is not necessarily prohibitive, preferred are less than 3, in particular less than 1% by weight. Higher contents are not excluded. The person skilled in the art can easily determine whether the monomer is suitable by, for example, checking whether an emulsion polymer A) prepared therewith triggers the polymerization in the desired time interval in the two-component or multicomponent system and if the polymerization proceeds rapidly and completely and the polymer has the desired properties ,

Also preferred are such polymers as activators in which one of the radicals R ³ to R ^{7 is} methyl while the remaining four radicals are hydrogen.

In addition, those polymers are useful, which are characterized in that in the formula (I) two of the radicals R ³ to R ^{7 are} methyl while the remaining three radicals are hydrogen.

Of the Proportion of the polymerizable activator A e) in component A) can between 0.1 and 95 wt .-% amount. Preferably, it is possible high, for example between 5 and 60% by weight, particularly preferably 10-60% by weight, in particular 20-50 Wt .-%. The upper limit is determined by the behavior of the selected one Activator determined in the emulsion polymerization. The expert will take care that by a too high proportion neither not acceptable levels of coagulum are formed, nor too high residual monomer contents remain. It may also be that specific effectiveness of the activator decreases with increasing installation quantity. As the polymerizable Activator is a rather expensive monomer component is the Specialist strive to make a compromise between possible high installation quantity and economic efficiency to find.

The Emulsion polymer A) is for the purposes of the invention constructed as a core-shell polymer.

Core-shell polymer here stands for a polymer by a two- or Multistage emulsion polymerization was prepared without the core-shell structure must necessarily be shown, for example electron microscopy. Will the polymerizable activator only built in the core, ie in the first stage, so carries Such a structure that the activator to the sufficient Swelling is not accessible to the peroxide and thus premature polymerization is prevented. A special embodiment The invention relates to the fact that the polar monomers the shell will be confined, core and shell, aside from the polymerizable activator in the core, but otherwise the same structure are. In another embodiment Core and shell differ significantly in monomer composition, which, for example, affects the particular glass transition temperature. In this case, it is advantageous if the glass transition temperature of the shell above the core, preferably above 60 ° C, more preferably above 80 ° C, especially above from 100 ° C. In addition, also in this Embodiment, the polar monomers limited to the shell be. Especially by the core-shell structure are particularly advantageous Achieved properties. This includes, among others, the better Protection of the activator against premature contact with the peroxide through a bowl or a plurality of bowls. The activator monomer is preferably installed in the core. So it may be go to make the cured polymers more flexible. In such cases, the core becomes relatively low in glass transition temperature set. The shell has higher glass transition temperature then the task, the desired swelling resistance and if necessary, to ensure isolation as a solid. The Weight ratio of core to shell depends on it on how well the activator should be protected or which Effects are expected by this structure. In principle it can between 1:99 and 99: 1, d. H. it's usually not critical as long as the purpose of the emulsion polymer A), the polymerization of the two- or multi-component system in the desired Way to activate, is not affected.

is intends to protect the activator through the shell, so you will usually limit the shell content to the necessary level, to allow a high Aktivatoranteil in the emulsion polymer.

Should by building special effects, such. B. a flexibilization the cured polymer systems by a core polymer be achieved with low glass transition temperature, so the core-shell ratio is up to tune the desired effects. Mostly the expert set the shell proportion between 10 and 50 wt .-%, preferably between 20 and 40 wt .-%, in particular between 25 and 35 wt .-%.

In this respect, the invention also relates to a process for the preparation of an emulsion according to the invention onspolymerisats, in which the components a) to e) of component A) polymerized in aqueous emulsion.

The emulsion polymerization is carried out in a manner generally known to those skilled in the art. The performance of an emulsion polymerization is exemplified in EP 0376096 B1 described.

Preferably an initiator is chosen that is compatible with the polymerizable Activator A e) does not form a redox system. Suitable, for example Azoinitiatoren as the Na salt of 4,4'-azobis- (4-cyanovaleriansäure).

Becomes for certain applications the solid A) is required, so this can be isolated in a known manner. The solid Component A) can for example by known methods the dispersion are obtained. These include spray drying, Frozen coagulation with suction and drying and pressing by means of extruder. The polymer is preferably carried out as a solid Spray drying won.

For however, the purposes of the present invention may also be preferred be that the component A) is not isolated. Because certain amount Generally do not disturb water in the targeted applications, Component A) may also be used as an aqueous dispersion to the system be added.

The Molar mass of component A) expressed as weight average molecular weight MW can be used, inter alia, the swelling resistance to compounds such as monomers to a certain extent influence. High weight average of Molecular weight MW tends to increase on the Swelling resistance, while lower weight means of Molecular weight MW lowering effect. This is the desired Pot life, among other things, determines whether the Professional chooses a high molecular weight or a rather low one.

If over the molecular mass no special effects are to be achieved, so the person skilled in the molecular weight MW is usually between 10,000 g / mol and 5,000,000 g / mol, preferably between 50,000 g / mol and 1,000,000 g / mol and most preferably between 100,000 g / mol and 500,000 g / mol. The molecular weight is determined by gel permeation chromatography certainly. The measurement takes place in THF, PMMA is used as calibration standard.

Of the Swelling resistance can also be determined by the choice of particle size be set. The larger the particle diameter the lower the swelling rate. A smaller middle one Particle diameter offers a higher swelling resistance for monomers.

The Primary particle size of component A) is usually between 50 nm and 2 microns, preferably between 100 nm and 600 nm and most preferably between 150 nm and 400 nm. The particle size is with measured on a Mastersizer 2000 Version 4.00.

In a particularly preferred modification of the process of the invention, the constituents a) to e) for the core and the constituents a) to d) for the shell are selected so that the glass transition temperature T _GS in the resulting polymer is at least one Shell is greater than the glass transition temperature T _{GK of} the core, wherein the glass transition temperatures T _G after EN ISO 11357 be determined.

Yet another process modification provides that one selects the ingredients a) to d) for the shell so that in the resulting polymer, the glass transition temperature T _GS at least one shell greater than 80, preferably greater than 100 ° C, wherein the glass transition temperature T _GS to EN ISO 11357 is determined.

The Emulsion polymerization is basically discontinuous or continuously as a batch or feed polymerization possible. It is also semi-continuous feasible. feed polymerization is preferred. Similarly, the preparation of A) is via a Miniemulsion polymerization possible. The procedures mentioned are well known to those skilled in the art.

• A) 0,8–69,94 Gew.-% eines Emulsionspolymerisats wie hierin oben beschrieben
• B) 30–99,14 Gew.-% zweier oder einer Mehrzahl ethylenisch ungesättigter Monomere;
• C) 0,05–10 Gew.-% Peroxide; gegebenenfalls
• D) 0–60 Gew.-% ungesättigte Oligomere; gegebenenfalls
• E) 0–2 Gew.-% eines Polymerisationsinhibitors; und gegebenenfalls
• F) 0–800 Gewichtsteile Hilfs- und Zusatzstoffe; wobei die Summe der Bestandteile A) + B) + C) + D) + E) 100 Gew.-% ergibt und sich die Menge von F) auf 100 Gewichtsteile der Summe A) + B) + C) + D) + E) bezieht, das dadurch gekennzeichnet, dass i) wenigstens ein Bestandteil B'' der Komponente B) für das Emulsionspolymerisat nicht oder nicht ausreichend anquellend wirkt; ii) wenigstens ein Bestandteil B'' der Komponente B) für das Emulsionspolymerisat A) anquellend wirkt, so dass der polymerfixierte Aktivator e) des Polymerisats A) mit der Komponente C) zur Umsetzung gelangen kann; iii) Komponente A) und Bestandteil B' bis zum Einsatz des Systems gemeinsam gelagert werden; und iv) Komponente B'' bis zur Anwendung des Systems von der Komponente A) getrennt gelagert wird.

The invention also relates to a two-component or multi-component system with controllable pot life curing by a redox initiator system

• A) 0.8-69.94% by weight of an emulsion polymer as described hereinabove
• B) 30-99.14% by weight of two or more ethylenically unsaturated monomers;
• C) 0.05-10% by weight of peroxides; possibly
• D) 0-60% by weight of unsaturated oligomers; possibly
• E) 0-2% by weight of a polymerization inhibitor; and optionally
• F) 0-800 parts by weight of auxiliaries and additives; the sum of the constituents A) + B) + C) + D) + E) being 100% by weight, and the amount of F) being 100 parts by weight of the sum A) + B) + C) + D) + E ), which is characterized in that i) at least one constituent B "of component B) does not act or does not sufficiently swell the emulsion polymer; ii) at least one constituent B "of component B) has a swelling effect for the emulsion polymer A), so that the polymer-fixed activator e) of the polymer A) can react with component C); iii) component A) and component B 'are stored together until use of the system; and iv) component B "is stored separately from component A) until the system is used.

at Component A) of the invention or multicomponent system is that described above Emulsion polymer with covalently incorporated activator e).

• i) wenigstens ein Bestandteil B'' der Komponente B) für das Emulsionspolymerisat nicht oder nicht ausreichend anquellend wirkt; und
• ii) wenigstens ein Bestandteil B'' der Komponente B) für das Emulsionspolymerisat A) anquellend wirkt, so dass der polymerfixierte Aktivator e) des Polymerisats A) mit der Komponente C) zur Umsetzung gelangen kann.

In addition, the two-component or multi-component system of the invention essentially comprises a component B) which has at least two different constituents B 'and B ". The component B) is characterized in particular by the fact that

• i) at least one constituent B "of component B) does not act or does not sufficiently swell the emulsion polymer; and
• ii) at least one component B "of component B) acts swelling on the emulsion polymer A), so that the polymer-fixed activator e) of the polymer A) can be reacted with component C).

Which Factors affecting the swelling capacity of the monomers has been partly already above in the description of the emulsion polymer specified.

in principle can be a great variety of monomers that in some Sage swell, used for the invention. It is important that the monomers used with regard to the swelling capacity selected and used for the component A) become. In this case, the person skilled in the art succeeds in knowing the present Inventions with few routine tests reliably the Component B) in such monomers belonging to the group B ' and to divide those monomers which belong to group B ". The monomers can then be equipped with this knowledge B 'and B' 'to the component A) are tuned and so can a System with the desired pot life available be put.

In principle, all methacrylate and acrylate monomers and styrene and mixtures thereof can be used as monomers. Subordinate proportions of other monomers such as vinyl acetate, vinyl versatate, vinyloxypolyethylene glycol, maleic and fumaric acid and their anhydrides or esters are possible as long as the copolymerization is not disturbed, but are not preferred. Criteria for the selection of monomers are their dissolving power, polymerization shrinkage, adhesion to the substrate, vapor pressure, toxicological properties and odor. Examples of (meth) acrylates are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenylethyl (meth) acrylate), 3,3,5-trimethylcyclohexyl ( meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methyl or ethyl triglycol methacrylate, butyl diglycol methacrylate, ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate and their higher homologs, dipropylene glycol di (meth) acrylate , Tripropylene glycol di (meth) acrylate and its higher homologues, 1,3- and 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, tri (meth) acrylate of an ethoxylated trimethylolpropane with 3 10 moles ethylene oxide, di (meth) acrylate, an ethoxylated bisphenol-A having 2-20 mols of ethylene oxide, preferably 2-10 moles of ethylene oxide and / or a polyethylene glycol with 1-15 ethylene oxide units and allyl (meth) acrylate. Further examples are (meth) acrylic acid, (meth) acrylamide, N-methylol (meth) acrylamide, monoesters of maleic and succinic acid with hydroxy ethyl methacrylate and the phosphoric acid ester of hydroxyethyl (meth) acrylate, the proportion of which is usually subordinate.

Under Another preferred is for component B) one or one Plurality of compounds selected from the group consisting from ethyl triglycol methacrylate, tetrahydrofururyl methacrylate, benzyl methacrylate, Isobornyl methacrylate, 1,4-butanediol dimethacrylate, hydroxypropyl methacrylate, Trimethylolpropane trimethacrylate, trimethacrylate of an ethoxylated Trimethylolpropane with 3-10 moles of ethylene oxide, dimethacrylate an ethoxylated bisphenol-A with 2-10 moles of ethylene oxide and / or a polyethylene glycol dimethacrylate having 1-10 Ethylene oxide units.

Especially preferred are (meth) acrylates having a molecular weight above 140 g / mol, more preferably above 165 g / mol and in particular above 200 g / mol.

methacrylates obtained against acrylates also for toxicological reasons the preference.

Next have long pot lives due to low swelling rate High molecular weight monomers still have the advantage of low emissions.

on the other hand As a rule, its viscosity increases with the molecular weight and the dissolving power for the emulsion polymer decreases, so that, in particular, when polymers or oligomers in appreciable Shares being used to compromise got to.

The Peroxide C) is the partner of the activator in the redox system. His share is usually between 0.05 and 10 wt .-%, preferably 0.1 to 5 wt .-%. Most is a proportion of 0.5-5 wt .-% chosen, preferably 0.5-3, in particular 0.5-2 Wt .-%. Decisive for the Peroxidanteil is that in the intended application, a complete cure done in the desired time and the cured System has the properties tailored to the purpose.

The Peroxide is often phlegmatized z. B. in plasticizers or water or another medium. The peroxide can, for example in aqueous phase.

Especially preferred for the invention is the peroxidic initiator in organic phase, for example an organic solvent or in a component of component B).

typical Peroxide contents of this peroxide formulation are 20-60 Wt .-%.

When Peroxides are most preferably dibenzoyl peroxide and dilauryl peroxide into consideration. The peroxides may be alone or in mixture of two or more non-individually mentioned peroxide compounds are present.

A Another variant is the peroxide in an emulsion polymer to absorb (component C '). In a further embodiment The invention therefore consists of component C of an emulsion polymer containing a peroxide (component C '). The emulsion polymer the component C 'may be the same or different structure as Component A, but contains no polymerizable activator as Comonomer. Typical peroxide levels in component C 'are below 20, in particular less than 10 wt .-%.

To Mixture of all components, the polymerization starts only then, when the polymer particles of both components A and C 'swelled are.

there As a rule, it is not critical whether the emulsion polymers A and C 'are the same or different, as long as any incompatibility does not adversely affect.

When Oligomers (component D)) of the system can be unsaturated Polyester, as well as polyurethane (meth) acrylates based on polyether, Polyester, or polycarbonate diols, and mixtures thereof be used. Furthermore, vinyl-terminated prepolymers based on acrylonitrile and butadiene. Further can epoxy (meth) acrylates and also star-shaped Copolymers can be used, as for example by polymerization of (meth) acrylates in the presence of polyfunctional mercaptans are accessible.

Preferably the oligomers are polyunsaturated.

It Furthermore, polymers based on polyacrylates, Polyesters, polyethers, polycarbonates or the corresponding copolymers be used. These can be both saturated as well as being unsaturated. The mixing ratio and the amount used depends on the intended application. The Polymers or their proportion are usually selected so that the viscosity of the mixture is not adversely affected becomes.

The Molar mass of the unsaturated oligomers is typically 500 to 20,000, especially 1,000 to 5,000 g / mol. Saturated polymers typically have molecular weights above 20,000, for example 50,000-200,000 g / mol. It deals in all cases weight average molecular weight.

The polymerization inhibitor (component E)) is optionally required to ensure sufficient storage stability of the mixture of components B), D), E) and F). The effect of the inhibitors is usually that they act as scavengers for the free radicals occurring during the polymerization. For further details on the usual specialist literature, in particular on the Römpp-Lexikon Chemistry; Publisher: J. Falbe, M. Regitz; Stuttgart, New York; 10th edition (1996); Keyword "antioxidants" and references cited at this point.

suitable Inhibitors include u. a. optionally substituted phenols, optionally substituted Hydroquinones, such as hydroquinone monomethyl ether (HQME), optionally substituted quinones, optionally substituted catechols, tocopherol, tert-butylmethoxyphenol (BHA), butylhydroxytoluene (BHT), octyl gallate, Dodecyl gallate, ascorbic acid, optionally substituted aromatic Amines, optionally substituted metal complexes of an aromatic amine, optionally substituted triazines, organic sulfides, organic polysulfides, organic dithiocarbamates, organic phosphites and organic Phosphonates, phenothiazine and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl.

Possibly. substituted hydroquinones and optionally substituted phenols preferably used. Particularly preferred are hydroquinone, hydroquinone monomethyl ether and 4-methyl-2,6-di-tert-butylphenol.

In As a rule, 0.2% by weight of inhibitor is sufficient; Share much lower, for example at 0.05 wt .-% or below. The pot life of the system after admixture of components A and C is According to the invention via the swelling of Controlled component A. Higher than 0.2% by weight inhibitor, z. B. 1 wt .-% or higher, which in systems of the state the technique sometimes used to extend the pot life, are therefore usually not necessary, but should not be excluded become. Preferred is a content of at most 0.2 wt .-%, in particular at most 0.05% by weight.

The Formulation can be customary in addition to the components described particulate fillers (component F), such as Titanium dioxide, carbon black or silicon dioxide, glass, glass beads, Glass powder, cement, quartz sand, quartz powder, sand, corundum, stoneware, Clinker, barite, magnesia, calcium carbonate, marble powder or Aluminum hydroxide, mineral or organic pigments and auxiliaries (Component F)).

excipients may be, for example: plasticizer, water, leveling agent, Thickeners, defoamers, adhesives or wetting agents. Preferably, besides possibly for the phlegmatization The plasticizer used in the peroxide is no further plasticizer contain.

The Particulate fillers usually have a grain diameter of about 0.001 mm to about 6 mm.

On One part by weight of polymer will usually be 0 to 8 parts by weight Fillers used.

• iii) Komponente A) und Bestandteil B' bis zum Einsatz des Systems gemeinsam gelagert werden; und
• iv) Komponente B'' bis zur Anwendung des Systems von der Komponente A) getrennt gelagert wird.

The system of the invention is also characterized in that

• iii) component A) and component B 'are stored together until use of the system; and
• iv) component B "is stored separately until the application of the system of component A).

This means that the emulsion polymer with the encapsulated activator and the non-swelling or insufficient swelling monomer component B ') give a storage-stable mixture. The polymerization is finally by addition of the swelling acting monomer B '' in guided the ways.

There are now various ways in which to store the system of the invention. So it can be in An embodiment of the invention may be of interest to store all components A) to F), with the exception of component B ").

• v) der Bestandteil B'' der Komponente B) und die Komponente C) bis zur Anwendung des Systems gemeinsam gelagert werden.

A particularly useful modification of the invention, however, provides that

• v) component B "of component B) and component C) are stored together until use of the system.

• vi) der Bestandteil B'' der Komponente B) und die Komponente C) bis zur Anwendung des Systems gemeinsam in einem nicht wässrigen System gelagert werden.

A particular variant of the two- or multi-component system of the invention is characterized in that

• vi) the component B "of component B) and component C) are stored together in a non-aqueous system until the system is used.

Especially expediently, the peroxide is readily available Solvent directly in the monomer B '' stored.

One important advantage of the invention is, inter alia, that you usually get by with a two-component system.

As mentioned it is particularly appropriate the components A), B), C), D), E) and F) together, with Exception of only one component of component B), which over has a sufficiently high swelling capacity to the emulsion polymer A) so far swell that the covalent at the core of the polymer A) bound activator component e) for the reaction with the peroxide component C) available stands. In this way, it is possible, for example, the pot life in To adjust the dependence of a single monomer, without that the hardening time of the system is changed. This opens up the systems according to the invention a broad field of application.

invention Two- or multi-component systems can be combined with large Advantage in adhesives, casting resins, floor coatings, Masses for reactive dowels, dental materials or in Insert sealing compounds.

With the inventive compositions a wide range of activator concentration (range of variation) realize. A particular advantage is that at high Activator concentrations in component A less of A before use must be added to the two- or multi-component system.

Also the possibility to vary the reactivity is advantageous. With constant addition amount of the component A can increase the reactivity through different concentrations of the activator can be varied in A.

The Pot life of the formulation from components A), B), C), D), E) and F) can by the swelling force of the monomers used in Component B) are influenced. While methyl (meth) acrylate has a high swelling power and thus to relatively low pot life leads, increase more hydrophobic monomers, such as 1,4-butanediol di (meth) acrylate and monomers with high molecular weight, such as ethyltrigycol (meth) acrylate usually the pot life.

The The invention relates to a two-component or multi-component system. This means, that in the sense of a "kit of parts" before the actual Application of the entire system, at least two subsystems are present, which mixes with the actual applications of the system become.

Of the particular advantage of the system according to the invention consists in that the components of the redox initiator system form together a storage-stable mixture. Especially advantageous is the presence of the components A) and C) in a storage-stable aqueous phase. Furthermore, the one mixture with the Components A) and C) also comprise parts of component B), as well as all other components D), E) and F), provided that that of the monomer component stored together with components A) and C) B) is unable, the component A) to a sufficient extent to swell. The actual hardening of the entire system is then only by mixing with a suitable monomer B) achieved.

The application is usually done by mixing all components A) to F) of the system together. The polymer A) is within a certain time by the monomer or the monomers B) swelled. Thus, the polymer-fixed activator component A e) is accessible to the peroxide and thus the polymerization reaction started.

Out close the long pot life after mixing the components, that the polymer-fixed activator A e) sufficiently in the polymer is hidden. Surprising is the fast and strong temperature rise at a given time, showing that with the invention Procedure a long pot life can be adjusted without that the subsequent polymerization is impaired.

The Mixing ratio is of the intended application dependent. This determines the amount of components used A-F. The mixing ratio of the used Components should preferably be chosen so that a complete Polymerization of the given system is achieved. Especially should suitably a sufficient amount of Redoxinitiatorsystems are available, wherein the activator at least predominantly in the form of an emulsion polymer (component A) is provided.

There the proportion of the polymerizable activator A e) in component A) can be chosen within wide limits, also exists for the amount of component A) a broad scope. So can the proportion of component A) is between 0.8 and 69.94% by weight, and again 0.1 to 95% by weight of the polymerizable activator contain. In general, the amount of activator on the used Proportion of peroxide matched. The peroxide is the partner of the Activator in the redox system. His share is usually between 0.05 and 10 wt .-%, preferably 0.1 to 5 wt .-%. Mostly a share from 0.5 to 5% by weight, preferably 0.5 to 3, in particular 0.5-2% by weight. Decisive for the peroxide content and the proportion of component A is that at the intended application to the desired extent complete polymerization in the desired Time is up and the hardened system depends on the purpose coordinated performance

Of the Proportion of an ethylenically unsaturated monomer (component B)) can be between 30 and 99.14 wt .-%. Preferably he 40-94.89 wt .-%, in particular 40-80 wt .-%. The proportion of an oligomer or polymer (component D) is 0-60 wt .-%, preferably 0-40 wt .-%, in particular 0-30% by weight.

Further The mixture can be between 0 and 800 parts by weight, based on the sum of A-D to 100 parts by weight, of fillers, Pigments and other excipients.

• A) 0,8–69,94 Gew.-% eines Polymerisats wie hierin oben beschrieben mit polymerfixierter Aktivatorkomponente;
• B) 30–99,14 Gew.-% eines oder einer Mehrzahl ethylenisch ungesättigter Monomere;
• C) 0,05–10 Gew.-% Peroxide; gegebenenfalls
• D) 0–60 Gew.-% Oligomere;
• E) 0,01–2 Gew.-% eines Polymerisationsinhibitors; und gegebenenfalls
• F) 0–800 Gewichtsteile Hilfs- und Zusatzstoffe;

wobei die Summe der Bestandteile A) + B) + C) + D) + E) 100 Gew.-% ergibt und sich die Menge von F) auf 100 Gewichtsteile der Summe A) + B) + C) + D) + E) bezieht.Preferred two or more component systems according to the invention comprise

• A) 0.8-69.94% by weight of a polymer as described hereinabove with polymer fixed activator component;
• B) 30-99.14% by weight of one or a plurality of ethylenically unsaturated monomers;
• C) 0.05-10% by weight of peroxides; possibly
• D) 0-60% by weight of oligomers;
• E) 0.01-2% by weight of a polymerization inhibitor; and optionally
• F) 0-800 parts by weight of auxiliaries and additives;

the sum of the constituents A) + B) + C) + D) + E) being 100% by weight, and the amount of F) being 100 parts by weight of the sum A) + B) + C) + D) + E ).

Furthermore, systems are also preferred containing from 5 to 45 wt .-% of component A),
From 40 to 94.89% by weight of component B),
0.1 to 5% by weight of component C),
0-40% by weight of component D);
0.01-0.2% by weight of component E)
and
0 to 800 parts by weight of component F),
the sum of the constituents A) + B) + C) + D) + E) being 100% by weight, and the amount of F) being 100 parts by weight of the sum A) + B) + C) + D) + E ).

Even more preferred are systems containing
From 5 to 45% by weight of component A),
From 50 to 94.50% by weight of component B),
From 0.5 to 5% by weight of component C),
0 to 30% by weight of component D);
0.01-0.1% by weight of component E)
and
0 to 800 parts by weight of component F),
the sum of the constituents A) + B) + C) + D) + E) being 100% by weight, and the amount of F) being 100 parts by weight of the sum A) + B) + C) + D) + E )

Especially the content of component D) is preferably 0 to 30 Wt .-%.

In particularly expedient embodiment comprises the Invention a system which is characterized in that component A) and component C) are stored together and until use the system at least one component of component B) separated from A) and C), wherein the swelling capacity of the separately stored component of component B) for the polymer A) is so high that the polymer-fixed activator of the polymer A) with the component C) can be reacted.

The System is basically suitable for all two-component systems such as adhesives, casting resins, floor coatings and others Reactive coatings, sealing compounds, impregnating compounds, Investment materials, reactive dowels, dental materials, production of artificial marble or other artificial stones, porous plastic molds for ceramic objects and similar applications. It is also suitable for use in unsaturated Polyester resins and their typical applications.

Especially preferred is the application of the described two- or multi-component system in adhesives, casting resins, floor coatings, masses for reactive dowels, dental materials or sealing compounds.

In an application as a casting resin, a high polymer content (Component A), for example between 30 and 70 wt .-%, advantageous be. The proportion of the activator in component A can then, for example, on 0.1 to 5 wt .-% based on component A are limited. Components B and D taken together are then between 69.9 and 30% by weight. The peroxide content is preferably 0.1 to 5% by weight.

in the Area of highly networked systems, it may be useful to check the salary to limit polymer (component A) and only as a carrier to use an activator. The proportion of component A is therefore preferably correspondingly low and, for example, between 1 and 10 wt .-%. The proportion of polymer-fixed in component A. Activator is accordingly high to choose and can be 10 or even up to 60 wt .-%, in some cases up to 95 wt .-% based on component A. The components B and D taken together are then between 98.9 and 90 wt .-%. Of the Peroxide content is preferably 0.1 to 5 wt .-%.

The The following examples and comparative examples serve to further Explanation of the invention

Preparation of the emulsion polymers

All Emulsion polymers were prepared by the feed process.

The original was stirred in the reaction vessel at 80 ° C for 5 min. Subsequently, the remaining feed 1 was added over a period of 3 h and feed 2 over a period of 1 h. Feeds 1 and 2 were emulsified before addition to the reaction mixture. Demineralized water was used. The batches are listed in Table 1. Table 1 Experiment No. template Inlet 1 Inlet 2 characterization 1 341.0 g water 0.72 g 10% C15 paraffin sulfonate paraffin sulfonate, Na salt solution salt solution 6.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 12.0 g of 10% C15 paraffin sulfonate, Na salt solution 24.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 400.0 g MMA 400.0 g water 12.0 g 10% C15 paraffin sulfonate, Na salt solution salt solution 24.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 380.0 g MMA 20 , 0 g of MAS 400.0 g of water FG: 38.8% mean particle size, device Mastersizer: 158 nm pH: 6.1 2 341.5 g water 0.72 g 10% C15 paraffin sulfonate, Na salt solution 6.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 12.0 g of 10% C15 paraffin sulfonate, Na salt solution 24.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 396.0 g MMA 4.13 g 2-N- (ethylanilino) -ethyl methacrylate 400.0 g of water 12.0 g of 10% C15 paraffin sulfonate, Na salt solution 24.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 380.0 g MMA 20.0 g MAS 400.0 g of water FG: 39.0% mean particle size, device Mastersizer: 171 nm pH: 6.1 3 341.5 g water 0.72 g 10% C15 paraffin sulfonate, Na salt solution 6.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 12.0 g 10% C15 paraffin sulfonate, Na salt solution 24.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 392.0 g MMA 8.20 g 2-N- (ethylanilino) -ethyl methacrylate 400.0 g of water 12.0 g of 10% C15 paraffin sulfonate, Na salt solution 24.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 380.0 g MMA 20.0 g MAS 400.0 g of water FG: 38.7% mean particle size, device Mastersizer: 176 nm pH value: 6.0 4 341.0 g water 0.72 g 10% C15 paraffin sulfonate, Na salt solution 6.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 12.0 g 10% C15 paraffin sulfonate, Na salt solution 24.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 388.0 g MMA 12.38 g 2-N- (ethylanilino) -ethyl methacrylate 400.0 g of water 12.0 g of 10% C15 paraffin sulfonate, Na salt solution 24.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 380.0 g MMA 20.0 g MAS 400.0 g of water FG: 38.9% mean particle size, Device Mastersizer: 189 nm pH: 6.1 5 341.0 g water 0.72 g 10% C15 paraffin sulfonate, Na salt solution 6.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 12.0 g 10% C15 paraffin sulfonate, Na salt solution 24.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 384.0 g MMA 16.50 g 2-N- (ethylanilino) -ethyl methacrylate 400.0 g of water 12.0 g of 10% C15 paraffin sulfonate, Na salt solution 24.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 380.0 g MMA 20.0 g MAS 400.0 g of water FG: 38.6% mean particle size, device Mastersizer: 167 nm pH value: 5.9 6 342.2 g water 0.72 g 10% C15 paraffin sulfonate, Na salt solution 6.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 12.0 g of 10% C15 paraffin sulfonate, Na salt solution 24.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 376.0 g MMA 24.80 g 2-N- (ethylanilino) -ethyl methacrylate 400.0 g of water 12.0 g of 10% C15 paraffin sulfonate, Na salt solution 24.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 380.0 g MMA 20.0 g MAS 400.0 g of water FG: 39.1% mean particle size, Device Mastersizer: 183 nm pH: 6.1 7 342.2 g water 0.72 g 10% C15 paraffin sulfonate, Na salt solution 6.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 12.0 g 10% C15 paraffin sulfonate, Na salt solution 24.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 368.0 g MMA 33.03 g 2-N- (ethylanilino) -ethyl methacrylate 400.0 g of water 12.0 g of 10% C15 paraffin sulfonate, Na salt solution 24.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 380.0 g MMA 20.0 g MAS 400.0 g of water FG: 39.0% mean particle size, instrument Mastersizer: 165 nm pH value: 6.3 8th 342.2 g water 0.72 g 10% C15 paraffin sulfonate, Na salt solution 6.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 12.0 g 10% C15 paraffin sulfonate, Na salt solution 24.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 360.0 g MMA 41.30 g 2-N- (ethylanilino) -ethyl methacrylate 400.0 g of water 12.0 g of 10% C15 paraffin sulfonate, Na salt solution 24.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 380.0 g MMA 20.0 g MAS 400.0 g of water FG: 38.8% mean particle size, device Mastersizer: 236 nm pH value: 6.0 9 343.9 g water 0.72 g 10% C15 paraffin sulfonate, Na salt solution 6.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 12.0 g 10% C15 paraffin sulfonate, Na salt solution 24.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 340.0 g MMA 62.40 g 2-N- (ethylanilino) -ethyl methacrylate 400.0 g of water 12.0 g of 10% C15 paraffin sulfonate, Na salt solution 24.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 380.0 g MMA 20.0 g MAS 400.0 g of water FG: 38.7% mean particle size, instrument Mastersizer: 198 nm pH: 6.1 10 262.5 g water 0.54 g 10% C15 paraffin sulfonate, Na salt solution 4.5 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 9.0 g 10% C15 paraffin sulfonate, Na salt solution 18.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 240.0 g MMA 62.10 g 2-N- (ethylanilino) ethyl methacrylate 300.0 g of water 9.0 g 10% C15 paraffin sulfonate, Na salt solution 18.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 285.0 g MMA 15.0 g MAS 300.0 g of water FG: 38.7% mean particle size, device Mastersizer: 289 nm pH value: 5.3 11 263.4 g water 0.54 g 10% C15 paraffin sulfonate, Na salt solution 4.5 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 9.0 g 10% C15 paraffin sulfonate, Na salt solution 18.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 225.0 g MMA 77.60 g 2-N- (ethylanilino) ethyl methacrylate 300.0 g of water 9.0 g 10% C15 paraffin sulfonate, Na salt solution 18.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 285.0 g MMA 15.0 g MAS 300.0 g of water FG: 38.0% mean particle size, device Mastersizer: 283nm pH: 5.2 12 264.1 g of water 0.54 g of 10% C15 paraffin sulfonate, Na salt solution 4.5 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 9.0 g 10% C15 paraffin sulfonate, Na salt solution 18.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 210.0 g MMA 93.1 g 2-N- (ethylanilino) ethyl methacrylate 300.0 g of water 9.0 g 10% C15 paraffin sulfonate, Na salt solution 18.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 285.0 g MMA 15.0 g MAS 300.0 g of water FG: 38.9% mean particle size, device Mastersizer: 340 nm pH value: 6.8 13 264.9 g water 0.54 g 10% C15 paraffin sulfonate, Na salt solution 4.5 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 9.0 g 10% C15 paraffin sulfonate, Na salt solution 18.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 195.0 g MMA 108.0 g 2-N- (ethylanilino) ethyl methacrylate 300.0 g of water 9.0 g 10% C15 paraffin sulfonate, Na salt solution 18.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 285.0 g MMA 15.0 g MAS 300.0 g of water FG: 39.3% mean particle size, device Mastersizer: 161 nm pH value: 5.2 14 177.05 g of water 0.36 g of 10% C15 paraffin sulfonate, Na salt solution 3.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 6.0 g of 10% C15 paraffin sulfonate, Na salt solution 12.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 120.0 g MMA 82.70 g 2-N- (ethylanilino) -ethyl methacrylate 200.0 g of water 6.0 g of 10% C15 paraffin sulfonate, Na salt solution 12.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 190.0 g MMA 10.0 g MAS 200.0 g of water FG: 38.7% mean particle size, device Mastersizer: 173 nm pH value: 5.3 15 177.6 g of water 0.36 g of 10% C15 paraffin sulfonate, Na salt solution 3.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 6.0 g of 10% C15 paraffin sulfonate, Na salt solution 12.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 110.0 g MMA 93.10 g 2-N- (ethylanilino) ethyl methacrylate 200.0 g of water 6.0 g of 10% C15 paraffin sulfonate, Na salt solution 12.0 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 190.0 g MMA 10.0 g MAS 200.0 g of water FG: 38.7% mean particle size, device Mastersizer: 164 nm pH value: 5.4 16 260.1 g of water 0.54 g of 10% C15 paraffin sulfonate, Na salt solution 4.5 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 9.0 g 10% C15 paraffin sulfonate, Na salt solution 18.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 210.0 g MMA 92.9 g 2-N- (ethylanilino) ethyl methacrylate 300.0 g of water 9.0 g 10% C15 paraffin sulfonate, Na salt solution 18.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 285.0 g MMA 15.0 g MAA 300.0 g of water FG: 38.2% mean particle size, device Mastersizer: 229 nm pH value: 6.1 17 260.1 g of water 0.54 g of 10% C15 paraffin sulfonate, Na salt 4.5 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 9.0 g 10% C15 paraffin sulfonate, Na salt solution 18.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 210.0 g MMA 92.9 g 2-N- (ethylanilino) ethyl methacrylate 300.0 g of water 9.0 g 10% C15 paraffin sulfonate, Na salt solution 18.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 270.0 g MMA 15.0 g MAA 15.0 g MAS 300.0 g water FG: 39.0% mean particle size, device Mastersizer: 255 nm pH value: 5.5 18 260.1 g of water 0.54 g of 10% C15 paraffin sulfonate, Na salt solution 4.5 g of 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 9.0 g 10% C15 paraffin sulfonate, Na salt solution 18.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 210.0 g MMA 92.9 g 2-N- (ethylanilino) ethyl methacrylate 300.0 g of water 9.0 g 10% C15 paraffin sulfonate, Na salt solution 18.0 g 10% 4,4'-azobis (4-cyanovaleric acid), Na salt solution 285.0 g MMA 15.0 g MAS 300.0 g of water FG: 39.1% mean particle size, device Mastersizer: 227 nm pH value: 5.3

MMA:

Methylmethacrylat

MAS:

Methacrylsäure

FG:

Feststoffgehalt

Abbreviations used in Table 1:

MMA:

methyl methacrylate

MAS:

methacrylic acid

FG:

Solids content

Preparation of a monomer-polymer mixture and determination of the swelling time

20 g (= 40 wt .-%) of the respective polymer (component A) are in a cup (0.2 l) submitted. 30 g (= 60 wt .-%) of an ethylenically unsaturated Monomers or a monomer mixture (component B) is added and Stir with a wooden spatula until the mixture as is no longer considered processable. This time is called the swelling or pot life indicated.

The Results are listed in Table 2. The experiments without Curing show how by incorporation of polar monomers the swelling resistance can be increased.

Gelierzeitmessung with the GELNORM - Gel Timer

Device Description:

The GELNORM gel timer is an automatic device for determining the gelling time of reaction resins based on the DIN 16945 , Sheet 1 and DIN 16916 ,

Unit design:

• Clamp holder, knurled screw, measuring punch, microswitch, Holding spring, test tube, test tube holder

Execution:

The in the experiments 1-19 (Table 1) obtained dispersions were dried up and the resulting solid was pulverized. Then, a mixture of 5 g of powder and 7.5 g of monomer was prepared. The Mixture was stirred for about 1 min. With a wooden spatula and into a test tube 160 mm × ∅ 16 mm (dead weight about 10 g) filled. The total weight of test tube and test mixture should always be 22 g to a good To ensure reproducibility of the measurement results.

The Test tube including retaining spring and test mixture was placed in the holder of the measuring head and at the same time the retaining spring mounted on the microswitch. Subsequently was the measuring stamp immersed in the mixture and attached to the clamp holder. Thereafter, the experiment was started at room temperature.

Upon reaching the gelation point, the time measurement was stopped by microswitch by pulling up the test tube. The device has a reading accuracy of one second. Table 2 Experiment No. composition Monomer component Swelling time [min] Gel time [min] Poly time [min] Peak temp. [° C] Core 50% Bowl 50% 1 100% MMA 95% MMA 5% MAS THFMA 31 17 - - 2 99% MMA 1% 2- (N-ethylanilino) ethyl methacrylate 95% MMA 5% MAS THFMA 20 13 144 26.5 3 98% MMA 2% 2- (N-ethylanilino) -ethyl methacrylate 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 24 37 1440 24 4 97% MMA 3% 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 30 47 215 47 5 96% MMA 4% 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 50 38 130 61 6 94% MMA 6% 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 34 43 101 68 7 92% MMA 8% 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 30 38 79 70 8th 90% MMA 10% 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 60 19 123 80 9 85% MMA 15% 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 60 17 98 97 10 80% MMA 20% 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 60 39 60 99 11 75% MMA 25% 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 36 52 66 102 12 70% MMA 30% 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 43 63 73 112 13 65% MMA 35% 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 15 21 35 116 14 60% MMA 40% 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 12 22 26 114 15 55% MMA 45% 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 21 20 46 111 16 70% MMA 30% 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 125 not measurable 188 80 17 70% MMA 30% 2- (N-ethylaniliono) -ethyl methacrylate 90% MMA 5% MAA 5% MAS THFMA > 450 not measurable > 450 22 18 70% MMA 30% 2- (N-ethylaniliono) -ethyl methacrylate 95% MMA 5% MAS THFMA 61 61 ' 90 100 19 70% MMA 30% 2- (N-ethylaniliono) -ethyl methacrylate 98% MMA 2% MAS 1,4-BDDMA: HP MA = 1: 1 20 36 24 144

MMA:

Methylmethacrylat

MAS:

Methacrylsäure

MAA:

Methacrylamid

THFMA:

Tetrahydrofurfurylmethacrylat

1,4-BDDMA:

1,4 Butandioldimethacrylat

HPMA:

Hydroxypropylmethacrylat

Abbreviations used in Table 2:

MMA:

methyl methacrylate

MAS:

methacrylic acid

MAA:

methacrylamide

THFMA:

tetrahydrofurfuryl

1,4-BDDMA:

1,4 butanediol dimethacrylate

HPMA:

hydroxypropyl methacrylate

Curing of films in thinner Layer:

Execution: 5 g of the respective polymer (component A) are placed in a beaker (0.2 l) and mixed with different amounts of MMA. The mixtures were each spiked with 1.3 g of BP-50-FT.

The following mixing ratios were investigated: Polymer (component A) methyl methacrylate Mixing ratio (wt% / wt%) BP-50-FT 5 g 11.65 g 30:70 1.3 g 5 g 15.00 g 25:75 1.3 g 5 g 20.00 20:80 1.3 g

The blends produced were doctored into films. The layer thickness varied between 0.85 mm and 0.07 mm. The curing The film was air-exposed and was complete within 60 minutes completed.

Determination of the polymerization times:

polymerization: Benzoyl peroxide BP-50-FT (BP-50-FT is a white flowable Powder, content 50% by mass of dibenzoyl peroxide, with a phthalic acid ester phlegmatized) becomes equimolar to the activator mixed with the monomers B and component A.

All Polymerizations were in the same mixing ratio, as already described in the determination of the pot life.

The Polymerization time is defined as the time that an approach of Start of polymerization (addition of initiators) until reaching the polymerization peak temperature required. As a result the required time and the peak temperature are indicated. The measurement is carried out by means of contact thermometer under recording the temperature profile. Storage tests of 2-N-ethylanilino-ethylmethacrylate-containing Polymer dispersions in the presence in the presence of benzoyl peroxide There were core-shell emulsion polymers as described above prepared in the feed process, in which 2-N-ethylanilino-ethyl methacrylate was incorporated as an amine component in the core. These serve as an amine component in a monomer-polymer system which cured with a peroxide-amine Redoxinitiatorsystem can be. The emulsion polymers have the in the table 3 composition given below.

The Storage experiments of dispersions in the presence of a benzoyl peroxide suspension were at a ratio of 2-N-ethylanilino-ethyl methacrylate: BPO = 1: 1 (molar). This was done in a 100 ml Wide mouth bottle weighed as much dispersion as a lot of 10 grams of powder and 7.8 grams of benzoyl peroxide (20% in water).

The Storage stability of the samples became daily visual checked. Furthermore, the samples were daily new Stirred to a good mixing with the BPO suspension to ensure. The final assessment was made after addition of MMA, by checking swelling and polymerization behavior were.

All Dispersions were unchanged after a storage period of 42 days stable (see Table 3).

For the storage experiments of dispersions in MMA in the ratio dispersion solid: MMA 1: 3 with benzoyl peroxide in a ratio of 1: 1 molar to 2-N (ethylanilino) -ethyl methacrylate (see Table 4) were weighed in a 100 ml wide-mouth flask as much dispersion as one Amount of 5 g powder would correspond. This was wur weighed in the 3.9 g of benzoyl peroxide (20% suspension in water) and a defined amount of MMA.

All Dispersions are polymerized within 3-4 hours (see Table 4), d. H. there is a swelling caused by MMA, the amine component was released and redox polymerization was started.

The conclusion is that 2-N-ethylanilino-ethyl methacrylate-containing aqueous dispersions having a K / S structure (aniline component in the core) are storage-stable in the presence of BPO suspensions. Upon addition of a swelling monomer to the aqueous system, curing takes place. Table 3: Storage experiments of aqueous dispersions with benzoyl peroxide (aqueous suspension) in the ratio 1: 1 (molar) to Ethylanilinoethylmethacrylat No. composition stability 20 = No. 18 from Tab. 1 u. 2 Core: 70% MMA 30% ethylanilinoethyl methacrylate Shell: 95% MMA 5% MAS Stable after 42 days 21 = No. 17 from Tab. 1 u. 2 Core: 70% MMA 30% ethylanilinoethyl methacrylate Shell: 90% MMA 5% methacrylic acid, 5% methacrylamide Stable after 42 days 22 = No. 16 from Tab. 1 u. 2 Core: 70% MMA 30% ethylanilinoethyl methacrylate Shell: 95% MMA 5% metacrylic acid Stable after 42 days TABLE 4 Swelling / polymerization experiments of aqueous dispersions in MMA in the ratio dispersion solids: MMA 1: 3 with benzoyl peroxide in a ratio of 1: 1 molar to ethylanilinoethyl methacrylate No. composition stability 23 = No. 20 Core: 70% MMA 30% ethylanilinoethyl methacrylate Shell: 95% MMA 5% MAS Polymerized after 5 hours 24 = No. 21 Core: 70% MMA 30% ethylanilinoethyl methacrylate Shell: 90% MMA 5% methacrylic acid, 5% methacrylamide Polymerized after 4 hours 25 = No. 22 Core: 70% MMA 30% ethylanilinoethyl methacrylate Shell: 90% MMA 5% methacrylic acid Polymerized after 5 hours

Storage of dispersion powders in different monomers

It Dispersions were prepared as described in Tables 1 and 2. From the dispersions were as described above, dispersion powder won.

The Storage experiments of isolated dispersion powders in monomers were at a ratio of polymer powder: monomer = 1: 3 (w / w) carried out. The samples were shaken daily and visually checked. Classified as storage or swelling stable Mixtures were subjected to a polymerization test, by carrying out the previously described storage test again was, but with the addition of BPO (benzoyl peroxide) molar in Ratio 1: 1 to the proportion of 2-N-ethylanilino-ethyl methacrylate.

C13-MA

= Methacrylsäureester eines Gemisches aus C₁₀-C₁₆-Alkoholen

C17,4-MA

= Methacrylsäureester von Talgfettalkohol (Gemisch aus C₁₂-C₂₀-Alkoholen)

1,6HDDMA

= 1,6-Hexadioldimethacrylat

1,12DDMA

= 1,12-Dodecandioldimethacrylat

PEG400DMA

= Polyethylenglykol-400 Dimethacrylat

E4BADMA

= ethoxyliertes Eisphenol-A Dimethacrylat mit 4 Ethylenoxideinheiten

TAPTMA

= ethoxyliertes Trimethylolpropantriacrylat (Sartomer SR 415)

The following monomers were tested:

C13-MA

= Methacrylic acid ester of a mixture of C ₁₀ -C ₁₆ -alcohols

C17,4-MA

= Methacrylic esters of tallow fatty alcohol (mixture of C ₁₂ -C ₂₀ alcohols)

1,6HDDMA

= 1,6-hexadioldimethacrylate

1,12DDMA

= 1,12-dodecanediol dimethacrylate

PEG400DMA

= Polyethylene glycol-400 dimethacrylate

E4BADMA

= ethoxylated bisphenol A dimethacrylate with 4 ethylene oxide units

TAPTMA

= ethoxylated trimethylolpropane triacrylate (Sartomer SR 415)

As a result, it should be noted that none of the tested dispersion powders (composition see Table 5) in the monomers C13-MA, C17,4-MA, 1,6HDDMA or 1,12-DDMA swelled within 37 days. When stored in PEG400DMA, E4BADMA or TAPTMA, the various dispersion powders have solidified after periods of different lengths and thus swelled (compare Table 5). This allows the storage of the encapsulated in the emulsion polymer activator together with a monomer such. B. C13-MA, C17.4-MA, 1,6HDDMA or 1,12-DDMA and the initiation of the polymerization by another monomer such. PEG400DMA, E4BADMA or TAPTMA. Table 5: Swelling experiments of dispersion powder with various monomers in the ratio dispersion solid: monomer 1: 3 No. composition monomer Storage after 25 = No. 23 Core: 70% MMA 30% ethylanilinoethyl methacrylate Shell: 95% MMA 5% MAS C13-MA C17,4-MA 1,6HDDMA 1,12DDMA PEG400DMA E4BADMA TAPTMA 37 days OK 37 days OK 37 days OK 37 days OK 4 days fixed 1 day fixed 1 day fixed 26 = No. 24 Core: 70% MMA 30% ethylanilinoethyl methacrylate Shell: 90% MMA 5% methacrylic acid, 5% methacrylamide C13-MA C17,4-MA 1,6HDDMA 1,12DDMA PEG400DMA E4BADMA TAPTMA 37 days OK 37 days OK 37 days OK 37 days OK 37 days OK 3 days fixed 1 day fixed 27 = No. 25 Core: 70% MMA 30% ethylanilinoethyl methacrylate Shell: 90% MMA 5% methacrylic acid C13-MA C17,4-MA 1,6HDDMA 1,12DDMA PEG400DMA E4BADMA TAPTMA 37 days OK 37 days OK 37 days OK 37 days OK 3 days fixed 2 days fixed 1 day fixed

QUOTES INCLUDE IN THE DESCRIPTION

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

Cited patent literature

• - DE 4315788 [0005]
• - DE 1544924 A [0005]
• - DE 2710548 [0005]
• - DE 10051762 [0006]
• WO 99/15592 [0007]
• - DE 10339329 A1 [0008, 0010]
• - EP 0376096 B1 [0066]

Cited non-patent literature

• - EN ISO 11357 [0029]
• - EN ISO 11357 [0074]
• - EN ISO 11357 [0075]
• - Römpp Lexicon Chemistry; Publisher: J. Falbe, M. Regitz; Stuttgart, New York; 10th edition (1996); Keyword "Antioxidants" [0100]
• - DIN 16945 [0143]
• - DIN 16916 [0143]

Claims (19)

An emulsion polymer obtainable by polymerization of a mixture of polymerizable constituents comprising a) from 5 to 99.9% by weight of one or a plurality of monomers having a water solubility <2% by weight at 20 ° C. selected from the group consisting of monofunctional (meth) acrylate monomers , Styrene and vinyl esters; b) 0 to 70 wt .-% of one or a plurality of monomers copolymerizable with the monomers a) monomers; c) 0 to 20 wt .-% of one or a plurality of di- or polyunsaturated vinyl compounds; d) 0 to 20 wt .-% of one or a plurality of polar monomers having a water solubility> 2 wt .-% at 20 ° C; and e) 0.1-95% by weight of at least one activator of the formula I,

wherein - R ^{1 is} hydrogen or methyl; X is a linear or branched alkanediyl group having 1 to 18 carbon atoms which may be monosubstituted or polysubstituted by hydroxyl groups and / or by C1-C4 alkoxy groups; - R ^{2 is} hydrogen or a linear or branched alkyl radical having 1 to 12 carbon atoms, which is optionally substituted one or more times with hydroxyl groups or C 1 -C 4 -alkoxy groups, wherein the hydroxyl groups may be partially esterified with (meth) acrylic acid; - R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} independently hydrogen or a linear or branched alkyl or alkoxy group having 1 to 8 carbon atoms, which may be monosubstituted or polysubstituted by hydroxyl groups; and where appropriate, two of the radicals R ³ to R ⁷ are joined together to form a five- to seven-membered ring and optionally form a fused aromatic ring system with the phenyl radical; wherein the activator e) is incorporated into the emulsion polymer via covalent bonds; wherein the emulsion polymer is obtainable by polymerizing the constituents a) to e) in a first stage as a core in the manner of a core-shell polymerization and then, in at least one further stage as shell, mixing the components a) to d) ; and wherein the components a) to e) together give 100% by weight of the polymerisable constituents of the mixture A). Emulsion polymer according to claim 1, characterized in that in the formula (I) of the activator e) the radical R ^{1 is} methyl. Emulsion polymer according to one of the preceding claims, characterized in that in the formula (I) of the activator e) X is an ethylene group -CH ₂ -CH ₂ -. Emulsion polymer according to one of the preceding claims 1 to 2, characterized in that in the formula (I) of the activator e) X is a 2-hydroxypropylene group -CH ₂ -CH (OH) -CH ₂ -. Emulsion polymer according to one of the preceding claims, characterized in that in the formula (I) of the activator e) R ^{2 is} selected from the group consisting of methyl, ethyl and 2-hydroxyethyl. Emulsion polymer according to one of the preceding claims, characterized in that in the formula (I) of the activator e) one of the radicals R ³ to R ^{7 is} methyl while the remaining four radicals are hydrogen. An emulsion polymerizate according to any one of claims 1 to 5, characterized in that in the formula (I) of the activator e) two of the radicals R ³ to R ^{7 are} methyl while the remaining three radicals are hydrogen. Emulsion polymer according to one of the preceding Claims, characterized in that the component a) one or more methacrylate monomers and / or acrylate monomers consists. Emulsion polymer according to one of the preceding Claims, characterized in that the component e) in an amount of 10-60 wt .-%, preferably 20-50 Wt .-%, is present. Emulsion polymer according to claim 8, characterized in that the component a) is methyl methacrylate. Emulsion polymer according to one of the preceding Claims, wherein the emulsion polymer thereby obtainable is that the components a) to e) according to the Claims 1 to 9 polymerized in aqueous emulsion. Emulsion polymer according to one of the preceding claims, characterized in that the constituents a) to e) for the core and the constituents a) to d) for the shell or the shells so selected that in the resulting emulsion polymer, the glass transition temperature T _GS at least one shell is greater than the glass transition temperature T _{GK of} the core, wherein the glass transition temperatures T _{G are determined} according to EN ISO 11357. Emulsion polymer according to claim 12, characterized in that the constituents a) to d) are selected for the shell so that the glass transition temperature T _{GS of} at least one shell is greater than 100 ° C in the resulting emulsion polymer, wherein the glass transition temperature T _GS according to EN ISO 11357 is determined. Curing by a redox initiator system Comprising two- or multi-component system with controllable pot life A) 0.8-69.94 wt .-% of an emulsion according to the Claims 1 to 13 B) 30-99.14 wt .-% of two or a plurality of ethylenically unsaturated monomers; C) 0.05-10% by weight of peroxides; possibly D) 0-60 % By weight of unsaturated oligomers; possibly e) 0.01-2% by weight of a polymerization inhibitor; and possibly F) 0-800 parts by weight of auxiliaries and additives; in which the sum of the components A) + B) + C) + D) + E) gives 100% by weight and the amount of F) is 100 parts by weight of the sum A) + B) + C) + D) + E), characterized in that i) at least one component B "of component B) for the Emulsion polymer does not act or does not swell sufficiently; ii) at least one component B "of component B) for the Emulsion polymer A) swelling acts, so that the polymer-fixed Activator e) of the polymer A) with the component C) for the reaction can reach; iii) Component A) and Component B 'to Use of the system can be stored together; and iv) Component B "until the system is used by the component A) is stored separately. Two- or multi-component system according to claim 14, characterized in that v) the constituent B "of the Component B) and component C) until use of the system be stored together. Two- or multi-component system according to claim 15, characterized in that vi) the component B "of the Component B) and component C) until use of the system stored together in a non-aqueous system. Two- or multi-component system according to one of Claims 14 to 16, comprising 5 to 45% by weight of component A), 40 to 94.89% by weight of component B), 0.1 to 5% by weight of component C), 0 to 40% by weight of component D); 0.01-0.2% by weight of component E); and 0 to 800 parts by weight of component F), the sum of the constituents A) + B) + C) + D) + E) being 100% by weight and the amount of F) being 100 parts by weight of the sum A) + B ) + C) + D) + E). Two- or multi-component system according to one of preceding claims, characterized in that component C) comprises dibenzoyl peroxide and / or dilauryl peroxide. Use of a two- or multi-component system according to claims 14 to 18 in adhesives, casting resins, Floor coatings and other reactive coatings, sealants, Impregnating compounds, investments, masses for Manufacture of artificial marble and other artificial stones, Masses for reactive dowels, dental materials, porous Plastic molds for ceramic objects or in unsaturated polyester resins and vinyl ester resins.