EP2167559A1

EP2167559A1 - Two or more-component system cured by a redox initiator system with controllable working life, and the use thereof

Info

Publication number: EP2167559A1
Application number: EP08774393A
Authority: EP
Inventors: Gerold Schmitt; Wolfgang Klesse; Joachim Knebel
Original assignee: Evonik Roehm GmbH
Current assignee: Evonik Roehm GmbH
Priority date: 2007-07-12
Filing date: 2008-06-27
Publication date: 2010-03-31
Also published as: JP2010532809A; TW200922946A; RU2010104647A; KR20100048992A; BRPI0813691A2; CA2693019A1; US20100286331A1; WO2009007253A1; AU2008274369A1

Abstract

The invention relates to a two or more-component system cured by a redox initiator system, with controllable working life, comprising A) 0.8% - 69.94% by weight of an emulsion polymer obtained by polymerization of a mixture; B) 30% - 99.14% by weight of one or a plurality of ethylenic unsaturated monomers; C) 0.05% - 10% by weight of peroxide; and optionally additional components. The invention is characterized in that components A) and components C) can be stored together, and at least one component of components B) is stored separately from components A) and C), wherein the separately stored component of components B) is selected in such a way that the swelling capacity of this component of components B) is so high for the polymer A) that the polymer-fixed activator e) of polymer A) can react with components C).

Description

By a redox initiator system curing two- or multi-component system with controllable pot life and its

use

The invention describes a curing by a redox initiator system two or more component system with controllable pot life and its application.

In particular, the invention relates to two- or multi-component systems in which the activator component of the

Redox initiator system can be stored together with the peroxide component. Expediently, in a two-component system according to the invention, all other constituents are stored together until they are used, with the exception of at least one constituent of the monomer component, and are stable in this case. The polymerization is triggered only by addition of a Monomerbestandteils. Finally, the invention also relates to the various applications of the two- or multi-component systems.

Redox initiation curing two-component systems based on radically polymerizable monomers have long been known. In general, the procedure is such that the missing redox system components or all redox system components are added to a liquid monomer or monomer mixture which may contain a redox component prior to use.

In addition, systems are described which additionally contain a polymer dissolved in the monomer or monomer mixture. Especially of dental applications, systems are known in which liquid monomer, a Perlpolymehsat and a redox initiator system are mixed before use to a highly viscous mass. Exemplary of a variety of publications on the subject are DE 43 15 788, DE OS 1 544 924 and 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 the hardening due to the required evaporation of the water, especially in thicker layers, takes a long time and larger amounts of water interfere with 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 stable in storage for weeks and must be heated to high temperatures (eg 130 ^° C.) for filming.

DE 103 39 329 A1 describes a two-component system with controllable pot life curing by a redox initiator system, consisting of an emulsion polymer or more emulsion polymers and an ethylenically unsaturated monomer or a monomer mixture of ethylenically unsaturated monomers, where both the emulsion polymer and the monomer or the monomer mixture may contain one of the components of a redox initiator system. 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. On the one hand, this is the security of the application. By overlaying, ie storing too long, for example, the concentration of the component encapsulated in the polymer may decrease, for example due to migration. As a consequence, the reactivity of the system may deviate from the desired values.

On the other hand, it is inherently difficult to achieve a high loading of the polymer with the encapsulated component in the system described in DE 103 39 329 A1. In practice, at higher loadings, e.g. 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.

Finally, even with a high degree of loading and just then the long-term safety of the load level must be ensured.

In addition, many systems of application security are becoming increasingly important. The components of the redox initiator system, essentially the activator component and the peroxidic component, are essential for the rate of cure of the overall system. Insofar as the two specified special constituents have to be stored separately from one another until they are cured, there is always the risk that an incorrectly too slow or too rapid hardening reaction will occur due to incorrect metering of one of the two components.

In view of the above-mentioned and discussed prior art, it was an object of the invention to provide room temperature curing two- or multi-component systems available whose pot life is adjustable within wide limits and still at a defined time without Rapidly and completely cure energy supply or external mechanical impulse.

Furthermore, the task was to achieve complete curing even in thin layers without exclusion of air.

A further object to be achieved according to the invention is to minimize odor nuisance and to keep the concentration of monomer in the air below the limit values applicable to the respective monomer during use.

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

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

Among other things, it was also an object of the invention to provide a system that can satisfy the aforementioned spectrum of properties in total and yet easy and safe to handle.

The indication of uses for the system according to the invention was to be made.

In addition, the object of the invention was also to reduce the number of components of the multicomponent system as much as possible, if possible to avoid three or more multicomponent systems and, if possible, to use two-component systems. Finally, it was also an object of the invention to provide a system which ensures the metering safety of the two components with regard to the mixing of activator and peroxide. If possible, the ratio of activator to peroxide should not be able to be changed by the user in order to be able to rule out difficulties in initiating the curing of the overall system.

The objects according to the invention or partial aspects of the objects according to the invention are achieved by a novel two-component or multi-component system with controllable pot life curing by means of a redox initiator system

A) 0.8 - 69.94 wt .-% of an emulsion polymer obtainable by polymerization of a mixture having

a) 5 to 99.9 wt .-% of one or a plurality of monomers having a water solubility <2 wt .-% at 20 ⁰ 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 ⁰ C; and e) 0.1-95% by weight of at least one activator of the formula I,

(I) wherein

R1 is hydrogen or methyl; X is a linear or branched alkanediyl group having 1 to 18

Carbon atoms which may be substituted one or more times with hydroxyl groups and / or with 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 by hydroxyl groups or C 1 -C 4 -alkoxy groups, where 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 polymer A) 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 subsequently in at least one further stage as shell a mixture of the constituents a) to d); and wherein the components a) to e) together give 100% by weight of the polymerisable constituents of the mixture A);

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 unsaturated oligomers; possibly

E) 0-2% by weight of a polymethylation 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 ),

wherein the system is characterized in that the component A) and the component C) are stored together and at least one component of the component B) is stored separately from the components A) and C), wherein the separately stored component of the component B) so is chosen so that the swelling capacity of this component of component B) for the polymer A) is so high that the polymer-fixed activator e) of the polymer A) with the component C) can be implemented.

In general, in the system of the invention, the components A) and C) are present together in mixture. This is particularly surprising since the activator component e) and the peroxide C) form the redox initiator system which regularly initiates the curing. The storage stability is achieved by the encapsulation of the activator component in the core of the core-shell emulsion polymer, so that only a reaction possibility with the activator component is given for the peroxide component when the emulsion polymer has been swollen by monomers with sufficiently high swelling capacity.

An important advantage of the invention is, inter alia, that one usually manages with a two-component system. If one does not store peroxide and encapsulated activator component, then one can possibly be forced to resort to a three-component system. However, this is less convenient than a two-component system. A common storage of peroxide and monomer would also not be a preferred alternative, since this would result in a poor storage stability.

In the case of the two-component or multicomponent system according to the invention, the components A), C), D), E) and F) are preferably present as a storable mixture, while the components B) are added to this mixture before use.

On the other hand, it may also be preferred to combine the components A), B), C), D), E) and F), with the exception of only one component of component B), which has a sufficiently high swelling power, to produce the emulsion polymer A ) to the extent that the activator component c) bound covalently to the core of the polymer A) is available for the reaction with the peroxide component C). In this way, it is possible, for example, to adjust the pot life as a function of a single monomer without changing the hardening time of the system. This opens up a broad field of application to the systems according to the invention.

Two or more component systems according to the invention can be used with great advantage in adhesives, casting resins, floor coatings, compositions for reactive dowels, dental materials or in sealing compounds.

With the compositions according to the invention, a broad range of the concentration of the activator (range of variation) can be realized. A particular advantage is that at high activator concentrations in component A, less of A must be added to the two or more component system prior to use. The possibility of varying the reactivity is also advantageous. With constant addition amount of component A, the reactivity can be varied by A different levels of the activator.

Component A is 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 ⁰ 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 ⁰ C; and e) 0.1-95% by weight of at least one activator, wherein the constituents a) to e) together comprise 100% by weight of the polymerisable

Components of the mixture, according to which the emulsion polymer = component A results, where e1) the activator is a compound 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 C 1 -C 4 alkoxy groups;

- R ^{2 is} hydrogen or a linear or branched alkyl radical having 1 to 12 carbon atoms, optionally one or more times with

Hydroxyl groups or C1 - C4 alkoxy substituted

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ independently of one another are hydrogen or a linear or branched alkyl or alkoxy group having 1 to 8 carbon atoms which may be mono- or polysubstituted by hydroxyl groups, where the hydroxyl groups are partially substituted by ( Meth) acrylic acid can be esterified; 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;

e2) wherein the activator e) is incorporated into the emulsion polymer via covalent bonds;

and wherein the polymer A) 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 constituents a) to d).

The notation (meth) acrylate herein and throughout the context of the invention includes both methacrylate, such as methacrylate. Methyl methacrylate, ethyl methacrylate, etc., as well as acrylate, e.g. Methyl acrylate, ethyl acrylate, etc., as well as mixtures of both.

The emulsion polymer = component A) is preferably composed essentially of (meth) acrylate monomers and styrene and / or styrene derivatives and / or vinyl esters. Particularly preferred is the structure of at least 80% methacrylate and acrylate monomers, most preferably the structure of exclusively methacrylate and acrylate monomers.

Examples of monofunctional methacrylate and acrylate having a solubility in water <2 wt .-% at 20 ⁰ C (component Aa)) acrylate, 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.

By styrene derivatives is meant, for example, 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 ⁰ C results, preferably above 80 ⁰ C and in particular above 100 ° C, when the emulsion polymer A) is to be isolated by drying. The glass transition temperatures are measured in accordance with EN ISO 11357. If the emulsion polymer A) is to be added to the two-component or multicomponent system as an aqueous dispersion, the glass transition temperature may be lower. To oppose the monomers B) a sufficiently high swelling resistance is usually a glass transition temperature above room temperature advantageous. It is preferably above 30 ^° C., more preferably above 40 ^° C., in particular above 60 ^° C. Thus, it is not excluded that in certain cases, glass transition temperatures below room temperature may be advantageous. This may for example be the case when the dissolving power of the monomers used for component B) is low, so that the swelling takes too long.

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:

Tg the glass transition temperature of the copolymer (in K), T _gA , T _gB , T _gC , etc., the glass transition temperatures of the homopolymers of the monomers A, B, C, etc. (in K). w _A , W _B , W _C USW. represent the mass fractions of the monomers A, B, C, etc. in the polymer.

The higher the glass transition temperature of the polymer, the greater the swelling resistance compared to the monomers added before the application and thus the pot life. Likewise, increasing the molecular weight / increasing the molecular weight of the polymer generally causes an increase in the swelling resistance.

In this respect, particularly preferred polymers are characterized in that a) consists of one or more methacrylate monomers and / or acrylate monomers. Especially useful is a) methyl methacrylate.

Examples of component A b) are maleic anhydride, itaconic anhydride and esters of itaconic and maleic acid. Their proportion of the emulsion polymer can be up to 70 wt .-%, preferably from 0-30% by weight, especially 0-10% by weight. Most preferably, component A b) is omitted.

The incorporation of higher levels 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.

Suitable polyunsaturated monomers (crosslinkers) which can be used successfully in the context of the invention include, among others, ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate and their higher homologs, 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.

The swelling resistance can also be controlled by the incorporation of polar monomers (component A d)), such as methacrylamide or methacrylic acid in the emulsion polymer. This increases with increasing amount of methacrylamide or methacrylic acid.

Examples of other polar monomers are acrylic acid, acrylamide, acrylonitrile, methacrylonitrile, itaconic acid, maleic acid or N-Methacryloyloxyethylethylenharnstoff and N-Methacryloylamidoethylethylenharnstoff. Also, N-methylolacrylamide or N-methylolmethacrylamide and their ethers are conceivable, provided that their proportion is limited so that despite crosslinking of the dispersion particles their Swelling is sufficiently possible and the initiation of the polymerization is not affected.

The proportion of N-methylolacrylamide or methacrylamide should preferably not exceed 10% by weight, based on component A). A content of less than 5% by weight, more preferably less than 2% by weight, in particular 0% by weight, is preferred.

Further polar monomers are hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, homologues of alkoxy-polyethylene glycol methacrylate, of alkoxypolypropylene glycol methacrylate, of methacryloyloxypolyethylene and polypropylene glycol and of vinyl oxypolyethylene and polypropylene glycol. All of the monomers mentioned may also be present as a mixed form of ethylene and propylene glycol repeating units. The degree of polymerization may be 2 to 150, preferably 2 to 25. Alkoxy is primarily methyl, ethyl and butyl radicals. Longer alkyl chains, e.g. C18, are also possible, but not preferred. Particularly preferred is a methyl radical.

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, the higher the required proportion of polar monomers in order to achieve a specific swelling resistance. Furthermore, the proportion of polar monomers to vote on the dissolving power of the monomers used in the formulation B.

In general, the proportion of polar monomers in the range of 0 and 20 wt .-%, preferably from 1 to 10 wt .-%, particularly preferably from 2 to 5 wt .-%, in particular from 3 to 5 wt .-% , based on component A). If short pot lives are desired, for example a few minutes, or if the solubility of the monomers in component B) is low, it may be advantageous to to limit the content to below 2% or to completely abstain from polar monomers.

Methacrylamide and acrylamide as well as 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 component Ae) to be used successfully in the context of the invention obeys the general formula I described above. The disclosure of the invention is understood to mean 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 eg the methanediyl (= methylene group), ethanediyl, propanediyl, 1-methylethanediyl, 2-methylpropanediyl, 1, 1-dimethylethanediyl, pentanediyl, 2-methylbutanediyl, 1, 1-dimethylpropanediyl, hexanediyl, heptanediyl , Octanediyl, 1, 1, 3,3-tetramethylbutanediyl, nonanediyl, isononanediyl, decanediyl, undecanediyl, dodecanediyl or hexadecanediyl.

The term linear or branched alkyl radical having 1 to 8 carbon atoms is meant for the invention radicals such. 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.

The term linear or branched alkyl radical having 1 to 12 carbon atoms for the invention means radicals having 1 to 8 carbon atoms as described above and, for example, the nonyl, isononyl, decyl, undecyl 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.

The term linear or branched alkoxy group having 1 to 8 carbon atoms for the invention is understood to mean alkoxy groups in which 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 the 1,1,3,3-tetramethylbutyl radical.

As the formula (I) shows, the possible

Activator components Ae) in general around (meth) acryloyl-functionalized amine derivatives. In general, the activator or accelerator components are based on modified amines, such as 2-N- (ethylanilino) ethanol or 2-N- (ethylanilino) propanol, and these amines are converted to polymerizable accelerator / activator components, preferably by introduction of (meth) acrylate. Accordingly, for example, m-toluidine and Xylidindehvate or other derivatives can be used as a starting point to obtain the activator or accelerator component.

Preferred activator / accelerator components Ae) include the following compound classes: 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 alkylaniline (mono, di, tri, tetra, penta) -, p). Examples of other 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) -toluidine. These substances are used singly or in a mixture of two or more.

Particularly suitable 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 multi-component systems is not impaired, for example by insufficient swellability of the emulsion polymethylate in component B) due to a too 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 in the two-component or multicomponent system contains

Polymerization triggers in the desired time interval and whether the polymerization is fast and complete 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.

The proportion of the polymerizable activator A e) in component A) can be between 0.1 and 95% by weight. Preferably, it is chosen as high as possible, for example between 5 and 60 wt .-%, particularly preferably 10 to 60 wt .-%, in particular 20 to 50 wt .-%. The upper limit is determined by the behavior of the selected activator in the emulsion polymerization. The skilled person will make sure that not too large amounts of unacceptable amounts of coagulum are formed, or too high residual monomer contents remain. It may also be that the specific activity of the activator decreases with increasing installation quantity. Since the polymerizable activator is a rather expensive monomer component is The skilled person will strive to find a compromise between the highest possible installation size and cost-effectiveness.

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

Core-shell polymer here stands for a polymer which has been prepared by a two-stage or multistage emulsion polymerization, without the core-shell structure being shown, for example, by electron microscopy. If the polymerizable activator is incorporated only in the core, that is to say in the first stage, then such a structure contributes to the fact that the activator is not accessible to the peroxide until swelling and thus premature polymerization is prevented. A particular embodiment of the invention relates to the fact that the polar monomers are confined to the shell, core and shell, apart from the polymehsierbaren activator in the core, but otherwise the same structure. In another embodiment, the core and the shell may differ significantly in the monomer composition, which has an effect, for example, on the particular glass transition temperature. In this case, it is advantageous if the glass transition temperature of the shell is above the core, preferably above 60 ⁰ C, more preferably above 80 ⁰ C, in particular above 100 ⁰ C. In addition, in this embodiment, the polar monomers on the Shell be limited. Especially by the core-shell structure particularly advantageous properties are achieved. Among others, this includes the better protection of the activator against premature contact with the peroxide by a shell or a plurality of shells. The activator monomer is preferably incorporated into the core. It may also be necessary to make the cured polymers more flexible. In such cases, the core is set at a relatively low glass transition temperature. The shell with a higher glass transition temperature then has the task of ensuring the desired swelling resistance and possibly the insulation as a solid. The weight ratio of core to shell depends on how well the activator is to be protected or what effects are expected from this setup. In principle, it may be between 99 and 99: 1, ie it is generally not critical as long as the purpose of the emulsion polymer A) to activate the polymerization of the two-component or multicomponent system in the desired manner is not impaired.

If it is intended to protect the activator by the shell, then the shell content will usually be limited to the extent necessary to allow a high Aktivatoranteil in the emulsion polymer.

If special effects, e.g. To achieve a flexibilization of the cured polymer systems by a core polymer with low glass transition temperature, the core-shell ratio is tuned to the desired effects. Most of the skilled person will adjust the shell content 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 polymer according to the invention, in which the components a) to e) of component A) are 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 described by way of example in EP 0376096 B1.

Preferably, an initiator is selected which forms no redox system with the polymerizable activator A e). For example, azo initiators such as the Na salt of 4,4'-azobis (4-cyanovaleric acid) are suitable.

The solid of component A) can be recovered from the dispersion by known methods. These include spray drying, Frozen coagulation with suction and drying and pressing by means of an extruder. The polymer is preferably obtained by spray drying.

However, for the purposes of the present invention, it is by far preferable that component A) is not isolated. Since some amount of water generally does not interfere with the intended applications, component A) may also be added to the system as an aqueous dispersion.

The molecular weight of component A), expressed as the weight-average molecular weight M _w, influences the swelling resistance to a certain extent. High weight average molecular weights M _w tend to increase the swelling resistance, while lower weight average molecular weights M _{w have a} lowering effect. Thus, the desired pot life is decisive, inter alia, whether the expert selects a high molecular weight or a rather low.

If no particular effects are to be achieved via the molecular weight, the person skilled in the art will generally have the molecular weight between 10,000 g / mol and 5,000,000 g / mol, preferably between 50,000 g / mol and 1,000,000 g / mol, and very particularly preferably between 100,000 g / mol and 500,000 g / mol. The molecular weight is determined by gel permeation chromatography. The measurement takes place in THF, PMMA is used as calibration standard.

The swelling resistance can also be adjusted by the choice of particle size. The larger the particle diameter, the lower the swelling rate.

The primary particle size of component A) is generally between 50 nm and 2 micrometers, preferably between 100 nm and 600 nm and most preferably between 150 nm and 400 nm. The particle size is measured using 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 _G κ of the core, wherein the glass transition temperatures T _{G are determined} according to EN ISO 11357.

Yet another process modification provides that the constituents a) to d) are selected for the shell such that in the resulting polymer the glass transition temperature T _G s of at least one shell is greater than 80, preferably greater than 100 ^° C., the glass transition temperature T _GS according to EN ISO 11357.

The emulsion polymerization is basically possible as a batch or feed polymerization, feed polymerization is preferred. Likewise, the preparation of A) via a Miniemulsionspolymerisation is possible. The procedures are known to the person skilled in the art.

The pot life of the formulation of components A), B), C), D), E) and F) can be influenced by the swelling power of the monomers used in component B). While methyl (meth) acrylate has a high swelling power and thus results in relatively short pot lives, more hydrophobic monomers such as 1,4-butanediol di (meth) acrylate and high molecular weight monomers such as ethyltriglycol (meth) acrylate tend to increase the pot life.

In principle, a wide variety of monomers which act in a degree of swelling can be used in the invention. It is important that the monomer (s) used are / are selected and used with regard to the swelling capacity for component A). In this case, with knowledge of the present inventions, the skilled person reliably achieves component B) on component A with a few routine tests. to vote and thus provide a system with the desired pot life.

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-thmethylcyclohexyl ( 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 , Propylene 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, Thmethylolpropanth (meth) acrylate, trimethylolpropane di (meth) acrylate, th (meth) acrylate of an ethoxylated trimethylolpropane with 3 - 10 moles of ethylene oxide, di (meth) acrylate of an ethoxylated bisphenol-A with 2 - 20 moles of ethylene oxide, preferably 2-10 moles of ethylene oxide and / or a polyethylene glycol dimethacrylate 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 Hydroxyethyl methacrylate and the phosphoric acid ester of hydroxyethyl (meth) acrylate, the proportion is usually subordinate.

Among others, preferred for component B) is one or a plurality of compounds selected from the group consisting of

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 of an ethoxylated bisphenol-A with 2-10 moles of ethylene oxide and / or one

Polyethylene glycol dimethacrylate with 1-10 ethylene oxide units.

Particular preference is given to (meth) acrylates having a molecular weight above 140 g / mol, particularly preferably above 165 g / mol and in particular above 200 g / mol.

Methacrylates are preferred over acrylates for toxicological reasons.

In addition to long pot life due to low swelling speed have

High molecular weight monomers still have the advantage of low emissions. On the other hand, their viscosity generally increases with the molecular weight and the dissolving power for the emulsion polymer decreases, so that a compromise must be made, in particular if polymers or oligomers are used in appreciable proportions.

The peroxide C) is the partner of the activator in the redox system. Its proportion is generally between 0.05 and 10 wt .-%, preferably 0.1 to 5% by weight. Usually, a proportion of 0.5 to 5 wt .-% is selected, preferably 0.5 to 3, in particular 0.5 to 2 wt .-%. Decisive for the Peroxidanteil is that in the intended application a complete cure in the desired time and the cured system has the properties tailored to the purpose.

The peroxide is usually phlegmatized e.g. in plasticizer or water or other medium.

Particularly preferred for the invention is the peroxidic initiator in the aqueous phase.

Typical peroxide contents of this peroxide formulation are 20-60% by weight.

Particularly suitable peroxides are dibenzoyl peroxide and dilauryl peroxide. Even more useful are aqueous phases of these two peroxides, either alone or in admixture with each other or other peroxide compounds not mentioned individually.

Another variant consists in absorbing the peroxide in an emulsion polymer (component C). In a further embodiment of the invention component C thus consists of an emulsion polymer containing a peroxide (component C). The emulsion polymer of component C may be the same or different structure as component A, but contains no polymerizable activator as a comonomer. Typical peroxide contents in component C are below 20, in particular below 10 wt .-%.

After all components have been mixed, the polymerization does not start until the polymer particles of both components A and C have swollen.

It is generally not critical whether the emulsion polymers A and C are the same or different composition, as long as any incompatibility does not adversely affect. As oligomers (component D)) unsaturated polyesters, and polyurethane (meth) acrylates based on polyether, polyester, or polycarbonate diols, and mixtures thereof can be used. Furthermore, vinyl-terminated prepolymers based on acrylonitrile and butadiene can be used. It is also possible to use epoxide (meth) acrylates and also star-shaped copolymers, as are obtainable, for example, by polymerization of (meth) acrylates in the presence of polyfunctional mercaptans.

Preferably, the oligomers are polyunsaturated.

It is also possible to use polymers based on polyacrylates, polyesters, polyethers, polycarbonates or the corresponding copolymers. These can be both saturated and unsaturated. The mixing ratio and the amount used is of the desired

Application dependent. The polymers or their proportion are usually selected so that the viscosity of the mixture is not adversely affected.

The molecular weight of the unsaturated oligomers is typically 500 to 20,000, in particular 1,000 to 5,000 g / mol. Saturated polymers typically have molecular weights above 20,000, for example 50,000-200,000 g / mol. In all cases, these are weight-averages of the 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, reference is made to the usual technical literature, in particular to the Rompp-Lexikon Chemie; Publisher: J. Falbe, M. Regitz; Stuttgart, New York; 10th edition (1996); Reference "Antioxidants" and cited references cited here. Suitable inhibitors include, inter alia, optionally substituted phenols, optionally substituted hydroquinones, such as hydroquinone monomethyl ether (HQME), optionally substituted quinones, optionally substituted pyrocatechols, 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 thazines, 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 are preferably used. Particularly preferred are hydroquinone, hydroquinone monomethyl ether and 4-methyl-2,6-di-tert-butylphenol.

In general, 0.2 wt .-% inhibitor are sufficient, usually the proportion is significantly lower, for example at 0.05 wt .-% or below. The pot life of the system after admixture of the components A and C is controlled according to the invention via the swelling of the component A. Higher levels than 0.2 wt% inhibitor, e.g. 1 wt .-% or higher, which are sometimes used in systems of the prior art to extend the pot life, are therefore usually not necessary, but should not be excluded. A content of not more than 0.2% by weight, in particular not more than 0.05% by weight, is preferred.

The formulation may in addition to the components described customary particulate fillers (component F), such as titanium dioxide, carbon black or silica, glass, glass beads, glass powder, cement, quartz sand, quartz, sand, corundum, earthenware, clinker, barite, magnesia, calcium carbonate, marble powder or aluminum hydroxide, mineral or organic pigments and auxiliaries (component F)). Adjuvants may be, for example: plasticizers, water, leveling agents, thickeners, defoamers, adhesives or wetting agents. Preferably, in addition to possibly used for the phlegmatization of the peroxide plasticizer no further plasticizer is included.

The particulate fillers usually have a particle diameter of about 0.001 mm to about 6 mm.

On one part by weight of polymer usually 0 to 8 parts by weight of fillers are used.

The invention relates to a two-component or multi-component system. This means that in terms of a "kit of parts" before the actual application of the entire system at least two subsystems are present, which are mixed together for the actual applications of the system.

The particular advantage of the system according to the invention consists in the fact that the components of the redox initiator system together form a storage-stable mixture. Particularly advantageous is the presence of components A) and C) in a storage-stable aqueous phase. Furthermore, a mixture with components A) and C) may also comprise parts of component B), as well as all other components D), E) and F), provided that it is stored together with components A) and C) Monomer component B) is not able to adequately swell component A). The actual hardening of the

Complete system is then achieved only by mixing with a suitable monomer B).

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

From the long pot lives after mixing the components, it can be concluded that the polymer-fixed activator Ae) is sufficiently stable in the

Is hidden polymer particles. Surprising is the rapid and strong increase in temperature at a certain point in time, which shows that a long pot life can be set with the method according to the invention, without the subsequent polymerization being impaired.

The mixing ratio depends on the intended application. This determines the amount of the components used A - F. The mixing ratio of the components used is preferably to be chosen so that a complete polymerization of the given system is achieved. In particular, a sufficient amount of a suitable

Redox initiator system are available, wherein the activator is provided at least predominantly in the form of an emulsion polymer (component A).

Since the proportion of polymehsierbaren activator A e) in component A) can be selected within wide limits, there is also a wide margin for the amount of component A). Thus, the proportion of component A) can be between 0.8 and 69.94 wt .-%, and in turn 0.1 to 95 wt .-% of the polymerizable activator included. As a rule, the amount of activator is adjusted to the proportion of peroxide used. The peroxide is the partner of the activator in the redox system. Its proportion is generally between 0.05 and 10 wt .-%, preferably 0.1 to 5 wt .-%. Usually, a proportion of 0.5 to 5 wt .-% is selected, preferably 0.5 to 3, in particular 0.5 to 2 wt .-%. Decisive for the peroxide content and the proportion of component A is that in the intended application, a desired complete polymerization takes place in the desired time and the hardened system provides the performance tailored to the application

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

Furthermore, the mixture may contain between 0 and 800 parts by weight, based on the sum of A - D to 100 parts by weight, of fillers, pigments and other auxiliaries.

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;

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), from 0.1 to 5% by weight of component C), 0-30% 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 40 to 94.89% by weight of component B),

From 0.5 to 5% by weight of component C),

From 0 to 30% 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)

The content of component D) is particularly preferably 0 to 30% by weight.

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

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 compounds, 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.

Particularly preferred is the application of the described two- or multi-component system in adhesives, casting resins, floor coatings, compositions 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 .-%, may be advantageous. The proportion of the activator in component A can then be limited, for example, to 0.1 to 5% by weight, based on component A. The components B and D taken together are then between 69.9 and 30 wt .-%. The peroxide content is preferably 0.1 to 5 wt .-%.

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

The following examples and comparative examples serve to further illustrate the invention

Preparation of the emulsion polymers All emulsion polymers were prepared by the feed process.

The original was stirred in a reaction vessel at 80 ^° C. for 5 minutes. 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

Table 1 continued

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 placed in a beaker (0.2 l). 30 g (= 60% by weight) of an ethylenic unsaturated monomer or a monomer mixture (component B) was added and stirred with a wooden spatula until the mixture is considered no longer processable. This time is given as the swelling or pot life.

The results are shown in Table 2. The tests without curing show how by incorporation of polar monomers of the swelling resistance can be increased.

Gel time measurement 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 DIN 16945, page 1 and DIN 16916.

Unit design:

Clamp holder, knurled screw, measuring punch, microswitch, retaining spring,

Test tube, test tube holder

Procedure: The dispersions obtained in Experiments 1-19 (Table 1) 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 filled into a test tube 160 mm x 0 16 mm (weight about 10 g). The total weight of the test tube and test mixture should always be 22 g to ensure good reproducibility of the measurement results. The test tube including holding spring and test mixture was placed in the holder of the measuring head and at the same time the retaining spring was mounted on the microswitch. Subsequently, the measuring punch was 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

Table 2 continues

Abbreviations used in Table 2:

MMA: methyl methacrylate

MAS: methacrylic acid

MAA: methacrylamide

THFMA: tetrahydrofurfuryl methacrylate

1, 4-BDDMA: 1, 4 butanediol dimethacrylate

HPMA: hydroxypropyl methacrylate

Curing films in a thin layer:

Procedure: 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 mixed with 1.3 g of BP-50-FT. The following mixing ratios were investigated:

The blends produced were laced into films. The layer thickness varied between 0.85 mm and 0.07 mm. Curing of the films was done in air and was complete within 60 minutes.

Determination of the polymerization times:

Polymerization Process: Benzoyl Peroxide BP-50-FT (BP-50-FT is a white flowable powder containing 50% by mass of dibenzoyl peroxide, with one

Phthalic acid phlegmatized) is mixed in equimolar amounts to the activator with the monomers B and component A.

All polymerizations were carried out in the same mixing ratio as already described in the determination of the pot life.

The polymerization time is defined as the time required for a start of polymerization (addition of initiators) until the polymerization peak temperature is reached. As a result, the required time and the peak temperature are indicated. The measurement is carried out by means of a contact thermometer recording the temperature profile. Storage Experiments of 2-N-ethylanilino-ethyl methacrylate-containing Polymer Dispersions in the Presence in the Presence of Benzoyl Peroxide Core-shell emulsion polymers were prepared as described above 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 can be cured with a peroxide-amine redox initiator system. The Emulsion polymers have the composition given in Table 3 below.

The storage experiments of dispersions in the presence of a benzoyl peroxide suspension were carried out at a ratio of 2-N-ethylanilino-ethyl methacrylate: BPO = 1: 1 (molar). For this purpose, as much dispersion was weighed in a 100 ml wide-mouth bottle as would correspond to an amount of 10 g of powder and 7.8 g of benzoyl peroxide (20% strength in water) were weighed.

The storage stability of the samples was visually checked daily. Furthermore, the samples were stirred up again daily to ensure good mixing with the BPO suspension. The final assessment was made after addition of MMA by monitoring swelling and polymerization behavior.

All dispersions remained stable after a storage time of 42 days (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 in a 100 ml

Wide neck bottle weighed as much dispersion as would correspond to an amount of 5 g of powder. For this purpose, 3.9 g of benzoyl peroxide (20% suspension in water) and a defined amount of MMA were weighed.

All dispersions are polymerized within 3 to 4 hours (see Table 4), d. H. there was swelling 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

Table 4

Swelling / polymerization experiments of aqueous dispersions in MMA in the ratio dispersion solid: MMA 1: 3 with benzoyl peroxide in a ratio of 1: 1 molar to Ethylanilinoethylmethacrylat

Claims

claims

1. Comprising a redox initiator system curing two- or multi-component system with controllable pot life

wherein

Hydroxyl groups or C 1 -C 4 -alkoxy groups is substituted, wherein the hydroxyl groups may be partially esterified with (meth) acrylic acid;

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 optionally F) 0-800 parts by weight of auxiliaries and additives;

characterized in that the component A) and the component C) are stored together and at least one component of the component B) is stored separately from the components A) and C), wherein the separately stored component of

Component B) is selected so that the swelling capacity of this component of component B) for the polymer A) is so high that the polymer-fixed activator e) of the polymer A) can be reacted with the component C).

2. comprising two or more component system according to claim 1

From 5 to 45% by weight of component A), from 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 to 0.2% by weight of component E); and

+ E).

3. two- or multi-component system according to claim 1 or 2, characterized in that in the polymer A) in the formula (I) of the activator e) the radical R ^{1 is} methyl.

4. Two- or multi-component system according to one of the preceding claims, characterized in that in the polymer A) in the formula (I) of the activator e) X is an ethylene group -CH ₂ -CH ₂ -.

5. Two- or multi-component system according to one of claims 1 to 3, characterized in that in the polymer A) in the formula (I) of the activator e) X is a 2-hydroxypropylene group -CH ₂ -CH (OH) -CH ₂ - is.

6. two- or multi-component system according to one of the preceding claims, characterized in that in the polymer A) in the formula

(I) of the activator e) R ^{2 is} selected from the group consisting of methyl, ethyl and 2-hydroxyethyl.

7. two- or multi-component system according to one of the preceding claims, characterized in that in the polymer A) 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.

8. two- or multi-component system according to one of claims 1 to 6, characterized in that in the polymer A) in the formula (I) of

Activator e) two of the radicals R ³ to R ^{7 are} methyl while the remaining three radicals are hydrogen.

9. two- or multi-component system according to one of the preceding claims, characterized in that in the polymer A) the

Component a) consists of one or more methacrylate monomers and / or acrylate monomers.

10. two- or multi-component system according to one of the preceding claims, characterized in that the polymer A) the

Component e) in an amount of 10-60 wt .-%, preferably 20-50 wt.% Is present.

11. Two- or multi-component system according to claim 9, characterized in that in the polymer A) the component a) is methyl methacrylate.

12. Two- or multi-component system according to one of the preceding claims, wherein the polymer A) is obtainable by polymerizing the components a) to e) according to claims 1 to 9 in aqueous emulsion.

13. Two- or multi-component system according to one of the preceding claims, characterized in that the constituents a) to e) for the core and the components a) to d) for the shell or the shells so chooses that in the resulting polymer A) the glass transition temperature T _{GS of} at least one shell is greater than the glass transition temperature T _G κ of the core, wherein the glass transition temperatures T _{G are determined} according to EN ISO 11357.

14. Two- or multi-component system according to claim 13, characterized in that the constituents a) to d) are selected for the shell so that in the resulting polymer A) the glass transition temperature T _G s of at least one shell is greater than 100 ⁰ C. , wherein the glass transition temperature T _GS according to EN ISO 11357 is determined.

15. Two- or multi-component system according to one of the preceding claims, characterized in that the component B) one or a

A plurality of compounds are selected from the group consisting of methyl or ethyl triglycol methacrylate, butyl diglycol 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 of an ethoxylated Bisphenol A with 2-10 moles of ethylene oxide and / or a polyethylene glycol dimethacrylate with 1-10 ethylene oxide units.

16. Two- or multi-component system according to one of the preceding claims, characterized in that the of the components A) and

C) separately stored component of component B) is methyl methacrylate (MMA).

17. Two- or multi-component system according to one of the preceding claims, characterized in that component C)

Dibenzoyl peroxide and / or dilauryl peroxide.

18. Use of a two- or multi-component system according to claims 1 to 17 in adhesives, casting resins, floor coatings and other reactive coatings, sealants, impregnating, investment materials, masses for the production 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.