MXPA06002146A - Monomer-polymer systems with a controllable pot life - Google Patents

Abstract

The invention relates to a dual component system with a controllable pot life. Said system can be hardened by a redox initiator system and comprises an emulsion polymer or a plurality of emulsion polymers and an ethylenically unsaturated monomer or a monomer mixture made from ethylenically unsaturated monomers. The emulsion polymer as well as the monomer or the monomer mixture can contain one of the components of a redox initiator system. Pot life is controlled by absorption of the redox initiator system on the polymer (A and B).

Description

SYSTEMS OF MONOMEROS-POLYMERS WITH A CONTROLLED CRISOL LIFE 1. Field of the invention The invention describes a two-component system with controllable life in a crucible, which harden through a redox initiator system and which consists of an emulsion polymer. or more than one emulsion polymer and of an ethylenically unsaturated monomer or of a monomer mixture composed of ethylenically unsaturated monomers, wherein both the emulsion polymer and the monomer or monomer mixture may comprise one of the components of an initiator system. Redox 2. Prior art Two-component systems hardening through redox initiation and based on monomers capable of free radical polymerization have been known for a long time. The method generally involves taking a liquid monomer or mixture of monomers which may comprise a redox component and, before use, add to it the missing components of the redox system or, respectively, all the components of the redox system. The systems described are those that also comprise a polymer dissolved in the monomer or monomer mixture. Other systems known especially for Dental applications are those wherein the liquid monomer, a pearl polymer and a redox initiator system are mixed, before use, to give a high viscosity composition. DE 43 15 788 (Degussa AG) describes an ampule comprising a hardenable binder. The binder is composed of a polymer, a reactive diluent and an initiator. The place of the initiator is inside a glass vial, and when the stopper is secured in the perforated hole the glass vial with the initiator breaks and the binder hardens and secures the stopper in the drilled hole. DE-A 1 544 924 describes a process of producing a material for dental repair for prosthesis repair by mixing a bead polymer composed mainly of methacrylic ester, such as methyl methacrylate and ethyl acrylate (92: 8) with monomers, for example 95 parts of methyl methacrylate and 5 parts of methacrylic acid or 85 parts of methyl methacrylate, 10 parts of oxypropylmethacrylate and 5 parts of methacrylic acid and adding to the redox initiator. The crucible lives obtained are from 4 to 5 minutes. DE 27 10 548 discloses a storage stable curable composition composed of monomers, oligomers and polymeric compounds and in addition to one or more components that help hardening. One or both of these components were surrounded by a protective envelope inhibiting reactions. The microcapsules have to be chemically inert with respect to the internal and external phase, resistant to diffusion and also resistant to fracture, elastic and heat-resistant. The curable composition further comprises a protective shell disintegrant, and if possible, also comprises additives. The protective wrap disintegrants are totally or at least to a degree composed of hollow microbeads that are not broken by forces normally exerted on the composition. For hardening, you found, forces are applied that at least to some extent break the protective wrappings by virtue of resultant crushing and friction effect of the stable hollow microbeads. A common disadvantage for all these systems is that once the components have been mixed together there is a limited available time (crucible life) for the operations, or that energy, for example in the form of crushing and friction forces has to be introduced during the application. Although crucible life can be extended to a certain extent by reducing the concentration of the redox components, this process is subject to limits because as the concentration of the redox components there is an adverse effect on the hardening. Another disadvantage of the formulations of the prior art is that the maximum allowed work concentrations (MPC) of volatile monomers, such as methyl methacrylate, may be exceeded. The use of less volatile monomers has only limited effectiveness in counteracting this disadvantage related to the application, since the bead polymers described above are not solvated sufficiently quickly by the less volatile monomers. In addition, the oxygen inhibition of the polymerization reaction is more pronounced when less volatile monomers are used than when methyl methacrylate is used. DE 100 51 762 provides monomer-polymer systems based on aqueous dispersions, having not only good mechanical properties but also the advantage of not emitting, or only emitting a very small amount of, monomers and also being easy to handle and have a high storage stability. For this purpose, mixtures of aqueous dispersions are used whose particles have been solvated with an ethylenically unsaturated monomer which always comprises one of the redox components. These solvated aqueous systems have virtually unlimited storage stability and do not harden until the water has vaporized and a film has consequently formed. The disadvantage of these systems is that, in particular in the case Of relatively thick capacity, the required vaporization of the water prolongs the hardening process and the relatively large proportions of water cause difficulties with many applications such as reactive adhesives. WO 99/15592 describes reactive plastisols which, after thermally gelling and hardening, provide films with good mechanical properties. These plastisols are composed of a known base polymer, prefey in the form of a spray-dried emulsion polymer, of a content of reactive monomers, composed of at least one monofunctional methacrylate monomer, of a plasticizer, and in addition, if appropriate, of other crosslinking monomers, fillers, pigments and auxiliaries. The base polymer can have a core / shell structure and comprises from 0 to 20% polar comonomers. The plastisols are stable in storage for a few weeks and must be heated to high temperatures (eg 130 ° C) for film formation. 3. OBJECTIVE It was an object of the invention to provide hardening systems at room temperature whose crucible life can be adjusted within wide limits and which nevertheless harden completely and rapidly, for example, in 100 minutes, prefey within less than fifty minutes, on a defined occasion without introduction of energy. The use of aqueous dispersions of polymers should also be avoided since the hardening process is too long and water causes problems in some applications. The use of a polymerization process allows the content of the added water to be so small that it does not cause problems in the application, for example if film formation is not required. The object also consisted in obtaining total hardening without excluding air, even in thin capable. Another objective to be achieved according to the invention was to minimize the undesie odor and maintain the monomer concentration in the air below the MPC values applicable to the respective monomer. 4. Obtaining the objective The objective of the invention is achieved through a system composed of the following components. Component A from 0.8 to 70% by weight, based on all polymers and monomers (component A and component B), of a polymer or polymer mixture prepared via aqueous emulsion polymerization and comprising 0.01 to 30% of a component, based on the totality of components A and B of a redox initiator system mainly absorbed in the polymer particles or in the polymer particles; Component B from 30 to 99% by weight, based on all the polymers and monomers (A and B) of at least one ethylenically unsaturated monomer; Component C from 0.01 to 5% by weight, based on all polymers and monomers (A and B), of at least one component of a redox initiator system that forms the partner of the initiator component absorbed in the particles of TO; and Component D from 0 to 800% by weight, based on all the polymers and monomers (A and B), fillers, pigments and other auxiliaries. In another embodiment of the invention, the redox components are present separately in two or more emulsion polymers (component A and component A 'and if appropriate A "), which are suspended before use, in an ethylenically monomer unsaturated or in a monomer mixture Components A and A 'and, if appropriate A "may have identical or different structure, but are always within the general definition of A. 5. Description of the invention Before use, the emulsion polymer prefey dehydrated by spraying with the absorbed initiator component is suspended, together with the D components, in a monomer or in a mixture of monomers comprising the second and, if appropriate, the third initiator component of the redox system. The suspended polymer is solvated, the absorbed initiator component is released and the polymerization reaction is thereby initiated. From the results of the experiments it can be concluded that at least a considerable portion of the initiator component has entered the particles as part of a process of volume increase, since the polymerization reaction does not begin until the solvation has occurred. It is probably not necessary that all the initiator component be in absorbed form within the particle. It is important that the portion available outside the particle is so small that it can not initiate a rapid polymerization reaction. It is important that most of the polymerization reaction does not continue until the particles have been solvated. Component A: The emulsion polymer Component A consists of the following monomers: a) from 5 to 100% by weight of monofunctional methacrylate monomers, whose solubility in water is <; 2% by weight at 20 ° C, b) from 0 to 70% by weight of monomers copolymerizable with the methacrylate monomer; c) from 0 to 5% by weight of a polyunsaturated compound, and d) from 0 to 20% by weight of a polar monomer whose solubility in water is > 2% by weight at 20 ° C. The emulsion polymer is in essence composed of methacrylate and acrylate monomers and in addition to styrene and / or styrene derivatives. A preferred structure consists of 90% methacrylate and acrylate monomers, and a particularly preferred structure consists exclusively of methacrylate and acrylate monomers. Component A a) Examples of monofunctional methacrylate and acrylate monomers whose solubility in water is < 2% by weight at 20 ° C are methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, ethylhexyl methacrylate, cyclohexyl methacrylate, tetrahydrofuryl methacrylate, isobornyl methacrylate, benzyl methacrylate, phenyl methacrylate, phenylethyl methacrylate , 3, 3, 5-trimethylcyclohexyl methacrylate. Methods for determining the water solubility of organic compounds are known to the person skilled in the art. In order to achieve a transition temperature of the vitreous state it is preferable to incorporate methacrylates having a carbon number > 4 in the side chain and acrylates. The monomers are combined in a beneficial manner such that a glass transition temperature above 60 ° C, preferably above 80 ° C and in particular above 100 ° C is provided. The glass transition temperatures are measured for EN ISO 11357. Given a known glass transition temperature for the homopolymers, the glass transition temperatures of the copolymers can be calculated by the following Fox formula: = WA + WB + Wc +. . . lg IgA gB TgC where Tg is the glass transition temperature of the copolymer (in K), TgA, TgB, TgC, etc., are the transition temperatures of the vitreous state of the homopolymers of the monomers A, B, C, etc., ( in K) WA, WB, Wc etc., are the contents by weight of monomers A, B, C etc. inside the polymer. The higher the glass transition temperature of the polymer, the higher the resistance to solvation, and therefore the longer the crucible life with respect to the monomers added before use. Raising the molecular weight also increases resistance to solvation. Component A b) Other monomers that can be used acetate vinyl and also styrene and / or styrene derivatives. Examples of the styrene derivatives are a-methylstyrene, chlorostyrene or p-methylstyrene. Component A d) The resistance to solvation can also be controlled through the incorporation of polar monomers, such as methacrylamide or methacrylic acid, into the emulsion polymer. This increases with an increasing amount of methacrylamide or methacrylic acid. Examples of other polar monomers are acrylic acid, acrylamide, acrylonitrile, methacrylonitrile, itaconic acid, maleic acid or N-methacryloyloxyethylethylene-urea. It is also possible to use N-methylolacrylamide or methacrylamide as long as its content is limited in such a way that it does not cause any pronounced cross-linking of the dispersion particles. The content of N-methylolacrylamide or methacrylamide should, if at all possible, not exceed 5% by weight, based on component A. Content below 2% by weight is preferred and 0% particularly preferred. The pronounced crosslinking would limit the volume increase of the particles in the formulation and therefore limit the homogenization. The content of the polar monomers depends mainly on the desired crucible life of the formulation, but it is also affected by the transition temperature of the vitreous state of the polymer. The lower the transition temperature of the vitreous state, the higher the content needed of polar monomers in order to achieve the particular resistance to solvation. further, the content of the polar monomers has to correspond to the solvent powder of the monomers used in the formulation. The content of polar monomers is generally in the range of 0 to 20%, preferably 1 to 10%, particularly preferably 2 to 10%, in particular 3 to 10%, based on component A. Methacrylamide and acrylamide, and also methacrylic acid and acrylic acid, are particularly effective and therefore preferred. The particular preference is given to a combination composed of methacrylamide or acrylamide with methacrylic acid or acrylic acid in weight ratios of 3: 1 to 1: 3. Component A c) Incorporation of relatively high contents of polyunsaturated monomers (crosslinking agents) limits the obtainable degree of volume increase in the formulation and may lead to the polymer having a nanoscale inhomogeneity. This is not necessarily a disadvantage in all cases, but preferably not desired. Content the polyunsaturated monomers are therefore limited to 5%, based on component A, preferably below 2%, in particular below 0.5%. It is particularly preferable to use non-polyunsaturated monomers as comonomers. Examples of polyunsaturated monomers are ethylene glycol dimethacrylate and also diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and higher homologs thereof, 1,3- and 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane dimethacrylate, triallyl cyanurate or allyl methacrylate. The polymer structure of the emulsion can also be that of a core-shell polymer. In one embodiment, the polar monomers are limited to the envelope, but in other respects the structure of the core and envelope are identical. In another embodiment, the core and the envelope may differ in their monomeric constitution. In this case it is an advantage that the transition temperature of the vitreous state of the envelope is greater than that of the core. In this embodiment, it is also possible that the polar monomers are limited to the envelope. The ratio by weight of core for wrapping is from 1:99 to 99: 1, that is to say generally not critical. The person skilled in the art will normally select the relatively complex core-shell structure only this can cause advantageous properties. A core with a transition temperature of the low vitreous state will generally be selected, for example in order to make the hardened films more flexible. In these cases, the envelope with a relatively high glass transition temperature has the function of providing resistance to solvation. For this purpose, the content of the envelope must be sufficiently high, for example 20%, based on component A or higher. On the other hand, if the content of the core is too low, it is impossible to exert a substantial influence on the properties of the film. The person skilled in the art will beneficially select core content greater than 30%, and more beneficially above 50%. The emulsion polymerization reaction is carried out in a manner known to the person skilled in the art. For example, EP 0376096 Bl describes the conduct of an emulsion polymerization reaction. The emulsion polymer comprises a component of a redox initiator system, i.e. either a peroxide or the accelerator component. In order to introduce a component of the redox initiator system into the dispersion particles, this is added during the preparation of the emulsion, ie emulsified together with the water, with monomers, with emulsifiers, and if appropriate, with other components. The component of the redox initiator system is therefore fed together with the emulsion into the reaction tank. Another possibility for introducing a component of the redox initiator system into the dispersion particle is to add this, if appropriate dissolved in a monomer or an inert solvent, to the dispersion subsequently, and allow it to enter the dispersion particles as part of a process of increasing volume. Another possible variant consists of absorbing the initiator component and the accelerator component within different emulsion polymers spray dried and then suspending them in a monomer or mixture of monomers. The polymerization reaction begins when both polymer beads have been solvated and therefore the initiator components were released. Normally it is not of critical importance in the present if the polymers of the emulsion have identical or different constitution. The different constitution could have the disadvantage in particular cases of providing cloudy polymers as a result of incompatibility, and this could be inconvenient for certain applications. The solid can be obtained from the dispersion via known processes. Among these is dehydration by aspersion, coagulation by freezing with filtration and dehydration by suction, and also isolation through compression by means of an extruder. The polymer is preferably obtained by spray drying. The molar mass of component A is 10,000 g / mol a ,000,000 g / mol, preferably from 50,000 g / mol to 1,000,000 g / mol and very particularly preferably from 100,000 g / mol to 500,000 g / mol. The molar mass is determined by means of gel permeation chromatography. The resistance to solvation can also be adjusted through the selection of particle size. The primary particle size of component A is from 50 nm to 2 microns, preferably from 100 nm to 600 nm and very particularly preferably from 150 nm to 400 nm. The particle size is measured with a sub-micro particle analyzer Coulter N4 MD. Component B: The monomers The crucible life of the formulation composed of components A, B, C and D can be influenced by the solvation power of the monomers used in component B. While methyl methacrylate has a high power of solvation and therefore leads to relatively low crucible lives, the monomers having higher hydrophobic character, for example 1,4-butanediol dimethacrylate, and the monomers having high molecular weight, for example 2- [2- (2-ethoxyethoxy) ethoxy] ethyl methacrylate, generally increase crucible life. The monomers that can be used are in principle any of the monomers of methacrylate and acrylate and styrene, and also mixtures thereof. The subordinate content of other monomers can be used as long as this does not cause problems with the copolymerization reaction, but are not preferred, examples are vinyl acetate, maleic acid, fumaric acid and its anhydrides or esters. The criteria for the selection of the monomers are their solvent potency, vapor pressure, toxicological properties and odor. Examples of methacrylates are methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, ethylhexyl methacrylate, cyclohexyl methacrylate, tetrahydrofuryl methacrylate, isobornyl methacrylate, benzyl methacrylate, phenyl methacrylate, phenylethyl methacrylate, 3, 3, 5-trimethylcyclohexyl methacrylate, ethyl glycol methacrylate, and also diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and higher homologues thereof, 1,3- and 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,22-dodecanediol dimethacrylate, glycerol dimethacrylate , trimethylolpropane trimethacrylates, trimethylolpropane dimethacrylate and allyl methacrylate.

Preference is given to methacrylates whose molar mass is greater than 140 g / mol, particularly preference is given to those which are above 165 g / mol, and in particular above 200 g / mol. Methacrylates are preferred over acrylates for toxicology reasons. The monomer mixture can also comprise subordinate amounts, ie up to 30%, preferably up to 10% and particularly preferably up to 5%, of functional monomers, such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, methacrylic acid, mono-2-methacryloyloxyethyl maleate or mono-2-methacryloyloxyethyl succinate. Another advantage of monomers with high molecular weight, together with high crucible lives due to very low solvation rate, are lower levels of emissions. Component C: The redox system The redox system consists, for example, of a peroxide and an accelerator component. Examples of peroxides that can be used are dibenzoyl peroxide and dilauryl peroxide. An accelerating component that can be used are the amines, such as N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine or N, N-bis (2-hydroxypropyl) -p -toluidine. The m-toluidine derivatives and the xylidine derivatives can be used accordingly.

Another redox initiator system that can be used, in addition to the aforementioned peroxide / amine systems, are the systems composed of hydroperoxides and vanadium activators. Examples of hydroperoxides that can be used are tert-butyl hydroperoxide, eumeno hydroperoxide and ketone peroxide. Examples of the ketone peroxides that can be used are methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide or cyclohexanone peroxide, individually or in a mixture. The vanadium activators that can be used are acidic vanadium phosphates in combination with coactivators such as lactic acid. This list of redox systems has no limits, and other redox systems can of course be used, examples of which are other metallic components, etc. Component D: The formulation for understanding, together with the described components, fillers of conventional particulates, for example titanium dioxide, carbon black or silicon dioxide, glass, glass beads, glass powder, quartz sand, quartz powder , other types of sand, corundum, clay products, clinker, barite, magnesia, calcium carbonate, marble powder or aluminum hydroxide or mineral pigments or organs and auxiliaries. Examples of auxiliaries can be: plasticizers, flow aids, thickeners, defoamers, adhesives or wetting agents. It is preferable that no plasticizer is present. The grain diameter of the particulate fillers is usually from about 0.001 mm to about 6 mm. It is normal to use 0 to 8 parts by weight of fillers for each part by weight of polymer. The ratio of the mixture The ratio of the components used must always be selected in such a way that total polymerization of the determined system is obtained. For this purpose, in particular, there must be a sufficient available quantity of a redox initiator system, at least one component of the redox initiator system available through the amount used of the component A. The mixing ratio also depends on the application desired. This determines the amount that is used of the A-D components. The polymer content (component A) can be from 0.8 to 70% by weight, and also in turn can comprise from 0.05 to 30% by weight of a component of a redox initiator system. The content of an ethylenically unsaturated monomer (component B) can be from 30 to 99% by weight. The mixture further comprises from 0.01 to 5% by weight of at least one component of a redox system that it is the partner of the initiator components absorbed within the components A. However, it is also possible that this component has also been absorbed into the polymer particles before use. The mixture may further comprise from 0 to 800% by weight of fillers, pigments and other auxiliaries. Applications The system is suitable for adhesives, casting resins, floor coatings, sealant compositions, reactive plugs, dental compositions and similar applications. Examples In an application such as casting resin, the high polymer content (component A) is preferred. This should be in the range of 40 to 70% by weight. The content of the redox component in component A is 0.01 to 5%, based on component A. With this, the content of an ethylenically unsaturated monomer (component B) is 58.8 to 30% by weight. The content of component C is 0.01 to 5% by weight. In the field of highly crosslinked systems, it may be useful to avoid the polymer content (component A) and use it merely as a carrier for a redox initiator component. The content of component A therefore corresponds very small and preferably 1 to 10% by weight. The content of the redox component absorbed within component A is correspondingly high and can be up to 10% by weight or even up to 30% by weight, based on component A. The monomer component is ethylenically unsaturated (component B) so It is 98.8 to 90% by weight. The content of component C is 0.01 to 5% by weight. Preparation of emulsion polymers All emulsion polymers were prepared through the feeding process. The initial charge was stirred at 80 ° C for 5 minutes in the reaction tank. The remainder of load 1 was then added over a period of 3 hours and load 2 was added over a period of 1 hour. Fillers 1 and 2 were emulsified before addition to the reaction mixture. The resulting dispersion was dehydrated by spray. The mixtures are listed in Table 1.

Table 1 1280 g MMA 1254.4 g MMA 25.6 g MAA Polymer 9 1280 g water, 1280 g water, 1280 g water, rNS: 160 nm, GNS core = 124 nm, 0.384 g Marion PS60, 6.4 g Marion PS60 6.4 g Marion PS60 SC: 39.6 % 0.192 gNaPS 2.4 g NaPS 2.4 g Trigones A-W70 1280 g MMA 1216.0 g MMA 64.0 g MAA Polymer 10 1280 g water, 1280 g water, 1280 g water, rNS: 151 nm, rNS core = 116 nm, 0.384 g Marion PS60 , 6.4 g Marion PS60 6.4 g Marion PS60 SC: 40.1% 0.192 g NaPS 2.4 g NaPS 2.4 g Trigones A-W70 1280 g MMA 1177.6 g MMA 102.4 g MAA Polymer 11 1280 g water, 1280 g water, 1280 g water, rNS: 184 nm, rNS core = 145 nm, 0.384 g Marion PS60, 6.4 g Marion PS60 6.4 g Marion PS60 SC: 40.4% 0.192 g NaPS 2.4 g NaPS 2.4 g Trigones A-W70 1280 g MMA 1152.0 g MMA 64.0 g MAA 64.0 g MA Polymer 12 1280 g water, 1280 g water, 1280 g water, rNS: 183 nm, 0.384 g Marion PS60, 6.4 g Marion PS60 6.4 g Marion PS60 SC: 39.3% 0.192 g NaPS 2.4 g NaPS 2.4 g Trigones A-W70 1280 gMMA 1216 gMMA 64gMAA Polymer 13 1280 g water, 1280 g water, 1280 g water, rNS: 187 nm, 0.384 g Marion PS60, 6.4 g Marion PS60 6.4 g Marion PS60 SC: 39.7% 0.192 gNaPS 2.4 gNaPS 36.5 g Trigones A- W70 1280 gMMA 1216 gMMA 64gMAA Polymer 14 1240 g water, 1280 g water, 1280 g water, rNS: 187 nm, rNS 0.384 g Marion PS60, 0.269 g 6.4 g Marion PS60 6.4 g Marion PS60 SC: 39.5% acid 4,4 ' -azo-bis (4- 4,4'-azo-bis acid (4- 36.6 g Triads Aiao-Corianole) Cianovalerian) 1216gMMA 0.143 gNaHC03 1.7gNaHC03 64gMAA 1280 gMMA Polymer 15 1280 g water, 2560 g water, 2.4 g Trigones A-W70 rNS: 135 nm, 0.384 g Marion PS60, 12.78 g Marion PS60 SC: 39.8% 0.192 gNaPS 2.4gNaPS 2496 gMMA 64 g MAA Polymer 16 1280 g water, 2560 g water, 2.4 g Trigones A-W70 r ^ g: 165 nm, 0.384 g Marion PS60, 12.78 g Marion PS60 SC: 39.6% 0.192 gNaPS 2.4gNaPS Table 1 rns: radius of the whole particle in nm Abbreviations: Marión PS 60: emulsifier, producer NaPS sodium persulfate Trigonox A-W70 encapsulated primer, producer: Akzo Nobel MMA: methyl methacrylate MA: methacrylic acid MAA: metraerilamide Preparation of a monomer-polymer mixture and determination of crucible life / solvation time. 20 g ((= 40% by weight) of the respective polymer (component A) are used as initial charge in a beaker (0.2 1). 30 g (= 60% by weight) of an ethylenically unsaturated monomer or a monomer mixture (component B) are added and shaken with a wooden spatula until it is observed that the mixture is no longer useful for operations. This time is called the time of solvation or life in a crucible. The results are listed in Table 2. The non-hardening experiments show how the resistance to solvation can be increased through incorporation of polar monomers.

Table 2 Life in crucible / solvation time / polymerization times 100% 92% MMA - 8% MAA + ETMA 207 0.0625% Trigonox A-W70 + 684 ppm tert-butyl hydroperoxide THFMA 107 Core Wrap 50% 100% MMA 100% MMA + 0.0625% 1.4-BDDMA 30 Trigonox A-W70 ETMA 12 100% MMA 98% MMA - 2% MA + 1,4-BDDMA 95 0.0625% Trigonox A-W70 ETMA 16 100% MMA 95% MMA - 5% MA + 1,4-BDDMA > 240 0. 0625% < 960 Trigonox A-W70 ETMA 24 100% MMA 90% MMA - 10% MA + 1,4-BDDMA > 1200 0. 0625% Trigonox A-W70 *) Peak temperature of polymerization Determination of polymerization times The polymerization time is defined as the time it takes a mixture from the start of the polymerization reaction (addition of initiators) to achieve a peak polymerization temperature. The indicated results are the time occupied and the maximum temperature. The measurement method used is a contact thermometer with recording of the temperature profile. The results are indicated in Table 2. All the polymerization reactions were carried out with a mixing ratio equal to that described above for the determination of crucible life. Polymerization process A: Means that 1.4% by weight of benzoyl peroxide with technical quality BP-50-ET (BP-50-FT being a white powder with flowability, 50% by weight of benzoyl peroxide content, phlegmatized with a phthalate), based on monomer, ie component B (0.42 g for 30 g of monomer) are mixed with 20 g of polymer powder (component A). The second redox component, the corresponding amine, is absorbed in component A and is supplied through the vision of component A. Polymerization process B: Means that 0.3% by weight of VN-2 (vanadium compound, 0.2% V , solution in monobutyl phosphate) + 0.5% by weight of lactic acid dissolve in the monomer phase, ie component B (90 mg VN2 + 150 mg of lactic acid for 30 g of monomer). The missing redox component, the hydroperoxide, is supplied via the addition of component A, in which it has been absorbed.

Claims (1)

CLAIMS 1. A two-component system hardened by a redox initiator system that has a controllable time limit, structured on the basis of the following components: Component A from 0.8 to 70% by weight, based on all polymers and monomers ( component A and component B), of a polymer or polymer mixture prepared via aqueous emulsion polymerization and comprising 0.01 to 30% of a component, based on all components A and B of a redox initiator system mainly absorbed in the polymer particles or in the polymer particles; Component B from 30 to 99% by weight, based on all the polymers and monomers (A and B) of at least one ethylenically unsaturated monomer; Component C from 0.01 to 5% by weight, based on all polymers and monomers (A and B), of at least one component of a redox initiator system that forms the partner of the initiator component absorbed in the particles of TO; and Component D from 0 to 800% by weight, based on all the polymers and monomers (A and B), fillers, pigments and other auxiliaries 2. The composition according to claim 1, which is composed of the following components: Component A from 3 to 60% by weight, based on all the polymers and monomers (component A and component B), of a polymer or polymer mixture prepared through aqueous emulsion polymerization and comprising 0.01 to 30% by weight of a component of a redox initiator system mainly absorbed in the polymer particles or polymer particles, Component B of 40 to 97% by weight, based on all the polymers and monomers (A and B), of at least one ethylenically unsaturated monomer, Component C of 0.01 to 5% by weight, based on all polymers and monomers (A and B), of at least one component of a redox initiator system that forms the partner of the initiator component absorbed in the particles of A, and Component D of 0 to 800% by weight, based on all polymers Y monomers (A and B), fillers, pigments and other auxiliaries. 3. The composition according to claim 1, composed of the following components: Component A from 5 to 60% by weight based on all the polymers and monomers (component A and component B), of a polymer or polymer mixture prepared through aqueous emulsion polymerization and comprising from 0.01 to 30% by weight of a component of a redox initiator system mainly absorbed in the polymer particles or polymer particles, Component B from 40 to 95% by weight, based on all the polymers and monomers (A and B), of at least one ethylenically unsaturated monomer, Component C from 0.01 to 5% by weight, based on all polymers and monomers (A and B), of at least one component of a redox initiator system that forms the partner of the initiator component absorbed in the particles of A, and Component D of 0 to 800% by weight, based on all polymers and monomers (A and B), fillers, pigments and others auxiliary 4. The composition according to claim 1, composed of the following components: Component A from 10 to 50% by weight, based on all the polymers and monomers (component A and component B), of a polymer or polymer mixture prepared by aqueous emulsion polymerization and comprising 0.01 to 30% by weight of a component of a redox initiator system mainly absorbed in the polymer particles or in the polymer particles. Component B from 50 to 90% by weight, based on all polymers and monomers (A and B), of at least one ethylenically unsaturated monomer, Component C from 0.01 to 5% by weight, based on the totality of polymers and monomers (A and B) of at least one component of a redox initiator system which forms the partner of the initiator component absorbed in the particles of A (component C) and Component D from 0 to 800% by weight, based on all polymers and monomers (A and B), fillers, pigments and other auxiliaries. The composition according to claim 1, characterized in that component A is a polymer composed of a) from 5 to 100% by weight of methacrylate monomers monofunctional, whose solubility in water is < 2% by weight at 20 ° C, b) from 0 to 70% by weight of monomers copolymerizable with the methacrylate monomer; c) from 0 to 5% by weight of a polyunsaturated compound, and from 0 to 20% by weight of a polar monomer whose solubility in water is > 2% by weight at 20 ° C. and component B of 2- (2- (2-ethoxyethoxy) -ethoxy) ethyl methacrylate, tetrahydrofuryl methacrylate or 1,4-butanediol dimethacrylate, and component C comprises, as a peroxide, dibenzoyl peroxide or dilauryl peroxide, and it comprises as an accelerating component N, N-bis (2-hydroxyethyl) -p-toluidine. 6. The use of a composition according to any of claims 1 to 5 as an adhesive. 7. The use of a composition according to any of claims 1 to 5 as a casting resin. 8. The use of a composition according to any of claims 1 to 5 as a floor covering. 9. The use of a composition according to any of claims 1 to 5 as a composition for reactive toppings. 10. The use of a composition according to any of claims 1 to 5 as a dental composition. 11. The use of a composition according to any of Claims 1 to 5 as sealing composition, it may be useful to avoid the polymer content (component A) and use it merely as a carrier for a redox initiator component. The content of component A therefore corresponds very small and preferably from 1 to 10% by weight. The content of the redox component absorbed within component A is correspondingly high and can be up to 10% by weight or even up to 30% by weight, based on component A. The monomer component is ethylenically unsaturated (component B) so It is 98.8 to 90% by weight. The content of component C is 0.01 to 5% by weight. Preparation of emulsion polymers All emulsion polymers were prepared through the feeding process. The initial charge was stirred at 80 ° C for 5 minutes in the reaction tank. The remainder of load 1 was then added over a period of 3 hours and load 2 was added over a period of 1 hour. Fillers 1 and 2 were emulsified before addition to the reaction mixture. The resulting dispersion was dehydrated by spray. The mixtures are listed in Table

1.