DE102012108950A1 - Polymerizable mixture, useful to prepare fiber reinforced molded body, as adhesive and in cartridge, comprises a specified range of alkylmethacrylate, preferably methylmethacrylate, and impact-resistant acrylic glass - Google Patents

Abstract

Polymerizable mixture comprises 30-97 wt.% of 1-6C-alkylmethacrylate, preferably methylmethacrylate, and 3-70 wt.% of impact-resistant acrylic glass. Independent claims are included for: (1) a composition comprising the polymerizable mixture and at least one fibrous filler; and (2) the preparation of fiber reinforced molded body comprising introducing fibers into the polymerizable mixture and hardening the polymerizable mixture.

Description

The invention relates to a polymerizable composition. Furthermore, the present invention describes curable compositions and fiber-reinforced moldings. Moreover, the invention relates to a process for the production of fiber-reinforced moldings. Furthermore, the present invention describes the use of the polymerizable composition as an adhesive and a cartridge filled with the polymerizable composition.

Fiber-reinforced moldings based on curable resins have long been known and are used in a variety of applications. Advantages of these moldings include their good mechanical properties, at an acceptable price and low weight. For example, fiber-reinforced plastics are widely used in aircraft construction and boat building. For the production of automobiles, however, these plastics have not been widely used, since the known plastics are difficult to repair. In particular, difficulties with the adhesiveness of subsequently applied paints should be mentioned. Furthermore, the previous plastics at a price that is comparable to the commonly used metals, such as steel or aluminum, too poor mechanical properties. In this context, reference should be made in particular to carbon-based body parts, which are used in particular in racing, but are extremely expensive to manufacture, so that due to the high cost associated with many advantages materials are used only very rarely.

Furthermore, 2-component adhesives based on (meth) acrylates have been used for a long time, but these are too hard for many tough plastics, so that the adhesive seam can be destroyed in heavy use, especially in cold weather.

In view of the prior art, it is an object of the present invention to provide a polymerizable composition and a molded article obtainable therefrom, which avoids the disadvantages mentioned. In particular, a molded article obtained from the polymerizable composition should have an excellent property profile. Accordingly, a generic molded article should exhibit excellent mechanical properties, such as a high impact strength with a high tensile strength. Furthermore, a molded article should be easy to repair, and a coating having a high adhesive strength should be able to be applied at a later time.

Furthermore, it was therefore an object of the present invention to provide a molded article which has a high resistance to chemicals. Furthermore, the molding should show a relatively low weight, based on the mechanical properties.

Moreover, it may be considered an object to provide a molded article that can be easily and inexpensively manufactured and processed. In this case, the preparation and processing of the polymerizable composition and the molding obtained therefrom should be as environmentally friendly and safe as possible.

Furthermore, the properties of the molding should remain over a long time, even with weathering.

Another object can be seen to provide a polymerizable composition which can be used as a coating composition, adhesive and / or casting compound. Here, the cured compositions should have excellent impact resistance, wear resistance, tear resistance, vibration resistance and tensile strength. Furthermore, the elastic modulus should be variable over a wide range, so that articles with a very high or relatively low modulus of elasticity can be obtained.

It was another object of the present invention to provide a polymerizable composition, which can be used in particular as an adhesive, which has a low foaming.

Moreover, the provision of a cartridge which enables a particularly simple processing of the polymerizable composition of the present invention was an object of the present invention.

These are solved as well as other tasks which are not explicitly mentioned, but which are readily derivable or deducible from the contexts discussed hereinbelow by a polymerizable composition having all the features of patent claim 1.

The present invention accordingly provides a polymerizable composition comprising
30-97 wt.% Alkyl methacrylate having 1-6 carbon atoms in the alkyl radical and
3-70 wt.% Impact-resistant acrylic glass.

This makes it possible to provide a polymerizable composition in an unpredictable manner, with the curable compositions, fiber-reinforced moldings, coating compositions and Adhesives are available that have an excellent property profile.

In particular, the molded articles obtained from polymerizable compositions or curable compositions of the present invention have excellent mechanical properties, such as high impact strength at a high tensile strength. Furthermore, the moldings can be easily repaired, with coatings having a high adhesive strength being applied at a later time.

Further, the molded articles of the present invention obtainable from the polymerizable compositions exhibit high chemical resistance and a relatively low weight in terms of mechanical properties.

Moreover, the polymerizable compositions and the curable compositions of the present invention and the molded articles obtainable therefrom can be easily and inexpensively produced and processed. In this case, the preparation and processing of the polymerizable compositions and the moldings obtainable therefrom can be carried out in a very environmentally friendly and safe manner.

Furthermore, the properties of the molded article of the present invention are maintained over a long time, even under weathering.

Here, the cured compositions have excellent impact resistance, wear resistance, tear resistance, vibration resistance and tensile strength. These properties are retained over a long period of time. The cured materials show a high permanent elasticity and a relatively high temperature stability. Furthermore, the cured compositions show surprisingly good mechanical properties even at very low temperatures, in particular outstanding impact toughness. Furthermore, the cured compositions have a high chemical resistance and a low tendency to form stress cracks. In addition, the polymerized compositions show a high weathering stability. Furthermore, the modulus of elasticity can be varied over a wide range, so that articles with a very high or relatively low modulus of elasticity can be obtained.

The polymerizable compositions can be used on a variety of substrates as an adhesive, the adhesive is particularly suitable for bonding a variety of materials.

Furthermore, the present invention provides polymerizable compositions having the said properties, which can be produced and processed particularly easily. In particular, the masses can be polymerized under very different conditions, wherein the processing time (pot life) can be adapted to the most diverse requirements. For example, the polymerizable compositions can be exposed to weathering after a short time. Furthermore, the compositions can be cured even at temperatures of -20 ° C. In addition, the polymerizable compositions can also be processed by relatively low skilled people. In addition, the polymerizable compositions are inexpensive to produce.

Furthermore, the polymerizable compositions may have a high transparency, so that adhesive seams, especially on transparent substrates with a high transparency, for example moldings made of polymethyl methacrylate are barely visible.

In addition, preferred polymerizable compositions show only little foaming. This property is particularly important in bonding two bevelled plastic moldings, since they are often carried out in the form of beads.

A polymerizable composition according to the invention comprises 30-97% by weight of alkyl methacrylate having 1-6 carbon atoms in the alkyl radical, preferably methyl methacrylate. The alkyl methacrylates are methacrylic acid esters of the C1-C6 alkanols. In addition to the particularly preferred methyl methacrylate (MMA), mention may be made, inter alia, of butyl and cyclohexyl methacrylate. The proportion of these monomers in the polymerizable composition is preferably 40 to 95% by weight, in particular 60 to 90% by weight, preferably 75 to 85% by weight. Higher proportions of alkyl methacrylate having 1-6 carbon atoms in the alkyl radical, in particular methyl methacrylate lead to moldings having a higher tensile strength.

An embodiment of the polymerizable composition according to the invention comprises in addition to the alkyl methacrylates having 1 to 6 carbon atoms in the alkyl radical preferably 1 to 5 wt .-%, preferably 1.5 to 3 and particularly preferably 2 to 2.5 wt .-% of one or more allyl compound with at least two polymerizable groups. In addition to the obligatory allyl group, the compound may comprise another ethylenically unsaturated double bond which is free radically polymerizable, such as a vinyl, an acrylic or a methacrylic group. The preferred compounds include allyl acrylate, allyl methacrylate, 1,3,5-tri-2-propenyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (triallyl isocyanurate), and 2 , 4,6-tris (2-propenyloxy) -1,3,5-triazine (triallyl cyanurate). Of the compounds mentioned, triallyl cyanurate is particularly preferred. With increasing share of Allyl compounds having at least two polymerizable groups improve the formability of the moldings at high temperatures without impairing the mechanical properties, for example the impact strength, to an unacceptable extent. However, this can adversely affect the tensile strength of the moldings.

In addition to the monomers mentioned, a polymerizable composition of the present invention may contain other monomers which are copolymerizable with the stated alkyl methacrylates, which are described, inter alia, in said publications DE 101 63 681 A1 and DE 198 26 412 A1 are described.

These are z. As C1-C10 alkyl esters of acrylic acid, such as butyl acrylate, 2-ethylhexyl acrylate, alkyl esters of methacrylic acid, which differ from the aforementioned alkyl methacrylates having 1 to 6 carbon atoms in the alkyl radical, (meth) acrylates with ether groups, in particular (meth) acrylates with Glycol groups such as butyl diglycol methacrylate (BDGMA) or functional monomers. The term functional monomers is understood in particular to mean compounds which have at least one further reactive group in addition to an unsaturated C-C double bond. These include in particular monomers having two or more ethylenically unsaturated C-C double bonds, which differ from the allyl compounds set out above, monomers having hydroxyl groups or monomers having acid groups.

Depending on the substrates to be bonded, in particular monomers with acid groups, preferably methacrylic acid, or hydroxy groups, for example hydroxyethyl methacrylate and / or hydroxypropyl methacrylate, may be used to improve the adhesive properties. The proportion of monomers having at least one acid group, preferably methacrylic acid, may preferably be from 0.1 to 10% by weight, more preferably from 0.2 to 5% by weight. The proportion of monomers having at least one hydroxyl group may preferably be in a range from 0.1 to 10% by weight, particularly preferably 0.2 to 5% by weight.

According to a particular aspect of the present invention, the polymerizable composition may preferably be 0 to 40% by weight, in particular 0.1 to 35% by weight, more preferably 1 to 30% by weight and especially preferably 5 to 20% by weight of C1- C10 alkyl esters of acrylic acid and / or (meth) acrylates containing ether groups, preferably ethylhexyl acrylate. Higher proportions of C1-C10-alkyl esters of acrylic acid, preferably of ethylhexyl acrylate, lead to moldings which can be formed very well, but generally have a lower tensile strength. Surprisingly, the impact strength and / or the tensile elongation at break can be improved by the use of C 1 -C 10 -alkyl esters of acrylic acid, preferably ethylhexyl acrylate, this improvement preferably being carried out at a proportion of C 1 -C 10 -alkyl esters of acrylic acid in the range from 15 to 30% by weight .-%, preferably 20 to 25 wt .-% can be achieved.

Of particular importance are polymerization crosslinkers, also referred to herein as crosslinkers, such as acrylic and methacrylic esters of polyhydric alcohols, which differ from the allyl compounds set forth above with at least two polymerizable groups. These include in particular (meth) acrylates derived from unsaturated alcohols, such as. As vinyl (meth) acrylate, and (meth) acrylates derived from diols or higher alcohols, such as. Glycol di (meth) acrylates, such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra- and polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4- Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate and diurethane dimethacrylate; (Meth) acrylates having three or more double bonds, such as. As glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate. The term (meth) acrylate includes esters of acrylic acid, methacrylic acid and mixtures thereof. The preferred acrylates include, for example, propanetriol triacrylate. Particular advantages can be achieved with methacrylic acid esters of polyhydric alcohols, such as butanediol dimethacrylate.

A crosslinker preferably has a molecular weight of less than 1500 g / mol, particularly preferably less than 1000 g / mol, more preferably less than 600 g / mol and especially preferably less than 400 g / mol.

According to one aspect of the present invention, the proportion of these crosslinkers, which differ from the allyl compounds set out above with at least two polymerizable groups, can be 0 to 10% by weight, preferably 0.01 to 5% by weight, particularly preferably 0, 05 to 3 wt .-% and particularly preferred is a proportion of 0.1-1 wt.%, Based on the weight of the polymerizable composition.

According to a further preferred embodiment, the proportion of crosslinker is 0.2 to 4 wt .-%, preferably 0.5 to 3 wt .-%. Higher levels of crosslinker lead to moldings which have a very high tensile strength. However, the formability decreases at high temperatures.

Surprisingly, the foaming of the polymerizable compositions in the polymerization can be reduced by the use of crosslinkers, with methacrylic acid esters of polyhydric alcohols such as butanediol dimethacrylate leading to particularly favorable results. By this configuration, in particular a very fast curing can be achieved without the formation of foam.

Usually, the polymerizable compositions are free-radically cured by using initiators. Depending on the nature of the use of the composition according to the invention, in particular the production of the fiber-reinforced moldings, different initiator systems can be used. In the production of impact resistant articles thermal initiators and / or systems can be used, which allow curing at room temperature.

Suitable thermal initiators include azo compounds, peroxy compounds, persulfate compounds or azoamidines. Non-limiting examples are dibenzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-amyl perester, preferably t-amyl peroxy-2-ethylhexanoate, 2,2'-azobis (2-methylpropionitrile) (AIBN), 2,2'-azobis (isobutyric acid amidine) hydrochloride, benzopinacol, dibenzyl derivatives, methyl ethyl ketone peroxide, 1,1-azobiscyclohexanecarbonitrile, methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, didecanoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, tert. Butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert -butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxyisobutyrate, tert -butylperoxyacetate, 1.1 Bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, and those from DuPont under the name ^® Vazo, for example ^® Vazo V50 and ^® Vazo W S available radical formers. It is expedient to be able to cure from 0.01% by weight to 15% by weight, preferably from 0.1% by weight to 10% by weight and particularly preferably from 0.5% by weight to 5% by weight of thermal initiator , based on the weight of the polymerizable mass, are used.

Systems which allow for curing at room temperature preferably include redox initiators or photoinitiators. Preferred photoinitiators include αα-diethoxyacetophenone (DEAP, Upjon Corp), n-butyl benzoin ether ( ^® Trigonal-14, AKZO) and 2,2-dimethoxy-2-phenylacetophenone ( ^® Irgacure 651) and 1-benzoylcyclohexanol ( ^® Irgacure 184), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ( ^® Irgacure 819), and 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-phenylpropan-1-one ( ^® Irgacure 2959 ), each of the company Ciba Geigy Corp. are commercially available. Redox initiators may preferably comprise at least one amine compound in addition to a free radical generator.

As a redox system has to harden the polymerizable mass at low temperatures tert. proven aromatic amine and benzoyl peroxide, this combination at low temperatures to -20 ° C is still used. Furthermore, a system of tert. Butyl mono-permaleinate (for example, 25% (about 0.13%)) + zinc iso-oktyl-thio-glycolate (for example, about 0.05%) are used with advantage, this system by a very low yellowing the polymerized masses and a uniform course of reaction distinguishes. In continuous processes for making sheets or sheets, a fast reaction is desired. Here has tert. Butyl mono-permaleinate, (for example, 25% (about 1.2%)) + calcium hydroxide (shepherd lime, for example, 0.3%) + pentaerythritol tetrakis-3-mercapto-propionate (for example, about 0.01 to 0, 15%) proven.

Preferably, aromatic tertiary amines are used, such as di-methylaniline or di-isopropoxy-p-toluidine.

Besides the monomers set forth above, the polymerizable compositions of the present invention comprise 3-70% by weight, preferably 10 to 40% and more preferably 15 to 30% by weight impact-resistant acrylic glass. Impact-resistant acrylic is a plastic based on acrylates, which is designed impact-resistant.

In the context of the present invention, the term "acrylate-based plastic" is understood as meaning a polymer obtainable by free-radical polymerization of (meth) acrylates. Preferred toughened acrylic glasses comprise at least 40% by weight, more preferably at least 60% by weight and most preferably at least 80% by weight of repeat units derived from (meth) acrylates. The poly (meth) acrylates can preferably be obtained by free-radical polymerization. Accordingly, the proportion by weight of repeating units results from the proportions by weight of corresponding monomers used for the preparation of the polymers. Of the (meth) acrylates mentioned, in particular methyl methacrylate is preferred.

The term (meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known and among others in DE 10 2008 001 596 A1 described this document for purposes of disclosure is incorporated by reference in this application.

Toughened acrylic preferably has a Charpy impact strength of at least 3 kJ / m ² , preferably at least 5 kJ / m ² , more preferably at least 10 kJ / m ² , especially preferably at least 30 kJ / m ² and particularly preferably at least 50 kJ / m ² up, measured according to ISO 179 / 1eU at 25 ° C and 50% relative humidity.

The impact resistance is imparted to the acrylic glass by a tough phase which has a low glass transition temperature, which is preferably at most -10 ° C, more preferably at most -20 ° C.

wobei x_n für den Massebruch (Gew.-%/100) des Monomeren n steht und Tg_n die Glasübergangstemperatur in Kelvin des Homopolymeren des Monomeren n bezeichnet. Weitere hilfreiche Hinweise kann der Fachmann dem Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) entnehmen, welche Tg-Werte für die geläufigsten Homopolymerisate angibt. The glass transition temperature can be influenced by the type and proportion of monomers used to prepare the toughening phase. In this case, the glass transition temperature Tg of the polymer in a known manner by means of differential scanning calorimetry (DSC), in particular according to DIN EN ISO 11357 be determined. Preferably, the glass transition temperature can be determined as the center of the glass stage of the second heating curve at a heating rate of 10 ° C per minute. Furthermore, the glass transition temperature Tg can also be calculated approximately in advance by means of the Fox equation. To Fox TG, Bull. Physics Soc. 1, 3, page 123 (1956) applies:

where x _n is the mass fraction (wt .-% / 100) of monomer n and Tg _{n is} the glass transition temperature in Kelvin of the homopolymer of the monomer n denotes. Further helpful hints can the expert the polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) which indicates Tg values for the most common homopolymers.

The toughening phase may, according to one embodiment, have an average particle size of preferably at most 100 nm, particularly preferably at most 70 nm, the particle size being based on the diameter of the weight average. The uniformity of the toughening phase contained in the plastic mixture is preferably 0.5 or less. More preferably, the uniformity is less than or equal to 0.2. According to a preferred embodiment, at least part of the tough phase may be covalently linked to the hard phase. The production of these impact-resistant acrylic glasses is detailed in DE 10 2008 001 596 A1 to which reference is made. This embodiment shows acceptable effectiveness at a low price. Impact-resistant acrylic glass with these characteristics are commercially available from Evonik Röhm under the trade name PLEXIGLAS ^® zk20, PLEXIGLAS ^® zk30, PLEXIGLAS ^® zk40 and PLEXIGLAS ^® zk50.

Impact-resistant acrylic glasses having a tough phase and having a particle diameter of at most 100 nm, preferably at most 70 nm, are preferably used only with a small proportion of polymethyl methacrylate without impact-resistant properties. The proportion of polymethyl methacrylate having a weight-average molecular weight of at least 50,000 g / mol without impact-resistant properties is preferably at most 150% by weight, more preferably at most 100% by weight and especially preferably at most 30% by weight, based on the weight of impact-resistant Acrylic glass having a toughening phase which has a particle diameter of at most 100 nm, preferably at most 70 nm.

According to a particularly preferred embodiment, the toughening phase has an average particle size of preferably at least 100 nm, more preferably at least 150 nm, the particle size being based on the diameter of the weight average. This embodiment leads to superior properties of the resulting molded articles.

In this case, the impact-resistant configuration can be achieved by the use of impact modifiers, which are preferably based on acrylate rubbers. Such impact modifiers are known per se. These are copolymers which have a core-shell structure, the core and the shell having a high proportion of the (meth) acrylates described above.

According to a particular aspect of the present invention, the impact-modified acrylate-based plastics may contain polymethyl methacrylates obtained by free-radical polymerization of mixtures containing from 80 to 100% by weight, preferably 90-98% by weight, of methyl methacrylate and optionally of 0- 20 wt .-%, preferably 2-10 wt .-% further radically polymerizable comonomers include, which were also listed above. Particularly preferred comonomers include C1 to C4 alkyl (meth) acrylates, in particular methyl acrylate, ethyl acrylate or butyl methacrylate. Impact-resistant acrylates, preferably polyalkyl (meth) acrylate molding compositions, preferably comprise polymethyl methacrylates whose average molecular weight M w ranging from 20,000 to 350,000 g / mol, preferably 30,000 g / mol to 200,000 g / mol, in particular 60,000 g / mol to 150,000 g / mol is located. Impact acrylic glass can preferably 1 to 99 wt .-%, more preferably 2 to 80 wt .-% and especially preferably 10 to 40 wt .-% polymethyl methacrylate.

Preferred impact-resistant plastics based on acrylates contain from 0.5 to 99% by weight, preferably from 20 to 98% by weight, particularly preferably from 60 to 90% by weight, of an impact modifier, based on the total weight of the impact-modified acrylic glass. The impact modifier can be obtained in a manner known per se by bead polymerization or by emulsion polymerization.

Preferred acrylate rubber modifiers in this case have a structure with at least two shells, which differ in their composition.

Such particles can be obtained, for example, by free-radical polymerization of mixtures which are generally at least 20% by weight, preferably 50 to 70% by weight, of methyl methacrylate, 20 to 80% by weight, preferably 25 to 45% by weight. Butyl acrylate and 0.1 to 2, preferably 0.5 to 1 wt .-% of a crosslinking monomer, for. B. a polyfunctional (meth) acrylate, such as. As allyl methacrylate and comonomers which can be copolymerized with vinyl compounds, preferably styrene.

Among the preferred comonomers include C1-C4 alkyl (meth) acrylates, such as ethyl acrylate or butyl methacrylate, preferably methyl acrylate, or other free-radically polymerizable vinyl monomers such. Styrene. The mixtures for the preparation of the aforementioned particles may preferably comprise 0 to 30, preferably 0.5 to 15 wt .-% comonomers.

According to a particular aspect of the present invention, the impact modifiers have a core or at least one shell which is crosslinked.

For example, an impact modifier may be a crosslinked polyacrylate rubber having a particle diameter of 100 to 5000 nm, preferably 150 to 2000 nm, to which more preferably a polyalkyl methacrylate shell, preferably polymethyl methacrylate, having a molecular weight in the range of 30,000 to 200,000 daltons has been grafted.

In this case, particularly preferred impact modifiers may have a three- or more-phase structure, wherein the core is composed of a crosslinked polymethyl methacrylate, on which a crosslinked shell has been polymerized, which preferably comprises polybutyl acrylate, which has been copolymerized with styrene. The shell obtained by copolymerization of butyl acrylate, styrene and a crosslinking agent, for example allyl methacrylate, is then polymerized in a shell of polymethyl methacrylate, preferably using a regulator, so that the resulting polymethyl methacrylate preferably has a molecular weight in the range from 30,000 to 200,000 daltons.

The production of core-shell impact modifier with a shell comprising controlled polymethylmethacrylate is described, inter alia DE 33 00 526 , submitted on January 10, 1983 at German Patent Office with the application number P3300526.5-44 ; and in US 3,793,402 filed on 5/11/71 with the US Patent Office (USPTO) application number 196,194; discloses, wherein the impact modifiers set forth in these documents and methods for their preparation by reference to this document for purposes of disclosure in the present application are inserted.

By an outer shell based on polymethyl methacrylate, the dispersibility of the impact modifier in the monomers of the reactive resin can be surprisingly improved.

Particularly preferred impact modifiers have, inter alia, the following structure: Core: Polymer having a methyl methacrylate content of at least 80% by weight, preferably at least 90% by weight, based on the weight of the core; Bowl 1: Polymer having a butyl acrylate content of at least 70% by weight, preferably at least 80% by weight, based on the weight of the first shell; Bowl 2: Polymer having a methyl methacrylate content of at least 80 wt .-%, preferably at least 90 wt .-%, based on the weight of the second shell.

For example, a preferred impact modifier may have the following structure: Core: Copolymer of methyl methacrylate (95.7% by weight), ethyl acrylate (4% by weight) and allyl methacrylate (0.3% by weight) Bowl 1: Copolymer of butyl acrylate (81.2% by weight), styrene (17.5% by weight) and allyl methacrylate (1.3% by weight) Bowl 2: Copolymer of methyl methacrylate (96% by weight) and ethyl acrylate (4% by weight)

The ratio of core to shell (s) of the impact modifier can vary widely. Preferably, the weight ratio of core to shell K / S is in the range from 20:80 to 80:20, preferably from 30:70 to 70:30, to modifiers with one shell or the ratio of core to shell 1 to shell 2 K / S1 / S2 in the range of 10:80:10 to 40:20:40, more preferably from 20:60:20 to 30:40:30 in modifiers with two shells.

The particle size of the impact modifier is usually in the range of 100 to 5000 nm, preferably 150 to 2000 nm and more preferably from 200 to 500 nm, without this being a restriction.

According to a preferred aspect, it may be provided that the core-shell polymer has a hard, dimensionally stable core, a first shell of a crosslinked polyacrylate and a particle diameter of 150 to 500 nm and a second shell which is at least partially grafted onto the first shell which is compatible with polymethylmethacrylate. The polymer to be grafted onto the first shell may preferably be a polymethylmethacrylate. The hard, dimensionally stable core may preferably be based essentially on a crosslinked polymethylmethacrylate. The polyacrylate of the first shell preferably has the glass transition temperatures set out above, so that, for example, a polybutyl acrylate which was obtained by copolymerization with styrene and a crosslinker is suitable. According to a particularly preferred embodiment, the core-shell polymer may be provided with a polymethylmethacrylate having a molecular weight in the range of 50,000 to 300,000 daltons. For example, the core-shell polymer can be mixed with a polymethyl methacrylate, which can be done by extrusion.

Preferably, the rubber particles are so large that they can act as individual particles (capsule particles). Most preferably, the crosslinking is so strong that it can withstand the swelling pressure of the monomers.

The production of impact modifier is, inter alia, in EP-A 0 113 924 . EP-A 0 522 351 . EP 0 528 196 A1 EP-A 0 465 049 and EP-A 0 683 028 described. The in the pamphlets EP-A 0 113 924 , submitted on Dec. 31, 1983 at European Patent Office with the application number 83113259.2 ; EP-A 0 522 351 , filed on 26.06.91 at the European Patent Office with application number 92110610.0 ; EP 0 528 196 A1 , filed on 22.07.92 at European Patent Office with the application number 92112513.4 ; EP-A 0 465 049 , filed on 19.06.91 at European Patent Office with application number 91305555.4 ; and EP-A 0 683 028 , submitted on 11.05.95 at European Patent Office with application number 95107103.4 ; and the process for their preparation are incorporated by reference to these publications for the purposes of disclosure in the present application.

The impact modifiers set out above can be used as impact-modified acrylic as such. However, impact-modified plastics based on acrylates with a matrix comprising polymethyl methacrylate are particularly preferably used. These can be prepared by blending spray-dried impact modifiers having a core-shell structure and a polymethyl methacrylate molding composition, such as Plexiglas ^® 7N is obtained. Impact-resistant acrylic glasses having a toughening phase whose particle diameter has at least 100 nm, preferably at least 150 nm, are preferred for the production of these plastic mixtures, also called blends.

Here, acrylic glasses, preferably polymethyl methacrylates with impact modifiers, which have a core-shell structure, are particularly preferred.

Impact-resistant acrylic lenses are commercially available from many manufacturers, such as Evonik under the trade name Plexiglas ^® zk, especially PLEXIGLAS ^® ZK4, PLEXIGLAS ^® ZK5, PLEXIGLAS ^® ZK6, PLEXIGLAS ^® zk5BR, PLEXIGLAS ^® zk5HC, PLEXIGLAS ^® zk6HF.

The present polymerizable compositions for producing a fiber-reinforced molding may preferably contain 5 to 50 wt .-%, preferably 5 to 40 wt .-% and particularly preferably 10 to 30 wt .-% impact-resistant acrylic glass, based on the weight of the polymerizable composition. Higher proportions of impact-resistant acrylic glass surprisingly improve the formability of the fiber-reinforced molded articles obtained from the masses. However, in this way, especially at high molecular weights of the polymers which may be present in the impact-resistant acrylic glasses, the processability can be adversely affected by a sharp increase in the viscosity.

According to one embodiment, the impact-resistant acrylic glass may be a bimodal or multimodal Distribution of the size of the toughening phase of the impact modifier. Such impact-resistant acrylic glasses can be obtained inter alia by mixing acrylic glasses whose tough phase has an average particle size of at most 100 nm, preferably at most 70 nm, and acrylic glasses having a toughening phase whose average particle size is at least 100 nm, preferably at least 150 nm.

Other constituents of the polymerizable compositions are known in the art and, for example, in the publications DE 101 63 681 A1 , filed on 21.12.2001 at the German Patent and Trademark Office with the application number DE 10163681.4 ; DE 198 26 412 A1 , filed on 16.06.1998 at the German Patent and Trademark Office with the application number DE 19826412.7 ; and DE 103 54 732 A1 , submitted on 21.11.2003 to the German Patent and Trademark Office with the application number DE 10354703.0.7 set forth the disclosure of the publications DE 101 63 681 A1 . DE 198 26 412 A1 and DE 103 54 732 A1 is incorporated by reference in this application.

According to a further embodiment, a polymerizable composition
10 to 30% by weight impact-resistant acrylic glass,
From 30 to 70% by weight of methyl methacrylate,
From 5 to 20% by weight of ethylhexyl acrylate,
0 to 5% by weight of butanediol dimethacrylate,
1 to 5 wt .-% triallyl cyanurate and / or allyl methacrylate and
0.1 to 2% by weight of aromatic amine
include, wherein the components set forth above add up to 100 wt .-%.

Furthermore, preferred polymerizable compositions may comprise at least one polymer which differs from the impact-resistant acrylic glasses set forth above. The preferred (meth) acrylate-based polymer can be added, for example, to adjust the viscosity of the reaction resin and the flow properties, as well as to improve the cure or to improve other properties of the resin or the cured coating. Preferably, the polymer is soluble or swellable in the reactive components of the resin. Accordingly, polymers based on (meth) acrylates can preferably be used. In particular, z. As poly (meth) acrylates suitable, which can be solved as a solid polymer in the ethylenically unsaturated compounds. They may also be referred to as so-called syrups, i. H. be used as partially polymerized masses of corresponding monomers.

Also contemplated are copolymers based on vinyl chloride, copolymers based on styrene, especially styrene-acrylonitrile (SAN), and copolymers comprising styrene and maleic anhydride, copolymers comprising styrene and methyl methacrylate, copolymers based on vinyl acetate, unsaturated polyesters, polyurethanes or Mixtures thereof or with the above-mentioned poly (meth) acrylates appropriate. Particularly successful example plexigum ^® P24 can from Rohm GmbH, which is a copolymer of about 20% methyl methacrylate and 80% butyl methacrylate, are used.

Preferably, the polymerizable composition may comprise at least 1% by weight, more preferably at least 5% by weight of polymer, which is different from the impact-resistant acrylic glasses set forth above. According to a particular aspect of the present invention, the proportion of polymer, based on the weight of the reaction resin, preferably in the range of 0 to 40 wt .-%, in particular 2 to 30 wt .-% and particularly preferably in the range of 5 to 20 wt .-%.

The reactive resins of the invention can preferably be cured by free radicals.

In addition, the polymerizable composition may contain conventional additives. These include, but are not limited to, antistatics, antioxidants, biostabilizers, chemical blowing agents, mold release agents, flame retardants, lubricants, colorants, flow improvers, lubricants, fillers, especially inorganic fillers, primers, inhibitors, catalysts, sunscreens, optical brighteners, organic phosphites, oils, pigments, Defoamers (Air Release Agents) and plasticizers.

The polymerizable composition particularly preferably comprises inhibitors. Inhibitors, such as, for example, hydroquinones, hydroquinone ethers, such as hydroquinone monomethyl ether or di-tert-butyl catechol, phenothiazine, N, N '- (diphenyl) -p-phenylenediamine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, p-phenylenediamine, methylene blue or hindered phenols are well known in the art. These compounds can be used singly or in the form of mixtures and are generally available commercially. For further details, reference is made to the usual technical literature, in particular to the Rompp-Lexikon Chemie; Editor: J. Falbe, M. Regitz; Stuttgart, New York; 10th edition (1996) ; Reference "Antioxidants" and cited references cited here. The proportion of inhibitors may preferably be in the range of 1 to 1000 ppm, in particular 10 to 500 ppm, based on the weight of the polymerizable composition.

The viscosity of the polymerizable composition may preferably be in the range from 20 to 1000 mPas, more preferably in the range from 80 to 600 mPas, as measured according to Brookfield at 25 ° C.

Another object of the present invention, which is based on a polymerizable composition according to the invention, is a curable composition which comprises a fibrous filler in addition to the reactive resin.

Suitable reinforcing fibers are in particular glass fibers, carbon fibers (carbon fibers) and plastic fibers. The plastic fibers include fibers of polyester, in particular polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyamide and high performance plastic fibers. Aramid fibers, particularly those of the so-called high modulus polymers such as polyparaphenylene terephthalamide (TM Kevlar or TM Twaron) and copolymers (e.g., TM Teijin HM50) containing over 30% of building blocks derived from terephthalic acid and para-phenylenediamine, are among the preferred high performance plastic fibers , as well as fibers of liquid crystalline polyesters and ultrahigh molecular weight polyethylene fibers (eg TM Dyneema). Of the fibers mentioned, particularly high-performance plastic fibers and carbon fibers are preferred, of which carbon fibers are particularly preferred.

According to a preferred aspect of the present invention, the fibers are used in the form of textile fabrics. Textile fabrics within the meaning of the invention are two-dimensional structures, for example knitted fabrics, knitted fabrics, woven fabrics, scrims or nonwovens of different thickness, as well as laminates of identical or different fabrics, if required in combination with application-specific mixture components. These are, for. For example, pigments, fillers, flame retardants and modifiers, such as plasticizers, lubricants. Of the textile fabrics mentioned, knitted fabrics, in particular knitted or knitted fabrics, are preferred. Shaped articles with a fabric based on knitted fabrics are particularly easy to reshape and yet show excellent mechanical stabilities based on the reinforcing fibers.

The curable composition may advantageously comprise at least 30% by weight, more preferably at least 40% by weight, and most preferably at least 50% by weight of reactive resin, based on the weight of the curable composition.

The curable compositions according to the invention can be prepared and processed in a particularly simple and safe manner. To prepare a curable composition, a fiber structure, in particular a flat fiber structure, can be provided with a reactive resin, which is subsequently cured.

Accordingly, a fiber-reinforced molded body may preferably have a tabular shape, wherein the thickness has a much smaller size than the width or the length. The thickness of the fiber-containing shaped body can be adapted to different requirements. According to a preferred embodiment, the thickness of the fibrous shaped bodies is preferably in the range of 0.1 to 40 mm, more preferably in the range of 1 to 10 mm.

The incorporation of the polymerizable composition in a textile fabric can be carried out in any known manner, wherein the curable composition or the polymerizable composition is particularly suitable for the production of fiber-matrix semifinished products. These include prepregs (preimpregnated fibers), SMC (Sheet Molding Compound) and BMC (Bulk Molding Compound). Here, preferred embodiments can be regarded as thermoplastic prepregs, since the fiber-reinforced molded articles obtainable according to the invention have a high mechanical stability and can be formed.

The polymerizable composition and / or the curable composition can be cured by the initiators set forth above under various conditions to give moldings, preferably fiber-reinforced moldings. The curing temperature may be, for example, in the range of -20 ° C to 100 ° C, preferably 0 to 80 ° C and more preferably 15 ° C to 60 ° C.

According to a preferred embodiment it can be provided that the polymerizable composition and / or the curable composition comprises at least one allyl compound. In this case, the curing can preferably be carried out such that at least a part of the allyl double bonds are present in the shaped body after curing. This can be achieved, for example, by curing at relatively low temperatures, preferably less than 90 ° C., more preferably less than 60 ° C.

Particularly surprising is in particular the possibility of being able to transform the obtained, hardened fibrous shaped bodies without the mechanical properties being thereby impaired in an unacceptable manner. Here, a precured flat shaped body at a temperature of at least 100 ° C, preferably in the range 120 ° C to 150 ° C over a period of 5 minutes to 20 hours, preferably 10 minutes to 1 hour and more preferably 20 minutes to 40 minutes a Shaping, for example by Be subjected to pressing. In this way, for example, body parts can be obtained reliably and inexpensively. The said transformation conditions are generally suitable for reacting preferably contained allyl double bonds, so that postcrosslinking takes place.

If allyl double bonds are contained in the shaped body to be formed, as stated above, the bodies formed at the temperatures mentioned exhibit particularly excellent mechanical properties, in particular high impact resistance and high heat resistance.

The transformation of a fibrous shaped body can be carried out by conventional methods such as deep drawing, vacuum deep drawing, pressing, thermoforming (s. Lechner (ed.) Macromolecular Chemistry, p. 384 ff, Verlag Birkenhäuser, Basel, 1993 ) and - preferably - after Hochdruckverformverfahren as exemplified in EPA 0 371 425 are described. In the latter case, the deformation takes place at higher pressures above 20 bar, preferably above 50 bar. The pressure to be used is determined in particular by the thickness of the shaped body to be formed and the temperature, as well as the shaped body used, in particular the composition of the polymerizable mass from which the shaped body was obtained. It may need to be determined in simple preliminary tests.

The fibrous shaped bodies obtainable according to the invention are novel and therefore likewise the subject of the present invention.

The polymerizable compositions of the present invention can be used in particular as adhesives. Furthermore, the polymerizable compositions can preferably be filled into cartridges, preferably multi-component cartridges, wherein the polymerizable compositions can be processed and used in a particularly simple and expedient manner. These multi-component cartridges are used for example in the publications DE 10 2005 000 056 A1 , registered on 10.05.2005 at the German Patent and Trademark Office with the application number DE 10 2005 000 056.8 ; DE 10 2005 017 599 A1 , filed on 16.04.2005 with the German Patent and Trademark Office with the application number DE 10 2005 017 599.6 and DE 10 2009 016943 A1 , filed on 08.04.2009 with the German Patent and Trademark Office with the application number DE 10 2009 016 943.1 wherein the disclosure of these documents, in particular with regard to the structure of the multi-component cartridges for disclosure purposes in the present application is inserted.

The articles obtainable by curing the polymerizable compositions or the curable composition exhibit excellent mechanical properties. Thus, preferred moldings obtainable according to the present invention have an impact strength of at least 12 kJ / m ² , particularly preferably at least 17 kJ / m ² and very particularly preferably at least 18 kJ / m ² DIN ISO 179 / 1eU can be measured (25 ° C / 50% relative humidity).

Furthermore, preferred moldings of the present invention are characterized by a high tensile elongation at break and a high maximum tensile stress. Preferably, the tensile elongation at break is at least 10%, more preferably at least 15%, measured according to EN ISO 527 at 25 ° C. The tensile strength of preferred shaped articles is at least 10 MPa, more preferably at least 15 MPa, measured according to EN ISO 527 at 25 ° C.

Furthermore, the hardness of the moldings obtainable from the polymerizable compositions can be adapted to specific requirements, the hardness of preferred moldings being in particular in the range from 20 to 45 N, measured according to Bracol.

The following examples serve to illustrate the present invention. The impact resistance of the cured samples was measured according to DIN ISO 179 / 1eU ,

In the following examples, all percentages are by weight, unless otherwise noted.

example 1

A reactive resin based on (meth) acrylate was prepared by mixing 69.38% methyl methacrylate, 28.0% impact resistant acrylic (PLEXIGLASS ^® zk6HF Evonik Ltd.), 1.5 wt .-% Butyldioldimethacrylat, 0.02 Stabilizer S16, 0 , 10 wt .-% pentaerythritol tetra (meth) acrylate, 0.10 wt .-% co-stabilizer (Alkanox 240 ^®), 0.10 wt .-% stabilizer (Macrolex ^® (0.05%)), 0.07 wt .-% Tinuvin ^® P, 0.03 wt .-% Borchi Gol LAC ^® 80 (polyether-modified methyl polysiloxane), 0.1 wt .-% Ethylglykolthioglykolat, 1.5 wt .-% and 0.6 wt .-% butanediol dimethacrylate Di-isopropoxy-p-toluidine prepared.

91% by weight of reactive resin was cured with 9% by weight of a hardener composition based on benzoyl peroxide (commercially available under the name Pentan 9A). The curing time was about 17 minutes.

The impact strength at 23 ° C / 50% rel. Humidity was 19.2 kJ / m ² . There was no hardening Foaming on. Barcol hardness was about 40 N. Adhesive tensile strength on aluminum was 138 kg / cm ² and on zinc sheet 285 kg / cm ² . When bonding polycarbonate, acrylic glass, styrene-acrylonitrile (SAN) and polyvinyl chloride (PVC) was so strong that a material fracture occurred.

Example 2

Example 1 was essentially repeated, except that instead of the impact-resistant acrylic glass PLEXIGLAS ^® zk6HF, which is a core-shell polymer having a toughening phase whose average particle size is at least 150 nm, a toughened acrylic glass with a toughening phase whose average particle size is at most 70 nm (PLEXIGLAS ^® zk50 from Evonik AG) was used. The other constituents of the polymerizable composition correspond to those set forth in Example 1, this composition also being hardened by the addition of benzoyl peroxide.

The impact strength at 23 ° C / 50% rel. Moisture was 25.4 kJ / m ² . During curing, no foaming occurred. The hardness according to Barcol was about 38 N.

Example 3

Example 1 was essentially repeated, but instead of 1.5 wt .-% butyl diol dimethacrylate, the corresponding amount of methyl methacrylate was used. The other constituents of the polymerizable composition correspond to those set forth in Example 1, this composition also being hardened by the addition of benzoyl peroxide.

The impact strength at 23 ° C / 50% rel. Humidity was 18.5 kJ / m ² . During curing, significant foaming occurred. Barcol hardness was about 42 N. Adhesive tensile strength on VA steel was 152 kg / cm ² and on zinc sheet was 283 kg / cm ² . When bonding polycarbonate, acrylic glass, styrene-acrylonitrile (SAN) and polyvinyl chloride (PVC) was so strong that a material fracture occurred.

Comparative Example 1

Example 1 was essentially repeated, except that acrylic glass without impact-resistant properties (PLEXIGLAS ^® 7N from Evonik AG) was used instead of the impact-resistant acrylic glass. The other constituents of the polymerizable composition correspond to those set forth in Example 1, this composition also being hardened by the addition of benzoyl peroxide.

The impact strength at 23 ° C / 50% rel. Humidity was 10.28 kJ / m ² . During curing, no foaming occurred. Barcol hardness was about 42 N. Adhesive tensile strength on aluminum was 120 kg / cm ² and on zinc sheet was 252 kg / cm ² . It turns out that the use of impact-resistant acrylic glass allows a higher adhesive tensile strength to be achieved than with conventional acrylic glass.

Example 4

A reactive resin based on (meth) acrylate was prepared by mixing 64.38% methyl methacrylate, 28.0% impact resistant acrylic (PLEXIGLASS ^® zk6HF Evonik AG), 5 wt .-% hydroxyethyl methacrylate, 1.5 wt .-% Butyldioldimethacrylat, 0.02 stabilizer S16, 0.10 wt .-% pentaerythritol tetra (meth) acrylate, 0.10 wt .-% co-stabilizer (Alkanox 240 ^®), 0.10 wt .-% stabilizer (Macrolex ^® (0.05 %)), 0.07 wt .-% Tinuvin ^® P, 0.03 wt .-% Borchi Gol LAC ^® 80 (polyether-modified methyl polysiloxane), 0.1 wt .-% Ethylglykolthioglykolat, 1.5 wt .-% butanediol dimethacrylate, and 0.6 wt .-% of di-isopropoxy-p-toluidine prepared.

91% by weight of reactive resin was cured with 9% by weight of a hardener composition based on benzoyl peroxide (pentane 9A).

The impact strength at 23 ° C / 50% rel. Humidity was 19.6 kJ / m ² . During curing, no foaming occurred. Barcol hardness was about 45 N. Adhesive tensile strength on aluminum was 159 kg / cm ² , on VA steel 163 kg / cm ² and on zinc sheet 236 kg / cm ² . When bonding polycarbonate, acrylic glass, styrene-acrylonitrile (SAN) and polyvinyl chloride (PVC) was so strong that a material fracture occurred.

Example 5

Example 4 was essentially repeated except that 1% by weight of methacrylic acid and a correspondingly smaller amount of methyl methacrylate were used. The other constituents of the polymerizable composition correspond to those set forth in Example 4, this composition also being hardened by the addition of benzoyl peroxide.

During curing, no foaming occurred. The adhesion tensile strength on aluminum was 185 kg / cm ² , on VA steel 195 kg / cm ² and on zinc sheet 376 kg / cm ² . When bonding polycarbonate, acrylic glass, styrene-acrylonitrile (SAN) and polyvinyl chloride (PVC) was so strong that a material fracture occurred.

Example 6

Example 4 was substantially repeated except that 2% by weight of methacrylic acid and a correspondingly lower amount of methyl methacrylate was used. The other constituents of the polymerizable composition correspond to those set forth in Example 4, this composition also being hardened by the addition of benzoyl peroxide.

During curing, no foaming occurred. The adhesion tensile strength on aluminum was 194 kg / cm ² , on VA steel 328 kg / cm ² and on zinc sheet 345 kg / cm ² . When bonding polycarbonate, acrylic glass, styrene-acrylonitrile (SAN) and polyvinyl chloride (PVC) was so strong that a material fracture occurred.

Example 7

Example 4 was substantially repeated, but with 10 wt .-% of an added acid group-containing polymer which contains 10% methacrylic acid (Neocryl ^® 817) and a correspondingly smaller amount of methyl methacrylate was used. The other constituents of the polymerizable composition correspond to those set forth in Example 4, this composition also being hardened by the addition of benzoyl peroxide.

During curing, no foaming occurred. The adhesion tensile strength on aluminum was 180 kg / cm ² .

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 10163681 A1 [0025, 0071, 0071]
• DE 19826412 A1 [0025, 0071, 0071]
• DE 102008001596 A1 [0041, 0045]
• DE 3300526 [0057]
• DE 3300526 A [0057]
• US 3793402 [0057]
• EP 0113924 A [0065, 0065]
• EP 0522351 A [0065, 0065]
• EP 0528196 A1 [0065, 0065]
• EP 0465049 A [0065, 0065]
• EP 0683028 A [0065, 0065]
• EP 83113259A [0065]
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Cited non-patent literature

• ISO 179 / 1eU [0042]
• DIN EN ISO 11357 [0044]
• Fox TG, Bull. Physics Soc. 1, 3, page 123 (1956) [0044]
• Handbook 2nd Edition, J. Wiley & Sons, New York (1975) [0044]
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• DIN ISO 179 / 1eU [0094]
• EN ISO 527 [0095]
• EN ISO 527 [0095]
• DIN ISO 179 / 1eU [0097]

Claims (14)

Polymerizable composition containing 30-97 wt.% Alkyl methacrylate having 1-6 carbon atoms in the alkyl radical, preferably methyl methacrylate, and 3-70 wt.% Impact-resistant acrylic glass. Polymerizable composition according to claim 1, characterized in that the polymerizable composition comprises 0.01-5 wt .-% crosslinker. Polymerizable composition according to claim 1 or 2, characterized in that the polymerizable composition comprises 1 to 5% by weight of allyl compound having at least two polymerisable groups, preferably allyl (meth) acrylate and / or triallyl cyanurate. Polymerizable composition according to at least one of the preceding claims, characterized in that the impact-resistant acrylic glass has a tough phase with a particle diameter of at most 100 nm. Polymerizable composition according to at least one of the preceding claims, characterized in that the impact-resistant acrylic glass comprises a core-shell polymer. Polymerizable composition according to claim 5, characterized in that the core-shell polymer grafted a hard, dimensionally stable core, a first shell of a crosslinked polyacrylate and a particle diameter of 150 to 500 nm and a second shell, at least partially grafted to the first shell which is compatible with polymethylmethacrylate. Polymerizable composition according to at least one of the preceding claims, characterized in that the composition comprises 15 to 30% by weight of alkyl acrylate having 1 to 10 carbon atoms. Polymerizable composition according to claim 7, characterized in that the composition comprises ethylhexyl acrylate. A curable composition comprising at least one polymerizable composition according to any one of claims 1 to 8 and at least one fibrous filler. A curable composition according to claim 9, characterized in that the fibrous filler is a sheet, preferably a woven, knitted, knitted or fleece based on carbon fibers. A fiber-reinforced molded article obtainable by curing a composition according to claim 9 or 10. A process for producing a fiber-reinforced molded article according to claim 11, which comprises introducing fibers into a polymerizable composition according to any one of claims 1 to 8 and curing the polymerizable composition. A method according to claim 12, characterized in that the fiber-reinforced molded body after curing at a temperature greater than 100 ° C is formed. Use of a polymerizable composition according to any one of claims 1 to 8 as an adhesive. A cartridge comprising a polymerizable composition according to any one of claims 1 to 8.