Process for the production of hydrophobic and reactive inorganic and / or organic fillers, fillers produced in this way and molded part produced from a polymer-based casting compound containing at least one such filler

Abstract

A process for the preparation of hydrophobic and reactive inorganic and / or organic fillers, comprising the steps of: (a) providing a filler having a specific surface, (b) mixing the filler with the solution of at least one hydrophobizing and activating reactive compound on a biological basis in a mixing unit in an amount of 0.15 × 10 -2 up to 5.0 × 10 -2 g per m 2filler surface at a speed of 20 rpm to 200 rpm for 12 minutes to 120 minutes, wherein the hydrophobizing and activating reactive compound on a biological basis is selected from the (meth)acryloyl monomer of the general formula: H2C=C(R1)C(O)-NH-CH2-CH2-OC(O)-R2, wherein R1 is H in the case of acrylic and CH3 in the case of methacrylic, wherein R2 is a fatty acid residue from the vegetable oil-based oils or from animal oils and / or fats, which reacts in bulk with the N-hydroxyethyl (meth)acrylamide, (c) evacuating the hydrophobized and activated inorganic and / or organic filler in a storage bag, box or drum or directly in a casting compound to produce a molded part.

Description

[0001] The invention relates to a process for producing hydrophobic and reactive inorganic and / or organic fillers. Such fillers are used, for example, as additives to polymer-based casting compounds from which composite moldings are produced.

[0002] Shrinkage and shrinkage stress are a common problem in many applications based on radically cured thermosetting materials, such as molded kitchen sinks, wash basins, bathtubs, or dental filling composite systems. Such composites typically contain a radically cured polymer binder, an initiator system, and silane-treated inorganic filler particles. Shrinkage is observed during curing of these composite systems, which can induce microcracks on the one hand and strong intrinsic stresses in the material on the other. In molded kitchen sinks, for example, this can lead to crack propagation in the material, resulting in water leakage or a reduction in mechanical properties. The same problems can occur with dental composite materials: stresses, microleakage, adhesive detachment, and ultimately pain for the patient.

[0003] This problem can be attributed to the high filler content in composite materials and the use of 3-methacryloxypropyltrimethoxysilane, which is immobilized on the surface of the quartz particles and exhibits lower mobility due to its relatively short triple chain. During polymerization, this limited mobility leads to rapid radical termination and the formation of short polymer chains, which, due to the high stiffness, places significant stress on the system. Thermally induced contractions or expansions of the material, as well as mechanical shocks, can act as sources of microcracks at the filler-matrix interface.

[0004] At the filler-matrix interface, natural stresses are concentrated due to the presence of many reactive groups on a rigid, inorganic surface. The surface of the quartz sand particles typically has 0.8 hydroxyl groups per square nanometer of surface. During the silanization process, almost every hydroxyl group reacts with a single silane molecule and forms a uniform hydrophobic silane layer, resulting in a superhydrophobic effect with very dense immobilization of the reactive methacrylate group. The high concentration of double bonds immobilized on the filler surface results in the polymerization of the short polymer chains and thus in the creation of regions with high residual stress. These stresses can be reduced by replacing the methacrylol silane with non-reactive silanes, but this affects the mechanical properties, such as:the impact strength is reduced due to the lack of bonding between filler and matrix.

[0005] The use of silane-treated inorganic and / or organic fillers treated with a silane coupling agent requires the hydrolysis of the hydrolyzable ester functions of the silane. For example, the hydrolysis of 1000 kg of 3-methacryloxypropyltrimethoxysilane results in the production of 387 kg of methanol, a flammable liquid with high vapor pressure that can be fatal if swallowed.

[0006] Furthermore, the silanization of fillers is technically carried out by thermal activation at temperatures of 60°C or higher. The energy required for this process is usually generated by burning natural gas or corresponding hydrocarbons, which contribute to CO2 emissions and increase process costs. After the silanization process, a curing period of several days is usually necessary until the desired hydrophobicity of the filler is achieved.

[0007] DE 32 15 890 A1 discloses a process for treating mineral fillers with hydrophobic surfactants. The treatment is carried out in an aqueous slurry of the fillers containing at least 25% water by weight, based on the total weight of the slurry, using 0.1 to 5.0% of the hydrophobic surfactant, based on the weight of the filler. Fatty acids and their derivatives serve as hydrophobic agents.

[0008] From DE 198 32 668 A1, a hardenable 2-component mortar composition is known, with hardenable organic and hardenable inorganic components and with hardeners, wherein the hardeners are separated from the respective hardenable component in a reaction-inhibiting manner, but can be activated for application or use, wherein epoxy and fine-particle cement are contained as hardenable components and amine and alkali water glass are contained as hardeners.

[0009] The object of the present invention is to eliminate the above-described technical and environmental problems of the prior art.

[0010] To achieve the object, a process for producing hydrophobic and reactive inorganic and / or organic fillers is proposed, comprising the steps of: (a) providing a filler with a specific surface, (b) mixing the filler with the solution of at least one hydrophobizing and activating reactive substance on a biological basis in a mixing unit in an amount of 0.15 × 10 -2 up to 5.0 × 10 -2 g / m 2 per m 2filler surface at a speed of 20 rpm to 200 rpm for 12 minutes to 120 minutes, wherein the hydrophobizing and activating reactive compound on a biological basis is selected from the (meth)acryloyl monomer of the general formula: H2C=C(R1)C(O)-NH-CH2-CH2-OC(O)-R2, wherein R1 is H in the case of acrylic and CH3 in the case of methacrylic, wherein R2 is a fatty acid residue from the vegetable oil-based oils or from animal oils and / or fats, which reacts in bulk with the N-hydroxyethyl (meth)acrylamide, (c) evacuating the hydrophobized and activated inorganic and / or organic filler into a storage bag, box or drum or directly into a casting compound to produce a molded part.

[0011] In contrast to the silanization process, which requires seven days of storage of the treated filler for the post-treatment reaction, the present invention proposes a technology that allows the filler to be used immediately after treatment. Furthermore, the inventive process does not require a heating process, whereas the silanization reaction is carried out by heating to at least 60°C for at least 30 minutes.

[0012] Hydrophobized and activated fillers of the present invention have different interfaces with the matrix. The double bond of the methacryloyl group, located near the filler surface, encapsulates the filler surface during polymerization and keeps the double bond on the side chains of the fatty acid available for copolymerization with the matrix. This leads to the formation of a less strained filler-matrix interface. This reduces stresses locally and in the molded parts as a whole.

[0013] The amounts of hydrophobizing and reactive substances to be activated on a natural basis depend on the specific filler surface and are therefore given in g / m 2 The amount of methacryloyl monomer used is chosen so that a monolayer of the methacryloyl monomer over the amine group with the hydroxyl group of the filler is preferred. The amount therefore depends on the density of the hydroxyl groups on the filler surface. For example, 0.8 -OH groups per nm 2 and 0.2 m 2 / g for quartz sand and from this the necessary amount of methacryloyl monomer can be determined.

[0014] The mixing time in the mixing unit, e.g., a rotary mixer, also varies depending on the filler composition. Particles with a larger diameter require less time to achieve a uniform distribution of the oil-based monomers over the filler surface. For finer particles, e.g., quartz or fruit kernel flour, the mixing time is longer.

[0015] According to the invention, an inorganic and / or organic filler is provided which has a hydrophobic and activated surface. The inorganic fillers can be selected from SiO2, Al2O3, TiO2, ZrO2, Fe2O3, ZnO, Cr2O5, carbon, metals and metal alloys, SiC, SiN, BN, or mixtures thereof.

[0016] The organic fillers are ground fruit kernels and / or fruit shells and can be selected from olive kernels, peach kernels, apricot kernels, cherry kernels, almond shells, argan shells, walnut shells or a mixture thereof.

[0017] Inorganic and organic fillers can be used in a combination of both types. The mixing ratio can be chosen arbitrarily.

[0018] The hydrophobized and activated surface of the inorganic and / or organic filler is formed by immobilizing at least one bio-based (meth)acrylated monomer comprising a bio-derived fatty acid group esterified with the (meth)acrylic group on the surface of the inorganic and / or organic filler.

[0019] The inorganic and organic fillers used in step (a) can have a grain size of 1 µm to 2000 µm. The present invention is based on the concept of hydrophobicizing and activating inorganic and / or organic fillers, including a surface treatment with at least one reactive biologically based compound.

[0020] The hydrophobicized and activated surface of the inorganic and / or organic filler is obtained by immobilizing at least one bio-based (meth)acrylated monomer containing a bio-derived fatty acid group comprising a group esterified with the (meth)acrylic group. The bio-based (meth)acrylated monomer is dissolved in the monomer contained in the polymer matrix of the molded part. The concentration of the bio-based (meth)acrylated monomer should be 1 to 20 wt.%, preferably 3 to 17.5 wt.%, in particular 5 to 15 wt.%.

[0021] The hydrophobizing and reactive biologically based compound to be activated used in step (b) is selected from the methacryloyl monomer based on oils of natural origin of the general formula: H2C=C(R1)C(O)-NH-CH2-CH2-OC(O)-R2, where R1 is H in the case of acrylic and CH3 in the case of methacrylic, where R2 is a fatty acid residue from the oils or fats of natural origin which reacts in the mass with the N-hydroxyethyl(meth)acrylamide.

[0022] Furthermore, the hydrophobizing and bio-based reactive compound to be activated used in step (b) can be dissolved in the at least one monomer present in the polymer matrix of the molded part.

[0023] Monofunctional monomers in the form of an acrylate monomer can be used as solvents. These can be selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, and Butyl acrylate, isobutyl acrylate, isodecyl acrylate, dihydroxycyclopentadienyl acrylate, ethyl diglycol acrylate, heptadecyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, hydroxyethyl caprolactone acrylate, polycaprolactone acrylate, hydroxypropyl acrylate, lauryl acrylate, stearyl acrylate, 2-(2-Ethoxy)ethyl acrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, ethoxylated 4-phenyl acrylate, trimethyl cyclohexyl acrylate, octyldecyl acrylate, tridecyl acrylate, ethoxylated 4-nonylphenyl acrylate, isobornyl acrylate, cyclic trimethylolpropane formal acrylate, ethoxylated 4-Lauryl acrylate, polyester acrylate, hyperbranched polyester acrylate, melamine acrylate, silicone acrylate, epoxy acrylate.

[0024] It is also possible to use a monofunctional monomer in the form of a methacrylate. This can be selected from methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, behenyl methacrylate, behenyl polyethylene glycol methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, stearyl polyethylene glycol methacrylate, isotridecyl methacrylate, ureido methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, methoxypolyethylene glycol methacrylate, glycidyl methacrylate, glycerol formal methacrylate, and tetradecyl methacrylate.

[0025] A polyfunctional monomer in the form of a polyfunctional acrylate can also be used as a solvent. This can be selected from 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, polybutadiene diacrylate, tetraethylene glycol diacrylate, and 3-methyl-1,5-pentanediol diacrylate.Ethoxyliertes Bisphenol-A-Diacrylat, Dipropylenglykoldiacrylat, ethoxyliertes Hexandioldiacrylat, 1,10-Decandioldiacrylat, alkoxyliertes Diacrylat, Tricyclodecandimethanoldiacrylat, propoxyliertes Neopentylglykoldiacrylat, Pentaerythrit-tetraacryllat, Trimethylolpropantriacrylat, ethoxyliertes Trimethylolpropantriacrylat, Ditrimethylolpropantetraacrylat, Tris(2-hydroxyethyl)isocyanurattriacrylat, Dipentaerythritol-pentaacrylat, Pentaerythritoltriacrylat, propoxyliertes Glycerintriacrylat, aliphatisches Urethantriacrylat, aliphatisches Urethandiacrylat, aromatisches Urethandiacrylat, aromatisches Urethantriacrylat, aromatisches Urethanhexaacrylat, Polyesterhexaacrylat, epoxidiertes Sojabohnenöldiacrylat.

[0026] In addition, a polyfunctional biomonomer in the form of a bio-based methacrylate can be used. This can be selected from triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, tricyclodecanedimethanol dimethacrylate, and trimethylolpropane trimethacrylate.

[0027] It is possible to use fatty acids in the form of vegetable oils. This can be selected from coconut oil, germ oil, rapeseed oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, almond oil, beechnut oil, Brazil nut oil, cashew oil, hazelnut oil, macadamia oil, mongongo oil, pecan oil, pistachio oil, walnut oil, pumpkin seed oil, grapefruit seed oil, lemon oil, orange oil, bitter melon oil, calabash oil, cucurbita oil, butternut seed oil, egusi seed oil, watermelon seed oil, borage seed oil, currant seed oil, black seed oil, acai oil, evening primrose oil, linseed oil, amaranth oil, apricot kernel oil, apple seed oil, argan oil, avocado oil, babassu oil, behen oil, salnus oil, cape chestnut oil, cocoa butter, cocklebur oil, cohune palm oil, coriander seed oil, date seed oil, Dika oil, grape seed oil, hemp oil, kapok seed oil, kenaf seed oil, lallemantia oil, marula oil, mustard oil, ramtill herb oil, nutmeg butter, perilla seed oil, persimmon seed oil, pequi oil, pili nut oil, pomegranate seed oil, poppy seed oil, pracaxi oil, plum kernel oil,Quinoa oil, rice oil, sacha inchi oil, sapote oil, patawa oil, shea butter, taramira oil, tea seed oil, tiger nut oil, tobacco seed oil, tomato seed oil, wheat germ oil, rhubarb oil, camelina oil, radish oil, salicornia oil, tung oil, copaiba oil, jatropha oil, jojoba oil, nagkesar oil, pongamia oil, dammar oil, stillingia oil, artichoke oil, murumuru butter, balanos oil, bladderpod oil, macassar kernel oil, burdock root oil, buriti oil, kukui nut oil, carrot seed oil, cuphea oil, mango oil, passionflower oil, rosehip seed oil, sea buckthorn oil, tamanu oil, tonka bean oil.

[0028] In addition, it is possible to use a fatty acid in the form of an essential oil. This can be selected from oud oil, ajwain oil, angelica root oil, anise oil, asafoetida, basil oil, Peru balsam, bay oil, bergamot oil, black pepper oil, buchu oil, birch oil, camphor oil, calamodin oil, caraway oil, cardamom oil, cedarwood oil, chamomile oil, calamus oil, cinnamon oil, lemon oil, lemongrass oil, sage oil, clove oil, coffee oil, coriander oil, lady's mint oil, costus root oil, cranberry seed oil, cubeb oil, cumin oil, cypress oil, curry leaf oil, davana oil, dill oil, immortelle oil, elemi oil, eucalyptus oil, fennel seed oil, galangal oil, galbanum oil, garlic oil, geranium oil, ginger oil, henna oil, helichrysum oil, horseradish oil, jasmine oil, juniper berry oil, lavender oil, lemon balm oil, moringa oil, Mugwort oil, myrrh oil, neem oil, oregano oil, spikenard oil, parsley oil, patchouli oil, perilla oil, peppermint oil, pine nut oil, rosemary oil, sandalwood oil, sassafras oil, savory oil, schisandra berry oil, mint oil, thyme oil.

[0029] In addition, a fatty acid in the form of an animal fat and / or oil can be used. This can be selected from fish oil, bear fat, chicken fat, crocodile fat, crocodile oil, cod liver oil, emu oil, pork fat, goose fat, duck fat, or shark liver oil.

[0030] According to the invention, the solution thus prepared from the solvent and the acrylamide functionalized with a fatty acid group is deposited on the surface of the solid fillers in a rotating powder mixer. The (meth)acrylic groups in the reactive (meth)acrylic monomers esterify to form a polymer matrix in order to be immobilized on the surface of the inorganic and / or organic filler particles (see Fig. 2). This diagram shows the process of filler encapsulation and bonding to the polymer binder.

[0031] The surface of inorganic and / or organic filler particles is functional due to the presence of functional groups, such as a hydroxyl group, on the quartz surface. These functional hydroxyl groups serve as immobilization centers for the biologically derived fatty acid monomer molecules of the invention. The fatty acid acrylamide molecules chemosorb onto the filler surface, forming a reactive (meth)acrylate layer with organic chains oriented outward from the surface. A water droplet applied to the quartz surface of the quartz particles modified with the acrylic monomer, e.g., olive oil-based, remains on the surface of the compacted filler particles for more than 240 seconds. The same effect is achieved using other oil-based (meth)acrylates. The double bond associated with the (meth)acrylamide is located near the filler surface.Such a morphology enables the formation of a uniform organic layer on the filler surface during polymerization. On the other hand, the double bond of the unsaturated fatty acids, located far from the filler surface, participates in the copolymerization process with the matrix monomers. This dimensional specificity in the bond between matrix and filler increases impact strength and thermal shock resistance, reduces the effects of the degree of crosslinking, and thus reduces the brittleness of the molded article.

[0032] In addition to the process, the invention further relates to a hydrophobic and reactive inorganic and / or organic filler produced by the process according to the invention.

[0033] Inorganic and organic fillers according to the invention preferably have a surface treated with at least one bio-based (meth)acrylate monomer containing a biologically derived fatty acid group with a group esterified to the (meth)acrylate group. Composites containing these disclosed inorganic and / or organic fillers with a surface treated with at least one bio-based (meth)acrylate monomer can exhibit reduced stresses during curing of the molded part. The cured molded part disclosed herein can exhibit reduced stresses, thereby satisfactorily improving the mechanical properties of the polymerized composite.

[0034] The invention further relates to the use of such a filler as an additive to a polymer-based casting compound. Such a casting compound is used to produce cast and cured molded parts, e.g., in the form of kitchen sinks, shower trays, etc.

[0035] Finally, the invention relates to a cured molded part, for example in the form of a kitchen or sanitary article, for example a kitchen sink or shower tray, produced using such a casting compound.

[0036] Further advantages and details of the invention will become apparent from the exemplary embodiments described below and from the drawings. In the drawings: Fig. Figure 1 shows the comparative spectra of the untreated quartz flour (bottom) and the hydrophobized and activated quartz flour. Fig. 2 a schematic representation of the process of filler encapsulation and connection to the polymer binder

[0037] In the following, an experimental example is presented to illustrate in detail the inorganic and / or organic fillers including the hydrophobized and activated surface of the invention, the casting compound of the invention and the molding of the invention. Example

[0038] Hydrophobization and activation of inorganic and / or organic fillers Components used: a) Inorganic and / or organic fillers:

[0039] Quartz sand (particle size 0.06 to 0.3 mm, manufacturer: Dorfner GmbH), quartz flour (1 to 50 µm, Dorfner GmbH), cristobalite flour (0.1 to 10 µm, Quartzwerke GmbH), olive kernel flour (1.0 - 100 µm, BioPowder Ltd), olive kernel particles (600 - 800 µm, BioPowder Ltd), peach kernel particles (300 - 600 µm, BioPowder Ltd) b) Bio-based monomers:

[0040] Isobornyl methacrylate, (IBOMA, Evonik Performance Materials GmbH), polyethylene glycol 200 dimethacrylate (PEG-200-DMA, Arkema) c) Vegetable oil-based methacryloyl monomers:

[0041] Olive oil-based monomer (OBM, North Dakota State University), soybean oil-based monomer (SBM, North Dakota State University)

[0042] The compositions for the preparation of hydrophobing and activating agents are prepared by dissolving vegetable oil-based methacryloyl monomers (OBM and / or SBM, North Dakota State University) in the bio-based monomers (IBOMA, Evonik Performance Materials GmbH) and / or PEG-200-DMA (Arkema). The reaction mixture was sonicated at 35 °C for 40 minutes (Bandelin Super RK 1028 H ultrasonic bath) until a clear yellowish solution was obtained. For comparison of the hydrophobing and activating agents, the compositions summarized in Table 1 were prepared. The data are given in weight percent. TABLE 1 Pattern 1 Pattern 2 Pattern 3 Pattern 4 Pattern 5 IBOMA 90 85 60 20 PEG-200-DMA 31 65 90 Mayor 10 2 15 5 SBM 13 9 5

[0043] All samples from Table 1 were used as hydrophobizing and activating agents for the treatment of inorganic and / or organic fillers in different ratios according to the specific surface area of ​​the filler particles (0.221 m 2 / g for quartz sand; 1.5 m 2 / g for quartz flour; 3.5 m 2 / g for cristobalite flour; 2.6 m 2 / g - olive kernel flour; 0.32 and 0.27 m 2 / g for olive or peach kernel particles). The data refers to the specific surface area per gram of filler.

[0044] The clear solution of vegetable oil-based methacryloyl monomers from samples 1-5 was used to hydrophobize and activate the inorganic and / or organic filler surfaces. The appropriate amount of the solution was added to the fillers, such as quartz sand (particle size 0.06 to 0.3 mm, Dorfner GmbH), quartz flour (1 to 50 µm, Dorfner GmbH), cristobalite flour (0.1 to 10 µm, Quartzwerke GmbH), olive kernel flour (1.0 to 100 µm, BioPowder Ltd), olive kernel particles (600 to 800 µm, BioPowder Ltd), and peach kernel particles (300 to 600 µm, BioPowder Ltd), and placed in a mixing cylinder. The cylinder was closed and placed on rotating rollers to evenly wet the filler particles with the hydrophobizing and activating agent. The mixtures prepared in this way were stirred for 2 hours at a rotation speed of 30 rpm.The hydrophobized fillers were then removed from the container and transferred for further use in the production of casting compounds. Fig. Figure 1 shows the IR spectrum of the as-received quartz flour (bottom) and the IR spectrum of the quartz flour treated with olive oil-based methacryloyl monomer. An intense peak at approximately 1650 cm-1 clearly confirms the presence of reactive double bonds capable of copolymerizing with the matrix monomers.

[0045] Table 2 summarizes the filler compositions that were hydrophobized and activated with the oil-based monomers from Table 1. The values ​​are given in weight percent. TABLE 2 Pattern 1 Pattern 2 Pattern 3 Pattern 4 Pattern 5 Quartz sand 0.06 to 0.3 mm 90 85 60 40 50 Quartz flour 1 to 50 µm 31 20 Cristobalite powder 0.1 to 10 µm 10 2 15 Olive kernel flour 1.0 - 100 µm 13 9 5 Olive stone granules 600 - 800 µm 45 Peach kernel granules 300 - 600 µm 25

[0046] These filler mixtures (samples 1 to 5) were used for the production of the casting compounds and the subsequent curing in the respective mold.

[0047] The typical formulation can be described as follows: 23.7 kg of recycled PMMA (XP-95, KFG, Germany) was dissolved in a mixture of 56.3 kg of recycled methyl methacrylate (r-MMA, Monomeros des Valles, Spain), 15 kg of isobornyl methacrylate, Visiomer Terra IBOMA (Evonik Performance Materials, Germany), and 5 kg of bio-based ethyl methacrylate (BCH-Bruehl, Germany) until a clear solution was obtained. 0.1 kg of bio-based stearic acid (Musim Mas, Singapore) was added to the PMMA solution in monomers. After the stearic acid had completely dissolved, 4.0 kg of Sarbio 6201, polyethylene glycol (200) dimethacrylate (Arkema, France), was added to the PMMA solution. 210 kg of the filler system from samples 1 to 5 were dispersed in this mixture.

[0048] This solution was used for the preparation of samples 1 - 5 by dispersing the corresponding hydrophobized filler mixtures, followed by the addition of the initiator system (2 wt.%, calculated from the monomer amount) from the mixture of Perkadox 16 and Laurox S (Nouryon, Netherlands) in a ratio of 1:2.

[0049] After adding the initiator system and degassing for 15 minutes, the casting compound was injected into the closed mold and heated to 100 °C for 30 minutes to cure and then cooled, after which the manufactured molded parts were removed from the molds.

[0050] In parallel, comparative molded parts were produced using an identical casting compound in each case, but containing identical but untreated fillers in identical concentrations instead of the fillers treated according to the invention, in order to be able to compare the properties of molded parts with fillers treated according to the invention with the properties of identical molded parts with untreated fillers.

[0051] The mechanical and thermal properties of the molded parts of samples 1 - 5 and the comparative molded parts (1a - 5a), which were produced using the untreated fillers in the same concentrations, were compared with those of the samples according to the invention. TABLE 3 Molded part 1 / 1a Molding 2 / 2a Molding 3 / 3a Molding 4 / 4a Molding 5 / 5a Impact strength, mJ / mm 2 3,7 / 3,3 3,3 / 3,0 3,4 / 3,2 3,4 / 3,2 3,5 / 3,2 Scratch test + / + + / + + / + + / + + / + Taber abrasion, mg 22 / 20 20 / 20 23 / 21 21 / 19 20 / 19 Resistance to dry heat + / + + / + + / + + / + + / + Resistance to temperature changes + / + + / + + / + + / + + / +

[0052] For the impact strength measurements, 12 specimens measuring 80 × 6 mm were cut from the molded part. The measurements were performed using a ZwickRoell HIT P pendulum impact tester.

[0053] To measure the scratch resistance, a sample (100 × 100 mm) was cut out, tested according to DIN EN 13310 (Erichsen 213 scratch tester) and the topography was measured before and after scratching (Mitutoyo Surftest SJ 500 P roughness tester).

[0054] For the Taber abrasion test, a sample (100 × 100 mm) was cut and an abrasion test was carried out using an Elcometer 1720.

[0055] The resistance to dry heat is based on the test method DIN EN 13310, in which the test piece is placed in the center of the molded part to be tested at a temperature of 180 °C for 20 minutes without leaving any visible changes to the structure of the sink.

[0056] The thermal shock resistance test procedure is based on the DIN 13310 test method, in which the test specimen (kitchen sink) is treated with cold and hot water for 1,000 cycles. Hot water (T=90°C) flows into the sink for 90 seconds, followed by a 30-second rest period, during which cold water (T=15°C) flows for another 90 seconds. The cycle is terminated by a 30-second relaxation period.

[0057] As the measurement results show, almost all molded parts according to the invention have improved properties compared to the comparison molded parts.

[0058] The impact strength has improved significantly, in some cases by 10% compared to the reference molded part.

[0059] The same applies to Taber abrasion.

[0060] All molded parts according to the invention also met the test requirements with regard to scratch resistance, resistance to dry heat and resistance to thermal shock.

[0061] Fig. Figure 1 shows the IR spectra of the quartz powder before and after treatment with olive oil-based methacryloyl monomer. The spectrum of the treated filler clearly shows the double bond of the monomer, which polymerizes with the matrix monomers and forms the less stressed interface between the filler and matrix, as well as the molded part as a whole. The intense peak at 1650 cm-1 clearly confirms the presence of a reactive double bond of the natural oil-based monomer, which can copolymerize by grafting onto the matrix.

[0062] Fig.Figure 2 shows the schematic of the quartz sand surface treated with the olive oil-based methacryloyl polymer, showing the double bonds of the methacryloyl moiety, which form the encapsulation layer on the sand surface, and the double bonds of the labile chains that copolymerize with the matrix monomers. The long CH2-CH2 fatty acid chain enables a flexible response to mechanical and thermal stresses. The amino group of the methacryloyl moiety of the molecules creates a strong bond with the filler surface.

Claims

[1] A process for the preparation of hydrophobic and reactive inorganic and / or organic fillers, comprising the steps of: (a) providing a filler having a specific surface, (b) mixing the filler with the solution of at least one hydrophobizing and activating reactive compound on a biological basis in a mixing unit in an amount of 0.15 × 10 -2 up to 5.0 × 10 -2 g per m 2filler surface at a speed of 20 rpm to 200 rpm for 12 minutes to 120 minutes, wherein the hydrophobizing and activating reactive compound on a biological basis is selected from the (meth)acryloyl monomer of the general formula: H2C=C(R1)C(O)-NH-CH2-CH2-OC(O)-R2, wherein R1 is H in the case of acrylic and CH3 in the case of methacrylic, wherein R2 is a fatty acid residue from the vegetable oil-based oils or from animal oils and / or fats, which reacts in bulk with the N-hydroxyethyl (meth)acrylamide, (c) evacuating the hydrophobized and activated inorganic and / or organic filler in a storage bag, box or drum or directly in a casting compound to produce a molded part. [2] Method according to claim 1, characterized by that in step (a) the inorganic filler is selected from SiO2, Al2O3, TiO2, ZrO2, Fe2O3, ZnO, Cr2O5, carbon, metals and metal alloys, SiC, SiN, BN or a mixture thereof. [3] Method according to claim 1, characterized by that in step (a) the organic filler is selected from ground fruit kernels and / or fruit shells and can be selected from olive kernels, peach kernels, apricot kernels, cherry kernels, almond shells, argan shells, walnut shells or a mixture thereof. [4] Method according to claim 2 and 3, characterized by that in step (a) the inorganic and organic fillers can be used in a combination of both types of fillers in any mixing ratio. [5] Method according to one of the preceding claims, characterized by that in step (a) the inorganic and organic fillers can have a grain size of 1 µm to 2000 µm. [6] Method according to one of the preceding claims, characterized bythat in step (b) the hydrophobizing and activating bio-based reactive compound is dissolved in the at least one monomer present in the polymer matrix of the molded part. [7] Method according to one of the preceding claims, characterized bythat the monomer used in step (b) as solvent for the hydrophobizing and activating bio-based reactive compounds is selected from monofunctional acrylic monomers such as methyl acrylate, ethyl acrylate, n-butyl acrylate, tert. Butyl acrylate, isobutyl acrylate, isodecyl acrylate, dihydroxycyclopentadienyl acrylate, ethyl diglycol acrylate, heptadecyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, hydroxyethyl caprolactone acrylate, polycaprolactone acrylate, hydroxypropyl acrylate, lauryl acrylate, stearyl acrylate, 2-(2-Ethoxy)ethalacrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, ethoxylated 4-phenyl acrylate, trimethyl cyclohexyl acrylate, octyldecyl acrylate, tridecyl acrylate, ethoxylated 4-nonylphenyl acrylate, isobornyl acrylate, cyclic trimethylolpropane formal acrylate, ethoxylated 4-Lauryl Acrylate, Polyester Acrylate, Hyperbranched Polyester Acrylate, Melamine Acrylate, Silicone Acrylate, Epoxy Acrylate. [8] Method according to one of claims 1 to 6, characterized bythat the monomer used in step (b) as solvent for the hydrophobizing and activating bio-based reactive compounds is selected from monofunctional methacrylic monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, behenyl methacrylate, behenyl polyethylene glycol methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, stearyl polyethylene glycol methacrylate, isotridecyl methacrylate, ureido methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, methoxypolyethylene glycol methacrylate, glycidyl methacrylate, glycerol formal methacrylate, tetradecyl methacrylate. [9] Method according to one of claims 1 to 6, characterized bythat the monomer used in step (b) as solvent for the hydrophobizing and activating bio-based reactive compounds is selected from polyfunctional acrylic monomers such as 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, polybutadiene diacrylate, tetraethylene glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, ethoxylated bisphenol A diacrylate, dipropylene glycol diacrylate, ethoxylated hexanediol diacrylate, 1,10-decanediol diacrylate, alkoxylated diacrylate, tricyclodecanedimethanol diacrylate, propoxylated neopentyl glycol diacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, dipentaerythritol pentaacrylate, Pentaerythritol triacrylate, propoxylated glycerol triacrylate, aliphatic urethane triacrylate, aliphatic urethane diacrylate, aromatic urethane diacrylate, aromatic urethane triacrylate, aromatic urethane hexaacrylate,Polyester hexaacrylate, epoxidized soybean oil diacrylate., [10] Method according to one of claims 1 to 6, characterized by that the monomer used in step (b) as solvent for the hydrophobizing and activating bio-based reactive compounds is selected from polyfunctional methacrylic monomers such as triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, tricyclodecanedimethanol dimethacrylate, trimethylolpropane trimethacrylate. [11] Method according to one of the preceding claims, characterized bythat the vegetable oil is selected from coconut oil, germ oil, rapeseed oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, almond oil, beechnut oil, Brazil nut oil, cashew oil, hazelnut oil, macadamia oil, mongongo oil, pecan oil, pistachio oil, walnut oil, pumpkin seed oil, grapefruit seed oil, lemon oil, orange oil, bitter melon oil, calabash oil, cucurbita oil, butternut seed oil, egusi seed oil, watermelon seed oil, borage seed oil, currant seed oil, black seed oil, acai oil, evening primrose oil, linseed oil, amaranth oil, apricot kernel oil, apple seed oil, argan oil, avocado oil, babassu oil, behen oil, salnus oil, cape chestnut oil, cocoa butter, burdock oil, cohune palm oil, coriander seed oil, Date seed oil, Dika oil, Grape seed oil, Hemp oil, Kapok seed oil, Kenaf seed oil, Lallemantia oil, Marula oil, Mustard oil, Ramtill herb oil, Nutmeg butter, Perilla seed oil, Persimmon seed oil, Pequi oil, Pili nut oil, Pomegranate seed oil, Poppy seed oil, Pracaxi oil, Plum kernel oil, Quinoa oil, Rice oil, Sacha inchi oil, Sapote oil, Patawa oil,Shea butter, taramira oil, tea seed oil, tiger nut oil, tobacco seed oil, tomato seed oil, wheat germ oil, rhubarb oil, camelina oil, radish oil, salicornia oil, tung oil, copaiba oil, jatropha oil, jojoba oil, nagkesar oil, pongamia oil, dammar oil, stillingia oil, artichoke oil, murumuru butter, balanos oil, bladderpod oil, macassar kernel oil, burdock root oil, buriti oil, kukui nut oil, carrot seed oil, cuphea oil, mango oil, passionflower oil, rosehip seed oil, sea buckthorn oil, tamanu oil, tonka bean oil. [12] Method according to one of the preceding claims, characterized by that the oil used is an essential oil. [13] Method according to claim 12, characterized bythat the essential oil is selected from oud oil, ajwain oil, angelica root oil, anise oil, asafoetida oil, basil oil, Peru balsam, bay oil, bergamot oil, black pepper oil, buchu oil, birch oil, camphor oil, calamondin oil, caraway oil, cardamom oil, cedarwood oil, chamomile oil, calamus oil, cinnamon oil, lemon oil, lemongrass oil, sage oil, clove oil, coffee oil, coriander oil, lady's mint oil, costus root oil, cranberry seed oil, cubeb oil, cumin oil, cypress oil, curry leaf oil, davana oil, dill oil, immortelle oil, elemi oil, eucalyptus oil, fennel seed oil, galangal oil, galbanum oil, garlic oil, geranium oil, ginger oil, henna oil, helichrysum oil, horseradish oil, jasmine oil, juniper berry oil, lavender oil, lemon balm oil, Moringa oil, mugwort oil, myrrh oil, neem oil, oregano oil, spikenard oil, parsley oil, patchouli oil, perilla oil, peppermint oil, pine nut oil, rosemary oil, sandalwood oil, sassafras oil, savory oil, schisandra berry oil, mint oil, thyme oil. [14] Method according to one of the preceding claims, characterized bythat in step (b) the concentration of the hydrophobizing and activating bio-based reactive compound in the monomer contained in the polymer matrix of the molded part and used as solvent should be from 1 to 20 wt.%, preferably from 3 to 17.5 wt.%, in particular from 5 to 15 wt.%. [15] Hydrophobic and reactive inorganic or organic filler prepared by the process according to any one of claims 1 to 14. [16] Use of a filler according to claim 15 as an additive to a polymer-based casting compound for producing a composite molded part or as part of a dental filling composite system. [17] A molded part made from a casting compound according to claim 16. [18] Moulding according to claim 17, characterized by that it is a kitchen sink, a sanitary object in the form of a washbasin, a shower tray, a bathtub, a toilet or a bidet.

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