Process for producing hydrophobized and reactive, inorganic and / or organic fillers, fillers thus produced, and molding produced from a polymer-based casting compound containing at least one such filler

Abstract

Process for producing hydrophobic and reactive, inorganic and / or organic fillers, comprising the steps of: (a) providing a filler having a defined surface area, (b) mixing the filler with the solution of at least one hydrophobizing and activating, biologically 5 based reactive compound in a mixing assembly in an amount of 0.15 \times 10^{-2} to 5.0 \times 10^{-2} g per m^2 filler surface area at a speed of 20 rpm to 200 rpm for 12 minutes to 120 minutes, (c) evacuating the hydrophobized and activated, inorganic and / or organic filler in a storage bag, a box or a drum, or directly in the casting compound.

Description

5 DESCRIPTION Process for producing hydrophobized and reactive, inorganic and / or organic fillers, fillers thus produced, and molding produced from a polymer-based casting compound containing at least one such filler The invention relates to a process for producing hydrophobized and reactive, inorganic and / or organic fillers. Such fillers are used for example as adjuvants to polymer-based casting compounds from which composite moldings are produced. 10 Shrinkage and shrinkage stress are a major problem in numerous applications based on radically cured thermoset materials, such as, for example, molded kitchen sinks, wash basins, bath tubs or composite dental filling systems. Composite materials of these kinds generally include a radically cured polymer binder, an initiator system, and silane-treated inorganic filler particles. In the curing of these composite systems, 15 shrinkage is observed which may give rise on the one hand to microcracks and on the other hand to severe intrinsic stresses in the material. In the case of molded kitchen sinks, for example, this may lead to crack propagation in the material, with the consequence of water leakage or of a reduction in the mechanical properties. The same problems may occur in dental composite materials: stresses, microleaks, 20 detachment of adhesive, and, ultimately, pain for the patient. This problem can be attributed to the high filler content of composite materials and to the use of 3-methacryloyloxypropyltrimethoxysilane, which is immobilized on the surface of the quartz particles and, with its relatively short triple chain, exhibits a 25 relatively low mobility. During polymerization, this limited mobility leads to rapid breaking of the radicals and to the formation of short polymer chains, which because of the high stiffness leads to severe loading of the system. Thermally induced contractions or expansions of the material and also mechanical impacts may act as a source of microcracks at the filler-matrix interface. 30 Date Rei;:ue / Date Received 2022-11-15 2 The filler-matrix interface is where the natural stresses are concentrated, owing to the presence of numerous reactive groups at a rigid inorganic surface. The surface of the quartz sand particles generally has 0.8 hydroxyl groups per square nanometer of surface area. During the silanization process, almost every hydroxyl group reacts 5 with an individual silane molecule and forms a unitary hydrophobic silane layer, leading to a superhydrophobic effect with very dense immobilization of the reactive methacrylate group. The high concentration of the double bonds immobilized on the filler surface results in the polymerization of the short polymer chains and hence in the formation of regions having a high inherent stress. The stresses can be reduced 10 by replacing the methacryloylsilane with nonreactive silanes, but this reduces the mechanical properties such as the impact strength, for example, owing to the lack of bonding between filler and matrix. The use of the silane-treated, inorganic and / or organic fillers which had been treated 15 with a silane coupling agent necessitates the hydrolysis of the hydrolyzable ester functions of the silane. The hydrolysis of, for example, 1000 kg of 3-methacryloylpropyltrimethoxysilane leads to the production of 387 kg of methanol, a flammable liquid with high vapor pressure, which can be fatal if swallowed. 20 Industrially, moreover, fillers are silanized by means of thermal activation at temperatures of 60°C or higher. The energy needed for this process is generally realized via the combustion of natural gas or corresponding hydrocarbons, which contribute to emission of CO2 and raise the process costs. After the silanization process, an aging time of several days is generally required until the desired 25 hydrophobicity of the filler is established. It is an object of the present invention to eliminate the above-described technical and environmentally relevant problems of the prior art. Date Rei;:ue / Date Received 2022-11-15 3 In order to achieve the object, a process is proposed for producing hydrophobic and reactive, inorganic and / or organic fillers, comprising the steps of: (a) providing a filler having a defined surface area, (b) mixing the filler with the solution of at least one hydrophobizing and activating, biologically based reactive compound in a mixing 5 assembly in an amount of 0.15 x 10-2 to 5.0 x 10-2 g per m2 filler surface area at a speed of 20 rpm to 200 rpm for 12 minutes to 120 minutes, ( c) transferring the hydrophobized and activated, inorganic and / or organic filler into a storage bag, a box or a drum, or directly into the casting compound. 10 In contrast to the silanization process, which requires seven-day storage of the treated filler for the post-reaction, the present invention proposes a technology which allows the filler to be used directly after the treatment. Moreover, the process of the invention does not necessitate any heating process, whereas the silanization reaction is carried out with heating to at least 60°C for at least 30 minutes. 15 Hydrophobized and activated fillers of the present invention have a different interface with the matrix. The double bond of the methacryloyl group, located close to the filler surface, encapsulates the filler surface during polymerization and keeps the double bond ready on the side chains of the fatty acid for copolymerization with the matrix. 20 These chains lead to the development of the less-stressed filler-matrix interface. This reduces stresses locally and in the moldings overall. The amounts of hydrophobizing, natural-based reactive substance to be activated are dependent on the specific filler surface area and are therefore indicated in g / m2. In 25 this case the amount of methacryloyl monomer used is selected such that construction of a monolayer of the methacryloyl monomer via the amine group with the hydroxyl group of the filler is preferred. The amount is therefore dependent on the density of the hydroxyl groups on the filler surface. It is possible, for example, to assume 0.8-OH groups per nm2 and 0.2 m2 / g for a quartz sand, and to determine the 30 required amount of methacryloyl monomer on that basis. Date Rei;:ue / Date Received 2022-11-15 4 The mixing time in the mixing assembly, a drum hoop mixer for example, is likewise varied depending on the composition of the fillers. Particles having a larger diameter require less time in order to achieve uniform distribution of the oil-based monomers 5 over the filler surface. In the case of fine particles, quartz or fruit stone flour, the mixing time is longer. Provided in accordance with the invention is an inorganic and / or organic filler which has a hydrophobized and activated surface. The inorganic fillers may be selected 10 from SiO2, Al2O3, TiO2, ZrO2, Fe2Q3, ZnO, Cr2Os, carbon, metals and metal alloys SiC, SiN, BN or mixtures thereof. The inorganic fillers are ground fruit stones and / or fruit shells and may be selected from olive stones, peach stones, apricot stones, cherry stones, almond shells, argan 15 shells, walnut shells, or a mixture thereof. The inorganic and organic fillers may be used in a combination of both kinds of fillers. The mixing ratio may be selected as desired. 20 The hydrophobized and activated surface of the inorganic and / or organic filler is formed by immobilization of at least one biobased (meth)acrylated monomer, which comprises a fatty acid group originating from biological cultivation and esterified with the (meth)acryloyl group on the surface of the inorganic and / or organic filler. 25 The inorganic and organic fillers used in step (a) may have a particle size of 1 μm to 2000 μm. The present invention is based on the approach of hydrophobizing and activating inorganic and / or organic fillers, including a surface treatment with at least one biologically based reactive compound. Date Rei;:ue / Date Received 2022-11-15 5 The hydrophobized and activated surface of the inorganic and / or organic filler is formed by immobilization of at least one biobased (meth)acrylated monomer, which contains a fatty acid group originating from biological cultivation and comprises a group esterified with the (meth)acryloyl group. The biobased (meth)acrylated monomer is dissolved in the monomer contained in the polymer 5 matrix of the molding. The concentration of the biobased (meth)acrylated monomer ought to be 1 to 20 wt%, preferably 3 to 17.5 wt%, more particularly 5 to 15 wt%. The hydrophobizing, biologically based reactive compound for activation, used in 10 step (b), may be selected from the methacryloyl monomer based on oils of natural origin, of the general formula: H2C=C(R1)C(O)-NH-CH2-CH2-O-C(O)-R2, where R1 in the case of acryloyl is H and in the case of methacryloyl is CH3, where R2 is a fatty acid radical from the oils of natural origin, which reacts in the bulk with the N-hydroxyethyl( meth)acrylamide. 15 Additionally the hydrophobizing, biobased reactive compound for activation that is used in step (b) may be dissolved in the at least one monomer present in the polymer matrix of the molding. 20 Solvents used may be monofunctional monomers in the form of an acrylate monomer. These may be selected from 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, hydroxyethylcaprolactone acrylate, polycaprolactone 25 acrylate, hydroxypropyl acrylate, lauryl acrylate, stearyl acrylate, 2-(2-ethoxy)ethyl acrylate, tetrahydroxyfurfuryl acrylate, 2-phenoxyethyl acrylate, ethoxylated 4-phenyl acrylate, trimethylcyclohexyl acrylate, octyldecyl acrylate, tridecyl acrylate, ethoxylate 4-nonylphenyl acrylate, isobornyl acrylate, cyclic trimethylolpropane formal acrylate, CA 3182049 Date reçue / Received date 2024-08-08 6 ethoxylated 4-lauryl acrylate, polyester acrylate, hyperbranched polyester acrylate, melamine acrylate, silicone acrylate, epoxy acrylate. It is possible, furthermore, to use a monofunctional monomer in the form of a 5 methacrylate. This may be selected from methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, behenyl methacrylate, behenylpolyethylene glycol methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, stearylpolyethylene glycol methacrylate, isotridecyl methacrylate, 10 ureidomethacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, methoxypolyethylene glycol methacrylate, glycidyl methacrylate, glycerol formal methacrylate, lauryltetradecyl methacrylate. As solvent it is also possible to use a polyfunctional monomer in the form of a 15 polyfunctional acrylate. This may be selected from 1,6-hexanediol diacrylate, polyethyleneglycol diacrylate, polybutadiene diacrylate, tetraethylene glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, ethoxylated bisphenol A diacrylate, di propylene glycol diacrylate, ethoxylated hexanediol diacrylate, 1, 10-decanediol diacrylate, ester diacrylate, alkoxylated diacrylate, tricyclodecanedimethanol 20 diacrylate, propoxylated neopentyl glycol diacrylate, pentaerythrityl tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, dipentaerythrityl pentaacrylate, pentaerythrityl triacrylate, propoxylated glyceryl triacrylate, aliphatic urethane triacrylate, aliphatic urethane diacrylate, aromatic 25 urethane diacrylate, aromatic urethane triacrylate, aromatic urethane hexaacrylate, polyester hexaacrylate, epoxidized soybean oil diacrylate. A polyfunctional biomonomer may be used, moreover, in the form of a biobased methacrylate. This may be selected from triethylene glycol dimethacrylate, ethylene 30 glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, Date Rei;:ue / Date Received 2022-11-15 7 1, 10-decanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, tricyclodecaned imethanol d imethacrylate, trimethylolpropane tri methacrylate. It is possible to use fatty acids in the form of plant oils. This may be selected from 5 coconut oil, germ oil, rapeseed oil, cotton seed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, almond oil, beechnut oil, para nut oil, cashew oil, hazelnut oil, macadamia oil, mongongo oil, pecan oil, pistachio oil, walnut oil, pumpkin seed oil, grapefruit kernel oil, lemon oil, orange oil, bitter melon oil, calabash oil, cucurbita oil, butternut seed oil, egusi seed oil, watermelon seed oil, 10 borage seed oil, blackcurrant seed oil, blackseed oil, acai oil, evening primrose oil, linseed oil, amaranth oil, apricot kernel oil, apple seed oil, argan oil, avocado oil, babassu oil, behen oil, sal nut oil, Cape chestnut oil, algoraba oil, cocoa butter, cocklebur oil, cohune oil, coriander seed oil, date seed oil, dika oil, grapeseed oil, hemp oil, kapok seed oil, kenaf seed oil, lallemantia oil, marula oil, mustard oil, ramtil 15 oil, nutmeg butter, ocher seed oil, perilla seed oil, persimmon seed oil, pequi oil, pilli nut oil, pomegranate oil, poppy oil, placaxi oil, plum kernel oil, quinoa oil, rice oil, sacha inchi oil, sapote oil, patawa oil, shea butter, taramira oil, tea seed oil, earth almond oil, tobacco seed oil, tomato seed oil, wheatgerm oil, castor oil, camelina oil, radish oil, Salicornia oil, tung oil, copaiba oleoresin, jatropha oil, jojoba oil, nagkesar 20 oil, pongamia oil, dammar oil, stilingia 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 kernel oil, rubber seed oil, sea buckthorn oil, tamanu oil, tonka bean oil. 25 It is possible, furthermore, to use a fatty acid in the form of an essence oil. This may be selected from oud oil, ajowan oil, angelica root oil, aniseed oil, asafoetida oil, basil oil, peru balsam, laurel oil, bergamot oil, black pepper oil, buchu oil, birch oil, camphor oil, calamondin oil, caraway oil, cardamom oil, cedarwood oil, camellia oil, calmus oil, cinnamon oil, lemon oil, lemongrass oil, sage oil, clove oil, coffee oil, 30 coriander oil, costmary oil, costus root oil, cranberry seed oil, cubeba oil, cumin oil, cypress oil, curryleaf oil, davana oil, dill oil, immortell oil, elemi oil, eucalyptus oil, Date Rei;:ue / Date Received 2022-11-15 8 fennel seed oil, galanga oil, galbanum oil, garlic oil, geranium oil, ginger oil, henna oil, strawflower oil, horseradish oil, jasmine oil, juniper berry oil, lavender oil, balm oil, moringa oil, mugwort oil, myrrh oil, neem oil, oregano oil, nard oil, parsley oil, patchouli oil, perilla oil, peppermint oil, pine kernel oil, rosemary oil, sandalwood oil, 5 sassafras oil, savory oil, schisandra berry oil, mint oil, thyme oil. 10 It is also possible to use a fatty acid in the form of an animal fat and / or oil. This may be selected from fish oil, bear grass, chicken fat, crocodile fat, crocodile oil, cod liver oil, emu oil, lard, goose fat, duck fat, shark liver oil. In accordance with the invention, the solution thus prepared, comprising the solvent and the arylamide functionalized with a fatty acid group, is deposited in a rotating powder mixer on the surface of the solid fillers. The (meth)acryloyl groups in the reactive (meth)acrylic monomers undergo esterification to form a polymer matrix, 15 which is immobilized on the surface of the inorganic and / or organic filler particles (see Fig. 2). The figure represents, schematically, the process of filler encapsulation and bonding to the polymer binder. The surface of inorganic and / or organic filler particles is functional through the 20 presence of functional groups, such as a hydroxyl group on the quartz surface, for example. These functional hydroxyl groups are used as immobilization centers for the biologically derived fatty acid monomer molecules of the invention. The fatty acidacrylomide molecules chemosorb on the filler surface and form a reactive (meth)acrylate layer with organic chains which point outward from the surface. The 25 water droplet applied to the quartz surface of the quartz particles, modified with the - for example - olive oil-based acrylic monomer, remains for more than 240 seconds on the surface of the filler particles compacted in this way to form a compact. The same effect is achieved when using other oil-based (meth)acrylates. The double bond connected to the (meth)acrylamide is located close to the filler surface. A morphology 30 of this kind enables the construction of a uniform organic layer on the filler surface during the polymerization. Moreover, the double bond of the unsaturated fatty acids, Date Rei;:ue / Date Received 2022-11-15 9 which is at a distance from the filler surface, participates in the process of copolymerization with the matrix monomers. This dimensional specificity in the bonding between matrix and filler increases the impact strength and the thermal cycling stability, reduces the effects of the degree of crosslinking, and so leads to a 5 reduction in the fragility of the molding. As well as the process, the invention also relates to a hydrophobic and reactive, inorganic and / or organic filler produced by the process of the invention. 10 Inorganic and organic fillers in accordance with the invention have a surface, preferably treated with at least one biobased (meth)acrylate monomer, which comprises a biologically derived fatty acid group with a group esterified to the (meth)acrylate group. Composite materials which comprise these laid-open, inorganic and / or organic fillers with a surface treated with at least one biobased (meth)acrylate 15 monomer are able to show the reduction in the stresses during the curing of the molding. The cured molding laid open here may have reduced stresses, thereby providing satisfactory improvement in the mechanical properties of the polymerized composite. 20 The invention additionally relates to the use of such a filler as an adjuvant to a polymer-based casting compound. A casting compound of this kind is used for producing cast and cured moldings, in the form, for example, of kitchen sinks, shower trays, etc. 25 The invention relates, lastly, to a cured molding in the form, for example, of a kitchen or sanitary article, e.g., a kitchen sink or shower tray, produced using such a casting compound. Date Rei;:ue / Date Received 2022-11-15 10 Further advantages and details of the invention are evident from the exemplary embodiments described below and also with reference to the drawings, in which: Fig. 1 shows the comparative spectra of the untreated quartz flour (bottom) and of 5 the hydrophobized and activated quartz flour. Fig. 2 shows a schematic representation of the operation of the filler encapsulation and joining to the polymer binder. 10 Presented below is an experimental example for illustrating the inorganic and / or organic fillers, including the hydrophobized and activated surface, of the invention, the casting compound of the invention, and the shaping of the invention in detail. Example 15 Hydrophobization and activation of the inorganic and / or organic fillers Components used: a) Inorganic and / or organic fillers: 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), 20 olive stone flour (1.0-100 μm, BioPowder Ltd), olive stone particles (600-800 μm, BioPowder Ltd), peach stone particles (300-600 μm, BioPowder Ltd) b) Biobased monomers: lsobornyl methacrylate (IBOMA, Evonik Performance Materials GmbH), polyethylene 25 glycol 200 dimethacrylate (PEG-200-DMA, Arkema) Date Rei;:ue / Date Received 2022-11-15 11 c) Methacryloyl monomers based on plant oil: Monomer based on olive oil (OBM, North Dakota State University), monomer based on soybean oil (SBM, North Dakota State University) s The compositions for producing hydrophobizing and activating agents are produced by dissolving plant oil-based methacryloyl monomers (OBM and / or SBM, North Dakota State University) in the biobased monomers (IBOMA (Evonik Performance Materials GmbH) and / or PEG-200-DMA (Arkema)). The reaction mixture was sonicated at 35°C for 40 minutes (Sandelin Super RK 1028 H ultrasound bath) until a 10 clear yellowish solution was obtained. For comparison of the hydrophobizing and activating agents, the compositions were produced as summarized in Table 1. The figures are reported in percent by weight. 15 TABLE 1 Specimen 1 Specimen 2 Specimen 3 Specimen 4 Specimen 5 IBOMA 90 85 60 20 PEG-200-DMA 31 65 90 OBM 10 2 15 5 SBM 13 9 5 All of the specimens from Table 1 were used as hydrophobizing and activating agents for treating the inorganic and / or organic fillers in the various proportions in accordance with the specific surface area of the filler particles (0.221 m2 / g for quartz sand; 1.5 m2 / g for quartz flour; 3.5 m2 / g for cristobalite flour; 2.6 m2 / g - olive stone 20 flour; 0.32 and 0.27 m2 / g for olive stone and peach stone particles respectively). The figures are based on the specific surface area per gram of filler. The clear solution of the plant oil-based methacryloyl monomers of specimens 1-5 was used for hydrophobizing and activating the inorganic and / or organic filler surface. Date Rei;:ue / Date Received 2022-11-15 12 The corresponding 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 stone flour (1.0- 100 μm, BioPowder Ltd), olive stone particles (600-800 μm, BioPowder Ltd), peach s stone particles (300-600 μm, BioPowder Ltd) and placed into a mixing cylinder. The cylinder was closed and placed on rotating rolls, in order for the filler particles to be uniformly wetted with the hydrophobizing and activating agent. The mixtures produced in this way were stirred for 2 hours at a rotary speed of 30 rpm. The fillers hydrophobized in this way were subsequently taken from the container and 10 transferred for further use for the production of casting compounds. Figure 1 shows the IR spectrum of the quartz flour (quartz flour as obtained, bottom) and the IR spectrum of the quartz flour treated with the olive oil-based methacryloyl monomer. An intense peak at around 1650 cm-1 unambiguously confirms the presence of reactive double bonds, which can be copolymerized with the matrix monomers. 15 Table 2 summarizes the filler compositions hydrophobized and activated with the oilbased monomers of Table 1. The figures are reported in percent by weight. Date Rei;:ue / Date Received 2022-11-15 s 13 TABLE 2 Specimen 1 Specimen 2 Specimen 3 Specimen 4 Specimen 5 Quartz sand 90 85 60 40 50 0.06 to 0.3 mm Quartz flour 31 20 1 to 50 μm Cristobalite flour 10 2 15 0.1 to 10 μm Olive stone flour 13 9 5 1.0-100 μm Olive stone 45 granules 600-800 μm Peach stone 25 granules 300-600 μm These filler mixtures (specimens 1 to 5) were used for producing the casting compounds and for subsequent curing in the respective mold. The typical formulation may be described as follows: 23.7 kg of recycled PMMA (XP-95, KFG, Germany) were 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 10 Materials, Germany) and 5 kg of biobased ethyl methacrylate (BCH-Bruehl, Germany) until a clear solution was obtained. 0.1 kg of biobased stearic acid (Musim Mas, Singapore) was added to the PMMA solution in monomers. When the stearic acid had dissolved completely, 4.0 kg of Sarbio 6201, polyethylene glycol(200) dimethacrylate (Arkema, France) were added to the PMMA solution. 210 kg of the 15 filler system from specimens 1 to 5 were dispersed in this mixture. Date Rei;:ue / Date Received 2022-11-15 14 This solution was used for producing specimens 1-5, by dispersing the corresponding hydrophobized filler mixtures, followed by the addition of the initiator system (2 wt%, calculated from the monomer amount) comprising the mixture of Perkadox 16 and s Laurox S (Nouryon, Netherland) in a ratio of 1 :2. Following addition of the initiator system and venting for 15 minutes, the casting compound was injected into the closed mold, which for curing was heated at 100°C for 30 minutes and subsequently cooled, after which the moldings produced were 10 removed from the molds. In parallel, comparative moldings were produced using a respectively identical casting compound, but containing, rather than the fillers treated in accordance with the invention, the same fillers but untreated, in identical concentration, in order to be 15 able to compare the properties of moldings with inventively treated fillers with the properties of the same moldings with untreated fillers. The mechanical and thermal properties of the moldings of specimens 1-5 and of the comparative moldings (1 a-Sa), produced using the untreated fillers in the same 20 concentrations, were compared with those of the specimens of the invention. Date Rei;:ue / Date Received 2022-11-15 15 TABLE 3 Molding Molding Molding Molding Molding 1 / 1 a 2 / 2a 3 / 3a 4 / 4a 5 / 5a Impact strength, mJ / mm2 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 +!+ +!+ +!+ +!+ +!+ Thermal cycling stability +!+ +!+ +!+ +!+ +!+ For the impact strength measurements, 12 samples with a size of 80 x 6 mm were cut from the molding. The measurements were carried out using a ZwickRoell HIT P s pendulum impact instrument. For the measurement of the scratch resistance, a sample (100 x 100 mm) was cut out and tested according to DIN EN 13310 (Erichsen 213 scratch instrument) and the topography before and after scratching was measured (Mitutoyo Surftest SJ 500 P 10 roughness instrument). For the Taber abrasion test, a sample (100 x 100 mm) was cut and an abrasion test was carried out with an Elcometer 1720. 15 The resistance to dry heat is based on the DIN EN 13310 test method, in which the test piece is placed at a temperature of 180°C for 20 minutes into the center of the molding under test, without leaving visible alterations on the structure of the sink. The test method of thermal cycling stability is based on the DIN 13310 test method, 20 in which the test molding (kitchen sink) is treated for 1000 cycles with cold-hot water. Hot water (T = 90°C) runs into the sink for 90 seconds, followed by a rest phase of Date Rei;:ue / Date Received 2022-11-15 16 30 seconds, in which in turn cold water {T = 15°C) runs for 90 seconds. The cycle is ended by 30 seconds of relaxation. As the measurement results show, virtually all of the moldings of the invention exhibit 5 improved properties relative to the comparative moldings. Hence there has been a distinct improvement in the impact strength, in some cases by 10% as compared with the comparative molding. 10 The same is true of the Taber abrasion as well. All of the moldings of the invention also met the test requirements in relation to scratch resistance, resistance to dry heat, and thermal cycling stability. 15 Figure 1 shows the IR spectra of the quartz flour before and after treatment with olive oil-based methacryloyl monomer. Clearly apparent in the spectrum of the treated filler is the double bond of the monomer, which polymerizes with the matrix monomers and forms the less-exposed interface between filler and matrix and also the molding overall. The intense peak of 1650 cm-1 unambiguously confirms the presence of a 20 reactive double bond of the natural oil-based monomer, which is able to copolymerize onto the matrix by grafting. Figure 2 shows the scheme of the quartz sand surface treated with the olive oilbased methacryloyl polymer, where the double bonds of the methacryloyl part, which 25 form the encapsulation layer on the sand surface, and the double bonds of the labile chains, which copolymerize with the matrix monomers, can be seen. The long CH2-CH2 fatty acid chain enables a flexible response to mechanical and thermal Date Rei;:ue / Date Received 2022-11-15 17 stresses. The amino group of the methacryloyl part of the molecules produces a strong bond to the filler surface. Date Rei;:ue / Date Received 2022-11-15

Claims

18 CLAIMS 1. Process for producing hydrophobic and reactive, inorganic and / or organic fillers, comprising the steps of: (a) providing a filler having a defined surface area, (b) mixing the filler with the solution of at least one 5 hydrophobizing and activating, biologically based reactive compound in a mixing assembly in an amount of 0.15 x 10-2 to 5.0 x 10-2 g per m2 filler surface area at a speed of 20 rpm to 200 rpm for 12 minutes to 120 minutes, wherein the hydrophobizing and activating, biologically based reactive compound is selected from the plant 10 oil-based methacryloyl monomer of the general formula: H2C=C(R1)C(O)-NHCH2- CH2-O-C(O)-R2, where R1 in the case of acryloyl is H and in the case of methacryloyl is CH3, where R2 is a fatty acid radical from the plant oil-based oils that reacts in bulk with the N-hydroxyethyl(meth)acrylamide, (c) evacuating the hydrophobized and activated, inorganic and / or organic filler in a storage 15 bag, a box or a drum, or directly in the casting compound.

2. Process according to Claim 1, wherein 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. 20 3. Process according to Claim 1, wherein in step (a) the organic filler is selected from ground fruit stones and / or fruit shells.

4. Process according to Claim 3, wherein the ground fruit stones and / or fruit 25 shells are selected from olive stones, peach stones, apricot stones, cherry stones, almond shells, argan shells, walnut shells, or a mixture thereof.

5. Process according to any one of Claims 2 to 4, wherein in step (a) the inorganic and organic fillers may be used in a combination of both kinds of 30 fillers in any desired mixing ratio. CA 3182049 Date reçue / Received date 2024-08-08 19 6. Process according to any one of Claims 1 to 5, wherein in step (a) the inorganic and organic fillers may have a particle size of 1 μm to 2000 μm.

7. Process according to any one of Claims 1 to 6, wherein in step (b) the hydrophobizing and activating, biobased reactive compound 5 is dissolved in the at least one monomer present in the polymer matrix of the molding.

8. Process according to any one of Claims 1 to 7, wherein the monomer used in step (b) as solvent for the hydrophobizing and activating reactive compounds 10 is selected from monofunctional acrylic monomers.

9. Process according to Claim 8, wherein the monofunctional acrylic monomers are selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, isodecyl acrylate, dihydroxycyclopentadienyl 15 acrylate, ethyl diglycol acrylate, heptadecyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, hydroxyethylcaprolactone acrylate, polycaprolactone acrylate, hydroxypropyl acrylate, lauryl acrylate, stearyl acrylate, 2-(2- ethoxy)ethyl acrylate, tetrahydroxyfurfuryl acrylate, 2-phenoxyethyl acrylate, ethoxylated 4-phenyl acrylate, trimethylcyclohexyl acrylate, octyldecyl acrylate, 20 tridecyl acrylate, ethoxylate 4-nonylphenyl acrylate, isobornyl acrylate, cyclic trimethylolpropane formal acrylate, ethoxylated 4-lauryl acrylate, polyester acrylate, hyperbranched polyester acrylate, melamine acrylate, silicone acrylate, epoxy acrylate. 25 10. Process according to any one of Claims 1 to 7, wherein the monomer used in step (b) as solvent for the hydrophobizing and activating, biobased reactive compounds is selected from monofunctional methacrylic monomers.

11. Process according to claim 10, wherein the monofunctional metharylic 30 monomers are selected from methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, behenyl methacrylate, behenylpolyethylene glycol methacrylate, cyclohexyl CA 3182049 Date reçue / Received date 2024-08-08 20 methacrylate, isodecyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, stearylpolyethylene glycol methacrylate, isotridecyl methacrylate, ureidomethacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, methoxypolyethylene glycol methacrylate, glycidyl methacrylate, glycerol formal 5 methacrylate, lauryltetradecyl methacrylate.

12. Process according to any one of Claims 1 to 7, wherein the monomer used in step (b) as solvent for the hydrophobizing and activating, biobased reactive 10 compounds is selected from polyfunctional acrylic monomers.

13. Process according to claim 12, wherein the polyfunctional acrylic monomers are selected from 1,6-hexanediol diacrylate, polyethyleneglycol diacrylate, polybutadiene diacrylate, tetraethylene glycol diacrylate, 3-methyl-1,5- 15 pentanediol diacrylate, ethoxylated bisphenol A diacrylate, dipropylene glycol diacrylate, ethoxylated hexanediol diacrylate, 1,10-decanediol diacrylate, ester diacrylate, alkoxylated diacrylate, tricyclodecanedimethanol diacrylate, propoxylated neopentyl glycol diacrylate, pentaerythrityl tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, 20 ditrimethylolpropane tetraacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, dipentaerythrityl pentaacrylate, pentaerythrityl triacrylate, propoxylated glyceryl triacrylate, aliphatic urethane triacrylate, aliphatic urethane diacrylate, aromatic urethane diacrylate, aromatic urethane triacrylate, aromatic urethane hexaacrylate, polyester hexaacrylate, epoxidized soybean oil diacrylate. 25 14. Process according to any one of Claims 1 to 7, wherein the monomer used in step (b) as solvent for the hydrophobizing and activating, biobased reactive compounds is selected from polyfunctional methacrylic monomers. 30 15. Process according to claim 14, wherein the polyfunctional methacrylic monomers are selected from triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol CA 3182049 Date reçue / Received date 2024-08-08 21 dimethacrylate, 1,10-decanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, tricyclodecanedimethanol dimethacrylate, trimethylolpropane trimethacrylate.

16. Process according to any one of Claims 1 to 15, wherein 5 the plant oil is selected from coconut oil, germ oil, rapeseed oil, cotton seed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, almond oil, beechnut oil, para nut oil, cashew oil, hazelnut oil, macadamia oil, mongongo oil, pecan oil, pistachio oil, walnut oil, pumpkin seed oil, grapefruit kernel oil, 10 lemon oil, orange oil, bitter melon oil, calabash oil, cucurbita oil, butternut seed oil, egusi seed oil, watermelon seed oil, borage seed oil, blackcurrant seed oil, blackseed oil, acai oil, evening primrose oil, linseed oil, amaranth oil, apricot kernel oil, apple seed oil, argan oil, avocado oil, babassu oil, behen oil, sal nut oil, Cape chestnut oil, algoraba oil, cocoa butter, cocklebur oil, cohune oil, 15 coriander seed oil, date seed oil, dika oil, grapeseed oil, hemp oil, kapok seed oil, kenaf seed oil, lallemantia oil, marula oil, mustard oil, ramtil oil, nutmeg butter, ocher seed oil, perilla seed oil, persimmon seed oil, pequi oil, pilli nut oil, pomegranate oil, poppy oil, placaxi oil, plum kernel oil, quinoa oil, rice oil, sacha inchi oil, sapote oil, patawa oil, shea butter, taramira oil, tea seed oil, 20 earth almond oil, tobacco seed oil, tomato seed oil, wheatgerm oil, castor oil, camelina oil, radish oil, Salicornia oil, tung oil, copaiba oleoresin, jatropha oil, jojoba oil, nagkesar oil, pongamia oil, dammar oil, stilingia 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, 25 passionflower oil, rosehip kernel oil, rubber seed oil, sea buckthorn oil, tamanu oil, tonka bean oil.

17. Process according to any one of claims 1 to 16, wherein the oil used is an essential oil. 30 18. Process according to Claim 17, wherein the essential oil is selected from oud oil, ajowan oil, angelica root oil, aniseed oil, asafoetida oil, basil oil, peru CA 3182049 Date reçue / Received date 2024-08-08 22 balsam, laurel oil, bergamot oil, black pepper oil, buchu oil, birch oil, camphor oil, calamondin oil, caraway oil, cardamom oil, cedarwood oil, camellia oil, calmus oil, cinnamon oil, lemon oil, lemongrass oil, sage oil, clove oil, coffee oil, coriander oil, costmary oil, costus root oil, cranberry seed oil, cubeba oil, cumin oil, cypress oil, curryleaf oil, davana oil, dill oil, immortell 5 oil, elemi oil, eucalyptus oil, fennel seed oil, galanga oil, galbanum oil, garlic oil, geranium oil, ginger oil, henna oil, strawflower oil, horseradish oil, jasmine oil, juniper berry oil, lavender oil, balm oil, moringa oil, mugwort oil, myrrh oil, neem oil, oregano oil, nard oil, parsley oil, patchouli oil, perilla oil, peppermint oil, pine 10 kernel oil, rosemary oil, sandalwood oil, sassafras oil, savory oil, schisandra berry oil, mint oil, thyme oil.

19. Process according to any one of claims 1 to 18, wherein in step (b) the concentration of the hydrophobizing and activating, biobased reactive 15 compound in the monomer which is in the polymer matrix of the molding and is used as solvent is from 1 to 20 wt%.

20. Process according to any one of claims 1 to 19, wherein in step (b) the concentration of the hydrophobizing and activating, biologically based reactive 20 compound in the monomer is from 3 to 17.5 wt% 21. Process according to any one of claims 1 to 20, wherein in step (b) the concentration of the hydrophobizing and activating, biologically based reactive compound in the monomer is from 5 to 15 wt%. 25 22. Hydrophobic and reactive, inorganic or organic filler, produced by the process according to any one of Claims 1 to 21. CA 3182049 Date reçue / Received date 2024-08-08 23 23. Use of a filler according to Claim 22 as adjuvant to a polymer-based casting compound for producing a composite molding or as part of a composite dental filling system.

24. Molding produced from a casting compound as set 5 forth in Claim 23.

25. Molding according to Claim 24, which is a kitchen sink, a sanitary article in the form of a wash basin, a shower tray, a bath tub, a WC, or a bidet. CA 3182049 Date reçue / Received date 2024-08-08