Process for the production of hydrophobic and reactive inorganic and / or organic fillers, fillers produced in this way and moldings produced containing such filler

Abstract

A method of manufacturing a hydrophobically active inorganic and / or organic filler, comprising the steps of: (a) providing a filler having a surface area, (b) mixing in a mixing device the filler with a solution of at least one hydrophobizing and biobased active compound in an amount of 0.15 x 10 ‑2 to 5.0 x 10 ‑2 gram per square meter of the surface area of the filler at a speed of 20 revolutions per minute to 200 revolutions per minute for 12 minutes to 120 minutes, (c) vacuumizing the hydrophobically active inorganic and / or organic filler in a storage bag, box or barrel or directly in a cast.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a hydrophobic active inorganic and / or organic filler. For example, this filler is used as an aggregate in a polymer-based castable, from which a composite molded body is manufactured. Background Technology

[0002] Shrinkage and shrinkage stress are common problems in many applications based on fully cured thermoplastic materials, such as molded kitchen sinks, washbasins, bathtubs, or dental filling composite systems. These composites typically contain a fully cured polymer binder, an initiator system, and silane-treated inorganic filler particles. During the curing process of these composite systems, shrinkage can be observed, leading to microcracks and generating strong internal stresses within the material. For example, in molded kitchen sinks, this can cause cracks in the material to propagate, resulting in leaks or reduced mechanical properties. The same problems can occur in dental composites: stress, microleakage, and adhesive detachment, thus causing patient discomfort.

[0003] These problems can be attributed to the high filler content in the composite material and the use of 3-methacryloxypropyltrimethoxysilane, which is fixed on the surface of the quartz particles and has low fluidity due to its relatively short triple chain. During polymerization, this limited fluidity leads to rapid breakage of free radicals and the formation of short polymer chains, resulting in strong stresses on the system due to high stiffness. Thermal shrinkage or expansion of the material, as well as mechanical shock, can all be sources of microcracks at the filler-matrix interface.

[0004] At the filler-matrix interface, initial stress is concentrated on the rigid inorganic surface due to the presence of numerous active groups. Typically, the surface of quartz sand particles has 0.8 hydroxyl groups per square nanometer. During silanization, almost every hydroxyl group reacts with a single silane molecule, forming a uniform hydrophobic silane layer, resulting in a superhydrophobic effect and allowing the active methacrylate groups to be very densely fixed. The high concentration of double bonds fixed on the filler surface leads to the polymerization of short polymer chains, creating regions of high internal stress. While inactive silanes can be used instead of methacrylate silanes to reduce stress, this will reduce mechanical properties such as impact strength due to the lack of bonding between the filler and matrix.

[0005] Inorganic and / or organic fillers treated with silane coupling agents require hydrolyzable ester functional groups of the silane. For example, hydrolyzing 1000 kg of 3-methacryloyloxypropyltrimethoxysilane produces 387 kg of methanol. Methanol is a highly flammable liquid with a high vapor pressure, and ingestion can be fatal.

[0006] Furthermore, the silanization of the filler is technically achieved through thermal activation at temperatures of 60°C or higher. The energy required for this process is typically obtained by burning natural gas or corresponding hydrocarbons, resulting in carbon dioxide emissions and increased process costs. Following the silanization process, a curing time of several days is usually required until the filler achieves the desired hydrophobicity. Summary of the Invention

[0007] The objective of this invention is to eliminate the aforementioned technical and environmental problems in the prior art.

[0008] To address this issue, a method for producing hydrophobically active inorganic and / or organic fillers is proposed, comprising the steps of: (a) providing fillers having a certain surface area; and (b) in a mixing apparatus, mixing the fillers with a solution of at least one hydrophobically active and bio-based activating substance at a concentration of 0.15 × 10⁻⁶. -2 Up to 5.0×10 -2 (c) Mix at a rate of g / m² of filler surface area for 12 to 120 minutes at a speed of 20 to 200 rpm. Transfer the hydrophobic active inorganic and / or organic filler to a storage bag, box or barrel or pour it directly into the castable.

[0009] The silanization process requires storing the treated filler for seven days before subsequent reactions. In contrast, this invention proposes a technique that allows the filler to be used immediately after treatment. Furthermore, the method according to the invention eliminates the need for a heating process, whereas the silanization reaction is carried out while heated to at least 60°C for at least 30 minutes.

[0010] The hydrophobic active filler of this invention has a distinct interface with the matrix. The double bonds of the methacryloyl groups near the filler surface encapsulate the filler surface during polymerization and prepare the double bonds on the fatty acid side chains for copolymerization with the matrix. This results in the establishment of a less stress-intensive filler-matrix interface, reducing stress in both localized and overall molded parts.

[0011] The amount of naturally hydrophobic and activated substances depends on the specific surface area of ​​the filler, and is therefore expressed in g / m². 2 The amount of methacrylamide monomer used herein is selected in such a way that a monolayer of methacrylamide monomer is preferably formed by the interaction of amino groups with the hydroxyl groups of the filler. Therefore, this amount depends on the density of hydroxyl groups on the filler surface. For example, for silica sand, it can be assumed that there are 0.8 -OH groups per nm² and 0.2 m² / g, thereby determining the required amount of methacrylamide monomer.

[0012] The mixing time in a mixing device (such as a drum ring mixer (Rhöhnrad-Mischer)) will also vary depending on the composition of the packing material. Larger diameter particles require less time to achieve a uniform distribution of oil-based monomers on the packing surface. For fine particles, quartz, or fruit kernel powder, the mixing time will be longer.

[0013] According to the present invention, an inorganic and / or organic filler is provided, the filler having a hydrophobic surface. The inorganic filler may be selected from SiO2, Al2O3, TiO2, ZrO2, Fe2O3, ZnO, Cr2O5, carbon, metals and metal alloys, SiC, SiN, BN, or mixtures thereof.

[0014] Organic fillers are ground fruit pits and / or shells, which may be selected from olive pits, peach pits, apricot pits, cherry pits, almond shells, argan shells, walnut shells, or mixtures thereof.

[0015] Inorganic and organic fillers can be used in combination. The mixing ratio can be selected arbitrarily.

[0016] The hydrophobic active surface of inorganic and / or organic fillers is formed by immobilizing at least one bio-based (meth)acrylic acid monomer, which includes bio-derived fatty acid groups, and esterifies the fatty acid groups with (meth)acrylic acid groups on the surface of the inorganic and / or organic fillers.

[0017] The particle size of the inorganic and organic fillers used in step (a) can be from 1 micrometer to 2000 micrometers. This invention is based on the design of hydrophobication and activation of inorganic and / or organic fillers, including surface treatment using at least one bioactive compound.

[0018] The hydrophobic active surface of the inorganic and / or organic filler is obtained by immobilizing at least one bio-based (meth)acrylic acid monomer comprising a bio-derived fatty acid group, which is esterified with a (meth)acrylic acid group. The bio-based (meth)acrylic acid monomer is dissolved in the monomer contained in the polymer matrix of the molded part. The concentration of the bio-based (meth)acrylic acid monomer should be 1 to 20% (by weight), preferably 3 to 17.5% (by weight), more preferably 5 to 15% (by weight).

[0019] Here, the hydrophobic and bio-based activated compound used in step (b) can be selected from methacryloyl monomers of naturally derived oils based on the following general formula: H2C=C(R1)C(O)-NH-CH2-CH2-C(O)-OO-R2, where R1 is H in the case of acryloyl and CH3 in the case of methacryloyl, and R2 is a fatty acid residue from a naturally derived oil, which reacts as a whole with N-hydroxyethyl (meth)acrylamide.

[0020] Furthermore, the hydrophobic and bio-based activated compound used in step (b) is dissolved in at least one monomer present in the polymer matrix of the molded part.

[0021] Monofunctional monomers in the form of acrylate monomers can be used as solvents. These monomers can be selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, isodecanyl acrylate, dihydroxycyclopentadienyl acrylate, diethylene glycol ethyl acrylate, heptadecanyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, hydroxyethylcaprolactone acrylate, polycaprolactone acrylate, hydroxypropyl acrylate, lauryl acrylate, stearyl acrylate, 2-(2-ethoxy)ethyl acrylate, tetrahydrofuran acrylate, 2-phenoxyethyl acrylate, ethoxylated 4-phenyl acrylate, trimethylcyclohexyl acrylate, octadecyl acrylate, tridecyl acrylate, ethoxylated 4-nonylphenyl acrylate, isobornyl acrylate, cyclotrimethylolpropane methyl acetal acrylate, ethoxylated 4-lauryl acrylate, polyester acrylate, hyperbranched polyester acrylate, melamine acrylate, silicone acrylate, and epoxy acrylate.

[0022] Alternatively, monofunctional monomers in the form of methacrylates can also be used. Monofunctional monomers can be selected from methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, docosyl methacrylate, docosyl polyethylene glycol methacrylate, cyclohexyl methacrylate, isodecanyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, polyethylene glycol stearyl methacrylate, isotridecyl methacrylate, urea methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, methoxy polyethylene glycol methacrylate, glycidyl methacrylate, glyceryl informal methacrylat, and lauryl methacrylate.

[0023] Multifunctional monomers in the form of acrylates can also be used as solvents. These multifunctional monomers can be selected from 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, polybutadiene diacrylate, tetraethylene glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, bisphenol A diacrylate oxyacetylene oxide, dipropylene glycol diacrylate, hexanediol diacrylate oxyacetylene oxide, 1,10-decanediol diacrylate, diacrylates, alkyl oxyacetylene diacrylate, tricyclodecanediethanol diacrylate, neopentyl glycol diacrylate oxyacetylene oxide, and pentaerythritol tetraacrylate. Trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, bis(trimethylolpropane)tetraacrylate, tri(2-hydroxyethyl)isocyanuric acid triacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate, aliphatic polyurethane triacrylate, aliphatic polyurethane diacrylate, aromatic polyurethane diacrylate, aromatic polyurethane triacrylate, aromatic polyurethane hexaacrylate, polyester hexaacrylate, epoxidized soybean oil diacrylate.

[0024] In addition, multifunctional biomonomers in the form of bio-based methacrylates can also be used. These multifunctional biomonomers 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-butanediol dimethacrylate, tricyclodecanedimethyl acrylate, and trimethylolpropane trimethacrylate.

[0025] Fatty acids can be obtained in the form of vegetable oils. Vegetable oils are selected from coconut oil, wheat germ oil, rapeseed oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, almond oil, beech nut oil, Brazil nut oil, cashew oil, hazelnut oil, macadamia nut oil, mangeberry oil, pecan oil, pistachio oil, walnut oil, pumpkin seed oil, grapefruit seed oil, lemon oil, orange oil, bitter melon oil, zucchini oil, zucchini oil, grey walnut seed oil, West African watermelon seed oil, watermelon seed oil, and borage seed oil. Gooseberry seed oil, black seed oil, acai berry oil, evening primrose oil, flaxseed oil, amaranth oil, almond oil, apple seed oil, argan oil, avocado oil, Brazilian palm oil (Babassuöl), moringa oil, salsa nut oil (Salnussöl), cape chestnut oil, carob oil, cocoa butter, cocklebur oil, feather palm oil, coriander seed oil, date palm seed oil, African mango oil (Dikaöl), grapeseed oil, hemp seed oil, kapok seed oil, kenaf seed oil, lallemantia seed oil (Lallemantiaöl), marula oil (Marula) Mustard oil, ramie oil, nutmeg oil, okra seed oil (Okra-Samenöl), perilla seed oil, persimmon seed oil, Brazilian peach fruit oil, Pilinussöl, pomegranate seed oil, poppy seed oil, Pracaxi nut oil, plum kernel oil, quinoa oil, rice oil, Inca inchi oil, Sapote oleifera oil, Batava coconut oil, shea butter, sesame rapeseed oil, tea seed oil, tiger nut oil, tobacco seed oil, tomato seed oil, wheat germ oil, castor oil, flaxseed oil, radish oil, sea sage oil, tung oil, Cuban balsam resin, jatropha oil, jojoba oil, ironwood oil (Nagkesaröl), Indian beech oil (Pongamiaöl), dammar oil (Dammaröl), tamarisk oil, artichoke oil, murumuru palm resin (Murumuru) Butter, soapberry fruit oil (Balanosöl), bladder pod oil, burdock seed oil, burdock root oil, mulberry fruit oil (Buritiöl), kukui fruit oil (Kukuinussöl), carrot seed oil, calyx flower oil (Kupheaöl), mango oil, passion fruit oil, rosehip seed oil, rubber seed oil, sea buckthorn oil, tamanu oil (Tamanuöl), and tonkabohnenöl.

[0026] In addition, fatty acids in the form of essential oils can also be used. Essential oils can be selected from oud oil, celery oil, angelica root oil, star anise oil, asafoetida oil, basil oil, Peruvian balsam, laurel oil, bergamot oil, black pepper oil, bauhinia oil, birch oil, camphor oil, calamodin oil, caraway oil, cardamom oil, cedarwood oil, camellia oil, white calamus oil, cinnamon oil, lemon oil, lemongrass oil, sage oil, clove oil, coffee oil, coriander seed oil, tansy oil, costus root oil, cranberry seed oil, long pepper oil, fennel oil, cypress oil, curry leaf oil, artemisia oil, and dill seed oil. Oils, including immortelle oil, elemi oil, eucalyptus oil, fennel seed oil, galangal oil, galangal oil, garlic oil, geranium oil, ginger oil, henna oil, strohmume oil, horseradish oil, jasmine oil, juniper berry oil, lavender oil, lemon balm oil, moringa oil, wormwood oil, myrrh oil, neem oil, oregano oil, mustard oil, parsley oil, patchouli oil, perilla oil, peppermint oil, pine nut oil, rosemary oil, sandalwood oil, sassafras oil, peppermint oil, schisandra oil, peppermint oil, and thyme oil.

[0027] According to the present invention, a solution prepared from a solvent and acrylamide functionalized with fatty acid groups is deposited on the surface of a solid filler in a rotating powder mixer. The (meth)acrylic acid groups in the active (meth)acrylic acid monomer are esterified into a polymer matrix to immobilize on the surface of the inorganic and / or organic filler particles (see [link to product]). Figure 2 This diagram schematically illustrates the process of filler encapsulation and the bonding process of polymer adhesives.

[0028] The surfaces of inorganic and / or organic filler particles are functionalized due to the presence of functional groups, such as hydroxyl groups on the surface of quartz. These functional hydroxyl groups serve as immobilization centers for the bio-derived fatty acid monomer molecules of this invention. Fatty acid acrylamide molecules undergo chemisorption on the filler surface, forming an active (meth)acrylate layer with organic chains extending outward from the surface. Water droplets applied to the quartz surface of quartz particles modified with, for example, olive oil-based acrylic monomers remain on the surface of the filler particles for more than 240 seconds, thus pressing the filler particles into a molded form. The same effect can be achieved when using other oil-based (meth)acrylates. The double bonds linked to (meth)acrylamide are close to the filler surface. This morphology enables the establishment of a uniform organic layer on the filler surface during polymerization. On the other hand, the double bonds of unsaturated fatty acids, located away from the filler surface, participate in the copolymerization process with the matrix monomers. This size specificity between the matrix and the filler increases impact strength and thermal shock resistance, reduces the influence of crosslinking, and thus reduces the fragility of the molded body.

[0029] In addition to this method, the present invention also relates to hydrophobic active inorganic and / or organic fillers manufactured according to the method of the present invention.

[0030] The inorganic and organic fillers according to the invention have surfaces preferably treated with at least one bio-based (meth)acrylate monomer, the surface containing bio-derived fatty acid groups with esterified (meth)acrylate groups. These disclosed inorganic and / or organic fillers, having surfaces treated with at least one bio-based (meth)acrylate monomer, result in composites containing these inorganic and / or organic fillers exhibiting stress reduction during the curing process of molded parts. The cured molded parts disclosed herein exhibit stress reduction, thereby satisfactorily improving the mechanical properties of the polymeric composites.

[0031] Furthermore, the present invention also relates to the use of this filler as an aggregate in polymer-based castables. This castable is used to manufacture cast-cured molded parts, such as kitchen sinks, shower trays, and the like.

[0032] Finally, the present invention relates to a cured molded part manufactured using such a casting material, such as a molded part in the form of kitchen or sanitary ware (e.g., a kitchen sink or shower tray). Attached Figure Description

[0033] Other advantages and details of the invention will become apparent from the embodiments described below and from the accompanying drawings. In the drawings:

[0034] Figure 1 The comparison spectra of untreated quartz powder (below) and hydrophobic and activated quartz powder are shown.

[0035] Figure 2 A schematic diagram illustrates the process of filler encapsulation and attachment to a polymer adhesive.

[0036] The following is an experimental example that details the inorganic and / or organic fillers (including the hydrophobic and activated surface of the present invention), the castable of the present invention, and the molding of the present invention. Detailed Implementation

[0037] Example

[0038] Hydrophobication and activation of inorganic and / or organic fillers

[0039] Components used:

[0040] a) Inorganic and / or organic fillers:

[0041] Quartz sand (0.06 to 0.3 mm particle size, manufacturer: Dorfner GmbH), quartz powder (1 to 50 microns, Dorfner GmbH), cristobalite powder (0.1 to 10 microns, Quartzwerke GmbH), olive pit powder (1.0 to 100 microns, BioPowder Ltd), olive pit granules (600 to 800 microns, BioPowder Ltd), peach pit granules (300 to 600 microns, BioPowder Ltd).

[0042] b) Bio-based monomers:

[0043] Isoborneol methacrylate (IBOMA, Evonik Performance Materials GmbH), polyethylene glycol 200 dimethacrylate (PEG-200-DMA, Arkema)

[0044] c) Vegetable oil-based methacryloyl monomer:

[0045] Olive oil-based monomer (OBM, North Dakota State University) and soybean oil-based monomer (SBM, North Dakota State University)

[0046] The compositions used to prepare the hydrophobic agent and activator were prepared by dissolving vegetable oil-based methacryloyl monomers (OBM and / or SBM, North Dakota State University) in bio-based monomers (IBOMA, Evonik Performance Materials, Inc.) and / or PEG-200-DMA (Arkema). The reaction mixture was sonicated at 35°C (Bandelin Super RK1028 H ultrasonic bath) for 40 minutes until a clear yellow solution was obtained. For comparison of the hydrophobic agent and activator, the components summarized in Table 1 were prepared. Data are in weight percentage.

[0047] Table 1

[0048] Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 IBOMA 90 85 60 20 PEG-200-DMA 31 65 90 OBM 10 2 15 5 SBM 13 9 5

[0049] All samples in Table 1 were used as hydrophobic agents and activators for treating inorganic and / or organic fillers in different proportions based on the specific surface area of ​​the filler particles (0.221 m² / g for quartz sand; 1.5 m² / g for quartz powder; 3.5 m² / g for cristobalite powder; 2.6 m² / g for olive pit powder; and 0.32 m² / g and 0.27 m² / g for olive pit and peach pit particles, respectively). These data refer to the specific surface area per gram of filler.

[0050] The inorganic and / or organic filler surfaces were hydrophobized and activated using a clear solution of vegetable oil-based methacryloyl monomers from samples 1-5. Appropriate amounts of the solution were added to fillers such as quartz sand (0.06 to 0.3 mm particle size, Döfner), quartz powder (1 to 50 μm, Döfner), cristobalite powder (0.1 to 10 μm, Kovacsvico Quartz Manufacturing), olive pit powder (1.0 to 100 μm, Bio-Enhanced Biotechnology), olive pit particles (600 to 800 μm, Bio-Enhanced Biotechnology), and peach pit particles (300 to 600 μm, Bio-Enhanced Biotechnology), and placed in a mixing tank. The mixing tank was closed and placed on a rotating roller to uniformly wet the filler particles with the hydrophobic agent and activator. The mixture prepared in this manner was stirred at 30 rpm for 2 hours. Subsequently, the thus hydrophobized filler was removed from the container and transferred for further use in the manufacture of castables. Figure 1 The infrared spectra of quartz powder (as obtained, shown in the figure below) and quartz powder treated with olive oil-based methacryloyl monomer are shown. At approximately 1650 cm⁻¹... -1 The strong peak at the point clearly confirms the presence of active double bonds, which can copolymerize with the matrix monomers.

[0051] Table 2 summarizes the composition of the fillers that have been hydrophobically modified and activated using the oil-based monomers in Table 1. Data are in weight percentage.

[0052] Table 2

[0053] Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Quartz sand 0.06-0.3 mm 90 85 60 40 50 Quartz powder 1-50 µm 31 20 0.1-10 µm cristobalite powder 10 2 15 Olive pit powder 1.0-100 µm 13 9 5 Olive pit particles 600-800 µm 45 Peach kernel particles 300-600 µm 25

[0054] These filler mixtures (samples 1 to 5) are used to manufacture castables and subsequently cure them in their respective molds.

[0055] A typical formula can be described as follows:

[0056] 23.7 kg of recovered PMMA (XP-95, KFG, Germany) was dissolved in a mixture of 56.3 kg of recovered methyl methacrylate (r-MMA, Monomeros des Valles, Spain), 15 kg of isobornyl methacrylate, VisiomerTerra 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 monomer (Musim Mas, Singapore) was added to the PMMA solution. After the stearic acid was completely dissolved, 4.0 kg of Sarbio 6201 and polyethylene glycol (200) dimethacrylate (Arkema, France) were added to the PMMA solution. 210 kg of the filler system from samples 1 to 5 was dispersed in this mixture.

[0057] The corresponding hydrophobic filler mixture was dispersed so that the solution was used to prepare samples 1-5, and then the initiator system of the mixture of Perkadox 16 and Laurox S (Nouryon, Netherlands) was added at a ratio of 1:2 (2 (wt)%, calculated based on the amount of monomer).

[0058] After adding the initiator system and degassing for 15 minutes, the casting material is injected into a closed mold, heated to 100°C, cured for 30 minutes, cooled, and then the molded part is removed from the mold.

[0059] Meanwhile, in each case, the same casting material is used to manufacture the comparative molded parts. This casting material does not contain the filler treated according to the present invention, but contains the same concentration of untreated filler, so that the characteristics of the molded parts containing the filler treated according to the present invention can be compared with the characteristics of the same molded parts containing the untreated filler.

[0060] The mechanical and thermal properties of the molded parts of samples 1-5 and the comparative molded parts (1a-5a) were compared with those of the samples according to the present invention, the comparative molded parts being manufactured using untreated fillers of the same concentration.

[0061] Table 3

[0062] Molded part 1 / 1a Molded part 2 / 2a Molded part 3 / 3a Molded part 4 / 4a Molded part 5 / 5a <![CDATA[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 + / + + / + + / + + / + + / + Tiber wear, mg 22 / 20 20 / 20 23 / 21 21 / 19 20 / 19 Dry heat resistance + / + + / + + / + + / + + / + thermal shock resistance + / + + / + + / + + / + + / +

[0063] To measure impact strength, 12 specimens measuring 80 × 6 mm were cut from the molded part. Measurements were performed using a ZwickRoell HIT P pendulum impact testing machine.

[0064] To measure scratch resistance, a sample (100×100 mm) was cut out and tested according to DIN EN 13310 (Erichsen 213 scratch tester), and surface characteristics were measured before and after scratching (Mitutoyo Surftest SJ 500 P roughness measuring instrument).

[0065] For the Tiber wear test, a specimen (100×100 mm) was cut out and the wear test was performed using an Elcometer 1720.

[0066] Dry heat resistance is tested according to the DIN EN 13310 test method, which involves placing the test specimen in the center of the molded part to be tested and subjecting it to a temperature of 180°C for 20 minutes without leaving any visible changes in the structure of the water tank.

[0067] The thermal shock resistance test method is based on DIN 13310, which involves treating the molded part (kitchen sink) with hot and cold water for 1000 cycles. Hot water (T=90°C) is poured into the sink for 90 seconds, followed by a 30-second settling period, during which cold water (T=15°C) is flowed for 90 seconds. The cycle ends with a 30-second settling period.

[0068] As the measurement results show, almost all molded parts according to the present invention have better performance than comparative molded parts.

[0069] For example, the impact strength is significantly improved, in some cases by 10% compared to the comparative molded parts.

[0070] This also applies to Tiber wear.

[0071] All molded parts according to the present invention also meet the test requirements for scratch resistance, dry heat resistance and thermal shock resistance.

[0072] Figure 1 Infrared spectra of quartz powder before and after treatment with olive oil-based methacryloyl monomer are shown. The double bonds of the monomer are clearly visible in the spectrum of the treated filler, which polymerize with the matrix monomer, forming a low-tension interface between the filler and the matrix, as well as the entire molded part. (1650 cm⁻¹) -1 The strong peak at the point clearly confirms the presence of active double bonds in the natural oil-based monomer, which can be copolymerized by grafting onto the matrix.

[0073] Figure 2This is a schematic diagram of a quartz sand surface treated with olive oil-based methacrylamide polymer. The diagram illustrates the double bonds of the methacrylamide molecules forming the encapsulation layer on the quartz sand surface, and the double bonds of the vulnerable chains copolymerized with the matrix monomers. The long CH2-CH2 fatty acid chains enable flexible responses to mechanical and thermal stresses. The amino groups of the methacrylamide moiety in the molecule form strong bonds with the filler surface.

Claims

1. A method for manufacturing a hydrophobic active inorganic and / or organic filler, comprising the following steps: (a) Providing a filler with a certain surface area, (b) In a mixing apparatus, mixing the filler with a solution of at least one hydrophobic and bio-based activated compound at a concentration of 0.15 × 10⁻⁶. -2 Up to 5.0×10 -2 (c) Vacuum the hydrophobic active inorganic and / or organic fillers in storage bags, boxes or barrels or directly in the castable. In step (a), the filler is an inorganic filler selected from SiO2, Al2O3, TiO2, ZrO2, Fe2O3, ZnO, Cr2O5, carbon, SiC, SiN, BN, or mixtures thereof; or, the filler is an organic filler selected from ground fruit pits and / or shells, selected from olive pits, peach pits, apricot pits, cherry pits, almond shells, argan shells, walnut shells, or mixtures thereof. In step (b), the hydrophobic and bio-based active compound has a weight concentration of 1 to 20 wt% in the monomer, which is present in the polymer matrix of the molded part and used as a solvent; the hydrophobic and bio-based active compound is selected from vegetable oil-based methacryloyl monomers of the following general formula: H2C=C(R1)C(O)-NH-CH2-CH2-C(O)-O-R2, wherein R1 is H in the case of acryloyl and CH3 in the case of methacryloyl, and wherein R2 is a fatty acid residue from a vegetable oil-based oil that reacts with N-hydroxyethyl (meth)acrylamide.

2. The method according to claim 1, characterized in that, In step (a), the inorganic filler and the organic filler are used in any mixing ratio.

3. The method according to claim 1, characterized in that, In step (a), the particle size of the inorganic filler and the organic filler is from 1 micrometer to 2000 micrometers.

4. The method according to claim 1, characterized in that, In step (b), the hydrophobic and bio-based activated compound is dissolved in at least one monomer present in the polymer matrix of the molded part.

5. The method according to claim 1, characterized in that, In step (b), the monomer used as a solvent for the hydrophobic and bio-based activated compound is selected from monofunctional acrylate monomers, wherein the monofunctional acrylate monomer is selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, isodecanyl acrylate, dihydroxycyclopentadiene acrylate, diethylene glycol ethyl acrylate, heptadecanyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, hydroxyethylcaprolactone acrylate, polycaprolactone acrylate, hydroxypropyl acrylate, and methyl acrylate. Cinnamyl acrylate, octadecyl acrylate, 2-(2-ethoxy)ethyl acrylate, tetrahydrofuran acrylate, 2-phenoxyethyl acrylate, 4-phenyl acrylate ethoxylate, trimethylcyclohexyl acrylate, octyldecyl acrylate, tridecyl acrylate, 4-nonylphenyl acrylate ethoxylate, isobornyl acrylate, cyclotrimethylolpropane methyl acetal acrylate, 4-lauryl acrylate ethoxylate, polyester acrylate, hyperbranched polyester acrylate, melamine acrylate, silicone acrylate, epoxy acrylate.

6. The method according to claim 1, characterized in that, The monomer used as a solvent for the hydrophobic and bio-based activated compound in step (b) is selected from monofunctional methacrylate monomers, wherein the monofunctional methacrylate monomers are selected from methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, docosyl methacrylate, docosyl polyethylene glycol methacrylate, cyclohexyl methacrylate, isodecanyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, octadecyl methacrylate, isotridecyl methacrylate, urea methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, methoxy polyethylene glycol methacrylate, glycidyl methacrylate, and glyceryl methacrylate.

7. The method according to claim 1, characterized in that, The monomer used as a solvent for the hydrophobic and bio-based activated compound in step (b) is selected from polyfunctional acrylate monomers, wherein the polyfunctional acrylate monomers are selected from 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, polybutadiene diacrylate, 3-methyl-1,5-pentanediol diacrylate, dipropylene glycol diacrylate, 1,10-decanediol diacrylate, alkyl oxyacrylate, tricyclodecanediethanol diacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, bis(trimethylolpropane tetraacrylate), tri(2-hydroxyethyl)isocyanurate triacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate, aliphatic polyurethane triacrylate, aliphatic polyurethane diacrylate, aromatic polyurethane diacrylate, aromatic polyurethane triacrylate, aromatic polyurethane hexaacrylate, polyester hexaacrylate, and epoxidized soybean oil diacrylate.

8. The method according to claim 1, characterized in that, The monomer used as a solvent for the hydrophobic and bio-based activating compound in step (b) is selected from polyfunctional methacrylate monomers, specifically ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,3-butanediol dimethacrylate, tricyclodecanediol dimethacrylate, and trimethylolpropane trimethacrylate.

9. The method according to claim 1, characterized in that, The oil group in vegetable oil-based methacryloyl monomers is derived from vegetable oils.

10. The method according to claim 9, characterized in that, The vegetable oils mentioned are selected from coconut oil, wheat germ oil, rapeseed oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower seed oil, sesame oil, soybean oil, sunflower seed oil, almond oil, beech nut oil, cashew oil, hazelnut oil, mangeberry oil, pistachio oil, walnut oil, pumpkin seed oil, grapefruit seed oil, gourd oil, grey walnut seed oil, watermelon seed oil, borage seed oil, currant seed oil, black seed oil, acai berry oil, evening primrose oil, flaxseed oil, amaranth oil, almond oil, apple seed oil, argan oil, avocado oil, Brazil palm oil, moringa oil, sal tree nut oil, cocoa butter, feather palm oil, date palm seed oil, grape seed oil, kapok seed oil, kenaf seed oil, marula oil, mustard oil, and ramie. Hemp seed oil, nutmeg oil, okra seed oil, perilla seed oil, persimmon seed oil, Brazilian peach fruit oil, prickly pear fruit oil, pomegranate seed oil, poppy seed oil, bakas fruit oil, plum kernel oil, quinoa oil, rice oil, sacha inchi oil, batawa wine coconut oil, shea butter, tea seed oil, tiger nut oil, tobacco seed oil, tomato seed oil, wheat germ oil, castor oil, linseed oil, sea privet oil, tung oil, jatropha oil, jojoba oil, ironwood oil, Indian beech oil, catalpa oil, artichoke oil, murum palm oil, bladder pod oil, tamarisk seed oil, burdock root oil, mauritius fruit oil, kukui fruit oil, carrot seed oil, calyx flower oil, rosehip seed oil, rubber seed oil, sea buckthorn oil, tamanu oil, tonka soybean oil.

11. The method according to claim 1, characterized in that, In step (b), the hydrophobic and bio-based active compound is present in the polymer matrix of the molded part at a weight concentration of 3% to 17.5% and is used as a solvent.

12. The method according to claim 1, characterized in that, In step (b), the hydrophobic and bio-based active compound is present in the polymer matrix of the molded part at a weight concentration of 5% to 15% and is used as a solvent.

13. A hydrophobic active inorganic or organic filler manufactured by the method according to any one of claims 1 to 12.

14. The filler according to claim 13 is used as an aggregate in a polymer-based castable for manufacturing composite molded parts, or as part of a dental filling composite system.

15. A molded part made of the castable material according to claim 14.

16. The molded part according to claim 15, characterized in that, The molded parts are sanitary ware in the form of kitchen sinks, washbasins, shower trays, bathtubs, toilet bowls, or bidets.

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