Method for producing a hybrid polymer material and hybrid polymer material produced according to this method

Abstract

A process for producing a hybrid polymer material based on a reactive polymer resin and one or more Si compounds from the group comprising silanes, siloxanes, silazanes and silicone resins, wherein, firstly, recycled plastic material as a quartz-free filler in combination with the reactive polymer resin and one or more Si compounds as well as additives forms a raw material, wherein the raw material further contains at least one alcoholate of zirconium, aluminum or titanium, and wherein the raw material is compacted and subsequently reacted and cured, wherein the proportion of the solid is 40 to 97 wt.% of the total mass of the raw material.

Description

[0001] The present invention relates to a method for producing a hybrid polymer material and to a hybrid polymer material produced according to this method.

[0002] Hybrid polymers are polymeric materials that combine structural units from different material classes at the molecular level and possess special properties and functionalities due to their composition. Such materials are frequently produced using the sol-gel process. Because of the unique properties of these materials, which often represent a combination of properties of the starting materials not readily available elsewhere, there is great interest in such hybrid polymeric materials and corresponding production processes, which should be as simple and easily adaptable as possible.

[0003] DE 10 2017 107 591 A1 describes a process for producing a hybrid polymer material in the form of an artificial stone by reacting a polymer resin with at least one Si compound selected from silanes, siloxanes, silazanes and silicone resins, as well as an inorganic solid and auxiliary materials to form a raw mass which is then compacted and hardened.

[0004] WO 97 / 39043 A1 primarily concerns foamed polyester polyurethanes for the production of lightweight components. The polymer contains a high proportion of fillers, which are surface-treated with a liquid reactive component in a preliminary step.

[0005] JP 2008-163252 A describes a curable composition for the production of non-reflective coatings for displays. The composition can include various fine particles as fillers, each produced in independent process steps and pretreated differently for incorporation into the polymer matrix of the composition.

[0006] It is therefore an object of the present invention to provide a method for producing a hybrid polymer material which is based on the use of inexpensive starting materials and is as easy to carry out as possible and leads to new hybrid polymer materials with advantageous properties.

[0007] The present problem is solved by a method according to the attached claim 1. A hybrid polymer material according to claim 8 is also the subject of the present invention. Advantageous embodiments of the invention are the subject of the directly or indirectly referenced claims.

[0008] It should be noted that this description uses references to commercially available products whose composition is generally not disclosed in full detail by the manufacturer, as these compositions are considered trade secrets. Furthermore, singular and plural forms of a term are used interchangeably in the description and the claims, and the mention of the singular form, e.g., "solid," includes the plural form, e.g., "solids," and vice versa, since the solid contained in the manufactured raw material can be named in its entirety, but may in fact be composed of various solids differing in type and / or size.In the context of the present invention, a solid of a different type refers to a solid that differs from another solid in terms of structure and / or material class; for example, a polymeric solid is a solid of a different type compared to a mineral solid or a rock.

[0009] In the inventive process for producing a hybrid polymer material, the components mentioned in claim 1 form a raw material, which is compacted and subsequently reacted and cured. Curing is carried out, for example, by heat treatment at a temperature in the range of room temperature to 350 °C, by a radical chain reaction, or by UV irradiation. The reaction generally takes place within the raw material during curing. In the presence of metals, autocatalytic or metal-catalyzed, and at least partially exothermic, reactions also occur.

[0010] During the investigations carried out within the scope of the present invention, it was unexpectedly found that the solid can be integrated or incorporated into the hybrid polymer material according to the invention and, depending on the particle size and / or quantity used, can exert special effects in a controllable manner.

[0011] In addition to recycled plastics, which are used in a proportion of 40 to 97 wt.% of the total mass of the raw material, a wide variety of materials can be used as solids according to the invention, in particular particulate plastics selected from the group comprising thermoplastics, thermosets, elastomers and mixtures of the same, powder resins, particulate fluoropolymers, fibers of all kinds, minerals, rocks, ores, metal oxides, metals, borides, carbides, nitrides, soapstone, calcined soapstone and vegetable solids, wherein the total amount of all solids in the raw material is a maximum of 97 wt.%.

[0012] The aforementioned groups of solids are grouped according to their origin or material type, or according to their influence on the properties of the available process products, and may therefore include overlaps or duplicate entries.

[0013] Particulate plastics, which include in particular thermoplastics, thermosets, and elastomers, are commonly available commercially and can generally be used in their pure form or in any mixtures. These mixtures can be blends of different plastics, varying in type, or differing in size and / or type. The term "plastics of other types" encompasses various polymers as such, but also polymers with the same basic structure but different molar masses, shapes, colors, and hardness.

[0014] With regard to thermoplastics, there are basically no restrictions on their fundamental applicability within the scope of the present invention. Examples include acrylonitrile styrene-acrylonitrile (ASA), acrylonitrile butadiene styrene (ABS), cellulose acetate (CA), and all carboxylic acid esters of natural cellulose, cellulose hydrate (CH), cycloolefin polymers (COC), ethylene ethyl acrylate copolymer (E / EA), ethylene propylene copolymer (EPM), fluoroethylene propylene (FEP), perfluoroalkoxy polymers (PFA), polyamide (PA), polybutylene terephthalate (PBT), polycarbonate (PC), thermoplastic polyesters, polyetherimide (PEI), polyetherketones (PEK, PEEK), polyethersulfone (PES), polyethylene (PE), polyethylene terephthalate (PET), polyimide (PI), polyketone (PK), polylactide (PLA), polymethacrylmethylimide (PMMI), polymethyl methacrylate (PMMA), polymethylpentene (PMP), polyoxymethylene (POM), polyphenylene ether (PPE), and polyphenylene sulfide. (PPS), polyphthalamide (PPA), polypropylene (PP), polystyrene (PS),Examples include polysulfone (PSU), polytetrafluoroethylene (PTFE) and fluorinated thermoplastics, polyvinyl acetate (PVAC), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), styrene-acrylonitrile copolymer (SAN) and thermoplastic starch (TPS).

[0015] According to the invention, acrylonitrile butadiene styrene (ABS), polyamides (PA), polylactate (PLA), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polyolefins such as polyethylene (PE) and polypropylene (PP), polystyrene (PS), polyetheretherketone (PEEK), polyvinyl chloride (PVC), polyphthalamide (PPA), polyimides (PI) and polytetrafluoroethylene (PTFE) are preferably used in the present process due to their widespread use and good and inexpensive availability.

[0016] The thermoplastics can be used in their pure form or in any mixture of one, two, or more. Mixtures with other solids mentioned herein are also possible and are part of the present invention. With regard to the thermoplastics, it is particularly noteworthy that, due to their reactive incorporation into the hybrid polymer structure, they can impart self-healing properties to the hybrid polymer material resulting from the process. Self-healing of surface defects or irregularities, such as those that may occur after polishing, or due to mechanical or chemical stress, can be observed, at least partially, after some time at room temperature, but can also be induced and / or accelerated by UV irradiation or increasing the temperature.It is assumed that this effect is due to the hybrid polymers formed, which contain corresponding thermoplastic components and generate internal, possibly locally limited compressive stresses, which then lead to self-healing.

[0017] Thermosets are also not subject to any restrictions regarding their fundamental applicability within the framework of the process according to the invention. Specific examples include Bakelite, chitin, epoxy resin, urea-formaldehyde resin (UF), melamine-formaldehyde resin (MF), phenyl-formaldehyde resin (PF), thermosetting polyesters, polyurethane (PUR), unsaturated polyesters (UP), silicone resins (SI), poly-DCPD resins, vinyl ester resins, VE resins, and PUR casting resins.

[0018] The thermosets can also be used in the process according to the invention in their pure form or in any mixture, as well as in any mixtures with one or more thermoplastics or other solids disclosed herein.

[0019] It has also been found that elastomers can generally be used within the scope of the present invention. Examples include crosslinking elastomers, thermoplastic elastomers (TPE) such as polyurethane elastomers (PUR, TPU), polyetheramides (TPA), polyester elastomers (TPC, TPE-E), and polyolefin elastomers such as ethylene-vinyl acetate copolymers (EVAC) and styrene copolymers (TPS). With elastomers, there are no restrictions regarding purity or mixtures, and they can be used in their pure form or in any mixtures with the other solids already mentioned. Similar to thermoplastic solids, elastomers also enhance or cause self-healing properties, and this is assumed to be based on a similar mechanism.

[0020] Furthermore, it is unexpected that the formation of hybrid polymeric structures is strongly favored when soluble polymers and / or the Si compounds are used in a small proportion of the crude mass, preferably in a proportion in the range of 0.1 wt.% to 5 wt.% of the crude mass, and particularly in a proportion of 0.5 wt.% to 2 wt.%, in a suitable solvent and incorporated into or applied to the crude mass. This incorporation can be carried out in any known manner, in particular by pouring and mixing, spraying, or flooding.

[0021] Powder resins deserve special mention, as they can also be used in the process according to the invention without any limitations. They are produced from cured thermoplastics and / or thermosets, ground into a powder, and are commercially available in this form. Specific examples of powder resins include phenolic resins (phenol-formaldehyde resin, PF resin), aminoplastics such as urea-formaldehyde resin (UF resin), melamine-formaldehyde resin (MF resin), epoxy resins such as polyester resins (UP resins), and ABS resins.

[0022] The powder resins are of particular importance here because they are technically common, readily available in a wide variety of forms with regard to their type and particle size, and therefore generally do not require any pretreatment for use in the process according to the invention.

[0023] The same applies to the powder resins regarding their applicability as to the aforementioned particulate plastics; they can be used in their pure form or in any mixtures, in particular also with other solids disclosed herein. Interestingly, the powder resins in particular lead to distinctly pronounced wavy structures, similar to those of brain convolutions, which are considered characteristic of the hybrid polymers presented here and result in improved hardness.

[0024] Due to their special properties, particulate fluoropolymers offer interesting possibilities within the scope of the present invention, but at the same time, these properties also pose certain challenges regarding their processing. It was therefore unexpected that fluoropolymers can be used without restriction in the present process for producing a hybrid polymer material, either in their pure form or as a mixture of different fluoropolymers and / or in combination with one or more other solids.

[0025] Fluoropolymers, in particular, impart special properties to the hybrid polymer active ingredient of the present invention due to their nature. Particularly noteworthy in this context is, for example, increased chemical resistance, but also the fact that they can reduce or at least partially prevent dust formation during cutting because they bind or encapsulate small particles released during cutting by melting. These advantageous effects are also demonstrated according to the invention by thermoplastic and elastomeric polymers. Furthermore, hybrid polymer materials according to the invention containing the aforementioned compounds also exhibit self-healing or regenerative properties.

[0026] Therefore, special, readily available fluoropolymers for the use according to the invention are selected from polytetrafluoroethylene (PFTE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-hexafluoropropylene vinylidene copolymer (THV), perfluoroalkoxy copolymer (PFA), ethylene tetrafluoro copolymer (ETFE), polyvinylidene fluoride (PVDF) and polychlorotrifluoroethylene (PCTFE) as well as mixtures of the same group.

[0027] There is generally no particular restriction regarding the particle size of the fluoropolymers, and they can therefore be used in the same sizes and fractions of different sizes as for the other solids disclosed herein, as specified below. However, it has proven advantageous for the fluoropolymers to have a particle size in the range of 1 nm to 600 µm, in particular a particle size in the range of 1 nm to 50 µm or in the range of 100 µm to 550 µm.

[0028] Regarding the plastics or polymeric starting materials that can be used, it is completely unexpected that these can generally be used in any mixing ratios with one another in the process according to the invention. This opens up a wide range of possibilities with regard to the choice of starting materials for use in a process for producing hybrid polymer materials.

[0029] Fibers, regardless of their type, are excellent starting materials for the present process for producing hybrid polymer materials and are preferably selected from the group comprising plant fibers, animal fibers, and synthetic fibers, as well as mixtures thereof. Examples of plant fibers used include hemp, linen, cotton, coconut, sisal, kapok, cellulose, libriform, bamboo, and jute fibers, as well as wood fibers in general. Examples of animal fibers used include wool and silk, and in particular, synthetic and / or technical fibers such as man-made fibers, aramid fibers, carbon fibers, ceramic fibers, rock wool, basalt fibers, glass fibers, and metal fibers, such as steel wool. Like the other solids disclosed herein, fibers can be used in any mixtures with each other and with other solids disclosed herein.This also applies, of course, to woven fabrics, knitted fabrics and nonwovens made from fibers, which may, for example, be included as reinforcing layers in the hybrid polymer material according to the invention.

[0030] Although fibers can generally be used in any length, for the purposes of the present invention fibers with a length in the range of 0.1 µm to 10 mm are preferred, in particular from 0.1 µm to 2 mm.

[0031] The inorganic solids used in this process are preferably selected from the group comprising minerals, rocks, ores, oxides, and metals, but also include borides, carbides, and nitrides. These are generally used to impart specific functional properties to the process product, such as hardness or strength, or to give it a particular optical appearance. The minerals and rocks include, in particular, natural and synthetic minerals, including quartz, quartz-containing minerals and rocks, minerals and rocks with low quartz content, and quartz-free minerals and rocks. Silicates and germanates are also included.

[0032] Specific examples of these starting materials, which can be used individually or in mixtures, are quartz, feldspar, basalt, mica, cristobalite, SiO2, Al2O3, SiC, SiN, BN, BC, Si3N4, Zr2O3, TiO2, Fe2O3, ZrO2, CuO, CuO2, ZnO, SnO, glass, glass fibers, TiC, metal oxides in general, aluminosilicates, zircon silicates, germanates, natural inorganic pigments such as earth colors, mineral white, titanium dioxide, synthetic inorganic pigments such as metallic effect pigments, carbon black and white pigments, iron oxide pigments.

[0033] In general, the inorganic solids used according to the invention comprise synthetic solids such as ceramics, silicates, germanates, metals, steel, metal oxides, borides, carbides and nitrides, and solids of natural origin such as silicates, germanates, minerals, metal oxides, in particular aluminum oxides, hydroxides, as well as rocks, iron ore, coal and aluminum ore. Synthetically produced representatives of these substances are also included.

[0034] In the process according to the invention, "recyclates usable" generally refers to all recycled plastic recyclates that can be used within the scope of the invention. In a preferred embodiment of the present invention, the recyclates are used in combination with a second solid of a different type disclosed herein, which offers particular advantages from an ecological and economic perspective, since these starting materials can be processed into high-quality, durable products and are inexpensive and available in large quantities.

[0035] Furthermore, it is a particular advantage that these recyclates can be used regardless of their type and origin and in mixed form, and that a complex separation process for plastic recyclates can be avoided.

[0036] Finally, it should be noted that plant-based solids in general can also be used within the scope of the invention; in particular, wood, straw, coconut shells, charcoal, nutshells, and bark can be used, for example. The use of plant-based solids makes it possible to obtain hybrid polymer materials that possess particularly good mechanical strength at a comparatively low density, as well as sound and heat insulation properties and / or an aesthetically pleasing appearance.

[0037] In the present process, the solids are generally used in particle sizes ranging from 10 nm to 10 mm and are employed as solids of the same type and size, as well as of different types and sizes. The proportion of all solids is up to 97 wt.% of the total mass of the raw material, of which, according to the invention, 40 to 97 wt.% is attributable to recycled plastics, and in which different fractions of varying sizes are particularly preferably used because the raw material can be compacted particularly well in this way.

[0038] In an independent embodiment of the present invention, the process according to the invention is characterized in particular by the use of generally particulate thermoplastics, thermosets, elastomers, and powdered resins alongside recycled plastics for at least a portion of the solids. Sufficiently fine fractions of these materials can advantageously also be used as support particles or filler particles, as well as melt particles or hybridization particles, if they partially or completely melt under the selected heat treatment conditions.

[0039] As already mentioned, it is possible to use any type of plastic waste or recyclate as a feedstock in the present process. A particularly noteworthy advantage is that no special and complex separation of plastic recyclates is required. Instead, they can be used in the resulting mixtures, and fiber-reinforced plastics or composite plastics can also be used. This is a tremendous advantage from both an economic and ecological perspective, since the plastic recyclates are inexpensive and available in large quantities. It should also be emphasized that the hybrid polymer materials disclosed herein can also be reused in this process, thus creating a closed material cycle.

[0040] As already mentioned, it was surprisingly discovered that the use of elastomeric and / or thermoplastic polymers for at least a portion of the solid material leads to hybrid polymer structures exhibiting regenerative or self-healing properties. Furthermore, the reactions to form the hybrid polymer material and / or the curing process require at least no or only minimal energy input. These reactions partially occur even at room temperature, making the process according to the invention surprisingly economical for this reason as well. This is particularly true for metals, which initiate the conversion to the hybrid polymers of the invention and the curing process even at a proportion of just 0.5 wt% of the raw material.Therefore, the solids can be used in a wide mixing ratio, generally in a range of 200:1 to 1:200, although other ranges, for example 20:1 to 1:20 or 10:1 or 1:10, are also preferred in order to specifically influence the property profiles.

[0041] In general, all hybrid polymer materials produced according to the invention possess good chemical resistance, are hydrophobic, and have good hardness. At the same time, they are easy to process and available in the form of sheets and three-dimensional molded parts, preferably as sheets, tiles, slabs, 3D molded parts, and, particularly preferably, as kitchen worktops, floor tiles, washbasins or sinks, shower trays, drywall elements, and facade elements.

[0042] The solids used in the present invention are in particle sizes in the range of 10 nm to 10 mm, i.e. they are either obtained and used in the appropriate size or are comminuted before use in the inventive method.

[0043] The strength, hardness, and density of the hybrid polymer material can be preferably adjusted by using different solid fractions of varying particle sizes. The use of coarse fractions with a particle size of 1 mm to 10 mm, medium fractions with a particle size of 250 µm to 1 mm, and / or fine fractions in the range of 10 nm to 250 µm is particularly preferred. The number of fractions used can be chosen arbitrarily, depending on the starting materials used and the desired density and / or hardness of the finished product. The use of fractions of varying sizes, especially three fractions, has often proven advantageous.However, a different number of fractions, such as one, two, four, five, or more, can of course also be used in certain cases, especially when considering fractions of different types of solids. It is also fundamentally possible to directly produce a desired particle size distribution and corresponding fractions using milling techniques.

[0044] According to the invention, reactive polymer resins known from the prior art are used as the polymer resin. In particular, these polymer resins are saturated or unsaturated polyester resins, phenolic resins, epoxy resins, polyurethanes, urethane acrylate, or polyamide resins. These are preferably used in a proportion of 3 wt.% to 40 wt.% of the total mass, and particularly preferably in a proportion of 5 wt.% to 20 wt.%. Mixtures of two or more different polymer resins can also be used to control the properties. For example, with urethane acrylate, only 0.25 wt.% is sufficient for the products manufactured with it to exhibit a particular hardness.

[0045] In order for the polymer resin to harden within a technically and economically acceptable timeframe, it is necessary, depending on the chosen polymer resin, to add a suitable starter in the form of a catalyst, or better yet, a starting catalyst, and / or an accelerator, also in the form of a catalyst, or better yet, an accelerator catalyst, to the polymer resin.

[0046] It is preferred to add a starter or peroxide catalyst as a starting catalyst in a proportion of 0.1 to 5 wt% of the resin and / or an accelerator or organometallic catalyst as an accelerating catalyst in a proportion of 0.01 to 5 wt% of the resin. For this purpose, for example, peroxide catalyst / starter, available under the name Trigonox 301, can be used in an amount of 2 wt% based on the resin, whereby amounts of 0.1 to 5 wt% are generally possible.

[0047] For example, cobalt can be used as an accelerating catalyst in a product called Octa-Soligen® Cobalt 6 from Borchers in an amount of 0.2 wt.%, based on the resin, whereby amounts of 0.01 to 2 wt.% are possible.

[0048] The essential effect of the present invention is based on the formation of hybrid polymer structures in the resulting material, whereby specific properties can be controlled by the targeted selection of the starting materials. A particular contribution to the formation of hybrid polymer structures is made by the silicon compounds from the group comprising silanes, siloxanes, silazanes, and silicone resins used in the process according to the invention, since these compounds, through reactive conversion, essentially form or create the link between the various inorganic and / or organic components of the raw material. The aforementioned wave-like or brain-like structures constitute a central element of these hybrid polymer structures.

[0049] The following silicon compounds are preferably used within the scope of the present invention: Alkylsilanes, such as methoxysilanes, ethoxysilanes, or chlorosilanes; hexadecyltrimethoxysilane, commercially available under the name Dynasylan 9116; methyltrimethoxysilane, commercially available under the name Dynasylan MTMS; M1-trimethoxy; isobutyltriethoxysilane, available under the name Dynasylan IBTEO; n-octyltriethoxysilane, available under the name Dynasylan OCTEO; isobutyltrimethoxysilane, available under the name Dynasylan IBTMO; methyltriethoxysilane, available under the name Dynasylan MTES; hexadecyltriethoxysilane and hexadecyltriethoxysilane; propyltriethoxysilane, available under the name Dynasylan PTEO; propyltrimethoxysilane, available under the name Dynasylan PTMO; octyltrimethoxysilane, available under the name Dynasylan OCTMO; octyltrichlorosilane, available under the name Dynasylan OCTCS, dodecyltrimethoxysilane and dodecyltriethoxysilane, octadecyltrimethoxysilane and octoxysilane, iso-octyltrimethoxysilane and iso-ethoxysilanen-Butyltriethoxysilane, n-Butyltrimethoxysilane.,

[0050] Arylsilanes such as phenyltriethoxysilane, available under the name Dynasylan 9265, and phenyltrimethoxysilane, available under the name Dynasylan 9165.

[0051] Aminosilanes and diaminosilanes, such as 3-aminopropyltrimethoxysilane, available under the name Dynasylan AMMO, DOG-TM 100, 3-aminopropyltriethoxysilane, available under the name Dynasylan AMEO, DOG TE 100, Genosil GF 93, 2-aminoethyl-3-aminopropyltrimethoxysilane, available under the name Dynasylan DAMO, DOG-DiAmino TM100, N-(n-butyl)-3-aminopropyltrimethoxysilane, triamino-functional propyltrimethoxysilane, available under the name Dynasylan Triamo, and 3-(2-aminoethylamino)propyldimethoxymethylsilane, available under the name Deolink DiAmino DM-100.

[0052] Fluoroalkylsilanes, such as tridecafluorooctyltriethoxysilane, available under the names Dynasylan 8261, Dynasylan 8263, nonafluorohexyltrimethoxysilane and heptadecylfluorodecyltrimethoxysilane.

[0053] Epoxysilanes, acetoxysilanes and silicic acid esters, such as tetraethyl orthosilicate, available under the name Dynasylan A, tetramethyl orthosilicate, available under the name Dynasylan M, di-tert-butoxydiacetoxysilane, available under the name Dynasylan BDAC, and 3-glycidyloxypropyltrimethoxysilane, available under the name Dynasylan GLYMO.

[0054] Siloxanes and cyclosiloxanes particularly noteworthy within the scope of the invention are hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, polydimethylsiloxane and octamethyltrisiloxane, in particular also those with different terminations, for example H-, OH- or CI-terminated siloxanes, as well as those with chain lengths other than those expressly mentioned.

[0055] It is particularly noteworthy, especially when using alkylsilanes and / or alkylsiloxanes, or siloxanes in general, that the resulting hybrid polymer material exhibits regenerative properties. Investigations in this area have shown that after treatment with acetone or abrasion with a standard household scouring pad, the artificial stone initially loses its gloss, but regains a significant amount of gloss after just 24 hours. If subsequently cleaned with water, the original gloss level is practically restored and in some cases even exceeded. This also occurs under artificial aging conditions, where the chemically or mechanically stressed sample is exposed to UV radiation for 24 to 48 hours.

[0056] Interestingly, regenerative properties are more pronounced when the described siloxanes are combined with fluoropolymers, thermoplastic and / or elastomeric polymers.

[0057] Examples of silazanes and polysilazanes that can be used according to the invention are, as polysilazane, the commercially available Durazane 1500 Rapid Cure and as silazane, hexamethyldisilazane, HMDS.

[0058] Examples of silicone resins include methylphenyl silicone resin solution, commercially available under the name REN 80, methoxy-functional methyl polysiloxane resin, available under the name MSE 100, silanol-functional methylphenyl silicone resin, available under the name REN 168, or the product available under the name Sy 409.

[0059] Examples of silane / siloxane mixtures used include commercially available products such as Koratect LO-N, an alkylated silane / siloxane mixture; Koratect SL 1, a mixture of isomeric octyltriethoxysilanes with iso-octyltriethoxysilane as the main component; and Dow Corning Z 6689, containing octyltriethoxysilane, methyltrimethoxysilane, titanium tetrabutanolate, octamethylcyclotetrasiloxane, and dimethyldimethoxysilane.

[0060] In a particular independent embodiment of the present invention, one or more silicon compounds are added in an amount between 0.1 and 40 wt.% of the total mass, and, if only monomeric silanes with exclusively aliphatic substituents with a chain length of C1 to C3 are used as one or more silicon compounds, a catalyst is added in an amount of 0.1 to 10 wt.% of the amount of silicon compound in addition to the silicon compound. This catalyst addition is generally independent of any catalyst already contained in the polymer resin and serves solely to increase the activity of the silicon atoms obtained in these compounds, enabling them to form corresponding links with the solid via oxygen atoms by forming covalent bonds. For example, greater hardness of the produced hybrid polymer material can be achieved in this way, but other improvements are also possible.In the case of silicon compounds exclusively with aliphatic substituents with a chain length of 1 to 3 carbon atoms, the reaction requires the addition of a catalyst. For silicon compounds with at least one substituent with a chain length greater than 4 carbon atoms, such a catalyst addition is not necessary. Silicon compounds with at least one aromatic substituent can also be used within the scope of the present invention without the addition of a catalyst.

[0061] Organometallic catalysts are generally used to increase the activity of these silicon compounds with exclusively C1 to C3 substituents, particularly commercially available organometallic catalysts, as these are relatively inexpensive and readily available in sufficient quantities and quality. Particularly good results are obtained with metal centers containing organic ligands of the elements titanium, zirconium, cobalt, copper, zinc, tin, iron, manganese, magnesium, aluminum, and boron. Organometallic catalysts containing these metals are therefore preferred. However, elements such as vanadium, chromium, nickel, molybdenum, silver, gallium, germanium, and bismuth also yield sufficiently good results, although usually only one type of catalyst is used for these silicon compounds.

[0062] Organometallic catalysts with alkyl groups, which can exist in n-form as well as in all iso-forms, are easy to process.

[0063] Examples of some organometallic catalysts derived from carboxylic acids are octoates, laurates, oxalates, decanetes and naphthenates.

[0064] Specific examples of such organometallic catalysts are cobalt(II) 2-ethylhexanoate, tin(II) 2-ethylhexanoate, dibutyltin dilaurate, dioctyltin dilaurate, zinc actate, zinc oxalate, zirconium octeate, zinc(II) 2-ethylhexanoate, copper oleate and copper naphthenate.

[0065] Other ligands that are useful and therefore important within the scope of the present invention are acetate, acetyl acetate, oleate and carboxylate, for example dibutyltin dicarboxylate, zinc acetate, cobalt acetate, bismuth carboxylate.

[0066] Acetylacetonates represent a particularly important group with numerous readily available and widely used representatives. Specific examples include aluminum(III) acetylacetonate, Al(acac)3, calcium(II) acetylacetonate, Ca(acac)2, chromium(III) acetylacetonate, Cr(acac)3, cobalt(III) acetylacetonate, Co(acac)3, iron(III) acetylacetonate, Fe(acac)3, copper(I) acetylacetonate, Cu(acac), copper(II) acetylacetonate, Cu(acac)2, manganese(III) acetylacetonate, Mn(acac)3, nickel(II) acetylacetonate, Ni(acac)2, vanadyl acetylacetonate, V(O)(acac)2, and zinc acetylacetonate, Zn(acac)2, to name just a few.

[0067] Another important group that can be used as catalysts are alcoholates and borates, wherein the addition of at least one alcoholate of zirconium, aluminum, or titanium is according to the invention. Particularly noteworthy examples of especially good catalysts are titanium isopropoxide, titanium tetrabutanoate, zirconium n-propoxide, aluminum isopropoxide, and triisopropyl borate. Within the scope of the present invention, these are preferably used as catalysts in a range of 0.01 wt.% to 5 wt.%.

[0068] With regard to these, it should be noted that they are not only used as catalysts, but also generally to increase the hardness of the hybrid polymer material according to the invention when used in larger quantities in the range of 0.5 wt.% to 30 wt.% of the total mass of the raw material components, and particularly in the range of 5 wt.% to 15 wt.%. Furthermore, aluminum, titanium, and zirconium compounds generally improve the mechanical and / or chemical resistance of the workpieces. They can also be used in combination with two or more of these compounds and lead to particularly good results with regard to the reactions to form the hybrid polymers when they are added directly to the solid(s) used before these are combined with other components of the raw material.

[0069] These catalysts and / or accelerators can also be used specifically for surface functionalization. For example, surfaces of hybrid polymer materials containing catalysts with Zn, Sn, or Cu content exhibit antibacterial, antifungal, algicidal, and / or antiviral properties.

[0070] To increase the reactivity and control the Si compound, in an independent embodiment of the process according to the invention, acids or bases are preferably added to the silicon compound in a proportion in the range of 0.5 to 10 wt.%. This results in hydrolysates and / or condensates of the silicon compounds used, which react with the solid and polymer resin to form essentially covalent bonds, although this reaction also occurs in principle without the addition of acid or base.

[0071] After adding and / or mixing the silicon compound with the mixture of solid and polymer resin, including any necessary catalysts, the mixture is blended until a homogeneous mass is obtained. This raw material is then shaped, compacted, and cured at room temperature up to 250 °C or 350 °C, preferably at 50 to 190 °C, and / or subjected to UV radiation, as is generally known. Activation by a short heat treatment, for example, 10 minutes at 150 °C, followed by curing at room temperature, is also possible and yields excellent results.

[0072] For the sake of completeness, the auxiliary materials will be briefly discussed. These include all starters, catalysts, colorants, and stabilizers that are generally known and commonly used in this field. Supporting particles and filler particles, which those skilled in the art use to vary the density and hardness of the process product, are also included. Since their use and application are familiar to those skilled in the art, they will not be discussed in more detail here.

[0073] It has proven particularly advantageous that the inventive method can be varied and adapted with regard to the design of the process steps, the use of the starting compounds, and the achievable product qualities. This is especially economically advantageous and allows for adaptation to the requirements of different application areas for the artificial stone to be produced.

[0074] In principle, there are various possible variations, each representing an independent embodiment of the method according to the invention.

[0075] In a first variant, the procedure is as already described herein, and the one or more Si compounds are mixed with a raw material produced from solid, polymer resin and auxiliary materials to obtain the modified raw material, which is then applied in form or as a mass carpet, compacted, reacted and cured.

[0076] According to a second variant, the Si compound and reactive polymer are first mixed, possibly with the addition of appropriate auxiliary substances, and then combined with the prepared solids.

[0077] In a third variant, the silicon compound, solid and auxiliary materials are first combined, then polymer is added and mixed again.

[0078] In a fourth variant, a raw material consisting of polymer and solid is produced as usual, applied as a layer, or shaped. Then, one or more silicon compounds are applied to the raw material. This application is primarily achieved by spraying, but can also be carried out by other methods such as printing, pouring, or flooding. This is followed by compaction, whereby the one or more silicon compounds are distributed throughout the upper layers and deep within the already shaped raw material by applying pressure.

[0079] The silicon compounds can also be used in the process according to the invention in a suitable solvent, which is advantageous in cases where these silicon compounds are usually commercially available dissolved in a solvent. It is particularly advantageous to use these compounds in a solvent when their viscosity needs to be reduced for improved processability, for example, during spraying. In this context, it can also be advantageous to include dissolved polymer, which leads to better distribution and thus promotes the formation of hybrid polymer structures.

[0080] According to a further, fifth variant of the inventive method, the one or more Si compounds are applied in a smaller quantity than in the variant described above, or after pre-compacting the raw mass.

[0081] These variants of the inventive method differ in part in the products resulting from the individual variants, which, although to varying degrees, fundamentally exhibit the properties already described. What they all have in common is the fact that the release of hazardous quartz fractions can be reliably avoided both during the production and processing of the artificial stone according to the invention. It is irrelevant whether this is achieved because the starting materials are selected to be exclusively quartz-free or low-quartz, or whether quartz or quartz-containing materials are used in combination with thermoplastic solids or Teflon, since any fine quartz particles that may arise during processing, particularly cutting, are encapsulated and / or bound and are not released as dust.

[0082] In the hybrid polymer material obtainable via the first three process variants, the entire raw material is modified by the addition of one or more silicon compounds, resulting in a uniform and homogeneous material. It is characterized in particular by good hardness and chemical resistance, hydrophobicity, and density.

[0083] The hybrid polymer material available according to the fourth variant behaves similarly, and the advantages described for the first variant are also present with only minor deviations. However, since this variant typically does not result in an absolutely homogeneous distribution of the added silicon compound in the raw material, minute defects or hairline cracks in the nanometer or millimeter range can occur. This is acceptable in many applications, however, and the advantages gained clearly outweigh these minor disadvantages.

[0084] The hybrid polymer material obtained according to the last described process variant shows significant differences in properties compared to the other two variants, because the shaped raw material is only modified superficially and the artificial stone exhibits greater hardness, chemical resistance and hydrophobicity on the modified surface, while the underside is not modified and on this side exhibits properties more like a cured polymer resin from the prior art.

[0085] This material is particularly suitable for kitchen worktops, wall, floor, and facade tiles / panels, 3D castings, sinks, kitchen basins, or shower trays, whose surfaces are exposed to a variety of stresses, while the opposite surface, for example the underside of a worktop, is not exposed to these stresses.

[0086] These advantageous properties of the process products obtainable with the inventive method, which can be realized according to the invention, result from the three-dimensional crosslinking within the entire substrate. Here, it is not only primarily the resins that crosslink with each other, as is the case with the simple curing of polymer resins in the prior art. Rather, according to the invention, crosslinking occurs between an organic component, the reactive polymer resin, the silicon compound, and the and / or other solids.

[0087] According to a particular aspect of the present invention, inorganic solids, regardless of whether they are quartz, quartz-containing, low-quartz, or quartz-free solids, as well as organic components, particles, and / or other types of solids, are chemically bound within the matrix. This prevents them from being, or at all can only be with great difficulty, torn from the matrix during further processing steps such as polishing, cutting, separating, and roughing, as well as during everyday use. Consequently, no new open pores and / or holes are formed on the surface of the hybrid polymer material. In particular, the use of quartz fractions with a grain diameter of <20 µm can be dispensed with, and the formation of correspondingly fine quartz dust during processing is not a concern, since, when combined appropriately with other solids, this dust is bound and not released as dust.Furthermore, the advantage is that the hybrid polymer structures formed according to the invention grow particularly well into cavities, be they pores or spaces, and therefore at least a part, and sometimes even completely, of fine fractions of solids can be dispensed with.

[0088] A particular advantage of the invention is therefore a stable bond between all components located in the substrate, as well as the independent filling or growth of the pores, defects and / or cracks that are still open before the hardening process through the growth of the hybrid polymer structures, i.e. structures with chemical, usually covalent bonds between the solids, polymer resin and added silicon compound, during the reactions taking place between the components contained in the modified raw material, in particular between the silicon compounds used or their hydrolysates and / or condensates formed at least partially in situ under the reaction conditions described later, as well as the inorganic and / or organic components, particles and fillers.

[0089] The invention specifically exploits the fact that the starting compounds and materials used react with each other to form hybrid structures, hybrid polymers, through the formation of chemical, covalent bonds, or bonds with a high covalent bonding content. Through the growth of the molecules and their cross-linking, even small cavities in the nanometer range are closed or filled, and glassy or solid, hard, sometimes stone-like structures are formed, which in turn are mechanically and chemically very stable.

[0090] Depending on the application of silicon compounds and / or their hydrolysates and / or condensates, the molecular size and growth can be precisely controlled. Ideally, short-, medium-, and long-chain silanes are used, optionally siloxanes, polysiloxanes, siliazanes, or polysilazanes, or their hydrolysates and / or condensates, as well as silicone resins. These lead to extremely dense packing and strong, spherical or "cloudy," interwoven molecular growth, and, consequently, to the self-closing of pores, both between and within the solids themselves. Furthermore, additional interlocking occurs during the reaction and growth process. This is particularly important when porous or brittle, particulate inorganic or organic compounds or fillers are to be used.The hybrid polymer structures growing into the pores of the fillers interlock them in addition to the chemical bonding, thus providing further stabilization.

[0091] For this reason, cheaper, quartz-free fillers can also be used, typically highly porous and less solid materials, without negatively affecting the properties of the final product. Quartz-free chamotte and / or quartz-free ceramic swarf are particularly noteworthy here, as they are extremely cost-effective materials. Recycled plastics and engineered stone, regardless of their origin, are also of particular importance in this context because they allow for the reuse and / or further processing of unavoidable production waste.

[0092] Furthermore, it has been shown that smaller quantities of resin can be used due to the growth of the polymers. This is of particular interest, as the resin is a key component in determining the price of the material composition.

[0093] For example, in the case of very open-pored fillers, the composition in an independent embodiment of the method according to the invention can nevertheless be selected such that, by adding support grain or filler grain with a grain diameter smaller than the pore diameter of the filler, usually in the range of 10 nm to 30 µm, the pores are filled to a large extent, at least in part of the filler.

[0094] Furthermore, adhesion-promoting reactive groups are ideally selected for the outer surfaces of the hybrid structures, which crosslink with the fillers or pigments also incorporated. Generally, reactive functional groups such as amino, carbonyl, or epoxy groups can be used as reactive groups. This results in a very advantageous improvement in adhesion to inorganic fillers from the hybrid polymer base. Three-dimensional crosslinking and matrix formation occur, eliminating the need for pre-silanization of the inorganic particles in the matrix, as is at least partially carried out in the prior art.

[0095] Due to the described incorporation of the hybrid polymer structures, it is also possible to selectively use porous solids. This can even be particularly advantageous, since the incorporation and interlocking of the hybrid polymer structures allows for a particularly strong integration of these porous solids into the resulting matrix.

[0096] The hybrid polymers obtained in this way, even in their simplest form, already exhibit structures that are composed of inorganic and organic components at the molecular level and chemically bonded together. They therefore possess properties of organic polymers on the one hand, but also interesting properties of inorganic materials on the other. This allows for the creation of substrates that exhibit the high flexibility of polymers while simultaneously being glass-like in hardness and chemically resistant like inorganic materials.

[0097] Since these hybrid polymers have no or practically imperceptible phase boundaries, the products manufactured according to the inventive method also exhibit excellent optical properties.

[0098] The following examples, which are not part of the invention, indicate some possible combinations of components that can be used to produce hybrid polymer materials. These represent only a small selection of possible combinations: Example 1 (metal-containing hybrid polymer material) Thermoplastic polyester PET (10 µm - 500 µm) 56,45% Titanium isopropoxide 5,64% Zirconium n-propoxide 5,64% epoxy resin 16,93% Peroxide starter (2% relative to epoxy resin) 0,34% Copper catalyst (0.2% relative to epoxy resin) 0,04% Polydimethylsiloxane 3,30% Polydimethylsiloxane (OH-terminated) 0,37% Stainless steel chips / powder (10 µm to 50 µm) 11,29% Example 2 (hybrid polymer material containing natural fibers) Polyamide (PA 50 µm - 600 µm) 55,05% Titanium isopropoxide 11,00% Phenolic resin 16,52% Peroxide starter (2% relative to phenolic resin) 0,33% Zinc catalyst (0.2% relative to phenolic resin) 0,03% Octyltriethoxysilane 2,48% Polydimethylsiloxane 0,28% Zirconium oxide powder (10 µm - 40 µm) 11,01% hemp fiber 2,75% Nonylphenol 0,55% Example 3 (hybrid polymer material containing rock wool (basalt fiber)) Thermoplastic polyester PET (50 µm - 500 µm) 30,00% Thermoplastic polyester PET (170 µm - 800 µm) 25,05% Titanium isopropoxide 5,50% Zirconium n-propoxide 5,50% Unsaturated polyester resin 16,52% Peroxide starter (2% relative to polyester resin) 0,33% Cobalt catalyst (0.2% relative to polyester resin) 0,03% Polydimethylsiloxane 2,48% Polydimethylsiloxane H-terminated 0,28% Aluminum oxide powder (corundum) (50 µm - 100 µm) 11,01% Rock wool (basalt fiber 1 µm - 300 µm) 2,75% Nonylphenol 0,55% Example 4 (carbon fiber and mineral-containing hybrid polymer material) Polyimide (PEI 75 µm to 400 µm) 41,68% Polycarbonat 12,18% Titanium tetrabutanolate 10,78% Melamine resin 16,16% Formic acid 50% (2.17% with respect to melamine resin) 0,35% Polydimethylsiloxane 2,42% Polydimethylsiloxane (H-terminated) 0,27% Aluminum oxide powder 10 µm - 40 µm) 10,77% Carbon fiber (10 µm - 150 µm) 5,39% Example 5 (Al2O3 and plastic-containing hybrid polymer material) Acrylonitrile butadiene styrene copolymer (ABS 30 µm to 600 µm) 55,05% Titanium tetrabutanolate 5,50% Zirconium n-propoxide 5,50% Unsaturated polyester resin 16,52% Peroxide starter (2% relative to polyester resin) 0,33% Tin catalyst (0.2% relative to polyester resin) 0,03% Polydimethylsiloxane 2,48% Hexadecyltrimethoxysilane 0,28% Aluminum oxide powder (10 µm - 40 µm) 13,76% Nonylphenol 0,55% Example 6 (hybrid polymer material containing powder resin and plastic) Polyphenylene sulfide (PPS 50 µm to 450 µm) 48,91 % Polyaryletherketone (PEEK 300 µm to 750 µm) 13,36% Zirconium n-propoxide 11,32% epoxy resin 16,98% Peroxide starter (2.18% relative to epoxy resin) 0,37% Polydimethylsiloxane (H-terminated) 2,83% Phenolic resin with hardener (hexamethylenetetramine) (rhenosine A) 5,66% Nonylphenol 0,57% Example 7 (hybrid polymer material containing fine-grained plastic) Polyethylene PE (800 µm to 1200 µm) 8,63% Polypropylene PP (200 µm to 500 µm) 12,43% Thermoplastic polyester (PET 85 µm to 350 µm) 47,47% Titanium isopropoxide 2,71% Zirconium n-propoxide 8,71 % Unsaturated polyester resin 17,13% Peroxide starter (3.33% relative to polyester resin) 0,57% Cobalt catalyst (0.33% relative to polyester resin) 0,06% Polysilazane 2,29% Example 8 (hybrid polymer material containing Teflon and plastic) Polyvinyl chloride PVC (20 µm to 550 µm) 48,28% Polyvinyl chloride PVC (10 µm to 300 µm) 8,15% Titanium tetraethanolate 12,07% Unsaturated polyester resin 17,20% Peroxide starter (0.65% relative to polyester resin) 0,11% Cobalt catalyst (0.07% relative to polyester resin) 0,01% PTFE (4 µm) 10,00% Phenol-formaldehyde resin 2,07% Polydimethylsiloxane (CI-terminated) 2,11% Example 9 (Plastic (3 fractions) and Teflon-containing hybrid polymer material) Thermoplastic polyester (PET 500 µm - 1500 µm) 31,12% Thermoplastic polyester (PET 90 µm - 480 µm) 26,37% Polyphthalamide (PPA 60 µm 180 µm) 4,19% Titanium isopropoxide 5,90% Unsaturated polyester resin 21,30% Peroxide starter (0.78% relative to polyester resin) 0,17% Nickel catalyst (0.08% relative to polyester resin) 0,02% PTFE (6 µm - 20 µm) 7,76% Polydimethylsiloxane-OH terminates 1,17% Hexadecyltrimethoxysilane 1,00% Urethane acrylate resin 1,00% Example 10 (hybrid polymer material containing recycled plastics) Polymethyl methacrylate (350 µm - 1 mm) 34,35% Recycled plastic (PET 20 µm to 250 µm) 34,35% Aluminum isopropoxide 5,73% Zirconium oxide 5,73% Vinyl ester resins 17,18% Peroxide starter (2.0% relative to vinyl ester resin) 0,34% Iron catalyst (0.2% relative to vinyl ester resin) 0,03% Polydimethylsiloxane 2,00% Methyltrimethoxysilane 0,28% Example 11 (hybrid polymer material containing wood and plastic) Thermoplastic polyester (PET 20 µm - 500 µm) 62,98% Wood fiber / shavings (1 µm - 100 µm) 5,73% Titanium isopropoxide 4,73% Zirconium n-propoxide 4,73% Aluminum isopropoxide 2,00% Unsaturated polyester resin 14,18% epoxy resin 3,00% Peroxide starter (2.40% relative to polyester resin) 0,34% Manganese catalyst (0.2% relative to polyester resin) 0,03% Polydimethylsiloxane 2,29%

[0099] The invention described above will be explained in more detail below with reference to the accompanying figures. These show: Fig.1 an electron microscope image of a hybrid polymer material with a mineral solid and PET, showing a complete coating of an Al2O3 particle with hybrid polymer structures; Fig. 2 an electron microscope image of a hybrid polymer material as in Fig. 1 with a cut Al2O3 particle; Fig. 3 an electron microscope image of a hybrid polymer material with PET as the solid; Fig. 4 an electron microscope image of a hybrid polymer material as in Fig. 3 in greater magnification; Fig. 5 an electron microscope image of a hybrid polymer material with finer PET fractions; Fig. 6 an electron microscope image of a hybrid polymer material with recycled plastic; Fig. 7 an electron microscope image of a hybrid polymer material as in Fig.6 in greater magnification; Fig. 8 an electron microscope image of a hybrid polymer material with hemp fibers; Fig. 9 an electron microscope image of a hybrid polymer material as in Fig. 8 in greater magnification; Fig. 10 an electron microscope image of a hybrid polymer material with wood; Fig. 11 an electron microscope image of a hybrid polymer material as in Fig. 10 with lower magnification; Fig. 12 an electron microscope image of a hybrid polymer material with carbon fiber; Fig. 13 an electron microscope image of a hybrid polymer material as in Fig. 12 in greater magnification; Fig. 14 an electron microscope image of a hybrid polymer material with a powder resin; Fig. 15 an electron microscope image of a hybrid polymer material with steel; Fig. 16 an electron microscope image of a hybrid polymer material with rock wool; Fig. 17 an electron microscope image of a hybrid polymer material with tetrafluoroethylene and Fig. 18 an electron microscope image of a hybrid polymer material made with quartz but without Si compounds.

[0100] Fig. Figure 1 shows an electron microscope image of a hybrid polymer material in which a mineral and polyethylene terephthalate (PET) were used as solids in the process according to the invention. In the center of the image, the mineral component, Al₂O₃, is clearly visible, encased by and embedded in hybrid polymer structures. The hybrid polymer structures are characterized by wavy, brain-like patterns. The parallel lines at the edge of the enclosed grain are a clear indication of the reactive bonding. This is in Fig.Image 2 is particularly easy to see, with a split Al2O3 grain clearly visible in the lower part of the image. Wave-like structures appear to grow from its edge without discernible phase boundaries, a characteristic of reactive bonding. In the left part of the image, slightly below the center, it can be seen that the hybrid polymer has formed up to a crack in the grain. The linear structures or faults arise due to the resulting local internal compressive stresses.

[0101] In the electron microscope image in Fig. Figure 3 shows a hybrid polymer material in whose production only polyethylene terephthalate (PET) was used as the solid component, which can be seen as a sharp-edged, semicircular structure. Here, too, the wave-like structures are visible without the formation of a phase boundary.

[0102] The above-described situation is clearer in the Fig. 4 to recognize, which are opposite Fig. 3 has double the magnification.

[0103] Also Fig. Figure 5 shows a hybrid polymer material produced exclusively with PET as a solid, but this time with a finer fraction. This was obtained by grinding with a stick blender. The wave-like hybrid polymer structures are particularly visible.

[0104] Fig. Figure 6 shows a hybrid polymer material containing recycled plastic, specifically a shredded laboratory beaker. Here too, there are wavy, hybrid polymer structures, but no discernible phase boundaries. This is further illustrated in a larger magnification in Figure 6. Fig. 7, which shows a section from the center of the image Fig. 6 shows.

[0105] In the Fig. 8 and Fig.Figure 9 shows the particularly good integration of hemp fibers into the hybrid polymer material. Figure 9 shows the particularly good integration of hemp fibers into the hybrid polymer material. Fig. 9 the reactive bonding of the hemp fiber through the seamless transition between fiber and polymer structure, without any indication of a phase boundary.

[0106] The Fig. 10 and Fig. Figure 11 shows the advantageous integration of a wood particle into the hybrid polymer material according to the invention at different magnifications, whereby the characteristic wave-like structures are again clearly visible.

[0107] Fig. Figure 12 shows a carbon fiber-reinforced hybrid polymer material and its excellent integration, but no phase boundaries. The portion of the image at the top center is enlarged. Fig.13 is reproduced, and one can clearly see the end face of a broken fiber, wavy, hybrid polymer structures and again no phase boundaries.

[0108] The in Fig. The hybrid polymer material shown in Figure 14 was produced using a powder resin as a solid and exhibits extremely fine and dense wave-like structures.

[0109] In Fig. Figure 15 shows a hybrid polymer material produced using stainless steel in the form of milling and drilling chips. This steel was used as it was generated, i.e., with residues of lubricant or lubricating oil.

[0110] At the in Fig. The 16th roughly diagonal elevation is a rock wool fiber, more precisely a basalt wool fiber, which is so well embedded that it is almost no longer visible. The characteristic wave-like structures are again recognizable in this figure, but no phase boundary.

[0111] In Fig. Figure 17 shows a hybrid polymer material with very fine Teflon. This forms part of the cloudy structure in the left part of the image, whereby the fine particles cause the hybrid polymer structural components to appear cloud-like at this resolution.

[0112] In comparison to the previous figures, in Fig. Figure 18 shows a material produced with quartz but without a silicon compound. The larger, smooth, and sharp-edged structures represent the quartz, while the porous or rough-looking areas represent cured polymer resin. In contrast to the other electron microscope images, the individual components are clearly distinguishable, and the wave-like structures that characterize the hybrid polymers according to the invention are completely absent.

[0113] In summary, it can be stated that according to the invention it has been possible to firmly and reactively incorporate a wide variety of substrates into a polymer matrix, resulting in process products whose properties can be controlled over a wide range by targeted selection of the solids used as starting materials.

Claims

A process for producing a hybrid polymer material based on a reactive polymer resin and one or more Si compounds from the group comprising silanes, siloxanes, silazanes and silicone resins, wherein, firstly, recycled plastic material as a quartz-free filler in combination with the reactive polymer resin and one or more Si compounds as well as additives forms a raw material, wherein the raw material further contains at least one alcoholate of zirconium, aluminum or titanium, and wherein the raw material is compacted and subsequently reacted and cured, wherein the proportion of the solid is 40 to 97 wt.% of the total mass of the raw material. Method according to claim 1, characterized in that at least one second solid of a different type is introduced into the raw mass. Method according to claim 1 or 2, characterized in that the solid is / are used in a mixture of fractions of different sizes and / or a mixture of different types and different sizes. Method according to one of the preceding claims, characterized in that the solid is used simultaneously in three fractions of different sizes. Method according to one of the preceding claims, characterized in that the solid comprises particles with a particle size in the range of 0.01 µm to 10 mm, in particular coarse fractions with a particle size of 1 mm to 10 mm, medium fractions with a particle size in the range of 250 µm to 1 mm and / or fine fractions with a particle size in the range of 0.01 µm to 250 µm. Method according to one of the preceding claims, characterized in that the ratio of the first solid to the second, differently characterized solid is from 200:1 to 1:

200. Method according to one of the preceding claims, characterized in that the alcoholate of zirconium, aluminium or titanium is an ethoxide, propoxide or butoxide and is preferably selected from titanium isopropoxide, titanium tetrabutanoate, zirconium n-propoxide and aluminium isopropoxide. Hybrid polymer material, in particular artificial stone, obtainable by a method according to one of the preceding claims. Hybrid polymer material according to claim 8 in the form of a plate, tile, slabs, a 3-D molded part and in particular in the form of a kitchen worktop, floor tile, a washbasin or sink, a shower tray, a wall or facade element, an insulation element or a dry construction element.

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