DE102019000789A1 - Hybrid polymer material - Google Patents

Abstract

The present invention relates to a method for producing a hybrid polymer material, such a material and its use and is characterized in particular by the fact that a large number of different solids, alone or in combination, together with a reactive polymer resin, one or more Si compounds and Usual auxiliaries can be used as starting materials.

Description

The present invention relates to a method for producing a hybrid polymer material, a hybrid polymer material produced by this method and the use thereof.

Hybrid polymers are polymeric materials that combine structural units of different material classes at the molecular level and have special properties and functionalities due to their composition. Such materials are often manufactured using the sol-gel process. Because of the special properties of these materials, which often represent a combination of properties of the starting materials that is not available in this way, there is great interest in such hybrid polymer materials and corresponding processes for producing the same, which processes should be as simple to carry out and easily adaptable as possible.

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 can be carried out as simply as possible and leads to new hybrid polymer materials with advantageous properties.

The present object is achieved by a method according to the appended claim 1. A hybrid polymer material according to claim 9 is also the subject of the present invention. Advantageous embodiments of the invention are the subject of the claims, which are directly or indirectly related.

In general, it should be noted that in this description references are made to commercially available products which, as a rule, are not given in detail by the manufacturer with regard to their composition, since these compositions are regarded as a trade secret. Furthermore, the singular and plural of a term are used interchangeably in the description and the claims, and the naming of the singular, example solid, includes the majority, example solids, and vice versa, since the solid contained in the raw material produced, for example, can be named in its entirety , but can actually be composed of different solids that differ in type and / or size. In the context of the present invention, a solid of a different type denotes a solid which differs in structure and / or class of substances from another solid, for example a polymeric solid is a different type of solid compared to a mineral solid or a rock.

In the method according to the invention 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, a solid or a mixture according to the type and / or size of different solids forms in combination a raw material with the reactive polymer resin and one or more Si compounds and auxiliary substances, the raw material being compacted and subsequently reacted and cured. The curing takes place, for example, by means of a heat treatment at a temperature in the range from room temperature to 350 ° C., by a radical chain reaction or by means of UV radiation. As a rule, the raw material is converted during curing. In the presence of metals, there are also autocatalytic or metal-catalyzed, at least partially exothermic reactions.

In the investigations carried out in the context of the present invention, it was found, completely unexpectedly, that practically any solid can be integrated or incorporated into the hybrid polymer material according to the invention and, depending on the particle size and / or amount used, has special effects in a controllable manner.

According to the invention, a wide variety of materials can be used as solids, in particular particulate plastics selected from the group consisting of thermoplastics, thermosets, elastomers and mixtures of the same, powder resins, particulate fluoropolymers, fibers of all types, minerals, rocks, ores, metal oxides, metals, borides, carbides, Nitrides, recycled plastic, recycled artificial stone, broken ceramic, soapstone, calcined soapstone and vegetable solids.

The above-mentioned groups of solids are grouped according to their origin or type of material or also according to their influence on the properties of the available process products and can therefore include overlaps or double mentions.

The particulate plastics, which comprise, in particular, thermoplastics, thermosets and elastomers, are usually commercially available and can generally be used as single types or in any mixtures. These mixtures can be mixtures of different plastics which differ according to their type or mixtures which differ according to their size and / or type, different plastics as such, but also polymers with the same basic structure but different molar masses , Shapes, colors and hardness understood.

With regard to the thermoplastics, there are basically no restrictions with regard to the basic usability within the scope of the present invention. Examples include acrylic ester-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 polyester, polyetherimide (El), polyether ketones (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), polyphenylene sulfide (PPS), polyphthalamide (PPA), polypropylene (PP), polystyrene (PS), polysulfone (PSU), polytetrafluoroethylene (PTFE) and fluorine-containing thermoplastics, polyvinyl acetate (PVAC), polyvinyl chloride (PVC), Polyvinylidene fluoride (PVDF), styrene-acrylonitrile il copolymer (SAN) and thermoplastic starch (TPS).

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), polyether ether ketone (PEEK), polyvinyl chloride (PVC), polyphthalamide (PPA), polyimide (PI) and polytetafluoroethylene (PTFE) are preferred because of their widespread use and good and favorable availability in the present process.

The thermoplastics can be used according to type or in any mixture of one, two or more. Mixtures with other solids mentioned herein are also possible and belong to the present invention. With regard to the thermoplastics, it should be emphasized that they can impart self-healing properties to the hybrid polymer material resulting from the process due to their reactive integration into the hybrid polymer structure. Self-healing of surface defects or non-uniformities, such as may occur after polishing, mechanical or chemical stress or stress, can be observed at least in part after some time at room temperature, but can also be caused by UV radiation or an increase in temperature effected and / or accelerated. It is believed 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.

Thermosets are also not subject to any restrictions with regard to their basic usability in the process according to the invention. Particular examples include bakelite, chitin, epoxy resin, urea-formaldehyde resin (UF), melamine-formaldehyde resin (MF), phenyl-formaldehyde resin (PF), thermosetting polyester, polyurethane (PUR), unsaturated polyester (UP), silicone resin (SI), poly -DCPD resins, vinyl ester resins, VE resins and PUR casting resins.

The thermosets can also be used in the process according to the invention as single types or in any mixture as well as in any mixtures with one or more thermoplastics or other solids disclosed in the present case.

It has also been found that elastomers can likewise be used in general within the scope of the present invention. Examples are crosslinking elastomers, thermoplastic elastomers (TPE), such as polyurethane elastomers (PUR, TPU), polyether amides (TPA), polyester elastomers (TPC, TPE-E), polyolefin elastomers, such as ethylene-vinyl acetate copolymers (EVAC) and styrene copolymers ( TPS). The elastomers are also not subject to any restrictions with regard to type purity or mixtures, and the same can be used individually or in any mixtures with the other solids already mentioned. Comparable to thermoplastic solids, elastomers also reinforce or require self-healing properties and it is believed that this is based on a similar mechanism.

It is also unexpected that the formation of hybrid polymer structures is greatly favored if soluble polymers and / or the Si compounds are present in a small proportion of the raw material, preferably in a proportion in the range from 0.1% by weight to 5% by weight .-% of the raw mass, in particular in a proportion of 0.5 % By weight to 2% by weight, used in an appropriate solvent and introduced into the raw material or applied to the same. This introduction can take place in any known manner, in particular by pouring and mixing, spraying or flooding.

Special mention needs to be made of powder resins, which in principle can likewise be used in the process according to the invention and without restriction. They are manufactured and ground from hardened thermoplastics and / or thermosets and are commercially available in this form. Particular examples of the powder resins are phenolic resins (phenol-formaldehyde resin, PF resin), aminoplasts, such as urea-formaldehyde (UF resin), melamine-formaldehyde resin (MF resin), epoxy resins, such as polyester resins (UP resins) and ABS - Resins.

The powder resins are of particular importance in the present case because they are technically familiar, are readily available in a variety of configurations with regard to their type and particle size, and therefore in principle do not require any pretreatment for use in the process according to the invention.

The same applies to the powder resins with regard to their usability as for the aforementioned particulate plastics; in the present case they can be used in single-variety form or in any mixtures, in particular also with other solids disclosed herein. Interestingly, powder resins in particular lead to distinctly pronounced wavy structures that are similar to those of brain twists and are regarded as characteristic of the present hybrid polymers and lead to improved hardness.

Particulate fluoropolymers offer interesting possibilities in the context of the present invention due to their special properties, but at the same time pose certain challenges with regard to their processing due to these properties. It was therefore unexpected that fluoropolymers can be used in the present process to produce a hybrid polymer material without restriction or as a mixture of different fluoropolymers and / or in combination with one or more other solids.

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 the formation of dust when cutting, because they bind or envelop small particles that are released during cutting, these advantageous effects also according to the invention thermoplastic and elastomeric polymers are shown. In addition, hybrid polymer materials according to the invention which contain the abovementioned compounds also show self-healing or regenerative properties.

Special, readily available fluoropolymers for use in accordance with the invention are therefore made of 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 comprehensive group.

There is in principle no particular restriction with regard to 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 indicated below. However, it has proven to be advantageous if the fluoropolymers have a particle size in the range from 1 nm to 600 μm, in particular a particle size in the range from 1 nm to 50 μm or in the range from 100 μm to 550 μm.

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

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 consisting of vegetable fibers, animal fibers and synthetic fibers and mixtures thereof. Here, as plant fibers, for example, hemp, linen, cotton, coconut, sisal, kapok, cellulose, libriform, bamboo and jute fibers and generally wood fibers are used, wool and silk as fibers of animal origin and in particular also synthetic and or technical fibers as general Synthetic 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 one another and with other solids disclosed herein. Of course, this also applies to fabrics, knitted fabrics and nonwovens made from fibers, which may be contained, for example, as reinforcing layers in the hybrid polymer material according to the invention.

Even if fibers can in principle be used in any length, for the purposes of the present invention fibers are preferred which have a length in the range from 0.1 μm to 10 mm, in particular from 0.1 μm to 2 mm.

The inorganic solids which can be used here are preferably selected from the group consisting of minerals, rocks, ores, oxides and metals, but also include borides, carbides and nitrides. These are generally used to give the process product certain functional properties such as hardness or strength or to give it a certain visual appearance. The minerals and rocks include in particular natural and synthetic minerals, including quartz, quartz-containing minerals and rocks, low-quartz minerals and rocks as well as quartz-free minerals and rocks. Silicates and germanates are also included.

Particular examples of these starting materials which can be used individually or in a mixture are quartz, feldspar, basalt, mica, cristobalite, SiO ₂ , Al ₂ O ₃ .SiC, SiN, BN, BC, Si ₃ N ₄ , Zr ₂ O ₃ , TiO ₂ , Fe ₂ O ₃ , ZrO ₂ , CuO, CuO ₂ , ZnO, SnO, glass, glass fibers, TiC, metal oxides in general, aluminum silicates, zirconium 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.

In general, the inorganic solids which are used according to the invention include 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 alumoxides, Hydroxides as well as rocks, iron ore, coal and aluminum ore. Synthetically produced representatives of these substances are also included.

Recyclates which can be used in the process according to the invention generally refer to all recycled materials which can be used in the context of the invention and are in particular selected from the group consisting of plastic recyclates, artificial stone recyclates, broken ceramic and mixtures of the same. In a preferred embodiment of the present invention, the recyclates are used in combination with a second solid of a different kind, which is disclosed herein, which provides advantages, particularly from an ecological and economic point of view, since these starting materials can be processed into high-quality, long-lasting products and inexpensively and in large quantities Are available.

It is also of particular advantage that these recyclates can be used regardless of their type and origin and in a mixed form and that there is no need for complex separation, for example for plastic recyclates, but also for all other recyclates.

Finally, it should be noted that vegetable solids can also be used in general within the scope of the invention, in particular, for example, wood, straw, coconut shells, charcoal, nutshells and bark can be used. The use of plant-based solids enables hybrid polymer materials to be obtained which have particularly good mechanical strength with a comparatively low density, sound and heat insulation properties and / or an optically appealing appearance.

In the present case, the solids are generally used in particle sizes in the range from 10 nm to 10 mm in the process according to the invention and are used as solids of the same type and size as well as of different types and sizes. The proportion of solids is preferably 40 to 97% by weight of the total mass of the raw mass, with different fractions of different sizes being particularly preferably used because the raw mass can be compacted particularly well in this way.

In an independent embodiment of the present invention, the process according to the invention is distinguished in particular by the use of generally particulate thermoplastics, thermosets, elastomers, powder resins and / or recycled plastics for at least some of the solids. Sufficiently fine fractions of the same can advantageously also be used as a support grain or filler grain and as a fusion grain or hybridization grain if they partially or completely melt under the chosen conditions of the heat treatment.

As already mentioned, it is also possible to use any type of plastic waste or recyclate as a starting material in the present process, a particular feature to be emphasized being that no special and complex separation of plastic recyclate is required. Rather, these can be used in the resulting mixtures, and fiber-reinforced plastics or composite plastics can also be used. This is an enormous advantage in economic and ecological terms, since the plastic recyclates are cheap and available in large quantities, although it should be emphasized that the hybrid polymer materials disclosed here can also be used again in this process and this results in a closed material cycle.

As already mentioned, it was surprisingly found that the use of elastomeric and / or thermoplastic plastics or polymers for at least part of the solid used leads to hybrid polymer structures which have regenerative or self-healing properties. Furthermore, the reactions to the hybrid polymer material and / or the curing at least partially require little or no energy input. Some of these reactions take place at room temperature, so that the process according to the invention is surprisingly economical for this reason too. This is particularly the case with metals which initiate the conversion to the hybrid polymers of the invention and hardening from a proportion of 0.5% by weight of the raw material. Therefore, the solids can be used in a wide mixing ratio, generally in a range from 200: 1 to 1: 200, with other ranges, for example 20: 1 to 1:20 or 10: 1 or 1:10, being preferred to influence the property profiles in a targeted manner.

In general, all hybrid polymer materials produced according to the invention have good chemical resistance, are hydrophobic and have good hardness. At the same time, they are easy to process and available in the form of plates and three-dimensional moldings, preferably as a plate, tile, slab, 3-D molded part and, particularly preferably as a kitchen worktop, base plate, sink or sink, shower tray, dry construction element, facade element.

The solids used in the context of the present invention are used here in particle sizes in the range from 10 nm to 10 mm, that is to say they are either obtained and used in an appropriate size or comminuted before use in the process according to the invention.

The strength and hardness as well as the density of the hybrid polymer material can preferably be adjusted by using different solid fractions of different 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 from 10 nm to 250 μm is particularly preferred. The number of fractions used can in principle be chosen arbitrarily and in accordance with the starting materials used, the desired density and / or hardness of the process product. It has often proven advantageous to use fractions that differ in size, in particular three fractions. However, a different number of fractions such as one, two, four or five fractions or more can of course also be used in certain cases, in particular if fractions of different types of solids are taken into account. In principle, it is also possible to produce a desired distribution of the particle size and corresponding fractions directly by grinding.

According to the invention, reactive polymer resins known from the prior art are used as the polymer resin. In particular, this polymer resin is a saturated or unsaturated polyester resin, phenolic resin, epoxy resin, polyurethane, urethane acrylate or polyamide resin. These are preferably used in a proportion of 3% by weight to 40% by weight of the total mass, particularly preferably in a proportion of 5% by weight to 20% by weight. Mixtures of two or more different polymer resins can also be used to control the properties. In the case of urethane acrylate, for example, 0.25% by weight is sufficient for the process products produced with this to have a particular hardness.

So that the curing of the polymer resin takes place with a technically and economically justifiable duration, depending on the polymer resin selected, it is necessary to have an appropriate starter in the form of a catalyst, better start catalyst, and / or an accelerator, also in the form of a catalyst, better acceleration -Catalyst to add to the polymer resin.

It is preferred for the polymer resin to use starter or peroxide catalyst as starting catalyst in a proportion of 0.1 to 5% by weight of the resin and / or accelerator or metal organyl catalyst as acceleration catalyst in a proportion of 0.01 to 5 Add% by weight of the resin. Peroxide Catalyst / starter, available under the name Trigonox 301, in an amount of 2% by weight, based on the resin, usable, generally amounts of 0.1 to 5% by weight being possible.

As an acceleration catalyst, for example, cobalt can be used in an amount of 0.2% by weight, based on the resin, of Occh-Soligen® Cobalt 6 from Borchers, with amounts of 0.01 to 2% by weight. % possible are.

The essential effect of the present invention is based on the formation of hybrid polymer structures in the resulting material, special properties being controllable through the targeted selection of the starting materials. The silicon compounds or compounds used in the process according to the invention from the group comprising silanes, siloxanes, silazanes and silicone resins play a special role in the formation of hybrid polymeric structures, since these compounds act as a kind of bridge between the different inorganic and / or contained therein through reactive reaction form or build up organic components of the raw mass. The wave-like or brain-turn-like structures already mentioned form a central element of these hybrid polymer structures.

• Alkylsilane, wie Methoxy-, Ethoxysilane oder Chlorsilane, Hexadecyltrimethoxysilan, kommerziell erhältlich unter der Bezeichnung Dynasylan 9116, Methyltrimethoxysilan, kommerziell erhältlich unter der Bezeichnung Dynasylan MTMS, M1-Trimethoxy, iso-Butyltriethoxysilan, erhältlich unter der Bezeichnung Dynasylan IBTEO, n-Octyltriethoxysilan, erhältlich unter der Bezeichnung Dynasylan OCTEO, iso-Butyltrimethoxysilan, erhältlich unter der Bezeichnung Dynasylan IBTMO, Methyltriethoxysilan, erhältlich unter der Bezeichnung Dynasylan MTES, Hexadecyltriethoxysilan und -trichlorosilan, Propyltriethoxysilan, erhältlich unter der Bezeichnung Dynasylan PTEO, Propyltriemethoxysilan, erhältlich unter der Bezeichnung Dynasylan PTMO, Octyltrimethoxysilan, erhältlich unter der Bezeichnung Dynasylan OCTMO, Octyltrichlorosilan, erhältlich unter der Bezeichnung Dynasylan OCTCS, Dodecyltrimethoxysilan und -triethoxysilan, Octadecyltrimethoxysilan und -ethoxysilan, Iso-Octyltrimethoxysilan und -ethoxysilan, n-Butyltriethoxysilan, n-Butyltrimethoxysilan.

The silicon compounds listed below are preferably used in the context of the present invention:

• Alkyl silanes, such as methoxy-, ethoxysilanes or chlorosilanes, hexadecyltrimethoxysilane, commercially available under the name Dynasylan 9116, methyltrimethoxysilane, commercially available under the name Dynasylan MTMS, M1-trimethoxy, iso-butyltriethoxysilane, available under the name Dynasylanilane IB, available under the name Dynasoxanilane IB, available under the name Dynasylanilane available under the name Dynasylan OCTEO, iso-butyltrimethoxysilane, available under the name Dynasylan IBTMO, methyltriethoxysilane, available under the name Dynasylan MTES, hexadecyltriethoxysilane and trichlorosilane, propyltriethoxysilane, available under the name Dynasylanysilaniloxysilane PTO , available under the name Dynasylan OCTMO, octyltrichlorosilane, available under the name Dynasylan OCTCS, dodecyltrimethoxysilane and triethoxysilane, octadecyltrimethoxysilane and ethoxysilane, iso-octyltrimethoxysilane and ethoxysilane, n-butyltriethoxysilane, n-butyltrimethoxysilane.

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

Aminosilanes and diamino silanes, such as 3-aminopropyltrimethoxysilane, available under the name Dynasylan AMMO, DOG-TM 100, 3-aminopropyltriethoxysylane, available under the name Dynasylan AM EO, DOG TE 100, Genosil GF 93, 2-aminoethyl-3-aminopropyltrimethoxysilane available under the name Dynasylan DAMO, DOG-DiaAmino TM 100, N- (n-butyl) -3-aminopropyltrimethoxysilane, triaminofunctional propyltrimethoxysilane, available under the name Dynasylan Triamo, and 3- (2-aminoethylamino) propyldimethoxymethylsilane DM-100.

Fluoroalkylsilanes, such as tridecafluoroooctyltriethoxysilane, available under the names Dynasylan 8261, Dynasylan 8263, Nonafluorohexyltrimethoxysilane and heptadecylfluorodecyltrimethoxysilane.

Epoxysilanes, acetoxysilanes and silicic acid esters, such as tetraethylorthosilicate, available under the name Dynasylan A, tetramethylorthosilicate, available under the name Dynasylan M, di-tert-butoxydiacetoxysilane, available under the name Dynasylan BDAC, and 3-glycidyloxypropyltrimethys available under the name Dynasylan Dynasylan GLYMO.

In the context of the invention particularly to be emphasized siloxanes and cyclosiloxanes are hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, polydimethylsiloxane and octamethyltrisiloxane, especially those with different scheduling erminierte Cl, for example, H, OH or siloxanes, as well as those having other chain lengths than those expressly mentioned.

Particularly noteworthy, especially when using alkylsilanes and / or alkylsiloxanes or generally siloxanes, is that the hybrid polymer material obtained has regenerative properties. Studies in this connection have shown that the artificial stone initially loses its shine after treatment with acetone or after abrasion with a household abrasive sponge, but regains its shine significantly after just 24 hours. If you then clean with water, the initial gloss value is practically reached again and in some cases even exceeded. This also takes place under conditions of artificial aging, in which the chemically or mechanically stressed sample was kept for 24 to 48 hours under UV radiation.

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

Examples of silazanes and polysilazanes which can be used according to the invention are the polysilazane which is commercially available under the name Durazane 1500 Rapid Cure and the silazane hexamethyldisilazane, HMDS.

Examples of silicone resins are methylphenyl silicone resin solution, commercially available under the name REN 80, methoxy-functional methylpolysiloxane 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.

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

In an independent particular embodiment of the present invention, one or more Si compounds are added in an amount between 0.1 and 40% by weight of the total mass and, if one or more Si compounds, only monomeric silanes with exclusively aliphatic substituents with a chain length of C ₁ to C ₃ are used, a catalyst in an amount of 0.1 to 10% by weight of the amount of the Si compound in addition to the Si compound. This addition of catalyst is basically independent of the catalyst already contained in the polymer resin and is used exclusively to increase the activity of the Si atoms obtained in these compounds, as a result of which they are able to form corresponding linkages with the solid with the formation of covalent bonds via oxygen atoms. For example, greater hardness of the hybrid polymer material produced can be achieved, but other improvements are also possible. In the case of Si compounds exclusively with aliphatic substituents with a chain length of 1 to 3 carbon atoms, only by adding a catalyst. In the presence of Si compounds with at least one substituent with a chain length that is greater than 4 carbon atoms, such addition of catalyst is not necessary. Si compounds with at least one aromatic substituent can also be used in the context of the present invention without addition of catalyst.

In principle, organometallic catalysts are used as catalysts for increasing the activity of these Si compounds with only C ₁ - to C ₃ substituents, in particular commercially available organometallic catalysts, since they are comparatively cheap and easy to obtain in sufficient measure and in sufficient quality. Particularly good results are obtained with metal centers with organic ligands of the elements titanium, zirconium, cobalt, copper, zinc, tin, iron, manganese, magnesium, aluminum and boron. Metal organyl catalysts which contain the metals mentioned are therefore preferred. However, elements such as vanadium, chromium, nickel, molybdenum, silver, gallium, germanium and bismuth also provide sufficiently good results, usually only using a type of catalyst for these Si compounds.

Metal organyl catalysts with alkyl groups are easy to process, and can be present both in the n form and in all iso forms.

Examples of some metal organyl catalysts based on carboxylic acids are octoates, laurates, oxalates, decanates and naphthenates.

Specific examples of such metal organyl catalysts are cobalt (II) -2-ethylhexanoate, tin (II) -2-ethylhexanoate, dibutyltin dilaurate, dioctyltin dilaurate, zinc acteate, zinc oxalate, zirconium octeate, zinc (II) -2-ethylhexanoate, copper oleate and copper naphthenate.

Further ligands which can be used within the scope of the present invention and are therefore important are acetate, acetylacetate, oleate and carboxylate, for example dibutyltin dicarboxylate, zinc acetate, cobalt acetate, bismuth carboxylate.

The acetylacetonates represent a particularly important group with numerous readily available and usable representatives. Particular examples are 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 , vanadylacetylacetonate, V (O) (acac) ₂ and zinc acetylacetonate, Zn ( acac) ₂ to show just a few.

Another important group that can be used as catalysts are alcoholates and borates. Particularly noteworthy examples of particularly good catalysts are titanium iso-propoxide, titanium tetrabutanolate, zirconium-n-propoxide, aluminum iso-propoxide and triisopropyl borate. In the context of the present invention, these are preferred as catalysts in a range from 0.01% by weight to 5 wt .-% used.

With regard to these, it should be noted that their use is particularly preferred because they can be used not only as catalysts, but generally also to increase the hardness of the hybrid polymer material according to the invention if they are used in larger amounts in the range of 0.5% by weight. % to 30% by weight of the total mass of the components of the raw material are used, in particular in a range from 5% by weight to 15% by weight. In addition, aluminum, titanium and zirconium compounds generally improve the mechanical and / or chemical resistance of the workpieces. In particular, they can also be used in combination of two or more and, with regard to the reactions to the hybrid polymers, lead to particularly good results if they are added directly to the solids or solids used before they are combined with other constituents of the raw material.

These catalysts and / or accelerators can also be used specifically for functionalizing the surfaces. For example, surfaces of hybrid polymer materials that contain catalysts with Zn, Sn or Cu components have an antibacterial, antifungal, algicidal and / or antiviral effect.

To increase the reactivity and to control the Si compound, it is possible in an independent embodiment of the process according to the invention to add acids or bases, preferably in a proportion in the range from 0.5 to 10% by weight, of the silicon compound mentioned. This produces hydrolysates and / or condensates of the silicon compounds used, which react with solid and polymer resin to form essentially covalent bonds, but this reaction also takes place in principle without the addition of acid or base.

After adding and / or mixing the Si compound with the mixture of solid and polymer resin with the catalysts which may be required, mixing is continued until a homogeneous mass is obtained. As is generally known, this raw mass is shaped, compressed and subjected to curing at room temperature to 250 ° C. or 350 ° C., preferably at 50 to 190 ° C., and / or UV radiation. Activation by a short heat treatment, for example 10 minutes at 150 ° C, and subsequent curing at room temperature is also possible and provides excellent results.

For the sake of completeness, the auxiliaries are briefly discussed. These include all the starters, catalysts, colorants and stabilizers that are generally known and commonly used in the field. Support grain and fill grain, which the person skilled in the art uses to vary the density and hardness of the process product, are also included. Since their use and application is familiar to a person skilled in the art, they are not dealt with in more detail here.

It has proven to be particularly advantageous that the process according to the invention can be varied and adapted with regard to the design of the process steps, the use of the starting compounds and the available product qualities. This is particularly economically advantageous and enables adaptation to the requirements for different areas of use of the artificial stone to be produced.

In principle, there are various possible variations, each of which represents an independent embodiment of the method according to the invention.

In a first variant, the procedure is as already described herein, and the one or more Si compounds are / are mixed with a raw material made from solid, polymer resin and auxiliaries in order to obtain the modified raw material, which is then applied, compressed, converted in the form or as a mass carpet and is cured.

According to a second variant, the Si compound and reactive polymer are mixed first, if appropriate with the addition of appropriate auxiliaries, and then combined with the prepared solids.

According to a third variant, first Si compound, solid and auxiliary substances are combined and then polymer is added and mixed again.

In a fourth variant, a raw mass of polymer and solid is produced as usual, spread out as a mass carpet or shaped. Then the one or more Si compounds are applied to the raw mass. The application is effected in particular by spraying on, but can also be carried out in other ways, for example printing, pouring or flooding. This is followed by compaction, the pressure or pressure distributing the one or more Si compounds in the spatially upper region and deep in the raw material which has already been formed.

In principle, the Si compounds can also be used in a suitable solvent in the process according to the invention and this is advantageous in cases in which these silicon compounds are usually offered commercially in solution in a solvent. It is particularly advantageous to use these compounds in a solvent if their viscosity is to be reduced for better processability, for example when spraying. It can also be advantageous to bring in dissolved polymer, which leads to a better distribution of the same and thereby favors the formation of hybrid polymer structures.

According to a further, fifth variant of the method according to the invention, the one or more Si compounds are applied in a smaller amount than in the variant described above or after the raw material has been precompressed.

These variants of the method according to the invention differ in part in the products resulting from the individual variants, which, although to a different extent, basically show the properties already described. Common to all is the fact that the release of health-endangering quartz fractions can be safely avoided both in the manufacture and in the processing of the artificial stone according to the invention. It does not matter whether this is done because the starting materials are selected so that they are without exception quartz-free or low-quartz starting materials, or whether quartz or quartz-containing materials are used in combination with thermoplastic solids or Teflon, since any fine quartz particles that are produced the processing, especially when cutting, are encased and / or bound and not released as dust.

In the hybrid polymer material obtainable according to the first three process variants, the entire raw mass is modified by adding the one or more Si compounds and is uniform and homogeneous. It is particularly characterized by good hardness and chemical resistance, hydrophobicity and density.

The situation with the hybrid polymer material obtainable according to the fourth variant is similar and the advantages described in the first variant are also present with only slight deviations. Since in this variant there is usually no absolutely homogeneous distribution of the added silicon compound in the raw material, the smallest defects or hairline cracks in the nm or pm range can occur. However, this is justifiable in many areas of application, and the advantages gained outweigh these minor disadvantages.

The hybrid polymer material obtained according to the last-described process variant shows clear differences in properties from the other two variants, because the raw material that has been shaped is only modified on the surface and the artificial stone on the modified surface shows greater hardness and chemical resistance and hydrophobicity, while the lower side is not modified and on this side rather has properties such as a cured polymer resin from the prior art.

This material is for example for kitchen worktops, wall; Floor, facade tiles / plates, 3-D castings, sinks, kitchen sinks or shower trays are particularly suitable, the surfaces of which are exposed to a variety of stresses, while the opposite surface, for example the underside of a worktop, is not exposed to these stresses.

These advantageous properties of the process products obtainable by the process according to the invention which can be achieved according to the invention result from the three-dimensional crosslinking within the entire substrate. Here, not only do the resins predominantly crosslink with one another, as is the case with simple curing of polymer resins from the prior art. Rather, according to the invention, crosslinking takes place between an organic portion, the reactive polymer resin, the silicon compound and the and / or the other solids.

According to a special aspect of the present invention, the inorganic solids, regardless of whether they are quartz, quartz-containing, low-quartz or quartz-free solids, and the organic constituents, particles and / or solids of another type are also chemically bound within the matrix, so that this during further processing steps such as Polishing, cutting, separating and roughing, as well as in daily use, can no longer be torn from the matrix, or only with great difficulty, and thus no new open pores and / or holes arise 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 there is no need to fear the occurrence of correspondingly fine-grained quartz dust even during processing, since these can be combined with other solids in a suitable combination and are not released as dust. There is also the advantage that the hybrid polymer structures which form in accordance with the invention grow particularly well in cavities, be they pores or gaps, and therefore at least some, in part also completely, of fine fractions of solids can be dispensed with.

A particular advantage of the invention is thus a stable binding of all components in the substrate to one another, as well as the independent filling or overgrowth of the pores, defects and / or cracks that are still open before the hardening process by 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 ongoing reactions between the components contained in the modified raw material, in particular between the silicon compounds used or their hydrolyzates and those formed at least partially in situ under the reaction conditions described later and / or condensates, as well as the inorganic and / or organic constituents, particles and fillers.

The invention makes specific use of the fact that the starting compounds and materials used react with one another to form hybrid structures, hybrid polymers, by forming chemical, covalent bonds or bonds with a high covalent bond fraction. Due to the growth of the molecules and their cross-linking, even small cavities in the nm range are closed or grow, and glass-like or massive, hard, partly stone-like structures are formed, which in turn are very mechanically and chemically stable.

Depending on the use of the Si compounds and / or their hydrolyzates and or condensates, the molecular size and the molecular growth can be controlled in a defined manner. Ideally, short-, medium- and long-chain silanes are used, optionally siloxanes, polysiloxanes, siliazanes or polysilazanes or their hydrolysates and / or condensates, but also silicone resins. These lead to the densest packing and to a strong spherical, or “cloudy”, interwoven molecular growth and, connected with or as a result of this, to a self-closing of the pore spaces, both between solids and within them an additional interlinking during the reaction and growth process. This is of particular importance if porous or brittle, particulate inorganic or organic compounds or fillers are to be used. The hybrid polymer structures that grow into the pores of the fillers interlock with them in addition to the chemical bonding and thus have a further stabilizing effect.

For this reason, cheaper, quartz-free fillers can also be used, for example, usually highly porous and less solid fillers, without adversely affecting the properties of the end product. Here, in particular, quartz-free chamottes and / or quartz-free ceramic fragments are to be mentioned, materials which are extremely inexpensive to obtain. In this context, plastic recyclates and artificial stone recyclates, regardless of their origin, are of particular importance because they enable reuse and / or further processing of production waste that is inevitable.

It has also been shown that, because of the growth of the polymers, smaller amounts of resin can be used. This is of particular interest since the resin in the material composition represents a particularly price-determining component.

In the case of very open-pore fillers, for example, 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 from 10 nm to 30 μm, the pores are largely filled, at least in part of the filler.

Furthermore, ideally adhesion-promoting reactive groups are selected on the outer sides of the hybrid structures, which crosslink with the fillers or pigments likewise introduced. In general, reactive functional groups such as amino carbonyl or epoxy groups can be used as reactive groups. In this way, there is a very advantageous improvement in adhesion to inorganic fillers from the hybrid polymer base. There is a three-dimensional crosslinking and matrix formation, wherein a pre-silanization of the inorganic particles in the matrix, as is at least partially carried out in the prior art, can be omitted.

Because of the ingrowth of the hybrid polymer structures described, it is also possible to use porous solids in a targeted manner. This can even be particularly advantageous, since the wax-in and interlocking of the hybrid polymer structures enables a particularly firm integration of these porous solids into the matrix formed.

In their simplest configuration, the hybrid polymers obtained in this way already have structures which are built up on a molecular level from inorganic and organic components and are chemically linked to one another. They therefore have properties of organic polymers on the one hand, but also interesting properties of inorganic materials on the other. In this way, substrates can be created which, on the one hand, have a high degree of flexibility, such as polymers, and yet can be glass-like hard and chemically resistant, like inorganic materials.

Since these hybrid polymers have no or practically imperceptible phase boundaries, excellent optical properties also result in the products produced by the process according to the invention.

The following examples give some of the combinations of components which are possible according to the invention and which can be used to produce hybrid polymer materials according to the invention. These only show a small selection of possible combinations:

Example 1 (metal-containing hybrid polymer material)

Thermoplastic polyester PET (10 µ - 500 µm) 56.45% Titanium isopropoxide 5.64% Zircon-n-propoxide 5.64% Epoxy resin 16.93% Peroxide starter (2% with respect to epoxy resin) 0.34% Copper catalyst (0.2% with respect to epoxy resin) 0.04% Polydimethylsiloxane 3.30% Polydimethylsiloxane (OH-terminated) 0.37% Stainless steel shavings / powder (10 µm to 50 µm) 11.29%

Example 2 (Hybrid polymer material containing natural fibers)

Polyamide (PA 50 µ - 600 µm) 55.05% Titanium isopropoxide 11.00% Phenolic resin 16.52% Peroxide starter (2% with respect to phenolic resin) 0.33% Zinc catalyst (0.2% with respect 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% Zircon-n-propoxide 5.50% Unsaturated polyester resin 16.52% Peroxide starter (2% with respect to polyester resin) 0.33% Cobalt catalyst (0.2% based on 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 (Hybrid polymer material containing carbon fiber and mineral)

Polyimide (PEI 75 µm to 400 µm) 41.68% Polycarbonate 12.18% Titanium tetrabutanolate 10.78% Melamine resin 16.16% Formic acid 50% (2.17% for melamine resin) 0.35% Polydimethylsiloxane 2.42% Polydimethylsiloxane (H-terminated) 0.27% Alumina powder (10 µm - 40 µm) 10.77% Carbon fiber (10 µm - 150 µm) 5.39%

Example 5 (Hybrid polymer material containing Al ₂ O ₃ and plastic)

Acrylonitrile-butadiene-styrene copolymer (ABS 30 µm to 600 µm) 55.05% Titanium tetrabutanolate 5.50% Zircon-n-propoxide 5.50% Unsaturated polyester resin 16.52% Peroxide starter (2% with respect to polyester resin) 0.33% Tin catalyst (0.2% based on polyester resin) 0.03% Polydimethylsiloxane 2.48% Hexadecyltrimethoxysilane 0.28% Alumina 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% Polyaryl ether ketone (PEEK 300 µm to 750 µm) 13.36 Zircon-n-propoxide 11.32% Epoxy resin 16.98% Peroxide starter (2.18% with respect 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-Part 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% Zircon-n-propoxide 8.71% Unsaturated polyester resin 17.13% Peroxide starter (3.33% based on polyester resin) 0.57% Cobalt catalyst (0.33% based on 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% based on polyester resin) 0.11% Cobalt catalyst (0.07% based on 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 µ - 1500 µ m) 31.12% Thermoplastic polyester (PET 90 µ - 480 µ m) 26.37% Polyphthalamide (PPA 60 µm 180 µm) 4.19% Titanium isopropoxide 5.90% Unsaturated polyester resin 21.30% Peroxide starter (0.78% based on polyester resin) 0.17% Nickel catalyst (0.08% based on polyester resin) 0.02% PTFE (6 µm - 20 µm) 7.76 Polydimethylsiloxane-OH terminated 1.17% Hexadecyltrimethoxysilane 1.00% Urethane acrylate resin 1.00% Polymethyl methacrylate (350 µm - 1 mm) 34.35% Plastic recyclate (PET 20 µm to 250 µm) 34.35% Aluminum isopropoxide 5.73% Zircon ethoxide 5.73% Vinyl ester resins 17.18% Peroxide starter (2.0% with respect to vinyl ester resin) 0.34% Iron catalyst (0.2% with respect 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 µ - 500 µ m) 62.98% Wood fiber / shavings (1µm - 100 µm 5.73% Titanium isopropoxide 4.73% Zircon-n-propoxide 4.73% Aluminum isopropoxide 2.00% Unsaturated polyester resin 14.18% Epoxy resin 3.00% Peroxide starter (2.40% with respect to polyester resin) 0.34% Manganese catalyst (0.2% based on polyester resin) 0.03% Polydimethylsiloxane 2.29%

• 1 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs mit einem mineralischen Feststoff und PET, auf der eine vollständige Umhüllung eines Al₂O₃-Partikels mit hybridpolymeren Strukturen zu erkennen ist;
• 2 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs wie in 1 mit einem aufgeschnittenen Al₂O₃-Partikel;
• 3 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs mit PET als Feststoff;
• 4 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs wie in 4 in stärkerer Vergrößerung;
• 5 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs mit feineren PET-Fraktionen;
• 6 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs mit Kunststoff-Recyclat;
• 7 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs wie in 6 in stärkerer Vergrößerung;
• 8 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs mit Hanffasern;
• 9 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs wie in 8 in stärkerer Vergrößerung;
• 10 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs mit Holz;
• 11 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs wie in 10 mit geringerer Vergrößerung;
• 12 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs mit Kohlefaser;
• 13 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs wie in 12 in stärkerer Vergrößerung;
• 14 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs mit einem Pulverharz;
• 15 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs mit Stahl;
• 16 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs mit Steinwolle;
• 17 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs mit Tretrafluorethylen und
• 18 eine Elektronenmikroskop-Aufnahme eines Hybridpolymer-Werkstoffs, der mit Quarz, aber ohne Si-Verbindungen hergestellt wurde.

The invention described above is explained in more detail below with reference to the accompanying figures. Show it:

• 1 an electron microscope image of a hybrid polymer material with a mineral solid and PET, on which a complete coating of an Al ₂ O ₃ particle with hybrid polymer structures can be seen;
• 2nd an electron microscope image of a hybrid polymer material as in 1 with a cut Al ₂ O ₃ particle;
• 3rd an electron microscope image of a hybrid polymer material with PET as a solid;
• 4th an electron microscope image of a hybrid polymer material as in 4th in higher magnification;
• 5 an electron microscope image of a hybrid polymer material with finer PET fractions;
• 6 an electron microscope image of a hybrid polymer material with plastic recyclate;
• 7 an electron microscope image of a hybrid polymer material as in 6 in higher magnification;
• 8th an electron microscope image of a hybrid polymer material with hemp fibers;
• 9 an electron microscope image of a hybrid polymer material as in 8th in higher magnification;
• 10th an electron microscope image of a hybrid polymer material with wood;
• 11 an electron microscope image of a hybrid polymer material as in 10th with lower magnification;
• 12th an electron microscope image of a hybrid polymer material with carbon fiber;
• 13 an electron microscope image of a hybrid polymer material as in 12th in higher magnification;
• 14 an electron microscope image of a hybrid polymer material with a powder resin;
• 15 an electron microscope image of a hybrid polymer material with steel;
• 16 an electron microscope image of a hybrid polymer material with rock wool;
• 17th an electron microscope image of a hybrid polymer material with tretrafluoroethylene and
• 18th an electron micrograph of a hybrid polymer material made with quartz but without Si compounds.

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 inventive method. The mineral component, Al ₂ O ₃ , encased by and incorporated into hybrid polymer structures can be clearly seen in the center of the picture. 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 connection. This is in 2nd can be seen particularly well, a split Al ₂ O ₃ grain being clearly visible in this image in the lower region of the image. Wave-like structures seem to grow from its edge, without any recognizable phase boundaries. The characteristic of a reactive connection. In the left part of the picture, slightly below the center of the picture, you can see that the hybrid polymer has developed right into a crack in the grain. The line-like structures or faults arise due to the resulting local internal compressive stresses.

In the electron microscope image in 3rd a hybrid polymer material can be seen, in the production of which only polyethylene terephthalate (PET) was used as a solid, which can be seen as a sharp-edged, semicircular structure. Here too, the wave-like structures can be recognized without the formation of a phase boundary.

The situation described above is clearer in the 4th to recognize the opposite 3rd has twice the magnification.

Also 5 shows a hybrid polymer material that was produced exclusively with PET as a solid, but this time with a finer fraction. This was obtained by crushing with a hand blender. The wave-like hybrid polymer structures are particularly recognizable.

6 shows a hybrid polymer material that contains a plastic recyclate, a shredded laboratory beaker. Here too there are wave-shaped, hybrid polymer structures, but no discernible phase boundaries. This in a larger magnification again 7 to see a section from the center of the picture 6 shows.

In the 8th and 9 the particularly good integration of hemp fibers in the hybrid polymer material is shown. Shows particularly well 9 the reactive connection of the hemp fiber through the seamless course between the fiber and the polymer structure, without even a hint of a phase boundary.

The 10th and 11 show the advantageous incorporation of a wood particle in the hybrid polymer material according to the invention in different magnifications, the characteristic undulating structures again catching the eye.

12th shows a hybrid polymer material made with carbon fiber and its excellent integration, but no phase boundaries. The part of the picture at the top of the picture in the middle is enlarged in 13 reproduced and you can clearly see the front side of a • broken fiber, wavy, hybrid polymer structures and again no phase boundaries.

The in 14 The hybrid polymer material shown was made with a powder resin as a solid and shows extremely fine and dense wavy structures.

In 15 a hybrid polymer material is shown, for the manufacture of which stainless steel in the form of milling and drilling chips was used. This steel was used as it is, that is, with residual lubricant or lubricating oil.

At the in 16 The diagonal elevation is a rock wool fiber, more precisely basalt wool fiber, which is so well integrated that it is almost no longer recognizable. In this figure, too, the characteristic wavy structures can be seen, but no phase boundary.

In 17th is a hybrid polymer material with very fine Teflon shown. These form part of the cloudy structure in the left part of the image, the fine-particle particles requiring that the hybrid polymeric structure portions be recognized as cloud-shaped at this resolution.

Compared to the previous figures, in 18th shown a material that is made with quartz, but without Si compound. The larger, smooth and sharp-edged structures show the quartz and the porous or rough-appearing areas of hardened polymer resin. In contrast to the other electron microscope images, the individual components can be clearly distinguished from one another and undulating structures which characterize the hybrid polymers according to the invention are completely absent.

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

Claims (10)

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, fibers in combination with the reactive polymer resin and one or more Si compounds and auxiliaries being a raw material form, the raw mass is compacted and subsequently converted and cured. Procedure according to Claim 1 , characterized in that the fibers are used sorted or as a mixture of different fibers and / or in combination with one or more other solids. Procedure according to Claim 1 or 2nd , characterized in that the fibers are selected from the group consisting of vegetable fibers, animal fibers and synthetic fibers and mixtures thereof. Procedure according to one of the Claims 1 to 3rd , characterized in that the fibers have a length in the range from 0.1 µm to 10 mm, in particular 10 µm to 2 mm. Method according to one of the preceding claims, characterized in that the fibers are contained in the raw material in a proportion of 0.1% by weight to 40% by weight, in particular 0.5% by weight to 25% by weight. %. Method according to one of the preceding claims, characterized in that the or the other solids are selected from the group consisting of thermoplastics, thermosets, elastomers, plastic recyclates, artificial stone recyclates, vegetable solids, natural minerals, rocks, ores, synthetic minerals, ceramics, metal oxides and metals and / or the further solids or solids are used simultaneously in one or more fractions of different sizes and / or different types. Method according to one of the preceding claims, characterized in that the raw mass further contains zirconium, aluminum and / or titanium compounds. Procedure according to Claim 7 , characterized in that the zirconium, aluminum and / or titanium compounds are soluble titanium compounds, especially their alkoxides, in particular their ethoxides, propoxides and / or butoxides. Hybrid polymer material obtainable by a process according to one of the preceding claims. Hybrid polymer material after Claim 9 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 sink or sink, a shower tray, a wall or facade element, an insulation element or a dry construction element.

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