WO2016166219A1

WO2016166219A1 - Hybrid silicic acid material, in particular for retaining anthropogenic impurities from an aquatic environment

Info

Publication number: WO2016166219A1
Application number: PCT/EP2016/058235
Authority: WO
Inventors: Katrin Schuhen
Original assignee: Universität Koblenz-Landau
Priority date: 2015-04-17
Filing date: 2016-04-14
Publication date: 2016-10-20

Abstract

The invention relates to a hybrid silicic acid material, in particular for removing anthropogenic impurities from water and/or for detecting anthropogenic impurities from water, comprising - structural units A, which each have the formula (I): wherein Z is a functional group, preferably selected from the group comprising carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amine group, amide group, carbon-carbon double bond, carbon-carbon triple bond, and combinations thereof, or a hetero atom, - structural units B, which each have the formula (II): R' = R'' = R''', R' = R'' ≠ R''', R' ≠ R'' = R''' or R' ≠ R''≠ R''' and R', R'' and R''' independently of each other are a divalent organic radical and n is an integer from 1 to 11, particularly 1 to 7, preferably 1 to 3, particularly preferably 1, and/or-structural units C, each of which have the formula (III#). The invention further relates to precursors, a method for producing a hybrid silicic acid material, a filter device, a cartridge, a discharge device, a contact pool, a method for the purification of water, a method for water analysis as well as to uses of the hybrid silicic acid material.

Description

Hybrid silica material, in particular for fixing anthropoqene contaminants from an aquatic environment

AREA OF APPLICATION AND PRIOR ART

The invention relates to a hybrid silicic acid material, precursors, a method for producing a hybrid silicic acid material, a filter device, a cartridge, a discharge device, a contact basin, a method for purifying water, a method for analyzing water and uses of the hybrid silica material.

It is only recently that the effects of anthropogenic pollution or stressors on the environment have been scientifically investigated: anthropogenic stressors by definition describe substances that enter the ecosystem through unnatural man-made processes and that disturb and / or negatively affect the natural balance of the ecosystem. One differentiates between inorganic and organic trace substance inputs as well as entries through micro plastics. Although the dangers of such nano- and micropollutants in the water for organisms and the aquatic system are now known, the cleaning methods are still in need of improvement. In particular, the detection methods for organic stressors are still in the development phase. In summary, three causes of water pollution caused by anthropogenic stressors can be cited, which illustrate the need for action to reduce the strain situation:

Industrialization: The production of chemical and pharmaceutical products requires water, which is put under pressure in synthesis processes. A purification usually takes place, but not all entries, for example plastic particles made of nonwoven clothing, can be removed.

Medicines and increased life expectancy of the people: The number of approved drugs in Germany is growing steadily and is estimated at about 3,000. Of these, only 100 active substances have been detected in drinking water. Drug use is particularly high in the elderly and, moreover, the proportion of people over the age of 60 has increased to 26% of the population. In other words, from 2004 to 2012, human phacoaconal consumption increased by around 45%. After their intended use, medicines usually enter the sewage system via excreta. Improper disposal: If waste is not disposed of properly, there is a risk to the environment and the water cycle. The improper disposal of medicines via sanitary facilities is also a problem because the drugs reach this route in high concentrations directly into the water cycle.

Activated carbon is often used to remove toxically relevant and undesirable trace substances, since it is particularly well suited due to its large surface structure. After use, the activated carbon is basically reusable and does not consume. The disadvantage, however, is that there is the possibility of desorption due to the adsorptive fixation of the trace substances.

The ozonization, which is normally used in the sewage treatment plant to disinfect the water, can also be used to remove trace substances. For this purpose, already treated water is brought into contact with ozone in a closed system. The effectiveness of ozonization has been proven, but it has, among other things, the disadvantage of the high energy demand for ozone production and the partially toxic reaction products.

The importance of membrane bioreactors (MBR) in biological wastewater treatment has steadily increased in recent years. It consists of a natural bioreactor with sewage sludge and various membranes for the filtration of dissolved substances. The disadvantage is that the filtration is only possible from a particle size of 0.05 μηι and in addition to high personnel costs and high equipment costs needed. A particular disadvantage here is that the filtration of micropollutants and drug residues succeed only inadequately.

Reverse osmosis is a process which is always used where highest purity is required. In this process, water loaded with a pump is forced through a synthetic semipermeable reverse osmosis membrane. This does not let the water molecules through, but impurities of the input water. Disadvantages of this filter technology: high volumes of wastewater (2-10 liters of tap water for 1 liter of osmosis water) and high energy requirements of the pumps and application only at the end user. Therefore, this method is unsuitable for the purification of surface waters.

The measuring methods for the identification of pharmacologically active substances by means of SPME (Solid Phase Microextraction) have only been carried out under controlled laboratory conditions and exist only in the form of specific individual analyzes SPME technology as a possible certification technique for organic stressors in waters of any concentration represents an immense challenge. Essentially, only organic stressors should be detected and no positively organic or naturally occurring compounds in the water.

From the publication by Michael Arkas and Dimitri Tsiourvas (Organic / inorganic hybrid nanospheres based on hyperbranched poly (ethyleneimine, Journal of Hazardous Materials (2009) Vol. 170, 35-42) encapsulated into silica for the sorption of toxic metal ions and polycyclic aromatic hydrocarbons from water) are known organic / inorganic hybrid silicanospheres, which can be used in wastewater treatment, with a focus on inorganic and organic contaminants.

The publication by Moscofian et al. (Removal of reactive dyes using organofunctionalized mesoporous silicas, Journal of Porous Materials (2013) Vol. 20, 1179-1 188) discloses a mesoporous inorganic / organic hybrids with mono- or bifunctional chains anchored on a silica support are. Using this material, the removal, which is based on adsorptive forces, was investigated by reactive dyes.

It is disclosed in the publication by Molina et al. (Tri-ureasil gel as a multifunctional organic inorganic hybrid matrix, Polymer Chemistry (2013) Issue 4, 1575-1582) a transparent, flexible, rubbery and insoluble organic-inorganic hybrid material, which inter alia for the removal of dyes by means of adsorptive forces suitable.

The publication by Lim et al. (Membrane assisted micro-solid phase extraction of pharmaceuticals with amino and urea-grafted silica gel, Journal of Chromatography A, (2013) Vol. 1316, 8-14) discloses a polar sorbent which is suitable for drugs such as amitriptyline ( Ami), carbamazepine (Cbz), ketoprofen (Ket) and diclofenac (Dfn).

The subject of US 2014/0186250 A1 (Applicant United States of America, Vanderbilt University) is an adsorptive material comprising a porous inorganic oxide material and at least one carbonyl group. Further, it is disclosed that the adsorptive material is suitable for adsorbing molecules from a liquid.

DE 10 2008 041 477 A1 (Applicant Wacker Chemie AG) discloses a porous membrane of organopolysiloxane copolymers which is suitable for the separation of mixtures of substances. The dissertation by Tusnelda E. Doli entitled "Photochemical and Photocatalytic Degradation of Carbamazepine, Ciofibrinic Acid, lomeprol and lopromid" (Volume 42, Series of the Department of Water Chemistry and the DVGW Research Center at the Engler-Bunte Institute of the University of Karlsruhe (TH)) , Karlsruhe 2004, publisher Fritz H. Frimmel) is concerned with the photochemical and photocatalytic degradation of pharmaceuticals.

Content of the dissertation by Andrea Butzen (née Hieb from Kevelaer) entitled "Development of methods for the determination of iodinated X-ray contrast media in different aqueous matrices by HPLC-MS" (University of Duisburg-Essen, 2007) are analytical methods, whereby the influence of an organic matrix on the quality of the measurement is examined.

The final report of Glasmeyer et al. entitled "Micropollutants in Surface Waters: Identifying the Need for Action in Municipal Wastewater Treatment Plants" (University of Osnabrück, 1 November 201 1) deals with studies simulating the levels of micropollutants in surface waters.

TASK AND SOLUTION

It is an object of the present invention to provide materials which are suitable for fixing anthropogenic impurities and, in particular, circumvent problems known from the prior art. In particular, the materials should be able to not only remove a single type of contaminant from water, but preferably allow the simultaneous removal of several different types of contaminants from water. A further object of the present invention is to provide precursors, in particular for the production of the materials, and methods of producing the materials, as well as a method for purifying and for examining water.

This object is achieved by a hybrid silicic acid material having the features of independent claim 1, an organosilicon precursor having the features of independent claim 12, a modified precursor according to claim 16, a precursor mixture having the features of claim 17, a process for producing a hybrid silicic acid material according to claim 18, a hybrid silica material according to claim 19 and a filter device, a cartridge or a contact basin according to claim 20. Preferred embodiments are defined in the subclaims. The wording of all claims is hereby incorporated by express reference into the content of the present specification. Other subjects of the invention, which solve the problem underlying the invention, are disclosed in the general description.

According to a first aspect, the invention relates to a hybrid silica material.

The hybrid silicic acid material is preferably provided for fixing, in particular covalent, fixation of impurities.

The hybrid silica material is particularly preferably provided for removing impurities from water and / or for detecting impurities from water.

The impurities are usually anthropogenic, i. man-made, impurities. Since impurities in water mean a load on the water, the impurities in this context are also often referred to as stressors.

The water may basically be groundwater or surface water, such as running water, standing water, sewage or drinking water.

The impurities may basically be organic impurities, inorganic impurities and / or plastic particles.

The organic impurities are preferably organic trace substances and the inorganic impurities are preferably inorganic trace substances.

The organic impurities may be selected from the group comprising industrial chemicals, industrial synthesis products, pharmaceuticals such as human and / or veterinary pharmaceuticals, medicaments, conjugates, intermediates (such as metabolites), degradation products and mixtures thereof.

The inorganic impurities are preferably metals, in particular heavy metals.

The plastic particles can be plastic particles with a diameter in the millimeter, nanometer or micrometer range. The plastic particles are preferably plastic particles with a diameter in the micrometer range, ie, so-called microplastic articles, in particular with a diameter of less than 50 μm. Microplastic articles are in the Usually the result of aging processes, in particular of mechanical or induced, for example, solar radiation induced, aging processes.

The hybrid silicic acid material according to the invention is characterized in particular by the following features:

Structural units A, which each have the formula I:

Formula I

in which

Z represents a functional group or a heteroatom, structural units B which have the formula II:

Formula I I

in which

R '= R "= R'", R '= R "φ R'", R '+ R "= R'" or R 'φ R "R'" and R ', R "and R'" are each independently of one another are a divalent organic radical and

n is an integer from 1 to 1, in particular 1 to 7, preferably 1 to 3, particularly preferably 1, and / or

Structural units C, which each have the formula III:

Formula III being

R has a divalent cyclic aliphatic radical or, which is preferred according to the invention, such a radical.

For the purposes of the present invention, the expression "hybrid silicic acid material", in particular "hybrid silica gel" is preferably understood to mean a silicic acid material, in particular a silica gel, whose preparation is a condensation, preferably polycondensation, of precursors with terminal, ie terminal, alkoxysilyl groups and / or or alkoxyalkylsily groups or which can be prepared or can be prepared by means of a condensation, preferably polycondensation, of precursors (precursor compounds) with terminal, ie terminal, alkoxysilyl groups and / or alkoxyalkylsily groups. Such a hybrid silica material, in particular hybrid silica gel, is preferably characterized in that it has tetrahedral structural units each having a silicon atom as the central atom, wherein the silicon atom - depending on the type of precursors used for the preparation of the hybrid silica material, in particular hybrid silica gel (trialkoxysilyl-, dialkoxymonoalkylsilyl - and / or monoalkoxydialkylsilymodifizierte precursors) in the tetrahedral structural units with three oxygen atoms and one carbon atom, two oxygen atoms and two carbon atoms or an oxygen atom and three carbon atoms is covalently bonded. The oxygen atoms (or the oxygen atom) are in each case covalently bonded to a silicon atom of an adjacent tetrahedral structural unit. The carbon atom (or the carbon atoms) is (are) part of an organic radical. With regard to the organic radicals, reference is made to the statements made below. Because of the silicon atoms thus contained in the hybrid silica material, in particular hybrid silica gel, as well as silicon-oxygen-silicon structural units (-Si-O-Si) and the organic radicals contained in the hybrid silica material, in particular hybrid silica gel, the hybrid silicic acid material according to the invention, in particular hybrid silica gel, can also be inorganic -organic hybrid silica material, in particular hybrid silica gel. In particular, that can Hybrid silicic acid material, in particular hybrid silica gel, may be referred to as a kind of inorganic-organic fixation material for impurities.

For the purposes of the present invention, the term "structural unit" or "structural units" is intended to mean a characteristic part of a hybrid silica material, hybrid material or precursor according to the invention. In this case, a smaller structural unit / smaller structural units may be part of a larger structural unit / of larger structural units of the hybrid silica material, hybrid material or Präkurosr, which in itself is also characteristic of the hybrid silica material, the hybrid material or the precursor / are.

The structural units A and C thus represent urea substance residues or groups-containing structural units, while the structural units B ring structures having three nitrogen atoms, preferably 1, 3,5-triazinane residues or groups (hexahydro-1, 3,5-triazine Residues or groups).

The hybrid silica material according to the invention is characterized in particular by the following advantages

> The hybrid silica material allows with particular advantage a covalent fixation of impurities. The risk of desorption thus does not exist. As a result, a reliable and particularly permanent fixation is possible, which is of particular value, in particular with regard to a sustainable water purification.

A covalent fixation is possible in particular via the structural units A and structural units C.

Thus, the structural units A allow with particular advantage a covalent fixation of organic impurities, in particular organic trace substances. The fixation is preferably based on condensation reactions and click-chemical reactions, in particular in a pH range of 6.4 to 8.5. The fixation is based on a reaction between the urea residue and the respective contaminant.

The nitrogen atoms of the structural units B allow, with particular advantage, a chelation or complex binding of inorganic impurities, in particular heavy metals. Due to the number of nitrogen atoms, a triple coordination and thus a permanent fixation of the inorganic impurities is possible. The structural units C are, as will be discussed in more detail below, preferably involved in the construction of tubular structures which are designed such that they can locate, ie capture, plastic particles, in particular microplastic particles.

> The lack of desorption risk increases the application possibilities of hybrid silicic acid material with particular advantage. In particular, this mass-suitable applications, for example in a sewage treatment plant for the rehabilitation of municipal wastewater and / or in the treatment of drinking water, realized. Furthermore, cartridge-based applications are conceivable.

> Depending on its chemical structure, the hybrid silicic acid material according to the invention can thus enable a simultaneous fixation of different impurity categories and, within one impurity category, a simultaneous fixation of different impurities (multifunctional hybrid silica material). For example, simultaneous fixation of organic and inorganic contaminants, organic contaminants and plastic particles, inorganic contaminants and plastic particles or organic contaminants, inorganic contaminants and plastic particles is possible (di- or trifunctional hybrid silica material). This is particularly advantageous in removing anthropogenic contaminants from an aquatic environment and / or detecting such contaminants in such an environment. In contrast, the previously known from the prior art solutions represent only isolated solutions for certain impurities.

The hybrid silicic acid material according to the invention further contributes to a simplification of water purification processes, in particular with regard to the number of work steps required for this purpose and the complexity of these processes.

> Furthermore, the hybrid silica material allows a simplification of water analysis methods. The hybrid silica material advantageously permits simultaneous sample preparation and, in particular, simultaneous sample analysis. As a result, for example, a rapid in situ condition assessment of water is possible.

> Another advantage of the hybrid silica material according to the invention consists in its location, space and time-independent usability. This is especially for one Cleaning of temporarily highly contaminated water, for example in the presence of point source entries, an advantage.

> Overall, the hybrid silicic acid material represents a resource-saving, cost-effective and, in particular, mass-capable option for the purification, treatment and / or analysis of water.

In a preferred embodiment, the hybrid silica material described below is a hybrid polysilicic acid material.

In a further embodiment, the hybrid silicic acid material has structural units A according to formula I, structural units B according to formula II or structural units C according to formula III.

In a further embodiment, the hybrid silicic acid material has structural units A according to formula I and structural units B according to formula I I. This allows a simultaneous fixation of organic contaminants and inorganic impurities.

In a further embodiment, the hybrid silicic acid material has structural units A according to formula I and structural units C according to formula III. This allows a simultaneous fixation of organic contaminants and plastic particles.

In a further embodiment, the hybrid silicic acid material has structural units B according to formula I I and structural units C according to formula III. This allows a simultaneous fixation of inorganic contaminants and plastic particles.

The hybrid silica material described in the three previous embodiments may also be referred to as a two-functional hybrid silica material.

In a particularly preferred embodiment, the hybrid silicic acid material has structural units A according to formula I, structural units B according to formula II and structural units C according to formula III. This allows simultaneous fixation of organic contaminants, inorganic contaminants and plastic particles.

In a further embodiment, adjacent structural units A, adjacent structural units A and B, adjacent structural units B, structural units B and C adjacent to one another, adjacent structural units C and / or adjacent to one another Structural units A and C are covalently linked via linker groups. The same can apply in particular to the structural units described below.

The linker groups are preferably provided to sufficiently space the structural units so that, in principle, each structural unit is capable of fixing an impurity.

The linker groups typically have divalent organic radicals or consist of such radicals.

The divalent organic radicals may be branched or unbranched.

In principle, the divalent organic radicals may be selected from the group consisting of or consisting of divalent alkyl radicals, divalent alkenyl radicals, divalent alkynyl radicals, divalent aryl radicals or combinations thereof. The divalent aryl radicals may in particular be a divalent phenyl radical (phenylene radical).

In an embodiment advantageous in terms of spacing, the organic radicals have at least 5 carbon atoms, in particular 5 carbon atoms up to 16 carbon atoms, preferably 6 carbon atoms to 14 carbon atoms, particularly preferably 8 carbon atoms to 12 carbon atoms.

In a further embodiment, the divalent organic radicals have an alternating sequence of carbon-carbon single bonds and carbon-carbon double bonds.

The divalent organic radicals have, in another embodiment, at least one functional group.

The term "at least one functional group" in the meaning of the present invention means a functional group (singular) or a plurality of, i.e., two or more, functional groups.

The at least one functional group may be selected from the group consisting of or consisting of carboxy group, oxycarbonyl group, carbamoyl group, carbonyl group, amine group, amide group, carbon-carbon double bond, carbon-carbon Triple bond, aryl group such as phenyl group, dialkoxysilyl group, monoalkoxymonoalkylsilyl group, dialkylsilyl group and combinations thereof.

In another embodiment, the structural units A, B and / or C are covalently linked to silicon atoms of the hybrid silicic acid material via (further) linker groups. According to the invention it is preferred if the (further) linker groups have an odd number of carbon atoms, in particular 3, 5, 7, 9 or 1 1 carbon atoms. In this way, it is possible to prevent the structural units A, B and / or C from reacting in the preparation of the hybrid silicic acid material (instead of alkoxy-silyl groups / alkoxyalkylsilyl groups of precursors used for the preparation of the hybrid silicic acid material). For further features and advantages of the linker groups mentioned in this paragraph, reference is made in full to the previous description.

In a preferred embodiment, Z in the formula I denotes a functional group which is selected from the group consisting of or consisting of carboxy group, oxycarbonyl group, oxysulfonyl group, carbamoyl group, carbonyl group, amine group, amide group, carbon-carbon double bond, carbonyl Carbon triple bond, aryl group such as phenyl group, dialkoxysilyl group, monoalkoxymonoalkylsilyl group, dialkylsilyl group and combinations thereof.

According to a particularly preferred embodiment, Z in the formula I is a carbonyl group (C = 0).

In an alternative embodiment, Z in the formula I is a heteroatom, preferably an oxygen atom.

According to a further embodiment, the structural units A are each part of a larger structural unit according to formula Ia:

Formula la being Y and Z are the same or different and each independently represents a functional group or a heteroatom, and

R-i is a divalent organic radical.

In principle, Y and Z may each independently be a functional group selected from the group consisting of carboxy group, oxycarbonyl group, oxysulfonyl group, carbamoyl group, carbonyl group, amine group, amide group, carbon-carbon double bond, carbon-carbon triple bond, aryl group such as phenyl group, dialkoxysilyl group, monoalkoxymonoalkylsilyl group, dialkylsilyl group and combinations thereof.

Alternatively, Y and Z may each represent an oxygen atom.

Preferably, Y and Z in formula Ia are the same and each represents a carbonyl group (C = O).

The divalent organic radical R 1 can in principle be branched or unbranched.

The divalent organic radical R 1 may further have at least 5 carbon atoms, especially 5 carbon atoms to 16 carbon atoms, preferably 6 carbon atoms to 14 carbon atoms, more preferably 8 carbon atoms to 12 carbon atoms.

The divalent organic radical R 1 may in particular have a divalent alkyl radical, divalent alkenyl radical, divalent alkynyl radical, divalent aryl radical or combinations thereof or may denote such a radical or a combination of the radicals mentioned in this paragraph. With regard to the carbon number of the radicals mentioned in this paragraph, reference is made to the previous paragraph.

The divalent organic radical R _\ may further comprise an alternating sequence of carbon-carbon single bonds and carbon-carbon double bonds.

The divalent organic radical R _\ may have a functional group (further) at least. The at least one functional group may for example be selected from the group consisting of or consisting of carboxy group, oxycarbonyl group, oxysulfonyl group, carbamoyl group, carbonyl group, amine group, amide group, ether group, carbon-carbon double bond, carbon-carbon triple bond, aryl group such as phenyl group, dialkoxysilyl group, monoalkoxymonoalkylsilyl group, dialkylsilyl group and combinations thereof.

Ri in formula Ia is preferably a divalent phenol radical (phenylene radical, -C ₆ H ₄ -).

In view of the comments made above, the structural units A 1 preferably have the formula Ia ^# :

Formula la *

According to a further embodiment, the structural units A or A 1 are each part of a larger structural unit A ₂ according to formula Ib:

Formula Ib where

Y and Z are the same or different and each independently represents a functional group or a heteroatom, and

Ri = R ₂ = F _3, i = Ft ₂ * Ft _3, i * Ft ₂ = ₃ or ri Φ R ₂ Φ R _3, and Ri, R ₂ and R ₃ are each inde ^¬ dependent mean a divalent organic residue from each other.

In principle, Y and Z may each independently of one another denote a functional group which is selected from the group consisting of or consisting of carboxy group, Oxycarbonyl group, oxysulfonyl group, carbamoyl group, carbonyl group, amine group, amide group, carbon-carbon double bond, carbon-carbon triple bond, aryl group such as phenyl group, dialkoxysilyl group, monoalkoxymonoalkylsilyl group, dialkylsilyl group and combinations thereof.

Alternatively, Y and Z may each represent an oxygen atom.

Preferably, Y and Z in formula Ib are the same and each represents a carbonyl group (C = 0).

The divalent organic radicals R _1; R ₂ and R ₃ may in principle each be independently branched or unbranched.

The divalent organic radicals R _1; R ₂ and R ₃ may also each independently have at least 5 carbon atoms, especially 5 carbon atoms to 16 carbon atoms, preferably 6 carbon atoms to 14 carbon atoms, more preferably 8 carbon atoms to 12 carbon atoms.

In particular, the divalent organic radicals R _1; R ₂ and R _{3 are} each independently a divalent alkyl, divalent alkenyl, divalent alkynyl, divalent aryl or combinations thereof, or each independently represents such a radical or a combination of the radicals mentioned in this paragraph. With regard to the carbon number of the radicals mentioned in this paragraph, reference is made to the previous paragraph.

Furthermore, the divalent organic radicals R _1; R ₂ and R ₃ each independently have an alternating sequence of carbon-carbon single bonds and carbon-carbon double bonds.

The divalent organic radicals R _1; R ₂ and R ₃ may each independently have at least one functional group. The at least one functional group may, for example, be selected from the group consisting of or consisting of carboxyl group, oxycarbonyl group, oxysulfonyl group, carbamoyl group, carbonyl group, amine group, amide group, ether group, carbon-carbon double bond, carbon-carbon triple bond, aryl group such as phenyl group, Dialkoxysilyl group, monoalkoxymonoalkylsilyl group, dialkylsilyl group and combinations thereof. Preferably, R ₂ and R _{3 are the} same, but R ₂ and R ₃ are different from R ^, ie, it is preferable Ri Φ R ₂ = R ₃ .

The divalent organic radicals R ₂ and R ₃ can furthermore each independently have an odd number of carbon atoms, in particular 3, 5, 7, 9 or 1 1 carbon atoms.

The divalent organic radicals R ₂ and R ₃ in the formula Ib are each independently of one another a divalent organic radical, in particular a divalent alkyl radical, having an odd number of carbon atoms, preferably having 3, 5, 7, 9 or 1 1 carbon atoms.

Particularly preferably, the divalent organic radicals R ₂ and R ₃ in the formula Ib each represent a divalent propyl radical (-CH ₂ CH ₂ CH ₂ -).

Furthermore, R 1 in the formula Ib is preferably a divalent phenyl radical (phenylene radical, -C ₆ H ₄ -).

The oxygen atoms (terminal oxygen atoms) covalently bonded to a silicon atom shown in formula Ib are preferably each covalently bonded to another silicon atom of an adjacent structural unit (not shown). In this case, the adjacent structural unit may have an organic radical which is identical or different from the organic radical shown in formula Ib.

According to a particularly preferred embodiment, the structural unit A _{2 has} the formula Ib ^# :

Formula Ib *

The oxygen atoms (terminal oxygen atoms) covalently bonded to a silicon atom shown in formula Ib * are preferably each covalently bonded to another silicon atom of an adjacent structural unit (not shown). In doing so, the have adjacent organic moiety which is the same or different than the organic residue shown in the formula lb ^# .

According to a further embodiment, the structural units A, or A _{2 are} each part of a larger structural unit A ₃ according to formula Ic:

Formula Ic

The oxygen atoms (terminal oxygen atoms) covalently bonded to a silicon atom shown in the formula Ic are preferably each covalently bonded to another silicon atom of an adjacent structural unit (not shown). In this case, the adjacent structural unit may have an organic radical which is identical or different from the organic radical shown in the formula Ic.

For further details on possible meanings of Y, Z, R _1; R ₂ and R _{3 are} referred to the previous embodiments.

According to a particularly preferred embodiment, the structural unit A _{3 has} the formula Ic ^# :

Formula Ic *

The oxygen atoms (terminal oxygen atoms) covalently bonded to a silicon atom shown in the formula Ic * are preferably each with another silicon atom covalently linked to an adjacent structural unit (not shown). In this case, the adjacent structural unit may have an organic radical which is identical or different from the organic radical shown in the formula Ic ^# .

In a further embodiment, the structural units A (in the case where Z is a carbonyl group) or (in the case where Y and Z are each a carbonyl group and Ri is a divalent phenyl radical) are each part of a larger structural unit having the empirical formula

In a further embodiment, the structural units A, A _1; A ₂ and / or A ₃ participate in the formation of tubular structures in the hybrid silica material or form such structures. The formation of the tube structures is preferably made possible by hydrogen bonds and, in the presence of divalent aryl groups, in particular divalent phenyl groups, preferably additionally by π-π interactions. In this embodiment, impurities are preferably fixed to the inner surfaces of the tube structures.

As already mentioned, it applies to the radicals represented in formula II that R ', R "and R'", that R '= R "= R'", R '= R "+ R'", R '+ R " R '"or R' + R" R '"and R', R" and R '"are each independently a divalent organic radical and n is an integer from 1 to 1 1, in particular 1 to 7, preferably 1 to 3, more preferably 1, is.

The divalent organic radicals R ', R "and R'" can in principle in each case be branched or unbranched independently of one another.

The divalent organic radicals R ', R "and R'" may furthermore each independently of one another have a divalent alkyl radical, alkenyl divalent radical, divalent alkynyl radical, divalent aryl radical or combinations thereof or in each case independently of one another such a radical or a combination of the radicals mentioned in this paragraph mean.

Furthermore, the divalent organic radicals R ', R "and R'" may each independently have a functional group which is preferably selected from the group consisting of or consisting of carboxy group, oxycarbonyl group, oxysulfonyl group, carbamoyl group, carbonyl group, amine group, amide group, ether group, Carbon-carbon double bond, carbon-carbon triple bond, aryl group such as phenyl group, dialkoxysilyl group, monoalkoxymonoalkylsilyl group, dialkylsilyl group and combinations thereof. The divalent organic radicals R ', R "and R"' are each preferably a divalent alkyl radical, in particular divalent methyl radical (methylene radical, -CH ₂ -).

Particularly preferably, the divalent organic radicals R ', R "and R'" each represent a divalent methyl radical (methylene radical, -CH ₂ -), where n = 1. In other words, it is particularly preferred according to the invention if the structural units B are structural units containing 1, 3,5-triazinane radicals and have the following formula II *:

Formula II *

Structural units B containing 3,5-triazinane radicals have proven to be particularly advantageous for fixing inorganic impurities, in particular heavy metals.

According to a further embodiment, the structural units B are each part of a larger structural unit according to formula IIa:

Formula IIa where R '= R "= R'", R '= R "φ R'", R 'φ R "= R'" or R 'φ R "R'" and R ', R "and R'" are each independently of one another are a divalent organic radical and n is an integer from 1 to 1, in particular 1 to 7, preferably 1 to 3, particularly preferably 1, and

R ₄ = R ₅ = R ₆ , R ₄ = R ₅ Φ R ₆ , R ₄ Φ R ₅ = R ₆ or R ₄ Φ R ₅ Φ R ₆ and R ₄ , R ₅ and R _{6 are} each independently one, too mean divalent organic radical.

The divalent organic radicals R ', R ", R'", R ₄ , R ₅ and R ₆ may in principle each be independently branched or unbranched.

The divalent organic radicals R ', R ", R'", R ₄ , R ₅ and R ₆ may furthermore each independently of one another have a divalent alkyl radical, divalent alkenyl radical, divalent alkynyl radical, divalent aryl radical or combinations thereof or in each case independently of one another such radical or a combination of the radicals mentioned in this paragraph.

Furthermore, the divalent organic radicals R ', R ", R'", R ₄ , R ₅ and R _{6 may} each independently have an alternating sequence of carbon-carbon single bonds and carbon-carbon double bonds.

The divalent organic radicals R ', R ", R'", R ₄ , R ₅ and R ₆ may each independently have at least one functional group. The at least one functional group may, for example, be selected from the group consisting of or consisting of carboxy group, oxycarbonyl group, oxysulphonyl group, carbamoyl group, carbonyl group, amine group, amide group, ether group, carbon-carbon double bond, carbon-carbon triple bond, aryl group, such as phenyl group, Dialkoxysilyl group, monoalkoxymonoalkylsilyl group, dialkylsilyl group and combinations thereof.

Preferably R '= R "= R'", wherein R ', R "and R'" each represent a divalent methyl radical and n = 1.

The divalent organic radicals R ₄ , R ₅ and R ₆ may furthermore each independently of one another have an odd number of carbon atoms, in particular 3, 5, 7, 9 or 1 1 carbon atoms.

R ₄ , R ₅ and R _{6 are} each independently of one another a divalent organic radical, in particular a divalent alkyl radical, having an odd number of carbon atoms, preferably having 3, 5, 7, 9 or 1 1 carbon atoms. Particularly preferably, R ₄ , R ₅ and R ₆ in the formula IIa each represent a divalent propyl radical (-CH ₂ CH ₂ CH ₂ -).

The oxygen atoms (terminal oxygen atoms) covalently bonded to a silicon atom shown in formula IIa are preferably each covalently bonded to another silicon atom of an adjacent structural unit (not shown). In this case, the adjacent structural unit may have an organic radical which is identical or different from the organic radical shown in formula IIa.

In view of the foregoing, the structural unit preferably has the formula IIa *:

Formula IIa *

The oxygen atoms (terminal oxygen atoms) covalently bonded to a silicon atom shown in formula IIa * are preferably each covalently bonded to another silicon atom of an adjacent structural unit (not shown). In this case, the adjacent structural unit may have an organic radical which is identical or different from the organic radical shown in formula IIa *.

In a further embodiment, the structural units B or Bi are each part of a larger structural unit B ₂ having the formula IIb:

Formula IIb

The oxygen atoms (terminal oxygen atoms) covalently bonded to a silicon atom shown in the formula IIb are preferably in each case covalently bonded to a further silicon atom of an adjacent structural unit (not shown). In this case, the adjacent structural unit may have an organic radical which is identical or different from the organic radical shown in formula IIb.

For further details on possible meanings of R ', R ", R'", n, R ₄ , R ₅ and R ₆ , reference is made to the preceding statements.

According to a particularly preferred embodiment, the structural unit B _{2 has} the formula IIb *:

Formula IIb * The oxygen atoms (terminal oxygen atoms) covalently bonded to a silicon atom shown in formula IIb * are preferably each covalently bonded to another silicon atom of an adjacent structural unit (not shown). In this case, the adjacent structural unit may have an organic radical which is identical or different from the organic radical shown in the formula IIb *.

In a further embodiment, the structural units B (in the case where R ', R "and R'" each denote a methylene group and n = 1) or (in the case where R ', R "and R'" are each a methylene group each n = 1 and R ₄ , R ₅ and R ₆ each represent a divalent propyl radical) each form part of a larger structural unit having the empirical formula

As already mentioned, for the radical R shown in formula III, R has a divalent cyclic aliphatic radical or preferably represents such a radical.

In a further embodiment, the divalent cyclic aliphatic radical of the formula III is a divalent monocyclic aliphatic radical.

The divalent cyclic aliphatic radical of the formula III may furthermore be selected, in particular, from the group consisting of or consisting of divalent cyclopentyl radical (C ₅ H ₈ -) and divalent cyclohexyl radical (C ₆ H ₁₀ -).

The divalent cyclic aliphatic radical R in the formula III preferably denotes a divalent cyclohexyl radical which is disubstituted in the structural units C of the formula III 1, 2.

Accordingly, the structural units C preferably have the formula III *:

Formula III *

In a further embodiment, the structural units C are each part of a larger structural unit Ci according to the following formula IIIa:

Formula l ila being

R has a divalent cyclic (in particular monocyclic) aliphatic radical or means such a radical.

The divalent cyclic aliphatic radical may furthermore be selected, in particular, from the group consisting of or consisting of divalent cyclopentyl radical (C ₅ H ₈ -) and dibutyl cyclohexyl radical (C ₆ H ₁₀ -).

Preferably, the divalent cyclic aliphatic radical in the formula IIIa is a divalent cyclohexyl radical which is 1, 2-disubstituted. In other words, the nitrogen atoms adjacent to the cyclohexyl radical in the formula IIIa are preferably covalently linked to the first carbon atom and the second carbon atom of the cyclohexyl radical.

The structural unit Ci therefore preferably has the formula IIIa *:

Formula l ila *

In a further embodiment, the structural units C or Ci are each part of a larger structural unit C ₂ according to formula II 1b:

O o

Formula IIIb where

R has a divalent cyclic (in particular monocyclic) aliphatic radical or denotes such a radical and

R ₇ , and R _{8 are the} same or different and each independently represents a divalent organic radical.

The divalent cyclic aliphatic radical may in particular be selected from the group consisting of or consisting of divalent cyclopentyl radical (-C ₅ H ₈ -) and divalent cyclohexyl radical (-C ₆ H ₁₀ -).

The divalent organic radicals R ₇ and R ₈ may each independently principle branched or unbranched.

The divalent organic radicals R ₇ and R ₈ may furthermore each independently of one another have a divalent alkyl radical, divalent alkenyl radical, divalent alkynyl radical, divalent aryl radical or combinations thereof or in each case independently represent such a radical or a combination of the radicals mentioned in this paragraph.

The divalent organic radicals R _7, and R ₈ may further independently an odd number of carbon atoms, in particular 3, 5, 7, 9 or 1 1 carbon atoms, have.

Preferably, R ₇ and R ₈ each represent an alkyl group having an odd number of carbon atoms, in particular having 3, 5, 7, 9 or 1 1 carbon atoms.

The divalent cyclic aliphatic radical in the formula IIIb preferably denotes a divalent cyclohexyl radical which is 1, 2-disubstituted. In other words, the nitrogen atoms adjacent to the cyclohexyl radical in formula IIIb are preferably covalently linked to the first carbon atom and the second carbon atom of the cyclohexyl radical.

The oxygen atoms (terminal oxygen atoms) covalently bonded to a silicon atom shown in formula IIIb are preferably each covalently bonded to another silicon atom of an adjacent structural unit (not shown). In doing so, the adjacent structural unit have an organic radical which is identical or different from the organic radical shown in the formula IIIb.

The structural unit C ₂ consequently preferably has the formula IIIb *:

- S i

O

\

Formula IIIb *

The oxygen atoms (terminal oxygen atoms) covalently bonded to a silicon atom and represented in the formula IIIb * are preferably each covalently bonded to a further silicon atom of an adjacent structural unit (not shown). In this case, the adjacent structural unit may have an organic radical which is identical or different from the organic radical shown in the formula IIIb *.

For further details on possible meanings of R ₇ and R ₈ , reference is made to the preceding statements.

In a further embodiment, the structural units C, Ci or C _{2 are} each part of a larger structural unit C ₃ according to formula IIc:

Formula IIIc The oxygen atoms (terminal oxygen atoms) covalently bonded to a silicon atom in the formula, which are never shown in the formula, are preferably each covalently bonded to a further silicon atom of an adjacent structural unit (not shown). In this case, the adjacent structural unit may have an organic radical which is identical or different from the organic radical never shown in the formula.

For further details on possible meanings of R, R ₇ and R ₈ , reference is made to the preceding statements.

In a preferred embodiment, the structural unit C _{3 has} the formula IIIc ^# :

Formula Never *

The oxygen atoms (terminal oxygen atoms) covalently bonded to a silicon atom in the formula Never * are preferably each covalently bonded to a further silicon atom of an adjacent structural unit (not shown). In this case, the adjacent structural unit may have an organic radical which is identical or different from the organic radical shown in the formula Never *.

In a further embodiment, the structural units C (in the case where R is a divalent cyclohexyl radical), d (in the case where R is a divalent cyclohexyl radical), C ₂ (in the case where R is a divalent cyclohexyl radical and R ₇ and R ₈ in each case a divalent propyl radical) or C ₃ (in the case where R is a divalent cyclohexyl radical and R ₇ and R _{8 are} each a divalent propyl radical) are each part of a larger structural unit having the empirical formula C ₄ H ₂ 6N ₄ O ₂ Si ₂ O ₃ , In a further embodiment, the structural units C or d are each part of a larger structural unit C ₄ according to formula II ld:

Formula l lld where

R has a divalent cyclic (in particular monocyclic) aliphatic radical or denotes such a radical,

R _{7 is} a divalent organic radical and

R _{9 is} a divalent cyclodextrin.

The silicon atoms flanking the cyclodextrin moiety are preferably each covalently linked to an oxygen atom of the cyclodextrin moiety. For example, R ₉ may be derived from a cyclodextrin molecule as shown in FIG. 6 or 7.

The cyclodextrin radical may in particular be a polyfunctionalized cyclodextrin radical. The cyclodextrin radical can be polyfunctionalized on its inner and / or outer ring side.

The divalent organic radical R ₇ can in principle be branched or unbranched.

The divalent organic radical R ₇ may furthermore have a divalent alkyl radical, divalent alkenyl radical, divalent alkynyl radical, divalent aryl radical or combinations thereof or may denote such a radical or a combination of the radicals mentioned in this paragraph. The divalent organic radical R ₇ may in particular have an odd number of carbon atoms, in particular 3, 5, 7, 9 or 1 1 carbon atoms.

The divalent organic radical R ₇ preferably denotes an alkyl group having an odd number of carbon atoms, in particular having 3, 5, 7, 9 or 1 1 carbon atoms.

The divalent cyclic aliphatic radical in the formula IIIc preferably denotes a divalent cyclohexyl radical which is 1,2-disubstituted. In other words, the nitrogen atoms adjacent to the cyclohexyl radical in formula IIIc are preferably covalently linked to the first carbon atom and the second carbon atom of the cyclohexyl radical.

The structural unit C ₄ consequently preferably has the formula IIId ^# :

i-Rg

Formula l lld *

For further details on possible meanings of R ₇ and R ₉ in the formula IIId * reference is made to the preceding statements.

In a further embodiment, the structural units C, Ci or C _{4 are} each part of a larger structural unit C ₅ according to formula Never:

Formula Never being R has a divalent cyclic (in particular monocyclic) aliphatic radical or denotes such a radical,

R ₇ , and R _{8 are the} same or different and each independently represents a divalent organic radical, and

R _{9 is} a divalent cyclodextrin.

The divalent organic radicals R ₇ and R ₈ may further independently comprise a divalent alkyl, divalent alkenyl, divalent alkynyl, divalent aryl, or combinations thereof, or each independently represents such a radical or a combination of the above in this paragraph residues.

The divalent organic radicals R ₇ and R ₈ may furthermore each independently of one another have an odd number of carbon atoms, in particular 3, 5, 7, 9 or 1 1 carbon atoms.

Preferably, the divalent organic radicals R ₇ and R ₈ each independently represent an alkyl group having an odd number of carbon atoms, in particular having 3, 5, 7, 9 or 1 1 carbon atoms. The divalent cyclic aliphatic radical in the formula IIId preferably denotes a divalent cyclohexyl radical which is 1, 2-disubstituted. In other words, the nitrogen atoms adjacent to the cyclohexyl radical in formula IIId are preferably covalently linked to the first carbon atom and the second carbon atom of the cyclohexyl radical.

The in the formula Never terminally (terminal) shown, with a silicon atom covalently bonded oxygen atoms are preferably each covalently connected to another silicon atom of an adjacent structural unit (not shown). In this case, the adjacent structural unit may have organic radicals which are identical or different from the organic radicals never shown in the formula.

The structural unit C ₅ particularly preferably has the formula Never *:

iR ₉

Si-q

Formula Never *

The oxygen atoms covalently linked to a silicon atom in the formula Never terminal are preferably covalently bonded to a further silicon atom of an adjacent structural unit (not shown). In this case, the adjacent structural unit may have organic radicals which are identical or different from the organic radicals shown in the formula Never *.

For further details on possible meanings of R ₇ , R ₈ and R ₉ in the formula Never *, reference is made to the preceding statements.

In an advantageous embodiment, structural units C, C _1; C ₂ , C ₃ , C ₄ and / or C ₅ involved in the construction of tubular structures or form such tubular structures. In other words, the structural units C, d, C ₂ , C ₃ , C ₄ and / or C _{5 may be} referred to as structuring units for the tubes to be formed. This is especially true in the event that the Structural units C the formula III * the structural units d the formula Ia *, the structural units C ₂ the formula II lb * the structural units C ₃ the formula I llc * the structural units C ₄ the formula II ld * and / or the structural units C ₅ die Formula N ie * own. The formation of the tube structures is preferably based on the formation of hydrogen bonds. The tubes are particularly advantageous in being able to trap plastic particles, in particular microparticles, preferably with a diameter <50 μm, via van der Waals interactions and / or electrostatic interactions. For this purpose, the tube structures can have an inner diameter of 10 nm to 100 μm, in particular 0.1 μm to 70 μm. The structural units C ₄ and / or C ₅ offer the additional advantage over the structural units C, C ₁ , C ₂ and / or C ₃ that due to the changed chemical environment between the interior and the exterior of the cyclodextrin residues an inclusion of inert particles by means of electrostatic Interactions can take place. The induced structural environment of the structural units C ₄ and / or C ₅ preferably causes the triggering of a key-lock mechanism, whereby the lid closes. In principle, polyhydroxyalkanoates such as polylactides and zeolite-like materials are conceivable as alternative materials to the cyclodextrin radicals described in the previous embodiments.

In a further embodiment, the hybrid silicic acid material has a BET specific surface area of from 10 m ² / g to 800 m ² / g, in particular from 50 m ² / g to 700 m ² / g, preferably from 150 m ² / g to 600 m ² / g (DIN ISO 9277: 2003-05: Determination of the specific surface area of solids by gas adsorption by the BET method (ISO 9277: 1 995).

The hybrid silicic acid material is provided in a further embodiment with at least one additive, in particular a detection reagent for impurities, a contrast agent, and / or a pharmaceutical. A suitable contrast agent is, for example, jopromide. Possible pharmaceuticals include, for example, carbamazepine, diclofenac, ibuprofen, and / or bezafibrate.

In a preferred embodiment, the hybrid silica material is a hybrid silica gel.

In another embodiment, the hybrid silica material is in dried form.

In a further embodiment, the hybrid silicic acid material has a residual moisture content of 0% to 80%, in particular 0% to 60%, preferably 0% to 50%, based on calcined silica (residual moisture content is determined for Si0 ₂ ). The hybrid silicic acid material is preferably a dried hybrid silica gel, in particular a hybrid silica xerogel or hybrid silica airgel.

In a further embodiment, the hybrid silicic acid material is in particulate, in particular pulverulent, form.

The hybrid silicic acid material may in particular have a mean particle diameter of 0.001 μm to 100 μm, in particular 0.002 μm to 70 μm.

In an alternative embodiment, the hybrid silica material is in a fibrous, especially hollow-fiber form.

In an alternative embodiment, the hybrid silica material is layered.

In an embodiment which is advantageous from a process point of view, the hybrid silicic acid material further comprises a carrier. In other words, according to an advantageous embodiment, the hybrid silica material is in the form of a supported hybrid silica material.

Preferably, the hybrid silica material is immobilized on the carrier. This can be increased in a particularly advantageous manner, the specific BET surface area of the hybrid silica material. In addition, the use of a carrier causes an increase in the particle size of the hybrid silica material. This is particularly advantageous in the case of a cartridge application, because this reduces the pressure loss over the bed and the risk of constipation can be reduced.

The carrier is preferably a polymeric carrier.

The support may in particular be selected from the group consisting of or consisting of polyethylene (PE), ultra-high molecular weight polyethylene (UHMWPE), polypropylene (PP), polycarbonate (PC), polymethacrylate (PMMA), polyethylene terephthalate (PET), polyarylsulfones (PPSU) , Polytetrafluoroethylene (PTFE), silica, porous silicates such as microporous silicates (pores <2 nm) or mesoporous silicates (pores between 2 nm and 50 nm), mesoporous materials (pores between 2 nm and 50 nm) such as MCM-41 (Mobil Composition of Matter No. 41) or MCM-48 (Mobile Composition of Matter No. 48), MCM-analogous structures with a defined pore volume, SBA materials, zeolites, titanium-silicon structures, and combinations thereof. The silica mentioned in the previous paragraph is preferably made from tetraethylorthosilicate and cetyltrimethylammonium bromide.

Alternatively, the carrier may be a non-polymeric carrier, preferably activated carbon or activated carbon-like materials. Activated carbon allows physical adsorption of impurities, thereby prolonging their contact time with the hybrid silica material. The longer contact time in turn causes an improvement of the cleaning effect. In addition, the use of the hybrid silica material requires a smaller amount of activated carbon, which can reduce costs, particularly municipal wastewater treatment costs.

The carrier can furthermore be connected to the hybrid silica material via covalent bonds or non-covalent bonds, in particular van der Waals forces. For example, the hybrid silica material may be in the form of a grafted hybrid silica material, i. the hybrid silica material may be supported on the carrier.

The hybrid silicic acid material in supported form preferably has a mean particle diameter of 0.01 μm to 500 mm, in particular 2 μm to 30 mm.

In another embodiment, the hybrid silica material is in the form of a filter material.

In a second aspect, the invention relates to an organosilicon precursor, i. an organosilicon precursor compound.

The precursor is preferably provided for producing a hybrid silica material, in particular for producing a hybrid silica material according to the first aspect of the invention.

In principle, the precursor may be a polymeric precursor. However, it is preferred according to the invention if the precursor is a monomeric or oligomeric precursor.

An oligomeric precursor is particularly preferred because such a precursor may have different structural units which are reactive with respect to impurities and thus permit the production of a multifunctional hybrid silica material according to the first aspect of the invention or multifunctional hybrid material according to the second aspect of the invention. The precursor is distinguished in particular by the fact that it contains at least one structural unit A ₀ according to formula I ₀ (divalent urea radical):

Formula I ₀

and / or at least one structural unit B according to formula II:

Formula II where

R '= R "= R'", R '= R "+ R'", R '+ R "= R'" or R '+ R "R'" and R ', R "and R'" are each independently of one another are a divalent organic radical and

n is an integer from 1 to 1, in particular 1 to 7, preferably 1 to 3, particularly preferably 1, having.

For further details on possible meanings of R ', R "and R'" reference is made to avoid repetition on the statements made within the scope of the first aspect of the invention formula II.

The term "at least one structural unit A ₀ " in the meaning of the present invention means a structural unit A ₀ (singular) or a plurality of, ie two or more, structural units A _0. The term "at least one structural unit A" in the sense of the present invention a structural unit A (singular) or a plurality of, ie two or more, structural units A. The expression "at least one structural unit B" in the context of the present invention means a structural unit B (singular) or a plurality of, ie two or more, Structural units B. The expression "at least one structural unit C" in the context of the present invention means a structural unit C (singular) or a plurality of, ie two or more, structural units C. The same applies mutatis mutandis to the expressions "at least one structural unit Α ^ ', "At least one structural unit A ₂ ", "at least one structural unit Β," at least one structural unit C and "at least one structural unit C ₄ ".

The at least one structural unit A, the at least one structural unit B and / or the at least one structural unit C are preferably covalently linked to one another via linker groups. With regard to the linker groups reference is made to avoid repetition on the corresponding statements in the context of the first aspect of the invention.

Furthermore, the at least one structural unit A, the at least one structural unit B and / or the at least one structural unit C are preferably linked covalently via (further) linker groups with an alkoxysilyl group or alkoxyalkylsilyl group, in particular a trialkoxysilyl group, dialkoxymonoalkylsilyl group or monoalkoxydialkylsilyl group. The alkoxy group may in particular be a methoxy and / or ethoxy group. The alkyl group may in particular be a methyl and / or ethyl group. Thus, the trialkoxysilyl group may be selected from the group consisting of or consisting of trimethoxysilyl group, dimethoxymonoethoxysilyl group, monomethoxydiethoxysilyl group and triethoxysilyl group. The dialkoxymonoalkylsilyl group may accordingly be selected from the group consisting of dimethoxymonomethylsilyl group, monomethoxymonoethoxymonomethylsilyl group, monomethoxymonoethoxymonoethylsilyl group, diethoxymonomethylsilyl group and diethoxymonoethylsilyl group. The monoalkoxydialkylsilyl group may accordingly be selected from the group consisting of monomethoxydimethylsilyl group, monomethoxymonomethylmonoethylsilyl group, monomethoxydiethylsilyl group, monoethoxydimethylsilyl group, monoethoxymonomethylmonoethylsilyl group and monoethoxydiethylsilyl group.

In a further embodiment, the precursor has at least two, ie two or more, in particular two or three, terminal, ie terminal, hydrolyzable silyl groups. The silyl groups may be the same or different and independently selected from the group consisting of or consisting of alkoxysilyl groups, alkoxyalkylsilyl group and combinations thereof. The silyl groups may in particular be selected independently of one another from the group comprising or consisting of trialkoxysilyl groups, dialkoxymnoalkylsilyl groups, monoalkoxydialkylsilyl groups and combinations thereof. Preferably, the silyl groups are independently selected from the group consisting of or consisting of trimethoxysilyl groups, dimethoxymonoethoxysilyl groups, monomethoxydiethoxy silyl groups, triethoxysilyl groups, Dimethoxymonomethylsilylgruppen, noethoxymonomethylsilylgruppen Monomethoxymo-, Monomethoxymonoethoxymonoethylsilylgruppen, diethoxy monomethylsilyl, noethoxydimethylsilylgruppen Diethoxymonoethylsilylgruppen, Monomethoxydimethylsilylgruppen, Monomethoxymonomethylmonoethylsilylgruppen, Monomethoxydiethylsilylgruppen, Mo, Monoethoxymonomethylmonoethylsilylgruppen, diethylsilyl Monoethoxy- and combinations thereof.

In a further embodiment, the at least one structural unit A _{0 is} part of at least one larger structural unit A according to formula I:

Formula I

In a further embodiment, the precursor has the following features:

at least one structural unit A according to formula I:

Formula I

in which

Z is a functional group or a heteroatom,

at least one structural unit B according to formula II:

Formula II where R '= R "= R'", R '= R "φ R'", R 'φ R "= R'" or R 'φ R "R'" and R ', R "and R'" are each independently of one another are a divalent organic radical and

at least one structural unit C according to formula III:

Formula III

in which

For further details on possible meanings of R, R ', R ", R'" and Z reference is made to avoid repetition on the statements made in the first aspect of the invention to the formula I, II and III.

In a further embodiment, the precursor has at least one structural unit A according to formula I, at least one structural unit B according to formula II or at least one structural unit C according to formula III.

In a further embodiment, the precursor has at least one structural unit A according to formula I and at least one structural unit B according to formula II.

In a further embodiment, the precursor has at least one structural unit A according to formula I and at least one structural unit C according to formula III. In a further embodiment, the precursor has at least one structural unit A according to formula I, at least one structural unit B according to formula II and at least one structural unit C according to formula I II.

Preferably, the at least one structure has the formula II ^# :

Formula I I *

The at least one structural unit C preferably has the formula II I *:

Formula I II *

The at least one structural unit A ₀ or the at least one structural unit A is preferably part of at least one larger structural unit according to formula Ia:

Formula la being

Ri means a divalent organic residue. For further details on possible meanings of R _1; Y and Z are referred to avoid repetition of the statements made in the context of the first aspect of the invention formula la.

The at least one structural unit preferably has the formula Ia ^# :

Formula la *

In a further embodiment, the at least one structural unit A ₀ or the at least one structural unit C is part of at least one larger structural unit Ci according to the following formula IIIa:

Formula lilac being

R has a divalent cyclic (in particular monocyclic) aliphatic radical or, which is preferred according to the invention, such a radical.

For further details on possible meanings of R reference is made to avoid repetition on the statements made in the context of the first aspect of the invention for formula IIIa.

The at least one structural unit Ci preferably has the formula IIIa *:

Formula IIIa ^#

In a further embodiment, the at least one structural unit A ₀ , the at least one structural unit C or the at least one structural unit Ci part of at least one major structural unit C ₄ according to the following formula IIId:

Formula l lld where

R _{7 is} a divalent organic radical and R _{9 is} a divalent cyclodextrin radical.

For further details on possible meanings of R, R ₇ and R ₉ reference is made to avoid repetition on the statements made in the context of the first aspect of the invention for formula IIIc.

The at least one structural unit C ₄ preferably has the formula IIId *: i ^' rg

Formula l lld *

For further details on possible meanings of R ₇ and R ₉ , reference is made to avoid repetition to the statements made in the context of the first aspect of the invention to the formulas III and N ie *.

For further features and advantages of the precursor, reference is made to the previous one.

According to a third aspect, the invention relates to a precursor which is selected from the group of the following precursors:

Precursor according to formula IV:

(R ⁶ ) (R ⁵ ) (R ⁴ O) S) (R ² ) (R ³ )

Formula IV where

Y and Z are the same or different and each independently represents a functional group or a heteroatom,

R ₂ = R ₃ , R ₂ Φ R ₃ , Φ R ₂ = R ₃ or Φ R ₂ Φ R ₃ and R _1; R ₂ and R ₃ each independently represent a divalent organic radical, R ¹ and R ^{4 are the} same or different and each independently represents a monovalent alkyl radical,

R ² and R ^{5 are the} same or different and each independently represents a monohydric alkoxy or alkyl radical and

R ³ and R ^{6 are the} same or different and each independently represents a monovalent alkoxy or alkyl radical,

Precursor according to formula V:

according to formula V

in which

R '= R "= R'", R '= R "φ R'", R 'φ R "= R'" or R 'φ R "R'" and R ', R "and R'" are each independently of one another are a divalent organic radical and

n is an integer from 1 to 1, in particular from 1 to 7, preferably from 1 to 3, particularly preferably 1,

R ₄ = R ₅ = R ₆ , R ₄ = R ₅ Φ R ₆ , R ₄ Φ R ₅ = R ₆ or R ₄ Φ R ₅ Φ R ₆ , and R ₄ , R ₅ and R _{6 are} each independently a divalent radical as well mean organic residue,

R ⁷ = R ¹⁰ = R ¹³ , R ⁷ = R ¹⁰ Φ R ¹³ , R ⁷ Φ R ¹⁰ = R ¹³ or R ⁷ Φ R ¹⁰ Φ R ¹³ and R ⁷ , R ¹⁰ and R ¹³ each independently form a monovalent Mean alkyl radical,

R ⁸ = R ¹¹ = R ¹⁴ , R ⁸ = R ¹¹ Φ R ¹⁴ , R ⁸ Φ R ¹¹ = R ¹⁴ or R ⁸ Φ R ¹¹ Φ R ¹⁴ , and R ⁸ , R ¹¹ and R ¹⁴ each independently of one another Alkoxy or alkyl radical and

R ⁹ = R ¹² = R ¹⁵ , R ⁹ = R ¹² Φ R ¹⁵ , R ⁹ Φ R ¹² = R ¹⁵ or R ⁹ Φ R ¹² Φ R ¹⁵ and R ⁹ , R ¹² and R ¹⁵ each independently form a monovalent Alkoxy or alkyl radical, and

Precursor according to formula VI:

Formula VI where

R ₇ , and R _{8 are the} same or different and each independently represents a divalent organic radical,

R ¹⁶ and R ^{19 are the} same or different and each independently represents a monovalent alkyl radical,

R ¹⁷ and R ^{20 are the} same or different and each independently represents a monohydric alkoxy or alkyl radical and

R ¹⁸ and R ^{21 are the} same or different and each independently represents a monovalent alkoxy or alkyl radical,

In the precursor according to formula IV, Y and Z may in each case in each case independently of one another denote a functional group which is selected from the group consisting of carboxy group, oxycarbonyl group, oxysulfonyl group, carbamoyl group, carbonyl group, amine group, amide group, carbon-carbon double bond , Carbon-carbon triple bond, aryl group (such as phenyl group), dialkoxysilyl group, monoalkoxymonoalkylsilyl group, dialkylsilyl group and combinations thereof.

Alternatively, Y and Z may each represent an oxygen atom. Preferably, Y and Z are the same and are a carbonyl group (C = O).

In principle, the divalent organic radicals R 1, R ₂ and R ₃ in the precursor according to formula IV can each be branched or unbranched independently of one another.

The divalent organic radicals R _1; R ₂ and R ₃ may each independently have at least one functional group. The at least one functional group may, for example, be selected from the group consisting of or consisting of carboxyl group, oxycarbonyl group, oxysulfonyl group, carbamoyl group, carbonyl group, amine group, amide group, ether group, carbon-carbon double bond, carbon-carbon triple bond, aryl group such as phenyl group, Dialkoxysilyl group, monoalkoxy monoalkylsilyl group, dialkylsilyl group and combinations thereof.

Preferably, R ₂ and R _{3 are the} same, but R ₂ and R ₃ are different from R 1, ie, it is preferable Ri Φ R ₂ = R ₃ .

The divalent organic radicals R ₂ and R ₃ may furthermore each independently of one another have an odd number of carbon atoms, in particular 3, 5, 7, 9 or 1 1 carbon atoms. The divalent organic radicals R ₂ and R ₃ each independently of one another are preferably a divalent organic radical, in particular divalent alkyl radical, having an odd number of carbon atoms, preferably having 3, 5, 7, 9 or 1 1 carbon atoms.

Particularly preferably, the divalent organic radicals R ₂ and R ₃ each represent a divalent propyl radical (-CH ₂ CH ₂ CH ₂ -).

Furthermore, R ₁ preferably denotes a divalent phenyl radical (phenylene radical, -C ₆ H ₄ -).

Preferably R ¹ and R ⁴ in the precursor of formula IV represent a monovalent alkyl group each independently, which is selected from the group comprising or consisting of a monovalent methyl radical and monovalent ethyl. Particularly preferably, R ¹ and R ⁴ each represent a monovalent methyl or ethyl radical.

Preferably R ² and R ⁵ wherein the precursor of the formula IV are each independently a monovalent alkoxy radical which is selected from the group comprising or consisting of monovalent methoxy and monovalent ethoxy radical, or a monovalent alkyl radical which is selected from the group comprising or consisting from einbindiger methyl radical and einbindiger ethyl radical. Particularly preferably, R ² and R ⁵ each represent a monohydric methoxy or ethoxy radical.

Preferably R ³ and R ⁶ in the precursor according to formula IV are each independently a monovalent alkoxy radical which is selected from the group comprising or consisting of monovalent methoxy and monovalent ethoxy radical, or a monovalent alkyl radical which is selected from the group comprising or consisting from einbindiger methyl radical and einbindiger ethyl radical. Particularly preferably, R ³ and R ⁶ each represent a monohydric methoxy or ethoxy radical.

In the precursor of formula V, the divalent organic radicals R ', R ", R''', R ₄ , R ₅ and R _{6 may} each independently be branched or unbranched.

Furthermore, the divalent organic radicals R ', R ", R'", R ₄ , R ₅ and R _{6 may} each independently of one another have a divalent alkyl radical, alkenyl divalent radical, divalent alkynyl radical, divalent aryl radical or combinations thereof or in each case independently one another such radical or a combination of the radicals mentioned in this paragraph. Furthermore, the divalent organic radicals R ', R ", R'", R ₄ , R ₅ and R _{6 may} each independently have an alternating sequence of carbon-carbon single bonds and carbon-carbon double bonds.

R ₄ , R ₅ and R _{6 are} each independently of one another a divalent organic radical, in particular a divalent alkyl radical, having an odd number of carbon atoms, preferably having 3, 5, 7, 9 or 1 1 carbon atoms.

Particularly preferably, R ₄ , R ₅ and R ₆ each represent a divalent propyl radical

R ⁷ , R ¹⁰ and R ¹³ in the precursor of the formula V are each independently of one another a monovalent alkyl radical which is selected from the group consisting of or consisting of a monovalent methyl radical and a monovalent ethyl radical. Preferably, R ⁷ , R ¹⁰ and R ¹³ each represent a monovalent methyl or ethyl radical.

Preferably, R ^8, R ¹¹ and R ¹⁴ in the precursor according to formula V are each independently a monovalent alkoxy radical which is selected from the group comprising or consisting of monovalent methoxy and monovalent ethoxy radical, or a monovalent alkyl radical which is selected from the group comprising or consisting of einbindiger methyl radical and einbindiger ethyl radical. Particularly preferably, R ⁸ , R ¹¹ and R ¹⁴ each represent a monohydric methoxy or ethoxy radical. R ⁹ , R ¹² and R ¹⁵ in the precursor of the formula V are each independently of one another a monovalent alkoxy radical which is selected from the group consisting of monohydric methoxy radical and monovalent ethoxy radical, or a monovalent alkyl radical which is selected from the group comprising or consisting of einbindiger methyl radical and einbindiger ethyl radical. Particularly preferably, R ⁹ , R ¹² and R ¹⁵ each represent a monohydric methoxy or ethoxy radical.

In the precursor of formula VI, the divalent cyclic aliphatic radical is preferably a divalent monocyclic aliphatic radical.

The divalent organic radicals R ₇ and R ₈ may each independently branched or unbranched in the precursor according to formula VI.

Preferably, the divalent cyclic aliphatic radical in the precursor of the formula VI is a divalent cyclohexyl radical which is present in a 1, 2-disubstituted form. In other words, the nitrogen atoms adjacent to the cyclohexyl radical in the formula VI are preferably covalently linked to the first carbon atom and the second carbon atom of the cyclohexyl radical.

R ¹⁶ and R ¹⁹ in the precursor according to formula VI are each independently of one another a monovalent alkyl radical which is selected from the group comprising or consisting of einbindiger methyl radical and einbindiger ethyl radical. Particularly preferably, R ¹⁶ and R ¹⁹ each represent a monovalent methyl or ethyl radical.

R ¹⁷ and R ²⁰ in the precursor according to formula VI are each independently of one another a monovalent alkoxy radical which is selected from the group consisting of monovalent methoxy radical and monovalent ethoxy radical, or a monovalent alkyl radical which is selected from the group comprising or consisting of einbindiger methyl radical and einbindiger ethyl radical. Particularly preferably, R ¹⁷ and R ²⁰ each represent a monohydric methoxy or ethoxy radical.

R ¹⁸ and R ²¹ in the precursor according to formula VI are each independently of one another a monovalent alkoxy radical which is selected from the group comprising or consisting of monovalent methoxy radical and monovalent ethoxy radical, or a monovalent alkyl radical which is selected from the group comprising or consisting of einbindiger methyl radical and einbindiger ethyl radical. Particularly preferably, R ¹⁸ and R ²¹ each represent a monohydric methoxy or ethoxy radical.

In a particularly preferred embodiment, the precursor is selected from the group consisting of or consisting of

Precursor according to formula IV ^# :

Formula IV *

Precursor according to formula V ^# :

Formula V * and

Precursor according to formula VI *:

Formula VI *

The precursor described in the context of the third aspect of the invention is preferably provided for producing a hybrid silicic acid material, in particular for producing a hybrid silicic acid material according to the first aspect of the invention.

With regard to further features and advantages of the precursor, reference is made in full to the previous description, in particular to the statements made in the context of the second aspect of the invention. According to a fourth aspect, the invention relates to a modified precursor having a precursor according to the second or third aspect of the invention and a carrier, wherein the precursor is immobilized on the carrier.

The carrier is preferably a polymeric carrier.

The support may in particular be selected from the group consisting of or consisting of polyethylene (PE), ultra-high molecular weight polyethylene (UHMWPE), polypropylene (PP), polycarbonate (PC), polymethacrylate (PMMA), polyethylene terephthalate (PET), polyarylsulfones (PPSU) , Polytetrafluoroethylene (PTFE), silica, porous silicates such as microporous silicates (pores <2 nm) or mesoporous silicates (pores between 2 nm and 50 nm), mesoporous materials (pores between 2 nm and 50 nm) such as MCM-41 (Mobil Composition of Matter No. 41) or MCM-48 (Mobile Composition of Matter No. 48), MCM-analogous structures with a defined pore volume, SBA materials, zeolites, titanium-silicon structures, and combinations thereof.

The silica mentioned in the previous paragraph is preferably made from tetraethylorthosilicate and cetyltrimethylammonium bromide.

The carrier may also be linked to the precursor via covalent bonds or non-covalent bonds, in particular van der Waals forces. For example, the hybrid silica material may be in the form of a grafted hybrid silica material, i. the hybrid silica material may be supported on the carrier.

The precursor described in the context of the fourth aspect of the invention is preferably provided for producing a hybrid silicic acid material, in particular for producing a hybrid silicic acid material according to the first aspect of the invention. With regard to further features and advantages of the precursor and of the carrier, reference is made in full to the previous description, in particular to the statements made in the context of the second and third aspects of the invention.

According to a fifth aspect, the invention relates to a precursor mixture which contains at least one precursor according to the second, third and / or fourth aspect of the invention, in particular two different precursors according to the second, third and / or fourth aspects of the invention.

The precursor mixture is preferably provided for the preparation of a hybrid silicic acid material, in particular for the production of a hybrid silicic acid material according to the first aspect of the invention.

In one embodiment, the precursor mixture comprises at least one precursor according to the second, third or fourth aspect of the invention.

In a further embodiment, the precursor mixture has at least one precursor according to the second and third aspects of the invention.

In a further embodiment, the precursor mixture has at least one precursor according to the second and fourth aspects of the invention.

In a further embodiment, the precursor mixture has at least one precursor according to the second, third and fourth aspects of the invention.

With regard to further features and advantages of the precursor mixture, in particular of individual precursors, reference is made in full to the previous description, in particular to the statements made in the context of the second, third and fourth aspects of the invention.

According to a sixth aspect, the invention relates to a method for producing a hybrid silicic acid material, in particular a hybrid silicic acid material according to the first aspect of the invention.

In the method, a precursor according to the second, third and / or fourth aspects of the invention or a precursor mixture according to the fifth aspect of the invention is subjected to a polycondensation, whereby a hybrid silica gel is obtained, which is optionally further processed. In one embodiment, a precursor according to the second, third or fourth aspects of the invention is subjected to a polycondensation, whereby a hybrid silica gel is obtained, which is optionally further processed.

In a further embodiment, a precursor according to the second and third aspect of the invention is subjected to a polycondensation, whereby a hybrid silica gel is obtained, which is optionally further processed.

In a further embodiment, a precursor according to the second and fourth aspect of the invention is subjected to a polycondensation, whereby a hybrid silica gel is obtained, which is optionally further processed.

In a further embodiment, a precursor according to the second, third and fourth aspect of the invention is subjected to a polycondensation, whereby a hybrid silica gel is obtained, which is optionally further processed.

As a rule, the polycondensation takes place in the context of a so-called sol-gel process.

The polycondensation is based on a hydrolysis of the precursors and subsequent condensation. The reactive groups here represent alkoxysilyl radicals and / or alkoxyalkylsilyl radicals of the precursors. First, a partial hydrolysis of the alkoxysilyl radicals takes place. The partially hydrolyzed precursors can then condense together with elimination of water. Starting from a dimer, trimers, tetramers, and other oligomers are formed until a particle is formed. Progressive particle growth and aggregation of sol particles results in secondary particles and an increase in viscosity. The result of the polycondensation process is finally a three-dimensional gel, which can then be further processed.

The polycondensation is carried out in a preferred embodiment in an aqueous solvent mixture. In addition to water, the solvent mixture preferably comprises an organic solvent. The organic solvent may be a protic solvent, an aprotic solvent or a mixture thereof. The organic solvent may for example be selected from the group comprising alcohols such as ethanol, ethers such as THF (tetrahydrofuran), chlorinated hydrocarbons such as dichloromethane and mixtures thereof. Furthermore, it is preferred if the polycondensation is carried out in the presence of a catalyst. The catalyst may be an acid, base, or nucleophile. For example, hydrochloric acid can be used as the acid. For example, caustic soda can be used as the base. As the nucleophile, for example, the fluoride anion (F) of a fluoride salt can function.

In a further embodiment, the polycondensation under reflux, in particular in a temperature range from 30 ° C to 150 ° C, preferably 50 ° C to 90 ° C, made.

In a further embodiment, the polycondensation is carried out during a period of 24 hours to 120 hours, in particular 72 hours to 120 hours or 24 hours to 72 hours, preferably 72 hours.

In a further embodiment, the hybrid silica gel obtained by polycondensation is already the hybrid silicic acid material to be produced.

In a preferred embodiment, however, the hybrid silica gel obtained by polycondensation is further processed. With regard to suitable further processing steps, reference is made to the statements made below.

In a preferred embodiment, the further processing of the resulting hybrid silica gel is in a drying of the hybrid silica gel. If drying takes place under normal pressure, a xerogel is obtained. In this case, the gel body shrinks strongly because act through the solvent in the pores of the gel network high capillary forces. During drying, reactive groups of contacting gel particles condense with each other, thereby changing the original microstructure of the gel. In other words, it is preferred according to the invention if the hybrid silica gel is further processed to form a xerogel or hybrid xerogel.

On the other hand, when drying the hybrid silica gel under increased pressure and elevated temperature, an airgel can be obtained. Under these conditions, the solvent in the pores of the gel network can be brought into a supercritical state. In this state, the solvent has lost its surface tension. There are no capillary forces. After draining the supercritical medium, the airgel remains. In other words, it can be provided according to the invention that the hybrid silica gel is further processed to form an airgel or hybrid ore bird. Alternatively, the resulting hybrid silica gel may be further processed into a powder or fibers.

A further processing of the hybrid silica gel to form so-called sol-gel layers is conceivable according to the invention.

In a preferred embodiment, the precursor or the precursor mixture is immobilized on a support before the polycondensation. In this case, the precursor and / or the precursor mixture can be immobilized covalently or noncovalently on the support. With regard to suitable carriers, reference is made in full to the previous description.

The method according to the invention can therefore in particular comprise the following steps: a) immobilizing a precursor according to the second or third aspect of the invention or a precursor mixture according to the fifth aspect of the invention on a support, b) polycondensing the immobilized precursor or immobilized precursor mixture to obtain a supported hybrid silica gel c) if necessary Further processing of the supported hybrid silica gel.

In an alternative embodiment, the hybrid silica gel obtained by polycondensation is immobilized on a support. In this case, the hybrid silica gel can be covalently or non-covalently immobilized on the support. With regard to suitable carriers, reference will also be made in full to the previous description.

For further features and advantages of the method, in particular the hybrid silica material, the hybrid silica gel, the precursor, the precursor mixture and the carrier, reference is made in full to the previous description.

According to a seventh aspect, the invention relates to a hybrid silicic acid material which can be obtained or produced by a process according to the sixth aspect of the invention.

For further features and advantages of the method and of the hybrid silica material, reference is made in full to the previous description. According to an eighth aspect, the invention relates to a filter device containing a hybrid silica material according to the first or seventh aspects of the invention.

With regard to further features and advantages of the filter device, in particular of the hybrid silica material, reference is made in full to the previous description.

According to a ninth aspect, the invention relates to a cartridge, preferably a filter cartridge, which contains a hybrid silica material according to the first or seventh aspect of the invention.

With regard to further features and advantages of the cartridge, in particular of the hybrid silica material, reference is made in full to the previous description.

According to a tenth aspect, the invention relates to a discharge device containing a hybrid silica material according to the first or seventh aspects of the invention.

With regard to further features and advantages of the discharge device, in particular of the hybrid silica material, reference is made in full to the previous description.

According to an eleventh aspect, the invention relates to a contact basin of a sewage treatment plant, wherein the contact basin contains a hybrid silicic acid material according to the first or seventh aspect of the invention. The contact basin is preferably a final contact basin. For the purposes of the present invention, the term "final contact basin" is to be understood as the last contact basin of a sewage treatment plant before the purified or treated water is returned to a natural watercourse.

With regard to further features and advantages of the contact basin, in particular of the hybrid silica material, reference is made in full to the previous description.

According to a twelfth aspect, the invention relates to a process for the purification of water, in particular for the treatment of drinking water or sanitation of wastewater.

In the method, water to be purified is passed through a hybrid silicic acid material according to the first or seventh aspect of the invention, through a filter device according to the eighth aspect of the invention, through a cartridge according to the ninth aspect of the invention, or through a contact basin according to the eleventh aspect of the invention. As a result, impurities contained in the water are fixed or bonded to the hybrid silicic acid material, whereby a cleaning effect is achieved.

With regard to further features and advantages of the method, in particular the hybrid silica material, reference is also made to the previous description.

According to a thirteenth aspect, the invention relates to a method for the examination of water for impurities.

In the method, the water to be examined is passed through a hybrid silica material according to the first or seventh aspect of the invention, through a filter device according to the eighth aspect of the invention, through a cartridge according to the ninth aspect of the invention or through a contact basin according to the eleventh aspect of the invention. Subsequently, the hybrid silica material is preferably examined for fixed or bound impurities and / or the water for remaining impurities.

According to the invention, it may be provided, for example, that the so-called TOC value (Total Organic Carbon value) and / or the so-called DOC value (Dissolved Organic Carbon value) of the water is investigated.

The investigation for impurities can be carried out by techniques known per se to the person skilled in the art. Examples include gas chromatography with mass spectrometry coupling (GCMS), liquid chromatography with mass spectrometry coupling (LCMS) and high performance liquid chromatography (HPLC).

With regard to further features and advantages of the method, in particular of the hybrid silica material and of the hybrid material, reference is likewise made to the previous description.

Finally, the invention relates to the use of a hybrid silicic acid material according to the first or seventh aspect of the invention

for the purification of water and / or

- to improve water quality and / or

- for the treatment of drinking water and / or

- for the rehabilitation of sewage and / or

- For the remediation of point source polluted water and / or

- for the remediation of natural waters and / or for condition checking, in particular quality control, of water and / or

- for the prevention of contamination in water and / or

for use as filter material and / or

for use in analytics, especially in solid phase microextraction.

With regard to further features and advantages of the hybrid silica material and of the hybrid material, reference is likewise made in full to the previous description.

Further features and advantages of the invention will become apparent from the following description of preferred embodiments in the form of embodiments, the accompanying figures and the claims. In this case, features can be implemented individually or in combination with each other. The embodiments described below are merely illustrative and for a better understanding of the invention and are in no way limiting.

1 . BRIEF DESCRIPTION OF THE DRAWINGS

Further advantages and aspects of the invention will become apparent from the claims and from the following description of preferred embodiments of the invention, which are explained below with reference to the figures. Showing:

Fig. 1 A: Basic structure of the precursors, whereby also three inorganic parts on an organic part are possible.

Fig. 1B: Principal mechanism of hybrid silicic acid material production.

FIG. 2A: Shown is the synthesis of N1, N4-bis ((3- (trimethoxysilyl) propyl) carbamoyl) terephthalamide (UTS), which is obtained by reacting terephthalic acid dichloride with 3-ureido-propyltrimethoxysilane.

2B shows the synthesis of N1, N4-bis ((3- (trimethoxysilyl) propyl) carbamoyl) terephthalamide hybrid silicic acid material (UTS-HS) which is obtained by reacting UTS with NaOH (basic) or HCl (acid, not shown).

Fig. 2C: Shown are two SEM (Scanning Electron Microscope) examinations of UTS-HS. FIG. 3A: Shown is the synthesis of 1,3,5-tris (3- (triethoxysilyl) propyl) -1,3,5-triazinane (TAC), which is prepared by reacting N, N, N ', N'- Tetramethylethane-1,2-diamine (TMEDA) - alternative to TMEDA also paraformaldehyde possible - is obtained with 3-aminopropyltriethoxysilane.

Figure 3B: Shown is the synthesis of 1,3,5-tris (3- (triethoxysilyl) propyl) -1,3,5-triazinane hybrid silica material (TAC-HS) prepared by reacting TAC in a basic (sodium hydroxide as Base) solvent mixture of water and ethanol is obtained.

Fig. 3C: Shown are three SEM (Scanning Electron Microscope) examinations of TAC-HS.

Fig. 4A: Schematic flow of polymer granules preparation.

Fig. 4B: Principle mechanism of removal of pharmaceuticals by means of hybrid silica material deposited on a polymer.

FIG. 5 shows the synthesis of the N1, N4-bis ((3- (trimethoxysilyl) propyl) carbamoyl) terephthalamide polymer granules, UTS being used as precursor and Ticona being the polymer.

Fig. 6: Shown is an exemplary section of a cyclodextrin molecule.

Fig. 7: Shown is an exemplary section of a cyclodextrin molecule.

2. DETAILED DESCRIPTION OF THE EMBODIMENTS

Generally, a temperature of 25 ° C should be understood to mean room temperature.

General Information and Techniques: The synthesis of the molecular precursors was carried out under a nitrogen atmosphere using a vacuum line and Schlenk technique. Terephthalic acid dichloride and 3-ureidopropyltrimethoxysilane were supplied by ABCR. Melting points were determined with a digiMelt electrothermal device from Scientific Instruments GmbH and are uncorrected. IR data were determined on a Perkin Elmer 2000 FT-IR spectrophotometer. SEM (Scanning Electron Microscope) images were taken with JEOL 200 CX and JEOL JEM 2010 microscopes obtained. SEM images were realized on a JEOL 6300F device.

The polymer Ticona is a research polymer of the type GUR4150 UHMW-PE. Preparation Precursors N1, N4 -bis ((3- (trimethoxysilyl) propyl) carbamoyl) terephthalamide (UTS)

The molecular precursor N1, N4-bis ((3- (trimethoxysilyl) propyl) carbamoyl) terephthalamide (UTS) is prepared by the reaction of terephthalic acid dichloride with 3-ureidopropyltrimethoxysilane (compare FIG. 2A).

Under an inert nitrogen atmosphere, add two equivalents of 3-ureidopropyltrimethoxysilane to one equivalent of terephthalic acid dichloride in THF solution. Then, two equivalents of sodium hydroxide are added and the reaction mixture is stirred for 48 hours. After removal of the solvent at 40 ° C / <1 mmHg, the residue is treated with 200 ml of deionized water. After filtration and drying by means of nitrogen flow, a slightly yellow solid was obtained. Yield: 80-95%; Melting point:> 260 ° C; IR (KBr pellet): \ z (cm ¹ ) = 3314 (NH), 1724 (CO), 1652 (CO), 1550 (NH); Elemental analysis: calculated (%) for

eq DCM: C 41.88, H 6.1 1, N 8.49; found: C 41.77, H 5.43, N: 10.20. 1, 3,5-tris (3- (triethoxysilyl) propyl) -1,3,5-triazinane (TAC)

In a heated and nitrogen-purged three-necked flask, one equivalent of TMEDA (N, N, N ', N'-tetramethylethane-1, 2-diamine) is placed in toluene dissolved and treated with three equivalents of 3-aminopropyltriethoxysilane. Alternatively, paraformaldehyde can be used instead of TMEDA. The reaction solution is refluxed to boiling and the stoichiometrically formed water is removed by means of a water separator. After removal of the solvent, the product is in the form of a viscous liquid (see Figure 3A).

Physical properties: viscous liquid. N ²⁰ : 1, 447. ¹ H NMR (CDCl ₃ ): 0.55, m, 2H; 1 .15, t, ³ J = 7.8Hz, 9H; 1 .52, m, 2H; 2.35, m, 2H; 3.23, b, 2H; 3.75, q, ³ J = 7.8 Hz, 6H. ¹³ C NMR (CDCl ₃ ): 7.95, 18.24, 20.90, 55.78, 58.25, 74.601. ²⁹ Si NMR (CDCl ₃ ): -44.98 ppm. Preparation of Hybrid Silica Gel N1, N4-bis ((3- (trimethoxysilyl) propyl) -carbamoyl) terephthalamide Hybrid Silica Material (UTS-HS)

For the synthesis of the N1, N4-bis ((3- (trimethoxysilyl) propyl) -carbamoyl) terephthalamide hybrid silica material (UTS-HS), N1, N4 -bis ((3- (trimethoxysilyl) propyl) carbamoyl) terephthalamide (UTS, 10g , 17.4 mmol) completely dissolved in THF (150 ml) in a 500 ml round-bottomed flask. As soon as water (200 ml) was added, a white precipitate appeared. The reaction mixture (white suspension) was fitted with a reflux condenser and immersed in an oil bath (80 ° C). The solution was then adjusted to pH 3-4 by adding 20 ml of an aqueous HCl solution (1 M). After two hours of refluxing, a white precipitate formed and was slowly cooled to room temperature and stirred for an additional 5 days at this temperature. The finished product was filtered off after this time, washed with 200 ml of water and dried at 80 ° C for 3 days in a drying oven. The molar ratio of the mixture was as follows: UTS / H 2 O / T HF / HCl 1: 20: 15: 2. The resulting white solid was filtered and washed successively with water. Careful drying of the gel at 110 ° C resulted in a white powder (Figure 2B).

Alternatively, UTS-HS can also be synthesized by employing a molar ratio of UTS / H ₂ O / THF / NaOH 1: 100: 100: 20 and adjusting the solution to a pH of 12 by adding a 2M NaOH solution instead of HCl. After the pH adjustment is slowly cooled to room temperature, forming a cloudy precipitate after 6 hours. The solvent is removed within 7 days by means of an applied temperature gradient. Yield: 87%; Melting point> 260 ° C; IR (KBr pellet): ((cm ¹ ) = 1560 (NH), 1635 (CO), 1652 (CO), 3455 (NH), 3744 (Si-O-Si). In other words, the IR analysis shows a band characteristic of the corresponding hybrid silica gel in the range of 1560 (NH), 1635 (CO), 1652 (CO), and 3455 cm ^-1 (NH) A strong band at 3744 will account for the Si-O-Si vibration of the corresponding Si Associated with junctions in the hybrid network. The adsorption properties of UTS-HS were investigated by means of the adsorption isotherm of Brunauer, Emmett and Teller (BET). The application of the BET equation gave a total surface area of 192.039 m ² / g.

The corresponding SEM (Scanning Electron Microscope) investigations show for this self-organized network a tubular structure in the form of about 100 nm long needles (see Figure 2C). On closer examination it becomes clear that the core of these needles is hollow. 1, 3,5-tris (3- (triethoxysilyl) propyl) -1,3,5-triazinane hybrid silica material (TAC-HS)

100 ml of 1, 3,5-tris (3- (triethoxysilyl) propyl) -1,3,5-triazinane (TAC), 50 ml of ethanol and 100 ml of water are introduced into a 250 ml two-necked flask. The reaction solution is heated to 80 ° C and treated with 0.1 ml of 2M NaOH solution. The resulting turbid solution is stirred for a further 12 h at 80 ° C. Thereafter, the stirring is stopped and from the cloudy solution is formed within 7 days, a white Neiderschlag. This is filtered off after the reaction is brought to RT and washed with water and acetone. After the crude product has been oven-dried at 80 ° C., the TAC-HS is present as a white, voluminous, porous powder (compare FIG. 3B).

SEM investigations were carried out analogously to the investigation of the UTS-HS.

Compact material with dendritic networks. The material is not hollow and has optimized surfaces, compared to UTS, for heavy metal fixation (see Figure 3C). UTS TAC HS

In a 100 ml two-necked flask, N1, N4 -bis ((3- (trimethoxysilyl) propyl) carbamoyl) terephthalamide (UTS) (0.460 g, 0.8 mmol) and 1, 3,5-tris (3- (triethoxysilyl ) propyl) -1, 3,5-triazinane (TAC) (0.070 g, 0.1 mmol) with 4.4 ml of THF and stirred for a few minutes at RT. The reaction solution is then added 0.15 ml (1 M) of HCl and 8.8 ml of H ₂ O, whereupon it becomes cloudy. It is further heated at 60 ° C for 3 days under reflux, the magnetic stirrer is turned off after one day. The resulting white solid is filtered off and washed several times with THF. The solid is then dried in a dry place at 60 ° C.

Claims

claims

Hybrid silicic acid material, preferably for the removal of anthropogenic impurities from water and / or for the detection of anthropogenic impurities from water, comprising

Structural units A, which each have the formula I:

Formula I

in which

Z is a functional group which is preferably selected from the group comprising carbonyl group, carboxy group, oxycarbonyl group, carbamoyl group, amine group, amide group, carbon-carbon double bond, carbon-carbon triple bond and combinations thereof, or denotes a heteroatom,

Structural units B, which each have the formula II:

Formula II where

R '= Ft "= Ft"', Ft '= Ft "Φ Ft"', Ft '+ Ft "= Ft"' or Ft 'Φ R "Ft"', and Ft ', Ft "and Ft"', respectively independently of one another are a divalent organic radical and n is an integer from 1 to 1, in particular 1 to 7, preferably 1 to 3, particularly preferably 1, and / or

Structural units C, which each have the formula III *:

Formula III *

Hybrid silicic acid material according to claim 1, characterized in that the structural units A are each part of a larger structural unit A ₂ according to formula Ib:

Formula Ib where

Y and Z are the same or different and each independently represents a functional group which is preferably selected from the group comprising carbonyl group, carboxy group, oxycarbonyl group, carbamoyl group, amine group, amide group, carbon-carbon double bond, carbon-carbon triple bond and combinations thereof, or denote a heteroatom and

Ri = R ₂ = Ft ₃ , Ri = Ft ₂ * Ft ₃ , Ri * Ft ₂ = ₃ or Φ R ₂ + R ₃ and R 1, R ₂ and R ₃ each independently represent a divalent organic radical.

Hybrid silicic acid material according to claim 1 or 2, characterized in that Z represents a carbonyl group or Y and Z each represent a carbonyl group.

Hybrid silicic acid material according to claim 2 or 3, characterized in that Ri is a divalent aryl radical, preferably a divalent phenyl radical.

Hybrid silicic acid material according to one of claims 2 to 4, characterized in that R ₂ and R _{3 are the} same and each have a bivalent organic radical, in particular each divalent alkyl radical having an odd number of carbon atoms, preferably having 3, 5, 7, 9 or 1 1 carbon atoms, mean.

6. hybrid silicic acid material according to any one of the preceding claims, characterized in that the structural units B are each part of a larger structural unit B ^ according to formula IIa:

Formula IIa where

R '= R "= R'", R '= R "+ R'", R '+ R "= R'" or R 'φ R "R'", and R ', R "and R'" are each independently of one another are a divalent organic radical and n is an integer from 1 to 11, in particular 1 to 7, preferably 1 to 3, particularly preferably 1, and

7. hybrid silicic acid material according to claim 6, characterized in that R ', R "and R'" are the same and each represents a divalent alkyl radical, preferably a divalent methyl radical, and n = 1.

8. hybrid silicic acid material according to claim 6 or 7, characterized in that R ₄ , R ₅ and R _{6 are the} same and each have a bivalent organic radical, in particular a bivalent alkyl radical having an odd number of carbon atoms, in particular 3, 5, 7, 9 or 1 1 carbon atoms, mean.

9. hybrid silicic acid material according to any one of the preceding claims, characterized in that the structural units C are each part of a larger structural unit C ₂ according to formula IIIb *:

wherein R ₇ and R _{8 are the} same or different and each independently represents a divalent organic radical, preferably having an odd number of carbon atoms, in particular having 3, 5, 7, 9 or 1 1 carbon atoms.

10. hybrid silicic acid material according to any one of claims 1 to 8, characterized in that the structural units C are each part of a larger structural unit C ₅ according to formula Never * are:

Formula Never * in which

R ₇ and R _{8 are the} same or different and each independently is a divalent organic radical, preferably having an odd number of carbon atoms, in particular having 3, 5, 7, 9 or 1 1 carbon atoms, and

R _{9 is} a divalent cyclodextrin.

1 1. Hybrid silica material according to one of the preceding claims, characterized in that the hybrid silica material is a hybrid silica gel, in particular a dried hybrid silica gel.

12. Organosilicon precursor, in particular for producing a hybrid silicic acid material according to one of the preceding claims, characterized in that the precursor from the group comprising or consisting of

Precursor according to formula IV:

Formula IV where

Y and Z are the same or different and each independently represents a functional group which is preferably selected from the group comprising carbonyl group, carboxy group, oxycarbonyl group, carbamoyl group, amine group, amide group, carbon-carbon double bond, carbon-carbon triple bond and combinations of which, or mean a heteroatom,

Ri = R ₂ = R ₃ , Ri = R ₂ * R ₃ , Ri * R ₂ = R ₃ or Φ R ₂ + R ₃ and R 1, R ₂ and R ₃ each independently represent a divalent organic radical,

R ¹ and R ^{4 are} identical or different and each independently of one another is a monovalent alkyl radical, in particular selected from the group consisting of a monovalent methyl radical and a monovalent ethyl radical, R ² and R ^{5 are} identical or different and are each independently a monovalent alkoxy radical, in particular selected from the group comprising monovalent methoxy radical and monovalent ethoxy radical, or a monovalent alkyl radical, in particular selected from the group comprising monovalent methyl radical and monovalent ethyl radical, and

R ³ and R ^{6 are} identical or different and are each independently a monovalent alkoxy radical, in particular selected from the group comprising monovalent methoxy radical and monovalent ethoxy radical, or a monovalent alkyl radical, in particular selected from the group comprising monovalent methyl radical and monovalent ethyl radical,

Precursor according to formula V:

Si (OR ⁷ ) (R ⁸ ) (R ⁹ )

i

R ₄

(R ¹⁵ ) (R ¹⁴ ) (R ¹³ O) S ^R 6 ^R 5

Si (OR ¹⁰ ) (R ¹¹ ) (R ¹² )

Formula V where

R '= R "= R'", R '= R "+ R'", R '+ R "= R'" or R 'φ R "R'", and R ', R "and R'" are each independently of one another are a divalent organic radical and n is an integer from 1 to 1, in particular 1 to 7, preferably 1 to 3, particularly preferably 1,

R ⁷ = R ¹⁰ = R ¹³ , R ⁷ = R ¹⁰ Φ R ¹³ , R ⁷ Φ R ¹⁰ = R ¹³ or R ⁷ Φ R ¹⁰ Φ R ¹³ and R ⁷ , R ¹⁰ and R ¹³ each independently form a monovalent Alkyl radical, in particular selected from the group comprising monovalent methyl radical and a monovalent ethyl radical, mean R ⁸ = R ¹¹ = R ¹⁴ , R ⁸ = R ¹¹ Φ R ¹⁴ , R ⁸ + R ¹¹ = R ¹⁴ or R ⁸ Φ R ¹¹ Φ R ¹⁴ and R ⁸ , R ¹¹ and R ¹⁴ each independently of one another Alkoxy radical, in particular selected from the group comprising monovalent methoxy radical and monovalent ethoxy radical, or monovalent alkyl radical, in particular selected from the group comprising monovalent methyl radical and a monovalent ethyl radical, and

R ⁹ = R ¹² = R ¹⁵ , R ⁹ = R ¹² R ¹⁵ , R ⁹ Φ R ¹² = R ¹⁵ or R ⁹ Φ ² Φ R ¹⁵ and R ⁹ , R ¹² and R ¹⁵ each independently represent a monovalent alkoxy radical, in particular selected from the group comprising monovalent methoxy radical and monovalent ethoxy radical, or monovalent alkyl radical, in particular selected from the group consisting of a monovalent methyl radical and a monovalent ethyl radical, and

Precursor according to formula VI:

(R ²¹ ) (R ²⁰ ) (R ¹⁹ O) Si ^' 8ϊ (Ο ¹⁶ ) ( ¹⁷ ) ( ^Ί0 )

Formula VI

in which

R ₇ and R _{8 are the} same or different and each independently represents a divalent organic radical,

R ¹⁶ and R ^{19 are} identical or different and each independently of one another are a monovalent alkyl radical, in particular selected from the group consisting of a monovalent methyl radical and a monovalent ethyl radical, R ¹⁷ and R ^{20 are} identical or different and are each independently a monovalent alkoxy radical, in particular selected from the group comprising monovalent methoxy radical and monovalent ethoxy radical, or monovalent alkyl radical, in particular selected from the group comprising monovalent methyl radical and monovalent ethyl radical, and

R ¹⁸ and R ^{21 are} identical or different and are each independently a monovalent alkoxy radical, in particular selected from the group comprising monovalent methoxy and monovalent ethoxy, or monovalent alkyl radical, in particular selected from the group comprising monovalent methyl radical and a monovalent ethyl radical.

13. organosilicon precursor according to claim 12, characterized in that the precursor according to formula IV has the following features:

- Y and Z are each a carbonyl group (C = 0) and / or

and or

R † is a divalent aryl radical, preferably a divalent phenyl radical, and / or

- R ₂ and R ₃ are the same and each represents a divalent alkyl radical having an odd number of carbon atoms, preferably having 3, 5, 7, 9 or 1 1 carbon atoms and / or

- R ¹ and R ⁴ are the same and each represents a monovalent methyl or ethyl radical and or

- R ² and R ⁵ are the same and each represent a monohydric methoxy or ethoxy radical and / or

- R ³ and R ⁶ are the same and each represents a monohydric methoxy or ethoxy radical.

14. organosilicon precursor according to claim 12, characterized in that the precursor according to formula V has the following features:

- R ', R "and R'" are the same and each represents a divalent alkyl group, preferably a divalent methyl group and / or

- R ₄ , R ₅ and R ₆ are the same and each represents a divalent alkyl radical having an odd number of carbon atoms, preferably having 3, 5, 7, 9 or 1 1 carbon atoms and / or

- R ⁷ , R ¹⁰ and R ¹³ are the same and each represents a monovalent methyl or ethyl radical and / or

- R ⁸ , R ¹¹ and R ¹⁴ are the same and each represents a monohydric methoxy or ethoxy radical and / or

R ⁹ , R ¹² and R ¹⁵ are the same and each represents a monohydric methoxy or ethoxy radical.

15. organosilicon precursor according to claim 12, characterized in that the precursor according to formula VI has the following features:

- R ₇ and R ₈ are the same and each represents a divalent alkyl radical having an odd number of carbon atoms, preferably having 3, 5, 7, 9 or 1 1 carbon atoms and / or

- R ¹⁶ and R ¹⁹ are the same and each represents a monovalent methyl or ethyl radical and / or

- R ¹⁷ and R ²⁰ are the same and each represents a monohydric methoxy or ethoxy radical and / or

- R ¹⁸ and R ²¹ are the same and each represents a monohydric methoxy or ethoxy radical.

16. A modified precursor comprising a precursor according to any one of claims 12 to 15 and a carrier on which the precursor is immobilized.

17. precursor mixture, in particular for producing a hybrid silicic acid material according to one of the preceding claims, containing at least one precursor, in particular at least two different precursors, according to any one of claims 12 to 16.

18. A process for producing a hybrid silicic acid material, in particular according to one of claims 1 to 1 1, wherein at least one precursor according to any one of claims 12 to 16 or a precursor mixture according to claim 17 is subjected to a polycondensation, whereby a hybrid silica gel is obtained, which optionally is further processed. Hybrid silicic acid material, obtainable or preparable by a method according to claim 18.

Filter device, cartridge or contact basin containing a hybrid silicic acid material according to any one of claims 1 to 11 or 19.