HK1201865B - Mixtures, particularly low in volatile organic compounds (voc), of olefinically functionalized siloxane oligomers based on alkoxy silanes - Google Patents

Description

Particularly low VOC mixtures of olefinically functionalized siloxane oligomers based on alkoxysilanes

The present invention relates to selected, in particular low VOC, compositions of ethylenically functionalized siloxane oligomers derived from ethylenically functionalized alkoxysilanes, which may be in the form of a mixture of ethylenically functionalized siloxane oligomers and which have at most one olefinic group per silicon atom, to a process for their preparation and to their use.

The use of mixtures of linear and cyclic siloxane oligomers in the production of thermoplastics and elastomers is a long established experience. Nowadays, however, there is an increasing demand for efforts to work in as low a VOC as possible, for example in the crosslinking of thermoplastics and also elastomers, in particular in the production of cables (VOC — volatile organic compounds).

The reaction of vinyltriethoxysilane, optionally in a mixture with alkyltriethoxysilane and/or tetraethoxysilane, by catalytic hydrolysis and condensation of acidic HCl in alcohol in the presence of a calculated amount of water is an established experience. The alcohol is subsequently removed. The acid used remains in the product or, in the case of hydrogen chloride (HCl), has to be removed again from the crude product produced after the reaction of the organofunctional alkoxysilane in an expensive and cumbersome step, so as not to aggravate the corrosion of the metal surfaces of the processing machines. This is accomplished by distillation of the crude siloxane product.

In applications, such as the production of filled cable materials, oligomers are often used with polymers and functionalized fillers in compounding machines. In the case of discontinuous processes, this takes place in internal mixers or on mixing rolls, and, in the case of continuous compounding processes, this takes place in twin-screw extruders or co-kneaders. Typical processing temperatures are here 130 ℃ and 270 ℃, i.e.at the point of addition of the silane compound (depending on the process), which is the inlet of the compounding machine or the polymer melt (depending on the process), temperatures above the boiling points of the silane monomer and the distillable oligomer prevail. Experience teaches that, in addition to unwanted active loss, the incidence of free silane compound deposition on the internal shell wall or on the exhaust area is increased. These deposits are based on the degradation products of evaporated silanes or distillable oligomers. Serious conditions may occur with these potentially alcohol-containing vapors, which may enter the inlet area and may contact the hot surface in the case of reverse venting. Such challenges also occur in partially filled areas of compounding assemblies, or in their vented areas. For these reasons, in general, the compounds used must have very high flash points. In the case of filled polymer compounds, it is also necessary to calculate the hydrolysis alcohol released, which is generated during the hydrolysis reaction of the ester groups of the silicon functional groups of the silane or silane oligomer in the compound. In summary, the reduction of VOCs (volatile organic compounds) is therefore a very important criterion for this technology.

As already mentioned above, the normal operating temperatures for compounding processes are generally above 101 ℃ and for e.g. kneading often occur at 170 ℃. 180 ℃. thus there is a continuing need for VOC-reduced and less corrosive oligomers which as far as possible no longer contain any acidic compounds, such as formic acid, HCl or chlorine-containing compoundsy 2010, Section 7.2 CorrosionResistance, page 200-²And in total may amount to up to 105 g/m in the presence of chloride². Thus, in the oligomers prepared according to the invention, the amount of hydrolysis and condensation catalyst is reduced as far as possible to a content in the weight ppm to weight ppt range, or to the detection limit.

However, as well as corrosion during processing, the presence of chloride/chloride ions or acids also plays an important part in end applications, such as in cable insulation systems. As well as possible corrosion on the insulated current conductor, possible negative effects influence the electrical properties of the cable insulation itself, it being absolutely necessary in the case of halogen-free compounds containing flame retardants to avoid corrosive and halogen-containing combustion gases. This requirement of course applies to all the raw materials used in these compounds.

These requirements will be fully met by avoiding or minimizing chloride and acid content in the siloxane oligomers of the present invention as previously described.

Furthermore, increasing interest has focused on silane systems which contain less and less organic solvents and are therefore more ecologically friendly. For this reason, there is a tendency to provide precondensed, low VOC silane systems which, however, must then be stabilized since they still contain the catalyst or from which the catalyst must be removed in an expensive and cumbersome step.

EP0518057B1 discloses a process for preparing mixtures of linear and cyclic siloxane oligomers. According to examples 1 and 6, the respective product mixtures were prepared by hydrolysis and condensation of vinyltrialkoxysilanes, or of mixtures of vinyl-and alkyltrialkoxysilanes, the hydrolysis and condensation being carried out using 0.63 mol of water per mole of Si in the silane used. Furthermore, in the process disclosed therein, the HCl catalyst cannot be completely removed, and about 50 to about 230 ppm of corrosion residual amounts of HCl remain even in the product distilled according to the process disclosed therein.

The mixture of oligomeric alkoxysilanes thus obtained contains a high content of alkoxy groups, since, depending on the amount of water used for hydrolysis, only small amounts of hydrolyzed alcohol are formed in the reaction, and in the oligomer mixture there is still a high VOC content which can be released in the form of alcohol in the case of the ingress of water in the application of the oligomer mixture. Furthermore, the alcohol can be released upon ingress of moisture or by continued condensation in the oligomer mixture. If the alcohol is released in this way during storage of the oligomer mixture, the result is generally an undesirable reduction in flash point. The product according to EP0518057B1 is subjected to severe distillation under vacuum in an expensive and energy-intensive manner in a work-up. The oligomer mixture is applied as a cross-linking agent to thermoplastic polyolefins by graft polymerization and hydrolytic condensation.

US 6,395,856B 1 discloses the hydrosilylation of oligomers containing organofunctional silicon, for example of vinylmethoxysilanolate obtained from the reaction of vinyltrimethoxysilane in the presence of formic acid in a protective gas without a diluent.

CN 100343311C describes silane oligomers obtained by catalytic hydrolysis and condensation of vinyltrimethoxysilane. The use of a metal salt catalyst (e.g., copper hydroxide) in combination with an acid is necessary. Removal of the catalyst is expensive and cumbersome and it is likely that catalyst residues and/or neutralization products remain in the product and have deleterious effects in many applications. Thus, this document discloses, for example, the removal of acids by neutralization with calcium carbonate and filtration of the resulting calcium salt.

In the prior art, the flash point drops in a few days during storage below 50 ℃ for several siloxane oligomers are due to too high a concentration of catalyst residues in the composition. Other compositions from the prior art, in turn, exhibit excessive mass loss of up to 25 wt% around 150 ℃, and substantial mass loss of about 50-90 wt% around 200 ℃.

JP 10298289A describes siloxanes with a high molecular weight in the 10000 g/mol range which are prepared by hydrolysis and precondensation or condensation of vinyl-or phenyl-functional alkoxysilanes in the presence of acid catalysts, which are subsequently removed from the product mixture by means of anhydrous anion exchangers. Such high molecular weight materials cannot be used in most applications due to high viscosity and insufficient reactivity.

Organosiloxane oligomers with multiple possible functional groups, average molecular weights in the range Mn = 350 and 2500 g/mol, and polydispersities (D = Mw/Mn) of 1.0-1.3 are described in JP 2004099872. The preparation takes place from very dilute aqueous solutions in the presence of a basic catalyst, with very low, economically undesirable space-time yields; in this way, 1 l of solution yielded 1 ml of isolated product. The teaching of JP 2004099872A cannot be reproduced in the disclosed way. For example, many times, example 1 could not be reproduced in the indicated manner.

It is an object of the present invention to provide further, in particular pure, olefinic siloxane oligomers, more particularly low VOC mixtures based on alkenyl alkoxysilanes, or in particular olefinically functionalized and alkyl functionalized siloxane oligomers, more particularly low VOC mixtures based on alkenyl-/alkyl-alkoxysilanes, and also to provide a process for preparing such mixtures. It further relates to the use of the low VOC silicone oligomers of the present invention to improve the processability of thermoplastics or elastomers and to improve the properties of the thermoplastics or elastomers produced therewith. Furthermore, the siloxane oligomers should have very high flash points andeven at high temperatures with an approved low VOC and should be able to be used in the field at elevated temperatures without further safety measures. The siloxane oligomers themselves also show only a small loss of mass at high temperatures, for example in extruders. The key point associated with processability is also the rapid dispersibility of the siloxane oligomer in thermoplastics, coupled with very low mass loss at a given temperature in extruder applications. It can be an additional advantage if the chlorine content, in particular the total chloride content and/or the content of other hydrolysable chlorides, is as small as possible. Furthermore, the olefinic siloxane oligomer should exhibit a high storage stability even over a prolonged period of storage and, at the same time, preferably, also an increase in viscosity, for example by avoiding gelation or flocculation or condensation of the mixture over a relatively long period of time. In addition, the amount of monomers in the ethylenically functionalized siloxane oligomer should be low, or preferably should no longer be present, any monomers which would lead to undesired subsequent crosslinking, and at the same time the process should be economically more profitable than the known corresponding processes. While another object is to produce a catalyst having a low VOC content and<3000, more particularly low, of a viscosity of less than or equal to 1000mPa s and preferably of greater than or equal to 5 mPa s, to ensure optimum processability of the siloxane oligomer in the application.

The object is achieved according to the independent claims; preferred embodiments are set forth in detail in the dependent claims and in the description.

It has surprisingly been found that olefinically functionalized alkoxysilanes and optionally alkylalkoxysilanes and optionally tetraalkoxysilanes can be converted easily and economically, optionally in the presence of a solvent, preferably an alcohol, into compositions of particularly low VOC olefinic siloxane oligomers by reaction with a specified amount of water of greater than or equal to 1.1 to 1.59 moles of water per mole of silicon atom in the alkoxysilane used (1.0 to 1.6 or 1.60 moles of water are also suitable), with substantial removal of the hydrolysis alcohol and optionally the solvent; in particular, only the solvent and/or the hydrolysis alcohol is removed by distillation. The fact that the siloxane oligomers obtained in this way already exhibit a very low total chloride content in the form of a bottom product is surprising. According to the invention, the compositions thus obtained have a particularly low chloride content and a particularly low VOC content.

In contrast to known oligomers, the compositions of the present invention and the siloxane oligomer compositions prepared by the process of the present invention do not require further processing, such as distillation of the siloxane oligomer composition. The compositions prepared, the siloxane oligomer bottoms, show properties which are comparable to or improved over known siloxane oligomers which have been purified by distillation and which have been obtained according to somewhat different methods. Thus, according to the present invention, the siloxane oligomer obtained no longer needs to be distilled itself, and instead it can be obtained and used in pure form as a bottom product. Thus, the composition can also be obtained in higher yields.

The present invention therefore provides compositions comprising an ethylenically functionalized siloxane oligomer having at most one ethylenic group on a silicon atom, said ethylenically functionalized siloxane oligomer having a Si-O-crosslinking structural element that forms a chain, cyclic, crosslinked, and/or three-dimensionally crosslinked structure, wherein at least one structure ideally corresponds to formula I

(R¹O)[(R¹O)_1-x(R²)_xSi(A)O]_a[Si(Y)₂O]_c[Si(B)(R⁴)_y(OR³)_1-yO]_bR³(I)，

-wherein the structural element is derived from an alkoxysilane, and

a in the structural element corresponds to an olefinic group and is chosen in particular from linear, branched or cyclic alkenyl-or cycloalkenyl-alkylene-functional groups having in each case 2 to 16C atoms, and

b in the structural element corresponds to a saturated hydrocarbon group and is chosen in particular from linear, branched or cyclic alkyl groups having 1 to 16C atoms,

y corresponds to OR³OR, independently of one another, correspond to OR in the crosslinked and optionally three-dimensionally crosslinked structure³Or O_1/2，

-wherein R is¹Independently of one another, corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4C atoms, and/or is optionally H,

- R³each independently of the others, corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4C atoms and/or is optionally H, and R²Each independently corresponds to a linear, branched or cyclic alkyl group having 1 to 15C atoms, more particularly 1 to 8C atoms, optionally having 1 to 6C atoms, and R⁴Each independently corresponding to a linear, branched or cyclic alkyl group having 1 to 15C atoms, more particularly 1 to 8C atoms, optionally having 1 to 6C atoms,

a, b, c, x and y independently correspond to integers, and 1. ltoreq. a, 0. ltoreq. b, 0. ltoreq. c, x independently of one another is 0 or 1, y independently of one another is 0 or 1, and (a + b + c). gtoreq.2,

in particular, the chlorine content, preferably the total chloride content, is less than or equal to 250 mg/kg, more preferably less than or equal to 150 mg/kg, preferably less than or equal to 100 mg/kg, more preferably less than or equal to 75 mg/kg, still more preferably less than or equal to 50 mg/kg, further preferably less than or equal to 35mg/kg, in particular in the composition in the form of a bottom product, and in particular

-wherein the structural element [ (R)¹O)_1-x(R²)_xSi(A)O]_a、[Si(B)(R⁴)_y(OR³)_1-yO]_bAnd [ Si (Y)₂O]_cOverall, i.e., all, preferably co-present in formula I, greater than or equal to 10%, based on all silicon atoms of formula I, as T structure, with the proviso that 1. ltoreq. a, 0. ltoreq. b, 0. ltoreq. c and (a + b + c). gtoreq.2Or, alternatively, all structural elements [ (R)¹O)_1-x(R²)_xSi(A)O]_aGreater than or equal to 5%, more particularly greater than or equal to 7.5%, preferably greater than or equal to 10%, more preferably greater than or equal to 11%, still more preferably greater than or equal to 13%, further preferably greater than or equal to 15%, alternatively greater than or equal to 20% or, according to a further preference, greater than or equal to 25% are present as T structures, based on the total number of silicon atoms in formula I. Also discloses a structural element [ (R)¹O)_1-x(R²)_xSi(A)O]_a、[Si(B)(R⁴)_y(OR³)_1-yO]_bAnd [ Si (Y)₂O]_cOverall, i.e. all, are present together in formula I, greater than or equal to 5%, preferably greater than or equal to 10%, based on all silicon atoms of formula I.

The invention also provides a composition comprising an ethylenically functionalized siloxane oligomer having at most one ethylenic group on a silicon atom, the ethylenically functionalized siloxane oligomer having a Si-O-crosslinking structural element that forms a chain, cyclic, crosslinked, and/or three-dimensionally crosslinked structure, wherein at least one structure ideally corresponds to formula I, the siloxane oligomer having a structural element derived from at least one alkoxysilane,

(i) derived from an olefinically functionalized alkoxysilane of the formula II,

A-Si(R²)_x(OR¹)_3-x(II)

wherein A corresponds to an olefinic group and is more particularly selected from linear, branched or cyclic alkenyl-or cycloalkenyl-alkylene-functional groups each having 2 to 16C atoms, wherein R²Independently of one another, is a linear, branched or cyclic alkyl radical having 1 to 15C atoms, and x is independently of one another 0 or 1, x is preferably 0, and R is¹Independently corresponding to a linear, branched and/or cyclic alkyl group having 1 to 4C atoms, more particularly to a methyl, ethyl or propyl group, or optionally an alkoxy group derived from formula IISilane mixtures or transesterification products, and

(ii) optionally derived from alkoxysilanes of formula III functionalized with saturated hydrocarbon groups,

B-Si(R⁴)_y(OR³)_3-y(III)

wherein B corresponds to an unsubstituted hydrocarbon radical and is more particularly selected from linear, branched or cyclic alkyl radicals having 1 to 16C atoms, wherein R is⁴Independently of one another, is a linear, branched or cyclic alkyl radical having 1 to 15C atoms, and y is independently of one another 0 or 1, and R³Independently corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4C atoms, more particularly to a methyl, ethyl or propyl radical, wherein B is preferably a methyl, ethyl or propyl radical and y is preferably 0, or optionally is a mixture of alkoxysilanes of the formula III or transesterification products thereof, and

(iii) optionally derived from Si (OR) of formula IV³)₄Wherein R is³Independently of one another, as defined above, wherein the chlorine content, more particularly the total chloride content, is less than or equal to 250 mg/kg, the structural elements being present together, greater than or equal to 10%, based on all silicon atoms of the siloxane oligomer, as T structure.

It is also disclosed that, together, greater than or equal to 5%, based on all silicon atoms of the siloxane oligomer, of the structural elements are present as T structures, more particularly greater than or equal to 7.5%, preferably greater than or equal to 10%, more preferably greater than or equal to 11%, still more preferably greater than or equal to 13%, further preferably greater than or equal to 15%, alternatively greater than or equal to 20% or, according to a further alternative, greater than or equal to 25%.

The chlorine content, preferably the total chloride content, is preferably less than or equal to 250 mg/kg, more preferably less than or equal to 35mg/kg down to the detection limit. Down to preferably less than or equal to 0.001 mg/kg.

The present invention provides compositions in which less than or equal to 15% (area%, GPC) of disiloxanes and tricyclosiloxanes, more preferably less than or equal to 12%, are present, wherein, in particular, greater than or equal to 10% of the T structures are produced in the siloxane oligomer, wherein the amount of trisiloxane, cyclotetrasiloxane, tetrasiloxane, cyclopentasiloxane, pentasiloxane and/or cyclohexasiloxane is preferably greater than or equal to 60% (GPC), more preferably greater than or equal to 65%, very preferably greater than or equal to 70% (area%, GPC) of the total composition. Alternatively or additionally, where preferred trisiloxanes, cyclotetrasiloxanes, tetrasiloxanes and cyclopentasiloxanes have been greater than or equal to 40% by area (GPC), preferably greater than or equal to 45%, more preferably greater than or equal to 50%, more preferably greater than or equal to 55%, very preferably greater than or equal to 60%, and especially less than or equal to 65% (area%, GPC) of the total composition. It is generally the case that the designations disiloxane, trisiloxane, tetrasiloxane, pentasiloxane encompass linear and/or branched siloxanes, respectively, and cyclotrisiloxane, cyclotetrasiloxane, cyclopentasiloxane or cyclopentasiloxane encompass cyclic siloxanes.

The amount of trisiloxane and cyclotetrasiloxane may also be greater than or equal to 15% by area (GPC), preferably greater than or equal to 20% (area%, GPC), of the total composition. And preferably less than or equal to 50%, more preferably less than or equal to 20%, and very preferably less than 15%. Alternatively or additionally, wherein it is preferred that the amount of tetrasiloxane and cyclopentasiloxane is already greater than or equal to 20% by area (GPC), preferably greater than or equal to 25%, more preferably greater than or equal to 30% (area%, GPC), and preferably less than or equal to 50%, more preferably less than or equal to 40% of the total composition. It is particularly preferred that greater than or equal to 70% of the siloxane oligomer is present in the composition in the form of disiloxanes, cyclotrisiloxanes, trisiloxanes, cyclotetrasiloxanes, tetrasiloxanes, cyclopentasiloxanes, pentasiloxanes and/or cyclohexasiloxanes, preferably greater than or equal to 75%, more preferably greater than or equal to 80%, still more preferably greater than or equal to 85%, preferably greater than or equal to 90%. In TGA, these particularly preferred siloxane oligomer compositions exhibit a mass loss of greater than or equal to 50% only above 240 ℃, more preferably above 250 ℃, and the temperature at which 50% mass loss occurs can also be as high as 530 ℃.

Also provided by the present invention are compositions in which greater than or equal to 30% (area%, GPC) has a Mw of 500-750 (relative Mw), more particularly from greater than or equal to 30% to 50%, more preferably from 35% to 45% has a Mw of 500-750.

The composition of the invention comprising a siloxane oligomer preferably exhibits a mass loss at 150 ℃ (TGA) of only less than 5%, and more preferably exhibits a mass loss at 200 ℃ of only less than or equal to 20%, more particularly less than or equal to 15%, more preferably less than or equal to 10% (mass loss in wt%).

The compositions obtainable according to the invention are therefore very suitable for use in hot extruders, since they release only few VOCs even at very high temperatures and exhibit a constant very low loss of mass and, owing to the constant low mass distribution, they exhibit uniform properties in application. By means of a particularly adjusted molar mass distribution, more particularly in the range of trisiloxanes, cyclotetrasiloxanes, tetrasiloxanes, cyclopentasiloxanes, pentasiloxanes and/or cyclohexasiloxanes, a uniform and rapid distribution in polymers and prepolymers, such as PE, PP, etc., can be achieved, wherein the mass loss during processing can at the same time be kept very small.

Furthermore, preferred compositions comprising the ethylenically functionalized siloxane oligomer and, in particular, the siloxane oligomer of the formula I have a weight average molecular weight (Mw) of greater than or equal to 500 g/mol, more particularly greater than or equal to 520-1100 g/mol, preferably 520-800 g/mol, more preferably 550-770 g/mol, and a number average molecular weight (Mn) of preferably greater than or equal to 450 g/mol, more particularly up to 800g/mol, preferably greater than or equal to 450-650 g/mol, and a polydispersity of preferably from 1.1 to 1.8, preferably from 1.13 to 1.45, more preferably from 1.1 to 1.3, still more preferably from 1.1 to 1.25 or from 1.1 to 1.21.

Particularly preferred are compositions comprising ethylenically functionalized siloxane oligomers and, in particular, siloxane oligomers of the formula I having a weight average molecular weight (Mw) of greater than or equal to 564-1083 g/mol. Of these, it is preferred that greater than or equal to 85%, preferably 90% (area%, GPC), have a molecular weight (Mw) of less than 1000 g/mol. In particular, a combination of a Mw of 500-750 (relative Mw) of greater than or equal to 30% (area%, GPC, Mw) and a Mw of from greater than or equal to 30% to 50%, more preferably from 35% to 45% of 500-750. All numbers are always to be understood as being based on the total composition.

Particularly preferred compositions have an ethylenically functionalized siloxane oligomer present in greater than or equal to 30% (area%, GPC) of the entire composition, more particularly greater than or equal to 30% to less than or equal to 50%, more preferably 35% to 50%, and having a molecular weight (Mw) of 500-700 g/mol in the composition. Also preferred are compositions comprising an ethylenically functionalized siloxane oligomer present as trisiloxane, tetrasiloxane, pentasiloxane, cyclotetrasiloxane, cyclopentasiloxane, and/or cyclohexasiloxane, and also as a mixture comprising at least two of the foregoing siloxanes, to an extent of greater than or equal to 60% (area%, GPC), more particularly greater than or equal to 65%, preferably greater than or equal to 70%. It is particularly preferred in the present invention if the composition of the invention has a mass loss of 50% by weight, as determined in particular simultaneously by TGA, which occurs at a temperature above 240 ℃, more particularly above 250 ℃. Furthermore, a particularly preferred composition for said application in an extruder shows a mass loss of less than or equal to 5 wt.%, more particularly less than or equal to 1-4 wt.%, preferably less than or equal to 1-3 wt.% of the composition at temperatures up to and including 150 ℃, as determined by TGA (platinum crucible, vented lid, 10K/min). Furthermore, alternatively or additionally, the composition exhibits a mass loss of less than 20 wt%, more particularly less than or equal to 15 wt%, preferably less than or equal to 10 wt%, optionally between 3 and 15 wt% of the composition at temperatures up to and including 200 ℃, as determined by TGA (platinum crucible, vented lid, 10K/min).

Weight average molecular weight (Mw)

And number average molecular weight (Mn)

In each case, n_iAmount of substance (= i-mer) mass]，M_iMolar mass of i-mer. Details concerning the definition of weight-average molecular weight and number-average molecular weight are known per se to the person skilled in the art and can optionally be found by the reader from sources including the internet (http:// de. wikipedia. org/wiki/molossverteilung) or from standard works of mathematics.

In the process of the present invention, the alkoxysilane of the formula II in which x is 0 can be reacted on its own or with an alkoxysilane of the formula III in which y is 1 or 0.

All alkyl radicals, e.g. R¹、R²、R³And R⁴Having 1 to 4C atoms, which may each, independently of one another, preferably be methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl and/or 2-methylbutyl having 5C atoms. Alkyl radicals R in the context of the invention²And R⁴May, independently of one another, correspond to linear, branched or cyclic alkyl groups having 1 to 15C atoms. Alkyl radical R²And R⁴Can be selected, independently of one another, from methyl, ethyl, propyl, butyl, isobutyl, n-butyl, tert-butyl, pentyl, n-pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, cyclohexyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, octyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, C₁₃H₂₇、C₁₄H₂₉And C₁₅H₃₁Radicals or cyclopentyl, ringsHexyl, and also alkyl-substituted cyclopentyl and cyclohexyl.

The transesterification product may comprise alkoxysilanes having different alkoxy groups, for example alkoxysilanes of the general formulae II, IV or I which are functionalized with methoxy and ethoxy groups. The siloxane oligomers and alkoxysilanes of the formulae II, III and IV can be present in the form of transesterification products. Thus, for example, the alkoxysilanes of the formula II can be present in the form of methoxysilanes, ethoxysilanes or mixed-functionalized methoxyethoxysilanes. Correspondingly, the alkoxysilanes of the formula III can also be methoxysilanes, ethoxysilanes or mixtures of mixed-functional methoxyethoxysilanes. Corresponding remarks apply to the ethylenically functionalized siloxane oligomer, more particularly to the ethylenically functionalized siloxane oligomer of formula I; as R¹And R³There may be methyl or ethyl groups and both groups, which may be present in the form of methoxy-functional oligomers and ethoxy-functional oligomers.

In addition to the aforementioned characteristics, the amount of monomeric alkoxysilane in the composition of the invention is significantly reduced. Accordingly, the present invention also provides compositions comprising an ethylenically functionalized siloxane oligomer wherein the amount of silicon atoms of the monomeric alkoxysilane is less than or equal to 3% up to as low as the detection limit or 0.0% (based on all silicon atoms), preferably less than 2% to 0.0%, more preferably less than or equal to 1.5% to 0.0%, and optionally preferably less than or equal to 2% to 0.0% by weight, more preferably less than or equal to 1% by weight, and the amount of monomer is still more preferably less than or equal to 0.5 to 0.0% by weight, and still more preferably less than 0.3 to 0.0% by weight. Monomeric alkoxysilanes are to be understood as alkoxysilanes of the general formulae II, III and/or IV and also their monomeric hydrolysis products. By for example²⁹Si NMR spectroscopy to detect the amount per percent.

According to a particularly preferred embodiment, the olefinic group a in formula I and/or II corresponds to a non-hydrolysable olefinic group, more particularly to a linear, branched or cyclic, alkenyl-or cycloalkenyl-alkylene-functional group, each having 2 to 16C atoms, preferably to a vinyl, propenyl, butenyl group, e.g. a 3-butenyl, pentenyl, hexenyl, ethylhexenyl, heptenyl, octenyl, cyclohexenyl-C1 to C8-alkylene group, preferably cyclohexenyl-2-ethylene group, e.g. a 3' -cyclohexenyl-2-ethylene group and/or a cyclohexadienyl-C1 to C8-alkylene group, preferably a cyclohexadienyl-2-ethylene group.

It is also preferred that the unsubstituted hydrocarbon radicals B in the formulae I and/or III may independently correspond to linear, branched or cyclic alkyl radicals having 1 to 16C atoms, more particularly methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, n-octyl, isooctyl, octyl or hexadecyl radicals. It is also preferred that the group B is independently selected from the group consisting of tert-butyl, pentyl, n-pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, heptyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, neooctyl, nonyl, decyl, undecyl, dodecyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 2-dimethylhexyl, 2, 3-dimethylhexyl, 2, 4-dimethylhexyl, 2, 5-dimethylhexyl, 3, 3-dimethylhexyl, 3, 4-dimethylhexyl, 3-ethylhexyl, 2, 3-trimethylpentyl, 2, 4-trimethylpentyl, 2,3, 3-trimethylpentyl, 2,3, 4-trimethylpentyl group, 3-ethyl-2-methylpentyl group, 3-ethyl-3-methylpentyl group, 2,3, 3-tetramethylbutyl group, C₁₃H₂₇、C₁₄H₂₉And C₁₅H₃₁A group. According to an alternative, the alkyl group may be a branched or cyclic group having 3 to 16C atoms or a linear group having 2 to 7C atoms.

It is particularly preferred if, in the formulae I and/or II, the olefinic group A is vinyl and, in the formulae I and/or II, independently of one another, the unsubstituted hydrocarbon radical B is selected from the group consisting of methyl, ethyl, propyl, butyl, isobutyl, n-butyl, tert-butyl, pentyl, n-pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, heptyl, octyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecylBase, C₁₃H₂₇、C₁₄H₂₉、C₁₅H₃₁And hexadecyl, and R¹Independently of one another, methyl, ethyl or propyl and R³Independently methyl, ethyl or propyl.

According to the invention, the structural element [ (R) in the formula I¹O)_1-x(R²)_xSi(A)O]_a、[Si(B)(R⁴)_y(OR³)_1-yO]_bAnd [ Si (Y)₂O]_cTogether, greater than or equal to 10% of all silicon atoms of formula I are present as T structures, more particularly greater than or equal to 11%, preferably greater than or equal to 13%, more preferably greater than or equal to 15%, optionally greater than or equal to 20% or, according to a further alternative, greater than or equal to 25%. Advantageously, it is also possible for greater than or equal to 7.5% to be present as T structure.

The ethylenically functionalized siloxane oligomer also preferably has a ratio of silicon atoms to A and B groups, with the proviso that a is greater than or equal to 1, B is greater than or equal to 0 and c is greater than or equal to 0, and (a + B + c) is greater than or equal to 2, the ratio of Si to (A + B groups) is from 1:1 to about 1.22:1, preferably from 1:1 to 1.15: 1.

The invention also provides compositions comprising ethylenically functionalized siloxane oligomers which have at most one olefinic group on a silicon atom, and in which, in particular, each is selected independently of the others,

(i) structural element [ (R) in the general formula I¹O)_1-x(R²)_xSi(A)O]_aGreater than or equal to 5%, more particularly greater than or equal to 7.5%, based on all the silicon atoms of formula I, present as T structure, further preferably greater than or equal to 10%, preferably greater than or equal to 11%, more preferably greater than or equal to 15%, alternatively greater than or equal to 20% or, according to another alternative, greater than or equal to 25%, and optionally greater than or equal to 7.5% of the total silicon atoms of formula I

(ii) Structural element [ (R) in the general formula I¹O)_1-x(R²)_xSi(A)O]_aAnd [ Si (B) (R) ]⁴)_y(OR³)_1-yO]_bAnd [ Si (Y)₂O]_cGreater than or equal to 50% of all the silicon atoms of formula I are present together as D structure, more particularly greater than or equal to 55%, preferably greater than or equal to 57.5%, more preferably greater than or equal to 60%, and optionally

(iii) Structural element [ (R) in the general formula I¹O)_1-x(R²)_xSi(A)O]_aLess than or equal to 35% of all silicon atoms of formula I are present as M structures, more particularly less than or equal to 30%, preferably less than or equal to 25%, more preferably less than or equal to 20%, alternatively less than or equal to 20%, or according to a further alternative less than or equal to 15%, and preferably more than 3% are present as M structures, and optionally

(iv.a) structural element [ Si (B) (R) in the general formula I⁴)_y(OR³)_1-yO]_bLess than or equal to 35% of the total silicon atoms of formula I are present as M structures, more particularly less than or equal to 30%, preferably less than or equal to 25% are present as M structures, more particularly less than or equal to 22%, preferably less than or equal to 20%, more preferably less than or equal to 18%, optionally preferably less than or equal to 15%, and preferably greater than 7%, and/or optionally

(iv.b) structural element [ Si (B) (R) in the general formula I⁴)_y(OR³)_1-yO]_bGreater than or equal to 5% is present as T structure, more particularly greater than or equal to 7.5%, more particularly greater than or equal to 10%, preferably greater than or equal to 11%, more preferably greater than or equal to 15%, optionally greater than or equal to 20%, or according to another alternative, greater than or equal to 25%, and/or optionally

(v) Structural element in general formula I [ Si (Y)₂O]_cGreater than or equal to 20% being present as D structure, or, more particularly, greater than 40% of the structural element [ Si (Y) ] of formula I₂O]_cPresent as D structure, more particularly greater than 45%, preferably greater than 50%, more preferably greater than 55%.

The invention also provides compositions comprising an ethylenically functionalized siloxane oligomer having more than one olefinic group on a silicon atom and each being independently selected from,

(iii) structural element [ (R) in the general formula I¹O)_1-x(R²)_xSi(A)O]_aLess than or equal to 35% of the total silicon atoms of formula I are present as M structures, more particularly less than or equal to 30%, preferably less than or equal to 25%, more preferably less than or equal to 20%, alternatively less than or equal to 20% or, according to another alternative, less than or equal to 15%, and preferably more than 3%, and, if present, (iv.a) the structural element in formula I [ si (b)) (R⁴)_y(OR³)_1-yO]_bLess than or equal to 20%, more particularly less than or equal to 18%, preferably less than or equal to 15%, and preferably more than 7% based on all the silicon atoms of formula I are present.

According to one alternative, the present invention provides a composition comprising an ethylenically functionalized siloxane oligomer having at most one olefinic group on a silicon atom, in particular an ethylenically functionalized siloxane oligomer of formula I, with the proviso that a is greater than or equal to 1 and b and c are 0, i.e. a pure olefinic siloxane oligomer without alkyl groups.

The present invention also provides compositions comprising an ethylenically functionalized siloxane oligomer having at most one olefinic group on a silicon atom, more particularly an ethylenically functionalized siloxane oligomer of formula I, with the proviso that a and b are greater than or equal to 1 and c is 0, more particularly no Q structure, i.e., no Si (O-) forming a Q structure₄Radical and no Si (O-)₄Pure olefinic and alkyl-functional siloxane oligomers of segments. The two above-mentioned compositions have the desired viscosity on the basis of these conditions and exhibit processing with them, application to surfaces, in their applicationOr outstanding properties in connection with polymer processing.

According to a further alternative, particularly preferred compositions comprise an ethylenically functionalized siloxane oligomer having at most one olefinic group on a silicon atom, and wherein the structural element in formula I [ (R) is¹O)_1-x(R²)_xSi(A)O]_aThe composition has an M structure of 3% to 35%, more particularly 5% to 33%, more preferably 5% to 25%, based on all silicon atoms of formula I, a being greater than or equal to 1, b being greater than or equal to 0 and c being greater than or equal to 0, more particularly provided that the structural element [ (R) in formula I¹O)_1-x(R²)_xSi(A)O]_aAt the same time from 50% to 75% are present as D structure, preferably from 50% to 70%, and optionally, moreover, greater than or equal to 8% are present as T structure, more particularly greater than or equal to 10%. In the alternative, b is additionally greater than or equal to 1, the structural element Si (B) (R) in the formula I⁴)_y(OR³)_1-yO]_bPresent in 3% to 35% as M structure, more particularly, provided c is 0. According to an alternative, a, b and c are greater than or equal to 1, the siloxane oligomer, calculated as the sum of all silicon atoms, having a T structure of less than 8%; in particular, the structural element [ (R) in the formula I¹O)_1-x(R²)_xSi(A)O]_aHas a T structure of less than 5%. These compositions also still exhibit the desired viscosity, in particular those having less than 5% of T structure, wherein additionally the saturated hydrocarbon radicals B preferably have from 1 to 6C atoms, more preferably from 1 to 4C atoms.

The amount of M, D, T or Q structure present is determined according to methods known to the person skilled in the art, for example preferably by²⁹Method of Si NMR.

The ratio of M: D: T structures in the olefinic siloxane oligomer of the invention is preferably from 5:10:1 to 3:5: 1.

More preferably the ratio of T to D structures in all structural elements of formula I is from 1:10 to 1:2, more particularly from 1:8 to 1:3, preferably from 1:6 to 1:3, more preferably from 1:5 to 1:3, more particularly additionally the amount of T structures in all structural elements of formula I is greater than or equal to 5%, preferably greater than or equal to 7.5%. Optionally preferably, the ratio of T to D structures in the olefinic siloxane oligomer is from 1:10 to 1:2, more particularly from 1:8 to 1:3, preferably from 1:6 to 1:3, more preferably from 1:5 to 1:3, more particularly additionally the amount of T structures in the siloxane oligomer is greater than or equal to 5%, preferably greater than or equal to 7.5%.

More particularly, in addition to the amount of T structures being greater than or equal to 10% of formula I in all structural elements of formula I, it is also preferred that the ratio of M to D structures is from 1:100 to 2.5:1, preferably from 1:10 to 2.5:1, particularly preferably from 1:100 to 1:2, more particularly from 1:5 to 1:2, further preferably from 1:5 to 1:1, more preferably from 1:4 to 1:2, or, in the alternative, in the olefinic siloxane oligomer. It has also been found to be advantageous for the amount of T structures to be greater than or equal to 7.5%.

The compositions having the aforementioned structure possess a high flash point and exhibit particularly low VOC contents in the case of subsequent applications. A notable advantage of the compositions of the present invention and the processes of the present invention is that the olefinic siloxane oligomers prepared, and more particularly the vinyl oligomers, differ from known oligomers in that no further work-up, such as distillation of the siloxane oligomer composition, is required.

According to the invention, an acidic catalyst which is gaseous under standard conditions, more particularly HCl, which is soluble in the aqueous phase or in the alcoholic phase, is used as hydrolysis and/or condensation catalyst. The reaction thus takes place under homogeneous catalytic conditions. It is a surprising advantage that the removal of the gaseous catalyst from the composition by the process of the present invention is almost completely successful.

Particular advantages of the ethylenically functionalized siloxane oligomers of the present invention also include that the reduced hydrolyzable VOC content and increased siloxane oligomer T structure content directly improve the processability of the siloxane oligomer with the polymer, for example, during kneading or compounding. In particular, there is an improvement in melt index, thereby reducing energy consumption during processing. Furthermore, the corrosion of iron-containing machines is reduced, since a further reduction of the chloride content can be achieved. In addition, the water absorption capacity of the polymers compounded with the siloxane oligomers of the present invention is reduced and, in addition, often their elongation at break and generally tensile strength are increased. The reduced water absorption capacity is beneficial in later application areas, for example in the production of filled cable materials, especially for cables which are buried in soil and subject to permanent moisture.

As explained below by way of example for the alkoxysilyl units, the definition of M, D, T and Q structure generally refers to the number of oxygens bound in a siloxane bond: r independently of one another is OR as defined above¹、OR³Group A or group B. Wherein M = [ -O ]_1/2–Si(R)₃]，D = [–O_1/2-Si(R)₂–O_1/2–]，T = [RSi(–O_1/2–)₃]And Q = [ Si (-O) ]_1/2–)₄]。–O_1/2For a more precise nomenclature of the nomenclature of these siloxane structures, the reference "R ö mppChemielixkon" -keyword: polysiloxane. for example, from the structural unit M, only dimers M which may be formed are M₂Such as hexaalkoxy disiloxane. Chain construction requires a combination of building blocks D and M, so that terpolymers (M) can be constructed₂D, octaalkoxy trisiloxane), tetramer (M)₂D₂) And so on up to M₂D_nThe linear oligomer of (1). The formation of cyclic oligomers requires structural unit D. In this manner, for example, a structure having D can be constructed₃、D₄、D₅Or a higher ring. When the structural units T and/or Q are present together, branched and/or crosslinked structural elements are obtained, below which it is also possible to have spiro compounds. Can think ofThe cross-linked structure of the image may be represented by T_n(n≥4)、D_nT_m(m<n)、D_nT_m(n>>m)、D₃T₂、M₄Q、D₄Q, etc. forms exist to give only a few conceivable possibilities. The building block M is also referred to as a polymerization inhibitor or transfer agent, while the D block is referred to as a chain former or ring former, and the T, or Q, block is also referred to as a network former. The use of tetraalkoxysilanes allows the introduction of the structural units Q due to the four hydrolyzable groups and the ingress of water and/or moisture, and thus the formation of a network (three-dimensionally crosslinked). In contrast, completely hydrolyzed trialkoxysilanes can lead to branching compounds in the structural element, i.e.T units [ -Si (-O-)_3/2]E.g. MD₃TM₂For oligomers with an oligomerization degree of n = 7, the respective functionality in the free valency of the silyloxy units can be defined in these structural representations.

Further details of the nomenclature understanding of M, D, T and Q structures, and related analytical methods, include the following:

- “Strukturuntersuchungen von oligomeren und polymeren Siloxanendurch hochauflösende²⁹Si-Kernresonanz”, H. G. Horn, H. Ch. Marsmann, DieMakromolekulare Chemie 162 (1972), 255-267；

- “Über die¹H-,¹³C- und²⁹Si-NMR chemischen Verschiebungen einigerlinearer, verzweigter und cyclischer Methyl-Siloxan-Verbindungen”, G.Engelhardt, H. Jancke; J. Organometal. Chem. 28 (1971), 293-300；

- “Chapter 8 - NMR spectroscopy of organosilicon compounds”,Elizabeth A. Williams, The Chemistry of Organic Silicon Compounds, 1989 JohnWiley&Sons Ltd., 511-533。

the compositions and/or siloxane oligomers may also preferably have trialkylsilane groups, for example trimethylsilane or triethylsilane groups, for example by adding alkoxytrialkylsilanes to adjust the degree of oligomerization.

To achieve the stated object, preference is given to compositions which provide a mixture of olefinic siloxane oligomers, in which, in particular, more than 20% by weight of the siloxane oligomers have a degree of oligomerization of greater than or equal to 4, optionally greater than or equal to 8, i.e. the number of silicon atoms (n) per oligomer is optionally greater than or equal to 8 (n>8) More preferably, the siloxane oligomer having T structure is contained in an amount of not less than (C:)>)5%, more particularly greater than or equal to 6%, wherein the simultaneous dynamic viscosity is preferably less than or equal to (C<)3000 mPas and more particularly greater than or equal to 5 mPas, preferably less than or equal to 1000, preferably less than or equal to 500 mPas and more particularly greater than or equal to 10 mPas, more preferably less than or equal to 250 mPas. It is preferred, furthermore, if the viscosity of the composition comprising the ethylenically functionalized silicone is less than or equal to 3000 mPa s and greater than 7mPa s, preferably less than or equal to 2500 and greater than 10 mPa s, optionally less than or equal to 1000mPa s and greater than or equal to 12 mPa s.

In general, the siloxane oligomer may be a linear and/or cyclic oligomer having M and D structures and a T structure. The tetraalkoxysilane is added only during preparation or prior to processing of the oligomer to form a siloxane oligomer having M, D, Q and optionally a T structure. The composition of the invention has a siloxane oligomer, more particularly a siloxane oligomer of formula I, in which the sum of (a + b) is an integer greater than or equal to 2, more particularly greater than or equal to 4 to 30, further preferably greater than or equal to 6 to 30, particularly preferably greater than or equal to 8 to 30, and c is optionally greater than or equal to 1, for example 1 to 20, more particularly 2 to 15. In the case of too high an oligomerization degree, it is not possible to achieve uniform and reproducible product properties in the siloxane oligomer. In order to adjust the degree of oligomerization during the preparation of the composition, it can therefore be advantageous to add an alkoxytrialkylsilane, for example preferably ethoxytrimethylsilane or methoxytrimethylsilane, to the composition to be prepared for chain termination at the desired point in time.

The compositions of the invention may have at least 20% by weight of siloxane oligomers for which the degree of oligomerization n of the ethylenically functionalized siloxane oligomers is greater than or equal to 4, more particularly greater than or equal to 6, very preferably greater than or equal to 4, optionally greater than or equal to 8. It is further preferred in the context of the present invention if, for at least 20% by weight of the siloxane oligomers, more particularly of the siloxane oligomers of the formula I, the sum of (a + b) is an integer greater than or equal to 5, more particularly the sum of (a + b) is greater than or equal to 6, preferably the sum of (a + b) is greater than or equal to 4, optionally greater than or equal to 8, wherein a is greater than or equal to 1 and b is equal to 0 or b is greater than or equal to 1, preferably a and b are each, independently of one another, greater than or equal to 2, more particularly independently greater than or equal to 4, and optionally wherein c in (a + b + c) is greater than or equal to 1.

According to a preferred alternative, b is greater than or equal to 1, more particularly greater than or equal to 2, preferably greater than or equal to 4. Further preferred is at least 20 wt% of an olefinically functionalized siloxane oligomer, more particularly of formula I, having a degree of oligomerization (a + b + c) of greater than or equal to 5, optionally a degree of oligomerization (a + b + c) of greater than or equal to 8, wherein a is greater than or equal to 1, and optionally b is greater than or equal to 1 and optionally c is greater than or equal to 1, wherein the siloxane oligomer content with T structure is greater than or equal to: (a + b + c)>)5% and preferably a viscosity of less than or equal to (C:)<) 1000 mPas. It is further preferred that the T structure content in the siloxane oligomer is greater than or equal to 10% and that the viscosity is at the same time less than or equal to 500 mPa s.

Particularly preferred compositions comprise siloxane oligomers, wherein

a) Siloxane oligomers and at least one structure of the formula I, each derived from alkoxysilanes of the formula II, having a vinyl group as olefinic group A, where R¹Independently of one another, corresponds to a methyl or ethyl group,

b) a siloxane oligomer and at least one structure of the formula I, respectively derived from an alkoxysilane of the formula II, having a vinyl group as olefinic group A, and fromAn alkoxysilane of the general formula III having a propyl group as unsubstituted hydrocarbon radical B, where R¹And R³Each independently of the other, corresponds to a methyl or ethyl radical, or

c) Siloxane oligomers and at least one structure of the formula I, derived from alkoxysilanes of the formulae II and IV and optionally III, respectively, selected from a) or b), where R is³Derived from formula IV and each independently of the other corresponds to a methyl or ethyl group.

It is also preferred that the compositions each independently comprise a siloxane oligomer having at least one structure derived from at least one ethylenically functionalized alkoxysilane of the formula II selected from vinyltriethoxysilane, vinyltrimethoxysilane and optionally from a structural element of the formula III and optionally at least one structure of the formula I wherein the alkoxysilane of the formula III is selected from methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, butyltriethoxysilane, butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltrimethoxysilane, isobutyltriethoxysilane, isobutyltrimethoxysilane, hexyltriethoxysilane, hexyltrimethoxysilane, n-hexyltriethoxysilane, a silicone oligomer derived from at least one ethylenically functionalized alkoxysilane of the formula II and optionally from a structural element of the formula I, N-hexyltrimethoxysilane, isohexyltriethoxysilane, isohexyltrimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, isooctyltriethoxysilane, isooctyltrimethoxysilane, undecyltriethoxysilane, undecyltrimethoxysilane, decyltriethoxysilane, decyltrimethoxysilane, nonadecyltriethoxysilane, nonadecyltrimethoxysilane, dodecayltriethoxysilane, dodecamethyltrimethoxysilane, C₁₃H₂₇Triethoxysilane, C₁₃H₂₇Trimethoxy silane, C₁₄H₂₉Triethoxysilane, C₁₄H₂₉Trimethoxy silane, C₁₅H₃₁-trimethoxySilane, C₁₅H₃₁Triethoxysilane, hexadecyltriethoxysilane and hexadecyltrimethoxysilane, dimethyldimethoxysilane (DMDMO), dimethyldiethoxysilane, propylmethyldimethoxysilane, propylmethyldiethoxysilane, n-octylmethyldimethoxysilane, n-hexylmethyldimethoxysilane, n-hexylmethyldiethoxysilane, propylmethyldiethoxysilane, cyclohexyltriethoxysilane, n-propyltri-n-butoxysilane, hexadecylmethyldimethoxysilane and/or hexadecylmethyldiethoxysilane, and mixtures of these silanes, or mixtures comprising at least two of these silanes, and transesterification products thereof.

It is further preferred that the compositions each independently comprise a siloxane oligomer having a derived structural element and optionally at least one structure of formula I formed from at least one ethylenically functionalized alkoxysilane of formula II selected from alkoxysilanes of formula II having an olefinic group a selected from at least one of the following: allyl, butenyl, 3-butenyl, pentenyl, hexenyl, ethylhexenyl, heptenyl, octenyl, cyclohexenyl-C1 to C8-alkylene, cyclohexenyl-2-ethylene, 3' -cyclohexenyl-2-ethylene, cyclohexadienyl-C1 to C8-alkylene and cyclohexadienyl-2-ethylene groups, wherein R is a radical of formula¹Independently of one another, corresponding to methyl or ethyl, or from at least one of the abovementioned olefinically functionalized alkoxysilanes of the formula II, particular preference being given to combinations of cyclohexenyl-2-ethylene-or cyclohexadienyl-2-ethylene-functionalized alkoxysilanes of the formula II and alkoxysilanes of the formula III, where at least one alkoxysilane of the formula III is selected from methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, butyltriethoxysilane, butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltrimethoxysilane, isobutyltriethoxysilane, orMethoxysilane, hexyltriethoxysilane, hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltrimethoxysilane, isohexyltriethoxysilane, isohexyltrimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, isooctyltriethoxysilane, isooctyltrimethoxysilane, undecyltriethoxysilane, undecyltrimethoxysilane, decyltriethoxysilane, decyltrimethoxysilane, nonadecyltriethoxysilane, nonadecyltrimethoxysilane, dodecayltriethoxysilane, dodecayltrimethoxysilane, C₁₃H₂₇Triethoxysilane, C₁₃H₂₇Trimethoxy silane, C₁₄H₂₉Triethoxysilane, C₁₄H₂₉Trimethoxy silane, C₁₅H₃₁Trimethoxy silane, C₁₅H₃₁Triethoxysilane, hexadecyltriethoxysilane and hexadecyltrimethoxysilane, and transesterification products thereof.

Additionally or alternatively to one or more of the aforementioned features, preferably after complete hydrolysis of all alkoxy groups, the composition of the invention has an alcohol content (VOC) of less than or equal to 20% by weight, more particularly less than or equal to 18% by weight, preferably less than or equal to 15% by weight, more preferably less than or equal to 12% by weight (including all values located therein, more particularly 19, 17, 16, 14, 13, 12, 11, 10, etc.), provided that the amount of water added is only as much as the amount of water required for hydrolysis. There was no further dilution for the assay.

Additionally or alternatively to one or more of the foregoing features, the composition preferably has a molar ratio of a groups to B groups of from 1:0 to 1:8, preferably from about 1:0 to 1:4, more preferably from 1:0 to 1:2, preferably from 1:0 to 1:1, preferably about 1:1.

It is further preferred in the present invention if the composition comprises an olefinic siloxane oligomer in which

(i) The ratio of silicon atoms (selected from the group consisting of ethylenically functionalized silicon atoms and from silicon atoms functionalized with saturated hydrocarbons) to alkoxy groups in the siloxane oligomer or optionally in formula I is from 1:0.3 to 1:2.0, more preferably from 1:1.0 to 1:1.8, yet more preferably from 1:0.4 to 1:1.5, 1:0.4 to 1:1.2, preferably from 1:0.4 to 1:1.1, more preferably from 1:0.4 to 1:0.9, further preferably from 1:0.4 to 1:0.8, more particularly from 1:0.4 to 1:0.7, with the proviso that the ethylenically functionalized siloxane oligomer is derived from alkoxysilanes of formulae II and III,

(ii) the ratio of silicon atoms (selected from the group consisting of ethylenically functionalized silicon atoms and from silicon atoms functionalized with saturated hydrocarbons) to alkoxy groups in the siloxane oligomer or optionally in formula I is from 1:0.5 to 1:2.5, more particularly from 1:0.5 to 1:1.0, optionally from 1:0.9 to 1:2.5, more particularly from 1:0.9 to 1:1.5, more particularly from 1:1.0 to 1:1.4, preferably from 1:1.0 to 1:1.3, more preferably from 1:1.0 to 1:1.2, provided that the ethylenically functionalized siloxane oligomer is derived from alkoxysilanes of formulae II and IV and formula III.

It is also preferred that the compositions of the present invention, additionally or optionally, may have an ethylenically functionalized siloxane oligomer, wherein the ratio of M structures to D structures of silicon atoms in the ethylenically functionalized siloxane oligomer is preferably in the range of 1:1.5 to 1:10, wherein preferably 5% of the silicon atoms are present as T structures. Preferred ratios of M structure to D structure are from 1:2 to 1:10 with greater than or equal to 5% of T structure, more particularly from 1:2.5 to 1:5, for example preferably about 1: 2.5; 1: 3.5; 1: 4.5; 1: 5; 1: 6; 1: 7; 1:8 or 1:9, and all values in between.

According to one alternative, compositions of purely ethylenically substituted siloxane oligomers are prepared, in particular siloxane oligomers of the general formula I in which a is an integer greater than or equal to 2, wherein preferably at least 20% by weight of the siloxane oligomers are present with a greater than or equal to 4, optionally greater than or equal to 8. Preferred olefinic groups are linear, branched or cyclic, alkenyl-, cycloalkenyl-alkylene-functional groups, each having 2 to 16C atoms, preferably vinyl, allyl, butenyl, e.g. 3-butenyl, pentenyl, hexenyl, ethylhexenyl, heptenyl, octenyl, cyclohexenyl-C1 to C8-alkylene, preferably cyclohexenyl-2-ethylene, e.g. 3' -cyclohexenyl-2-ethylene and/or cyclohexadiene-C1 to C8-alkylene, preferably cyclohexadienyl-2-ethylene groups. The composition may optionally be based on a siloxane oligomer that has been prepared in the presence of a tetraalkoxysilane.

In accordance with a second preferred alternative, compositions of ethylenically substituted and alkyl substituted siloxane oligomers are prepared, more particularly siloxane oligomers of the general formula I having a greater than or equal to 1 and b greater than or equal to 1, and in particular at least 20% by weight of the siloxane oligomers have an integer (a + b) greater than or equal to 4, preferably greater than or equal to 8. These compositions are further preferred if the molar ratio of A groups to B groups is from 1:0 to 1:8, more particularly the ratio of a: B is from 1:0 to 1:8, more particularly from 1:0 or from 1:1 to 1: 8. The composition may optionally be based on a siloxane oligomer that has been prepared in the presence of a tetraalkoxysilane.

Corresponding to a further preferred alternative, vinyl-and alkyl-substituted siloxane oligomers are prepared, more particularly siloxane oligomers of the general formula I in which a is greater than or equal to 1 and B is greater than or equal to 1, and in particular 20% by weight of the siloxane have (a + B) greater than or equal to 4, optionally an integer greater than or equal to 8, preferably the molar ratio of the a groups to the B groups is from 1:0 to 1:8, more particularly a: B is from 1:0 to 1:8, more particularly from 1:0 or from 1:1 to 1: 8. The composition may optionally be based on a siloxane oligomer that has been prepared in the presence of a tetraalkoxysilane.

Further preferred, the composition comprises a siloxane oligomer having structural elements obtainable OR derived from at least one alkoxysilane, derived from an olefinically functionalized alkoxysilane of the formula II, and optionally derived from an alkoxysilane of the formula III functionalized with a saturated hydrocarbon radical, and optionally derived from Si (OR)³)₄Wherein preferably at least 20% by weight of the siloxane oligomers have a (a + b + c) of greater than or equal to 4, optionally greater than or equal toDegree of oligomerization of 8.

The structural element (monomeric siloxane unit) consistently refers to structural unit M, D, T or Q alone, i.e., the structural unit is derived from an alkoxy-substituted silane and is formed by at least partial hydrolysis to optionally full hydrolysis and at least partial condensation to a condensate. According to the invention, siloxane oligomers having the following structural elements, for example, preferably: (R)¹O)[(R¹O)_1-x(R²)_xSi(A)O]_aR¹；(R¹O)[(R¹O)_1-x(R²)_xSi(A)O]_a；[(R¹O)_1-x(R²)_xSi(A)O]_a；[(R¹O)_1-x(R²)_xSi(A)O]_aR¹；(R³O)[Si(Y)₂O]_c；[Si(Y)₂O]_cR³；(R³O)[Si(Y)₂O]_cR³；[Si(Y)₂O]_c；(R³O)[Si(B)(R⁴)_y(OR³)_1-yO]_bR³；[Si(B)(R⁴)_y(OR³)_1-yO]_bR³；[Si(B)(R⁴)_y(OR³)_1-yO]_b；(R³O)[Si(B)(R⁴)_y(OR³)_1-yO]_bR³They can form chain, cyclic and/or crosslinked structures and, in the presence of tetraalkoxysilanes or their hydrolysis-and/or condensation products, also three-dimensionally crosslinked structures. The structural elements having a free valence on the Si atom are satisfied covalently by-O-Si, and the free valence on the O atom is satisfied by-Si bridges of the other structural elements, alkyl groups or optionally hydrogen. These structural elements may take a disordered or statistical arrangement in the condensate, which may also be controlled by the order of addition or by the conditions of hydrolysis-and/or condensation, as will be appreciated by those skilled in the art. Formula I does not replicate the composition or structure that actually exists. Which corresponds to an idealisation possibilityAnd (4) showing.

The compositions preferably comprise siloxane oligomers which are produced by statistical and/or disordered homolytic hydrolysis or cohydrolysis and/or homolytic condensation or cocondensation and/or block condensation of the structural elements based on alkoxysilanes of the formulae II, III and/or IV substituted according to the invention by A or B groups and/or which are formed under selected test conditions.

Thus, the substitution pattern of the structural elements is also applied to chain-like, cyclic, cross-linked and/or three-dimensionally cross-linked siloxane oligomers in compositions which are not described in idealized form, wherein the silyl groups of the substituted siloxane oligomers may independently be: wherein Y is OR³The radicals OR, independently of one another, OR in the crosslinked and/OR three-dimensionally crosslinked structure³Or O in siloxane bonds_1/2-, having the radicals A and/or B, R as defined above³Substantially corresponding to alkyl groups in the siloxane oligomer, e.g. for R³As defined, wherein in the crosslinked and/OR three-dimensional crosslinked structure, there may also be present groups OR³Each independently of the other with O_1/2Form siloxane bonds, and/or these groups may be independent of one another with O_1/2Exist, and optionally independently have R²And/or R⁴And, as defined, corresponds to an alkyl radical having 1 to 15C atoms, at-OR¹In R¹Also as defined, alkyl groups having 1 to 4C atoms.

The invention also provides a composition comprising an ethylenically functionalized siloxane oligomer, more particularly at least one siloxane oligomer according to idealized formula I, said composition further comprising as an additional component at least one organic solvent, organic polymer, water, salt, filler, additive, pigment or a mixture of at least two of said components. The components may be added to the composition during the preparation of the composition and at a later point in time.

A particular advantage of the composition of the invention is that it has a very low chloride content as a result of its preparation and thus leads to a considerable improvement in the fire-protection properties during the processing of the cable material. An important advantage of the present invention is therefore that as a bottom product, optionally after removal of the hydrolysis alcohol and any solvent optionally added, it can be used directly in an economical manner according to the invention. A further advantage of the compositions according to the invention is that, with an increased content of T-structures and at the same time a dynamic viscosity of <3000 mPa s, which leads to improved elongation at break of the thermoplastics and elastomers processed therefrom with good processability in the extruder, and also the tensile properties can be improved.

The compositions of the invention of ethylenically functionalized siloxane oligomers have an alcohol content (preferably a content of free alcohol) of from less than or equal to 2% by weight to 0.0001% by weight, more particularly less than or equal to 1.8% by weight, preferably less than or equal to 1.5% by weight, more particularly less than or equal to 1.0% by weight, very particularly less than or equal to 0.5% by weight, based on the composition, up to the detection limit. The composition has such a low alcohol (preferably free alcohol) content over a period of at least 3 months, preferably over a period of 6 months. These low VOC contents can be ensured by the process of the present invention, which provides compositions of silicone oligomers having a low alkoxy content with a particularly low chlorine content.

A particular advantage of the process according to the invention is evident when solvents and acidic hydrolysis-and/or condensation catalysts are used in combination under homogeneous catalytic conditions. The acidic catalysts used according to the invention are soluble in the solvent, the alkoxysilane and the siloxane oligomer prepared. In addition, alkoxysilanes and siloxane oligomers are soluble in solvents. As a result of these measures, it is now possible for the first time to obtain siloxane oligomers of particularly narrow molar mass distribution without expensive and troublesome distillations, and at the same time to obtain compositions of high purity and virtually catalyst-free, more particularly hydrolyzable chlorine-and/or total chloride-free siloxane oligomers in the form of bottoms.

By the addition and/or amount of solvent, preferably alcohol, it is possible to optimize the molecular weight and the molecular weight distribution in combination with the water amount and in this way to avoid the formation of high molecular weight oligomers to the maximum. The relatively high molecular weight unwanted oligomers are formed only at very low levels.

Another aspect of the composition of the invention and the process of the invention is that the process is operated without the use of basic catalysts, more particularly without the use of nitrogen-containing compounds, or without the use of acidic sulfur-containing ion exchangers. Both of these catalysts lead to heterogeneous catalytic conditions. Thus, for example, aqueous ammonia solutions lead to the formation of emulsions and the conversion on ion exchangers containing sulfonic acid groups or sulfuric acid groups also leads to heterogeneously catalyzed conditions. It has been found that heterogeneous catalysis conditions are not suitable for producing the desired narrow molecular weight distribution siloxane oligomers. The composition of the invention is therefore free of acidic sulphur-containing groups, more particularly of sulphur acid groups or sulphonic acid groups, and/or of nitrogen-containing compounds, more particularly of nitrogen-containing compounds introduced by means of a basic catalyst. It is also possible in the process of the invention to work without metal oxides, optionally in combination with acids; the composition of the invention is therefore free of metal residues introduced by the addition of metal oxides, such as more particularly copper oxide, iron oxide, aluminum oxide, copper halides, iron halides, copper hydroxide, iron hydroxide, aluminum hydroxide. The compositions of the invention therefore preferably contain only the metals inherently present, preferably in an amount of less than 0.001 to 0.1ppm by weight. Accordingly, it is possible in the process of the invention to dispense with the addition of basic compounds, such as calcium carbonate for neutralization. The compositions of the invention therefore do not contain additionally added calcium, and they preferably contain less than or equal to 1% by weight, more particularly less than or equal to 0.1% by weight to 0.1ppm (by weight) of calcium. The compositions and methods are therefore free of nitrogen-containing compounds, free of calcium-containing compounds, free of metal-containing compounds, more particularly free of metal oxides, and free of sulfur-containing compounds, more particularly free of acidic sulfur-containing compounds.

The invention also provides a process for preparing a composition comprising an ethylenically functionalized siloxane oligomer, and in particular, a composition obtainable by such a process, wherein

(i) (at least) one olefinically functionalized alkoxysilane of the formula II

Wherein in formula II A corresponds to an olefinic group selected in particular from linear, branched or cyclic alkenyl-or cycloalkenyl-alkylene-functional groups each having 2 to 16C atoms, R²Independently corresponds to a linear, branched or cyclic alkyl group having 1-15C atoms, and x is 0 or 1, and R¹Independently corresponding to linear, branched and/or cyclic alkyl groups having 1 to 4C atoms,

(ii) in the presence of an acidic hydrolysis-and/or condensation catalyst, more particularly in the presence of HCl, a saturated or unsaturated organic acid, such as formic acid, acetic acid and/or a fatty acid, such as myristic acid, and/or a polyfunctional organic acid, such as citric acid, fumaric acid

(i.1) optionally with (at least) one alkoxysilane of the general formula III,

wherein, in formula III, B corresponds to a saturated hydrocarbon group, R³Independently of one another, is a linear, branched or cyclic alkyl radical having 1 to 4C atoms, and R⁴Is a linear, branched or cyclic alkyl radical having 1 to 15C atoms and y is 0 or 1, and

(i.2) optionally with (at least) one tetraalkoxysilane of the formula IV in which R is³Independently of one another, are linear, branched and/or cyclic alkyl radicals having 1 to 4C atoms,

(iii) optionally in the presence of a solvent (preferably an alcohol), with a specified amount of water of greater than or equal to 1.1 to 1.59mol, preferably 1.0 to 1.5mol, of water per mole of silicon atoms in the alkoxysilane used (i.e. at least the alkoxysilane of the general formula I and optionally additionally selected from the general formulae III and IV) to give an oligomer, in particular x =0 and y =0, and

(iv) substantially removing the hydrolysis alcohol and the solvent optionally present, and obtaining a composition more particularly comprising a siloxane oligomer,

(v) more particularly, the chlorine content, more particularly the total chloride content, is less than or equal to 250 mg/kg, more particularly less than or equal to 150 mg/kg, preferably less than or equal to 100 mg/kg, more preferably less than or equal to 75 mg/kg, further preferably less than or equal to 50 mg/kg, further preferably less than or equal to 35mg/kg, with a hydrolysable chloride content preferably less than or equal to 8 mg/kg, preferably less than or equal to 5mg/kg, and

(vi) wherein greater than or equal to 10% of the silicon atoms in the ethylenically functionalized siloxane oligomer are present as T structures, based on the total number of silicon atoms in the siloxane oligomer, and optionally

(vii) Wherein a composition comprising an ethylenically functionalized siloxane oligomer is obtained or obtained as a bottom product.

Advantageously, the composition is obtained or obtained in step (iv) after step (iv) or preferably as a last step. The composition is preferably in the form of a bottom product. According to the invention, the composition is obtained as a bottom product, optionally after removal of the hydrolysis alcohol and any added solvent.

According to a preferred alternative, (i) at least one alkoxysilane of the formula II is reacted with (i.1) at least one alkoxysilane of the formula III in step (II) in the presence of a hydrolysis and/or condensation catalyst. According to another preferred alternative, (i) at least one alkoxysilane of the general formula II is reacted with (i.2) at least one alkoxysilane of the general formula IV in step (II) in the presence of a hydrolysis and/or condensation catalyst. According to another preferred alternative, (i) at least one alkoxysilane of the formula II is reacted in step (II) with (i.1) at least one alkoxysilane of the formula III and (i.2) at least one alkoxysilane of the formula IV in the presence of a hydrolysis and/or condensation catalyst. Advantageously, it is also possible to use in (iii) the specified amount of water which is greater than or equal to 1.0 to 1.6 mol of water per mole of silicon atoms in the alkoxysilane used.

The present invention also provides a process for preparing a composition comprising an ethylenically functionalized siloxane oligomer, and in particular also relates to a composition obtainable by such a process with steps (i), (ii), (iii) and (iv) and optionally (i.1) and/or (i.2), wherein a composition comprising an ethylenically functionalized siloxane oligomer according to (vi) is obtained, wherein in particular, based on the total number of silicon atoms in the siloxane oligomer, greater than or equal to 10% of the silicon atoms in the ethylenically functionalized siloxane oligomer are present as T structures, and in (vii), the composition comprising the ethylenically functionalized siloxane oligomer is obtained as a bottom product after step (iv) or (v). According to these variant embodiments of the process, the chlorine content obtainable in the composition is, optionally only, less than or equal to 250 mg/kg. The compositions according to these variant embodiments have the molar mass distribution mentioned before, independently of the chlorine content, and in particular exhibit the stated TGA values. The invention therefore also provides compositions of olefinic siloxane oligomers, which, independently of the chlorine content or the total chloride content, have a molecular weight (Mw) of greater than or equal to 85%, preferably 90% (area%, GPC), of less than 1000 g/mol. In particular, in combination with a Mw of greater than or equal to 30% (area%, GPC, Mw) having a relative Mw of 500 to 750, greater than or equal to 30% to less than or equal to 50%, more preferably greater than or equal to 35% to less than or equal to 45%, preferably having a Mw of 500 to 750. All numbers are always to be understood as being based on the total composition.

According to a preferred embodiment, the alkenyl-functionalized alkoxysilane of the formula II is optionally reacted with an alkylalkoxysilane of the formula III in the presence of a condensation catalyst. Further preferably, an alkenyltrialkoxysilane and optionally an alkyltrialkoxysilane are each reacted. The reaction optionally takes place in the presence of a solvent, preferably the corresponding alcohol of the alkoxysilane. In the process of the invention, it is particularly advantageous to use from 0.001 to 5 volume units of the corresponding alcohol per volume unit of alkoxysilane, more particularly trialkoxysilane. It is also preferred to use 0.25 to 1 volume unit per volume unit of trialkoxysilane.

According to one particularly preferred process variant, the reaction takes place in step (iii) in the presence of an alcohol in an amount of from 0.05 to 2.5 volume units of alcohol per volume unit of alkoxysilane, more particularly from 0.1 to 2.0, preferably from 0.2 to 1.5, more preferably from 0.2 to 1.0 or from 0.2 to 0.9 volume units of alcohol per volume unit of alkoxysilane, respectively, with a specified amount of water. Preferably, 0.5 plus/minus 0.4 volume units of alcohol per volume unit of alkoxysilane. Preferably in the present invention, in the case of the reaction of VTMO or VTEO, the alcohol used for dilution plus metering, from 0.5 to 2.5, from 0.5 to 2.0, and/or at least once in step (iv) during step (iv), or subsequently, the specified amount is metered in and removed subsequently. For the subsequent metering in (iv) or subsequently, it is also possible to meter in a plurality of times from 0.001 to 5 units by volume of alcohol per unit by volume of alkoxysilane, more particularly from 0.1 to 2.5 units by volume of alcohol. These measures may be repeated arbitrarily, preferably 1 to 10 times, more preferably 1 to 5 times. The alcohol distilled off beforehand, in particular after the purification step, can be used again for removing chlorides and water. This can preferably take place in step (30.i), as explained below, in (30.i) the specified amount of alcohol being added at least once, preferably 2 to 6 times, during the work-up by distillation. Alternatively, it is preferable that water is used in an amount of 1.0 to 1.5mol per mol of silicon atom in the alkoxysilane used.

According to the invention, used as hydrolysis and/or condensation catalyst is an acidic catalyst (more particularly HCl) which is gaseous under standard conditions, which can be dissolved in the aqueous or alcoholic phase.

The solvent used and/or the alcohol used is anhydrous, the solvent or alcohol used having a water content of in particular less than or equal to 1ppm by weight. In case the solvent contains water, this water content has to be taken into account in the reaction.

As ethylenically functionalized alkoxysilanes, preference is given to using silanes of the formula II,

wherein a is a linear, branched or cyclic alkenyl-or cycloalkenyl-alkylene-functional group having 2 to 18C atoms, respectively, more particularly 2 to 16C atoms, preferably 2 to 8C atoms, more preferably an alkenyl group having one to two double bonds, preferably vinyl, allyl, butenyl, pentenyl, hexenyl, ethylhexenyl, heptenyl, octenyl and cyclohexenyl-C1 to C8-alkylene, preferably cyclohexenyl-2-ethylene, such as 3-cyclohexenyl-2-ethylene, and/or cyclohexadienyl-C1 to C8-alkylene, more particularly cyclohexadienyl-2-ethylene groups, wherein x is particularly 0, and R is a linear, branched or cyclic alkenyl-or cycloalkenyl-alkylene-functional group, more particularly having 2 to 16C atoms, preferably having 2 to 8C atoms, and more preferably having one to two double bonds, preferably vinyl, allyl, butenyl, pentenyl, hexenyl¹Independently a linear, branched and/or cyclic alkyl group having 1 to 4C atoms, more particularly a methyl, ethyl or propyl group.

As alkoxysilanes of the general formula III, preference is given to using alkoxysilanes having unsubstituted hydrocarbon radicals B,

the unsubstituted hydrocarbon radical B is a linear, branched or cyclic alkyl radical having 1 to 16C atoms, more particularlyMethyl, ethyl, propyl, isobutyl, octyl and hexadecyl groups. And in the formulae II and III, R²And R⁴Preference may be given, independently of one another, to methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl and also alkyl groups known to the person skilled in the art, including structural isomers. According to an alternative preferred embodiment, unsubstituted hydrocarbons having branched and/or cyclic alkyl groups having 3 to 16C atoms are used as group B. According to another preferred alternative of the invention, linear alkyl groups having 1 to 7C atoms are used as unsubstituted hydrocarbon radicals B.

The invention also provides a process in which in the olefinically functionalized alkoxysilane of the formula II, x is 0 and optionally in the alkoxysilane of the formula III functionalized with a saturated hydrocarbon group, y is 0. Alternatively, x may be 0 and y may be 1, or x may be 1 and y may be 0.

At least partial hydrolysis, and in particular at least partial co-condensation, is present; preferably, the condensable, partially hydrolyzed alkoxysilanes are substantially completely condensed. Particularly preferably, the partial hydrolysis and condensation only take place to the extent desired for the preparation of oligomers having the preferred degree of oligomerization.

According to the invention, the hydrolysis alcohol is removed, preferably by distillation, and the composition of the invention is obtained. A particularly gentle distillation of the hydrolysed alcohol and/or solvent takes place under reduced pressure. Depending on the process steps, it is possible to carry out a particularly economical process without addition of solvents. According to the invention, the composition prepared in this way, after removal of the hydrolysis alcohol and any solvent, does not have to be purified again on its own, more particularly, does not have to be distilled again on its own, and is suitable for use according to the invention. Depending on the work-up, the composition may optionally be filtered or decanted after removal of the hydrolysis alcohol. The process of the invention is therefore much more economical than the known processes in which the oligomers have to be purified by distillation in order to be suitable for further use.

The present invention also provides a process in which at least one ethylenically functionalized alkoxysilane of the general formula II is each independently selected from vinyltriethoxysilane, propenyltriethoxysilane, butenyltriethoxysilane, pentenyltriethoxysilane, hexenyltriethoxysilane, ethylhexenyltriethoxysilane, heptyltriethoxysilane, octenyltriethoxysilane, cyclohexenyl-C1 to C8-alkylenetriethoxysilane, cyclohexenyl-2-ethylenetriethoxysilane, 3-cyclohexenyl-2-ethylenetriethoxysilane, cyclohexadienyl-C1 to C8-alkylenetriethoxysilane, cyclohexadienyl-2-ethylenetriethoxysilane, vinyltrimethoxysilane, propenyltrimethoxysilane, heptyltriethoxysilane, octenyltriethoxysilane, etc, Butenyltrimethoxysilane, pentenyltrimethoxysilane, hexenyltrimethoxysilane, ethylhexenyltrimethoxysilane, heptenyltrimethoxysilane, octenyltrimethoxysilane, cyclohexenyl-C1 to C8-alkylenetrimethoxysilane, cyclohexenyl-2-ethylenetrimethoxysilane, 3' -cyclohexenyl-2-ethylenetrimethoxysilane, cyclohexadienyl-C1 to C8-alkylenetrimethoxysilane and cyclohexadienyl-2-ethylenetrimethoxysilane, and, independently of each other,

at least one alkoxysilane of the general formula III is each independently selected from methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, butyltriethoxysilane, n-butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, n-hexyltriethoxysilane, isohexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, n-octyltriethoxysilane, isooctyltriethoxysilane, undecyltriethoxysilane, decyltriethoxysilane, nonadecyltriethoxysilane, dodecyltriethoxysilane, C₁₃H₂₇Triethoxysilane, C₁₄H₂₉Triethoxysilane or C₁₅H₃₁Triethoxysilane, hexadecyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane,Isopropyltrimethoxysilane, butyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, n-hexyltrimethoxysilane, isohexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, n-octyltrimethoxysilane, isooctyltrimethoxysilane, undecyltrimethoxysilane, decyltrimethoxysilane, nonadecyltrimethoxysilane, dodecyltrimethoxysilane, C₁₃H₂₇Trimethoxy silane, C₁₄H₂₉Trimethoxysilanes or C₁₅H₃₁Trimethoxy silane and hexadecyl trimethoxy silane and optionally transesterification products, and, independently of one another,

the alkoxysilane of the general formula IV is selected from tetraethoxysilane and tetramethoxysilane. And transesterification products thereof comprising ethoxy-and methoxy groups.

According to the process of the invention, after carrying out steps i, ii, iii and iv and optionally steps i.1 and/or i.2, a composition comprising a siloxane oligomer is obtained, said composition having already a low chlorine content, more particularly a low total chloride content, of the invention of less than or equal to 250 mg/kg, more particularly less than or equal to 150 mg/kg, preferably less than or equal to 100 mg/kg, more preferably less than or equal to 75 mg/kg, still more particularly less than or equal to 50 mg/kg, more particularly less than or equal to 35mg/kg, wherein the hydrolysable chloride content is less than 8 mg/kg, preferably less than or equal to 5mg/kg, and wherein preferably greater than or equal to 5% of the silicon atoms in the ethylenically functionalized siloxane oligomer (based on the total number of silicon atoms in the siloxane oligomer) are present in the T structure.

The reaction takes place in the presence of a specified amount of water of more than 1.0 mol of water per mole of silicon atom, preferably of more than or equal to 1.05 to 1.60 mol of water per mole of silicon atom in the alkoxysilane of the formula II and optionally of at least one silane of the formula III and/or of the formula IV used, more particularly of 1.1 to 1.58 mol of water per mole of silicon atom in the alkoxysilane of the formula II and optionally of the formula III and/or of the formula IV used, preferably of more than or equal to 1.2 to 1.58 mol of water, more preferably of more than or equal to 1.25 to 1.57 mol of water. All numbers including moles of water within the disclosed ranges have also been disclosed herein, more particularly as low as the second decimal number, such as 1.06; 1.07; 1.08; 1.09; 1.11; 1.12; 1.13; 1.14; 1.15; 1.16; 1.17; 1.18; 1.19; 1.21; 1.22; 1.23; 1.24; 1.26; 1.27; 1.28; 1.29; 1.30; 1.31; 1.32; 1.33; 1.34; 1.35; 1.36; 1.37; 1.38; 1.39; 1.40; 1.41; 1.42; 1.43; 1.44; 1.45 of; 1.46; 1.47; 1.48; 1.49; 1.50; 1.51; 1.52; 1.53; 1.54; 1.55; 1.56. the water is preferably completely demineralized. It will be clear to one skilled in the art that water may be introduced first, added in portions, added continuously or added to the process with one or all of the silanes. The water is preferably metered in continuously or at least at intervals over a period of time of less than 1 minute to 100 minutes, and the reaction of the alkoxysilane is preferably carried out at a reaction temperature preferably ranging from 40 ℃ to 80 ℃, more preferably from 50 ℃ to 80 ℃, more particularly at a pH of less than 7. The water content of the added solvent (e.g. alcohol) has to be taken into account as water in the process.

In general, according to part/step iii (29.i, see claim 29) of the process of the invention, the amount of water or water can be metered in continuously or at least at intervals over a period of 1 to 1000 minutes, and a temperature of 5 to 90 ℃, in particular 37 to 88 ℃, preferably 40 to 85 ℃, more particularly preferably 45 to 83 ℃, very particularly 50 to 80 ℃ can be set in the reaction mixture, and the preferred pH is 7 or less; optionally, water and catalyst and optionally with a solvent, more particularly with an alcohol. Then the reaction can take place, preferably (29.ii, see claim 29) treating the mixture (29.i, see claim 29) (i.e. the reaction mixture) and/or further reacting the mixture optionally for at least 10 minutes to 36 hours, more particularly 10 minutes to 8 hours, at 5 to 80 ℃, preferably at 40 to 80 ℃, preferably with mixing therein; the reaction mixture can optionally also be reacted subsequently during cooling. To adjust the molecular weight, alkoxytrialkylsilanes, more particularly alkoxytrimethylsilanes, can be added to the process. The composition obtained in this way can then be decanted or heated to distill off the alcohol, for example hydrolyzed alcohol. The alcohol, optionally including a catalyst, more particularly HCl, is removed from the crude product by distillation, preferably with heating under reduced pressure.

According to a preferred embodiment, in the process according to part iv, the hydrolysis alcohol and optionally the solvent, more particularly the added alcohol, are removed by distillation, and preferably (30.i, see claim 30) at least once, preferably two to six times, adding the specified amount of alcohol during the distillative workup, and/or (30.ii, see claim 30) adding the specified amount of a reducing agent, more particularly an inorganic reducing agent, such as an alkali metal, alkaline earth metal, aluminum or metal hydride, between or before the distillative removal of the hydrolyzed alcohol and optionally the solvent, more particularly the alcohol, or a base, such as preferably HMDS or another amine or alkali metal alkoxide is useful, and subsequently filtering or decanting the olefinically functionalized siloxane oligomer in the form of the bottom product and/or contacting the olefinic siloxane oligomer with an ion exchanger.

According to a first alternative, the precipitate or floc formed by filtration and/or decantation can be substantially removed from the composition comprising the siloxane oligomer. It is preferred to add the stated amount of reducing agent, more particularly an inorganic reducing agent, very particularly a metallic reducing agent, for example an alkali metal, preferably sodium, or as an alkaline earth metal, preferably magnesium or calcium, or aluminum, and as a metal hydride, preferably lithium aluminum hydride, or as a base, preferably gaseous ammonia, Lithium Diisopropylamide (LDA), lithium isopropylhexylamide, Hexamethyldisilazane (HMDS), and as an alkali metal alkoxide, for example sodium or potassium methoxide or ethoxide, or an alkali metal alkylate, for example butyllithium. Also possible are metal hydrides known to the person skilled in the art, such as NaH, or lithium aluminium hydride, or bases which form sparingly soluble precipitates with hydrogen chloride, which can additionally be used in the process in order to further reduce the chlorine or chloride content of the composition. Suitable bases for this process should not form water in the reaction with the catalyst (e.g., HCl) or with organically bound chlorine (e.g., Cl-Si).

In all process variants according to the invention, the alcohol already present and/or the alcohol formed in the reaction is removed from the reaction mixture substantially, preferably completely. The distillative removal of the alcohol is preferably carried out under reduced pressure. This distillative removal of the alcohol corresponds to a work-up of the composition, since after this step a composition comprising siloxane oligomers is obtained or obtained which has a defined total amount of chlorides, more particularly in the form of a bottom product, and which preferably has a defined polydispersity, preferably D = 1.10 to 1.42, more preferably D = 1.10 to 1.21, in particular for siloxanes derived from alkoxysilanes of the general formula II. Alternatively, for siloxanes derived from alkoxysilanes of formulas II and III, the polydispersity D may be from 1.20 to 1.43. The distillative removal of the alcohol is preferably carried out until the temperature obtained at the top of the column corresponds to the boiling temperature of water or to the boiling temperature of the siloxane oligomers. Optionally, until an alcohol content of less than or equal to 1.0 wt.%, preferably less than or equal to 0.5 wt.%, is detected. Generally, the resulting compositions of the present invention are substantially solvent-free, more particularly alcohol-free. The composition obtained in this way preferably corresponds directly to the composition of the invention and preferably does not itself need to be further purified.

The process of the invention can be operated discontinuously or continuously. The composition and at least one processing aid, such as a silicone oil, e.g., polydimethylsiloxane, paraffin wax, paraffin oil, or a mixture comprising one of these processing aids, can be mixed before or after the alcohol is removed.

According to a preferred variant of the process, the alkoxysilanes of the formulae II, III and/or IV are partially hydrolyzed and condensed in the presence of an acidic catalyst, more particularly hydrogen chloride. If desired, hydrolysis and condensation can also take place in the presence of HCl and a cocatalyst. Contemplated co-catalysts include fatty acids. Alternatively, it is also possible to use HCl and saturated or unsaturated organic acids, such as formic acid, acetic acid and/or fatty acids, optionally with myristic acid, and/or polyfunctional organic acids, such as citric acid, fumaric acid, as catalysts or together with HCl as co-catalysts.

According to the process, it is further preferred that the ratio of the silane of the formula II to the silane of the formula III to be used is from 1:0 to 1:8, and/or the ratio of the silane of the formula II to the silane of the formula IV to be used is from 1:0 to 1:0.22, preferably from 1:0 to 1:0.20, more particularly from 1:0 to 1:0.15, further preferably from 1:0 to 1:0.10, more preferably from 1:0 to 1:0.05, the silane of the formula II and the silane of the formula III preferably being used in a ratio of about 1:0, or about 1:1, or in a ratio of 1:0 to 1:2, preferably from 1:0 to 1:1. Alternatively, also preferred are processes wherein the silane of formula II and the silane of formula IIII are used in a ratio of 1:0 to 1:2, preferably about 1:1, and/or the silane of formula II and the silane of formula IV are used in a ratio of 1:0 to 1:0.20, preferably 1:0 to 1:0.10, more preferably 1:0 to 1:0.5, further preferably in a ratio of 1:0.10 to 1:0.05 or about 1: 0.1. The siloxane oligomers produced in the stated proportions exhibit particularly homogeneous properties with regard to their properties; silanes of the general formula IV are preferably used in order to achieve stronger crosslinking in the oligomer or also to achieve stronger crosslinking of the oligomer with the substrate.

It is particularly preferred, according to one alternative, that the silanes of the formula II and III are used in a ratio of about 1: 1; according to another preferred alternative, the silanes of the formula II and IV are used in a ratio of about 1: 0.1.

According to one embodiment, the reaction according to the invention of the olefinically functionalized alkoxysilanes of the general formula II and optionally silanes III and/or IV is carried out with hydrolysis and condensation catalysts in the presence of a specified amount of water of more than 1.0 to 1.6 mol of water per mol of silicon atoms in the alkoxysilane and 0.2 to 8 times the weight of alcohol, based on the weight of the silane used. According to one alternative, it is also possible to add from 0.0001 to 5 units by volume of alcohol per unit by volume of silane of the formulae II, III and/or IV. Preferably, in the process of the invention, only 0.2 to 0.6, more preferably 0.2 to 0.5 times the small weight of alcohol, based on the silanes of the general formulae II, III and/or IV, is used.

Preferred alcohols correspond to the hydrolyzed alcohols formed by at least partial hydrolysis-and/or condensation. They include ethanol or methanol. It is clear to the person skilled in the art that the reaction can also be carried out in the presence of other conventional solvents, preferably those which can be distilled off easily and preferably completely, which can be, for example, but not conclusively, ethers, ketones, hydrocarbons or esters. Useful solvents may also be acetates, THF, ketones, ethers or hydrocarbons. It is clear to the person skilled in the art that, for commercial and economic reasons, the alcohol used as solvent is also formed as hydrolysis alcohol. Mixtures of alcohols can therefore also be used in principle. In all process variants, the solvent and the alcohol formed in the reaction are preferably removed from the reaction mixture by distillation.

According to another preferred process variant, the degree of oligomerization of at least 20% by weight of the siloxane oligomers having n as the number of silicon atoms is set such that n is greater than or equal to 4, optionally greater than or equal to 8, for them. Further preferably, by the process of the invention, in particular, more than 5% of the ethylenically functionalized silicon atoms are obtained as T structures; preferably, it may also be greater than 7.5%, preferably greater than 10%, more preferably greater than 11% or greater than 15% and above 22%; additionally or alternatively preferably, greater than 5% of the silicon atoms functionalized with saturated hydrocarbons in the siloxane oligomer are also present as T structures.

In the process of the invention, the viscosity of the composition is set preferably at less than or equal to 1000 mPas, more preferably at less than or equal to 740 mPas, very preferably at less than or equal to 500 to about 5 mPas.

Furthermore, in the process, the composition comprising the olefinic siloxane oligomer, more particularly the bottom product, preferably after distillative removal of the solvent and the alcohol, may be contacted with an ion exchanger, more particularly an anion exchanger, preferably an amine-functionalized ion exchanger, in order to further reduce the chloride content. In this process step, it is advantageous that this measure does not alter the degree of oligomerization and/or the degree of branching of the product compared to distillation. In the case of distillation, the siloxane oligomers will necessarily separate into low, medium and high boilers (bottoms). According to the invention, the degree of oligomerization of the siloxane oligomers remains the same by using ion exchangers, and the chloride content can be further reduced. By contacting with the ion exchanger, the chloride content or chlorine content in the olefinic siloxane oligomer in ppm by weight, based on the siloxane oligomer supplied to the ion exchanger, can preferably be reduced by at least 80%. It is further preferred that the content of chlorine in ppm by weight in the olefinic siloxane oligomer is reduced by at least 85%, preferably at least 90%, more particularly at least 92%, more particularly at least 95%, and still more preferably at least 98%, based on those supplied. Depending on the ethylenically functionalized siloxane oligomer and depending on the initial concentration of chlorine, the flow rate and the contact time with the anion exchanger, it may be preferred to reduce the chlorine content to less than or equal to 100 mg/kg, preferably to less than or equal to 50 mg/kg, more particularly to less than or equal to 25 mg/kg.

In the case of an ethylenically functionalized siloxane oligomer having a chlorine content, i.e. having hydrolysable chlorine, more particularly a chlorine-functionalized alkylalkoxysilane and/or an alkylalkoxysilane having HCl, the hydrolysable chloride content can be reduced by at least 80%, more particularly at least 85%, preferably at least 90%, more particularly at least 92%, more particularly at least 95%, and further preferably at least 98%, preferably at a flow rate of from 0.01 m/h to 15 m/h, preferably up to 5 m/h, more particularly up to 2.5 m/h; in the present invention, in particular, the ethylenically functionalized siloxane oligomer does not undergo further condensation, and the anion exchanger column preferably has a diameter of 3 cm and a height of 15 cm. Very good results with a reduction of hydrolyzable chlorine of up to 80% are also obtained at flow rates of up to 10 m/h.

In the process of the invention, the anion exchanger has a carrier poly (having quaternary alkylammonium groups) and/or having tertiary dialkylamino groupsThe compound, in particular, the quaternary alkylammonium groups essentially have hydroxide ions as counterions and/or the tertiary dialkylamino groups are in the form of the free base. It is particularly preferred in the context of the present invention if the basic anion exchanger is a styrene-divinylbenzene copolymer having trialkylammonium groups, more particularly in the OH form, and/or a styrene-divinylbenzene copolymer having dialkylamino groups in the form of free bases. When using basic anion exchangers of styrene-divinylbenzene copolymers having trialkylammonium groups in the form of chlorides, the chlorides are converted into the OH form before use, for example with alkali metal hydroxide solutions. The alkali metal hydroxide solution used is preferably potassium hydroxide, sodium hydroxide or other water-soluble or water/alcohol-soluble bases, e.g. ammonia or alkali metal carbonates such as Na₂CO₃The aqueous solution of (a). After conversion of the anion exchanger to the OH form, the anion exchanger is rinsed with alcohol before being contacted with the olefinic siloxane oligomer, in order in particular to exclude excess water. The alcohol used is preferably the alcohol which will be formed by hydrolysis of the respective alkoxy group. Methanol in the case of methoxy groups in alkoxysilanes or ethanol in the case of ethoxy groups.

Quaternary ammonium groups include not only alkylammonium but also N-alkyl-imine-functional groups, such as N-alkylpyridinium groups. Suitable alkyl groups contain 1 to 20C atoms, preferably 1 to 4C atoms, and are preferably methyl or ethyl groups. According to the invention, the weakly basic anion exchangers are loaded with hydroxide ions and in particular they have nitrogen-containing groups.

According to the invention, it is further preferred for the alkoxysilanes of the general formulae II, III and/or IV to be at least partially hydrolyzed and condensed in the presence of the specified amounts of water and of a hydrolysis and condensation catalyst, for example an inorganic acid, such as HCl, for example an organic saturated or unsaturated carboxylic acid, such as formic acid and/or fatty acids; and preferably the alcohol is removed, more particularly the hydrolysed alcohol and any added alcohol. The hydrolysis alcohol and/or the added alcohol correspond to the free alcohol. It is particularly preferred that the amount of free alcohol in the total composition is from less than 2% to 0.01% by weight, more particularly from less than 2% to 0.01% by weight, very preferably from less than or equal to 1% to 0.01% by weight, up to as low as the detection limit.

It has surprisingly been shown that the functionalized siloxane oligomers obtained by the process of the invention are more stable to hydrolysis due to a further reduction in the chlorine content, although in contrast to the situation hitherto, without laborious distillation of them. Thus, the siloxane oligomers of the present invention prove to be more stable than the known oligomers and, at the same time, their VOC content is reduced relative to the oligomers of the prior art.

The content of solvent (e.g. VOC), more particularly of free alcohol, which is stable over a period of 3 to 6 months, is preferably less than or equal to 2% by weight, more particularly less than or equal to 1% by weight, more preferably less than or equal to 0.4% by weight, preferably less than or equal to 0.3% by weight, based on the total composition.

The compounds of formula II that can be used in the process of the invention are as follows: vinyltriethoxysilane (VTEO), Vinyltrimethoxysilane (VTMO), allyltriethoxysilane, allyltrimethoxysilane, butenyltriethoxysilane, butenyltrimethoxysilane, cyclohexenyl-alkylene-trimethoxysilane, more particularly cyclohexenyl-2-ethylene-trimethoxysilane, more particularly 3 '-cyclohexenyl-2-ethylene-triethoxysilane and/or 3' -cyclohexenyl-2-ethylene-trimethoxysilane, cyclohexadienyl-alkylene-triethoxysilane, hexenyltriethoxysilane, hexenyltrimethoxysilane, ethylhexenyltrimethoxysilane, ethylhexenyltriethoxysilane, octenyltriethoxysilane, octenyltrimethoxysilane, methoxy-substituted compounds being particularly preferred.

The alkylalkoxysilane compounds of the general formula III which can be used are preferably as follows:

in the compounds of the formula III, y is 0 or 1, where B is a linear or branched alkyl radical having 1 to 18C atoms, more particularly having 1 to 8C atoms, preferably a methyl, ethyl, more particularly an n-propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, hexadecyl or octadecyl radical, R⁴Is a linear, branched or cyclic alkyl radical having 1 to 15C atoms, more particularly having 1 to 8C atoms, preferably methyl, ethyl, more particularly n-propyl, isopropyl and/or octyl, and R³Is a linear and/or branched alkyl group having 1 to 3C atoms, more particularly a methyl, ethyl and/or isopropyl or n-propyl group. Particularly preferably, B is a methyl, ethyl, propyl, octyl, hexadecyl or octadecyl radical, R is⁴Is a methyl or ethyl group, and R¹Are methyl or ethyl groups, particularly preferably methoxy-substituted compounds.

Preferred compounds of formula III are set out below by way of example: methyltrimethoxysilane, Methyltriethoxysilane (MTES), Propyltrimethoxysilane (PTMO), dimethyldimethoxysilane (DMDMO), dimethyldiethoxysilane, propylmethyldimethoxysilane, propylmethyldiethoxysilane, isopropyltriethoxysilane, n-Propyltriethoxysilane (PTEO), n-octylmethyldimethoxysilane, n-hexylmethyldimethoxysilane, n-hexylmethyldiethoxysilane, propylmethyldiethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, isooctyltrimethoxysilane, isopropyltriethoxysilane, n-hexyltriethoxysilane, propylmethyldiethoxysilane, isopropyltriethoxysilane, n-octyltriethoxysilane, n-, Cyclohexyltriethoxysilane, n-propyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexadecyltriethoxysilane, hexadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, octadecylmethyldiethoxysilane, octadecylmethyldimethoxysilane, hexadecylmethyldimethoxysilane and/or hexadecylmethyldiethoxysilane, as well as mixtures of these silanes, or mixtures comprising at least two of the aforementioned silanes.

Particularly preferred combinations of compounds of the formulae II, III and/or IV are used for preparing the olefinically functionalized siloxane oligomers or olefinically functionalized siloxane oligomers obtainable therefrom. According to the invention, the following compounds, separated by a semicolon, are each reacted: vinyltriethoxysilane; vinyl trimethoxysilane; vinyltriethoxysilane and Tetraethoxysilane (TEOS); vinyltrimethoxysilane and tetramethoxysilane; vinyltriethoxysilane and methyltriethoxysilane; vinyltriethoxysilane, methyltriethoxysilane and tetraethoxysilane; vinyltrimethoxysilane and methyltrimethoxysilane; vinyltrimethoxysilane, methyltrimethoxysilane and tetraethoxysilane or tetramethoxysilane; vinyltriethoxysilane and ethyltriethoxysilane; vinyltriethoxysilane, ethyltriethoxysilane, and tetraethoxysilane; vinyltrimethoxysilane and ethyltrimethoxysilane; vinyltrimethoxysilane, ethyltrimethoxysilane and tetraethoxysilane or tetramethoxysilane; vinyltriethoxysilane and propyltriethoxysilane; vinyltriethoxysilane, propyltriethoxysilane, and tetraethoxysilane; vinyltrimethoxysilane and propyltrimethoxysilane; vinyltrimethoxysilane, propyltrimethoxysilane and tetraethoxysilane or tetramethoxysilane; vinyltriethoxysilane and isobutyltriethoxysilane; vinyltriethoxysilane, isobutyltriethoxysilane and tetraethoxysilane; vinyltrimethoxysilane and isobutyltrimethoxysilane; vinyltrimethoxysilane, isobutyltrimethoxysilane and tetramethoxysilane; vinyltrimethoxysilane and heptyltrimethoxysilane; vinyltrimethoxysilane and heptyltriethoxysilane; vinyltrimethoxysilane and hexyltrimethoxysilane; vinyltrimethoxysilane and hexyltriethoxysilane; vinyltriethoxysilane and octyltriethoxysilane; vinyltriethoxysilane, octyltriethoxysilane, and tetraethoxysilane; more particularly vinyltriethoxysilane and tetraethoxysilane in a ratio of 1:0.20 to 1: 0; vinyltrimethoxysilane and octyltrimethoxysilane; vinyltrimethoxysilane, octyltrimethoxysilane and tetramethoxysilane; more particularly vinyltrimethoxysilane and tetramethoxysilane in a ratio of 1:0.2 to 1: 0; vinyltriethoxysilane and hexadecyltriethoxysilane; vinyltrimethoxysilane and hexadecyltrimethoxysilane; vinyltriethoxysilane and tetramethoxysilane and hexadecyltriethoxysilane in a ratio of 1:0.2 to 1: 0; vinyltrimethoxysilane and tetramethoxysilane and hexadecyltrimethoxysilane in a ratio of 1:0.2 to 1:0.

Also particularly preferably used in the process of the invention are at least one cyclohexenyl-2-ethylene-trialkoxysilane, 3' -cyclohexenyl-2-ethylene-trialkoxysilane or cyclohexadienyl-C1 to C8-alkylene group, each independently. Alternatively, it is also particularly preferred as a combination in the process of the invention that at least one cyclohexenyl-2-ethylene-trialkoxysilane, 3' -cyclohexenyl-2-ethylene-trialkoxysilane or cyclohexadienyl-C1 to C8-alkylene group can be reacted independently with one of the aforementioned alkylalkoxysilanes, respectively.

Particularly preferred processes are based on, or alternatively, preferred siloxane oligomers are obtainable by, the reaction of: a) vinyltriethoxysilane, b) vinyltrimethoxysilane, c) vinyltriethoxysilane and propyltriethoxysilane, vinyltrimethoxysilane and propyltrimethoxysilane, vinyltrimethoxysilane and propyltriethoxysilane, or vinyltriethoxysilane and propyltrimethoxysilane, or by a), b), c) separately reacting with tetraethoxysilane, or a), b), and c) separately reacting with tetramethoxysilane.

Additionally or alternatively to one of the aforementioned features, furtherAt least one silicone oil, such as polydimethylsiloxane, paraffin oil or a mixture comprising one of these processing aids, can be used as a processing aid in the process. A particularly preferred processing aid is polydimethylsiloxane, which preferably has a thickness of about 150 to 400 mm²A dynamic viscosity of about 200 mm, particularly preferably²Or about 350 mm²Viscosity in/s.

The invention also provides the following process for producing this composition, and the compositions obtainable by this process, in particular with a particularly low chlorine content, preferably with the following individual steps:

1) at least one ethylenically functionalized alkoxysilane of the formula II, optionally an alkoxysilane of the formula III and/or an alkoxysilane of the formula IV, optionally as a mixture, preferably as an initial charge, is introduced, optionally with addition of a solvent for dilution, preferably an alcohol corresponding to the hydrolyzed alcohol.

2) At least one acidic hydrolysis and/or condensation catalyst, for example HCl, an organic saturated or unsaturated carboxylic acid and a defined amount of water are added. The pH set here is preferably less than 7, preferably from 1 to 6, more particularly from 3 to 5. Optionally, a mixture (1+2) comprising at least one silane of the general formulae II, III and/or IV can be prepared, optionally with an alcohol in an amount of 0.2 to 8 times by weight, based on the silane of the general formulae II, III and/or IV (step (2 a)), more particularly methanol or ethanol, depending on the alkoxysilane used, and the specified amount of water (step (2 a)), preferably at least one acidic hydrolysis-and/or condensation catalyst, for example HCl, is dissolved in the specified amount of water. The pH is set here to preferably less than 7, preferably from 1 to 6, more particularly from 3 to 5.

Step (2 a): for this purpose, the alkoxysilane and the specified amount of water, which is greater than or equal to 1.0 to 1.6 mol of water, preferably 1.05 to 1.59, more preferably 1.1 to 1.58, very preferably greater than 1.2 to 1.57, more particularly 1.25 to 1.55 mol of water per mole of silicon atom of the alkoxysilane of the formula II and optionally III and/or IV, and all values included within these limits, for example 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.30, 1.31, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.41, 1.42, 1.43, 1.44, 1.45, 1.48, 1.54, 1.51, 1.48, 1.54, 1.48, 1.50, 1.51, 1.25, 1.29, 1.30, 1.31, 1.32, 1.35, 1.48, 1.54, 1.48. The specified amount of water may be metered in continuously or at least one interval over a period of 1 to 1000 minutes (29. l, see claim 29). The temperature of the reaction mixture is set to preferably carry out the reaction at 5 to 90 ℃, preferably at 20 to 55 ℃, more preferably at 30 to 40 ℃ or at about 35 ℃. After the addition of the mixture, the temperature of the reaction mixture formed is further increased, more particularly set to the reflux temperature of the alcohol. For example, by heating the reaction mixture to a temperature of from 40 to 80 ℃, preferably to a temperature of from 50 to 80 ℃, more preferably to about 55 to 80 ℃, to a temperature of about the boiling point of the alcohol according to the invention. The reaction mixture may be subsequently reacted (29.ii, see claim 29) at a reaction temperature of 5 to 80 ℃, preferably 40 to 80 ℃, preferably while mixing, e.g. stirring, over a period of at least 10 minutes to 36 hours, preferably 10 minutes to 8 hours.

3) After the reaction was terminated, the alcohol was removed. The heating under reflux is preferably carried out for several hours, for example from about 2 to 10 hours, preferably from 3 to 5 hours, more particularly about 3.5 hours, and subsequently

4) The alcohol, including the hydrolysed alcohol and the introduced alcohol, is removed by distillation (preferably under reduced pressure and at elevated temperature), and optionally water is removed, preferably until the reaction mixture or the resulting composition is substantially solvent-free, more particularly alcohol-free. Preferably, the alcohol is distilled at a bottom temperature of from 0 ℃ to 100 ℃ and a pressure of from 300 bar to 1 mbar, and the HCl is distilled off at the same time, more particularly at a temperature of from 40 ℃ to 100 ℃ and a pressure of from 250 bar to 10 bar.

5) Then theThe atmospheric pressure can be set and (30.i, see claim 30) the specified amount of alcohol can be subsequently added and/or (step 30.ii) the specified amount of alkali metal, preferably sodium, alkaline earth metal, preferably magnesium or calcium, aluminum, metal hydride, preferably lithium aluminum hydride, or base, more particularly gaseous ammonia, lithium diisopropylamide, lithium isopropylhexylamide, hexamethyldisilazane, alkali metal alkoxides, for example sodium or potassium methoxide or ethoxide, alkali metal alkylate, for example butyllithium, can be added. Optionally, a further distillation is carried out under reduced pressure, the mixture being reacted with addition of alkali metal. After distillation, the bottom product may be filtered or decanted. Alternatively or additionally, it may be contacted with an ion exchanger as described above. Thereby obtaining a free alcohol content of less than: (A) according to the invention<) 2% by weight and chlorine content<250 ppm by weight (based on the composition) of a composition of an ethylenically functionalized siloxane oligomer, the composition having a viscosity of less than or equal to 1000mPa s.

It will be clear to the person skilled in the art that the functionalized siloxane oligomers prepared in this way may be diluted with a diluent or may be mixed or compounded with a polymer, for example a thermoplastic base polymer, such as PE, PP or an elastomer, such as EVA, depending on their desired application. Additional thermoplastic base polymers and elastomers are given below by way of example; the person skilled in the art knows that generally all thermoplastic base polymers or elastomers are suitable. The person skilled in the art is aware of the customary diluents for alkoxysilanes, examples which may be mentioned here being alcohols, ethers, ketones, hydrocarbons or mixtures thereof. Depending on their intended use, compositions of functionalized siloxane oligomers may thus be prepared as concentrates or diluted compositions having from 99.9 to 0.001% by weight of functionalized siloxane oligomer in the total composition, and all values lying in between. Preferred diluents contain from 10 to 90 wt.% of the functionalized siloxane oligomer, more particularly from 20 to 80 wt.%, further preferably from 30 to 70 wt.%.

The thermoplastic base polymers used for the purposes of the present invention are, in particular, acrylonitrile-butadiene-styrene (ABS), Polyamides (PA), polymethyl methacrylate (PMMA), Polycarbonate (PC), Polyethylene (PE), for example LDPE, LLD PE, m-PE, polypropylene (PP), Polystyrene (PS), polyvinyl chloride (PVC), chloroprene, as well as polymers based on ethylene units, ethylene-vinyl acetate copolymers (EVA), EPDM or EPM, and/or celluloid or silane copolymerised polymers, and base polymers prepared, for example, from unsaturated functional monomers comprising silanes, for example VTMO, VTEO, and monomers, for example ethylene and other olefins, and monomer and/or prepolymer precursor compounds of these base polymers, for example ethylene, propylene. Further preferred elastomers may be selected from the series of ethylene-propylene rubbers (EPR), ethylene-propylene-diene rubbers (EPDM), styrene-butadiene rubbers (SBR), Natural Rubbers (NR), acrylate copolymer rubbers (ACM), acrylonitrile-butadiene rubbers (NBR) and/or polybutadiene rubbers (BR).

The invention also provides compositions obtainable by reaction of an olefinic alkoxysilane of the formula II, optionally with at least one alkoxysilane of the formula III and/or IV, in the presence of a specified amount of water of greater than or equal to 1.1 to 1.59mol per mole of silicon atoms in the alkoxysilane used, and preferably of a solvent, for example an alcohol, more particularly compositions comprising an olefinically functionalized siloxane oligomer in which the amount of silicon atoms having the structure T is greater than 10%, more particularly greater than or equal to 11%, and in which the total chloride content of these compositions, based on the total composition, is at the same time advantageously less than 250 mg/kg, more particularly less than 80 mg/kg, further preferably less than 50 mg/kg. The composition thus obtained can be readily diluted with a diluent at any time.

In order to allow a fast distribution in the extruder, while not suffering excessive mass loss in the hot extruder, an equilibrium ratio between the molecular weight Mw and the TGA temperature at which 5% or 50% mass loss occurs should be maintained. The above-mentioned compounds generally show a 50% mass loss at temperatures significantly above 200 c, more particularly above 220 c. The compositions of the invention are therefore very suitable for use in extruders, while at the same time allowing a rapid distribution of the siloxane oligomers in the thermoplastic owing to the very narrowly defined molecular weight. Also contributing to this efficient distribution is the slightly increased T structure in the siloxane, as the molecules are more compact.

The invention also provides the use of the compositions of the invention or of the compositions prepared by the process of the invention, as adhesives, as crosslinkers by graft polymerization and/or hydrolytic condensation in a conventional manner for producing mineral-filled polymers (compounds) and/or polymers, prepolymers grafted with ethylenically functional siloxane oligomers, for producing polymers, prepolymers grafted with ethylenically functional siloxane oligomers and/or mineral-filled thermoplastics or elastomers, preferably mineral-filled thermoplastics, elastomers or prepolymers thereof, in the grafting or polymerization of thermoplastic polyolefins, as drying agents, more particularly as water scavengers, for silicone sealants, in crosslinkable polymers for producing cables, for producing crosslinkable polymers, in emulsions and/or as oil phase together with organosilanes or organopolysiloxanes, materials for filler modification (filler coating), resin modification, resin additives, surface modification, surface functionalization, surface hydrophobization, as a constituent in coating systems, as a constituent in sol-gel systems or mixed systems, mixed coating systems, for modifying cathode and anode materials in batteries, as electrolyte liquids, as additives in electrolyte liquids, for modifying fibers, more particularly glass fibers and natural fibers, and for modifying textiles, for modifying fillers for the artificial stone industry, as building protection agents or as a constituent in building protection agents, as additives for mineral hardening, for modifying wood, wood fibers and cellulose. In connection with the use of the composition in combination with an organosilane or organosiloxane according to the present invention, the entire disclosure of EP 1205481B 1, more particularly the disclosure of paragraph [0039], and the list of organosilanes and organosiloxanes disclosed therein, is incorporated. Furthermore, the entire disclosure of DE 102011086863.1, filed by the German patent and trademark office on 7.2011, on 22.11.2011, is incorporated as subject matter of the present invention.

The present invention is illustrated in more detail by the following examples, but the present invention is not limited to these specific examples.

Examples

Determination of molecular weight:the molar mass and the molar mass distribution can be determined by Gel Permeation Chromatography (GPC). Publications, including "model Size-Exclusion Liquid Chromatography", Andre Striegel et al, Verlag Wiley&For calibrating the method for siloxane analysis, e.g. divinyltetramethoxydisiloxane or divinyltetraethoxydisiloxane may be used as standards the percentage of olefinic siloxane oligomers in relation to the present invention corresponds to the data per hundred area, which can be determined from the GPC analysis, MZ-analystechnik columns used: column: 50x8.0 mm, MZ-Gel SDplus (styrene/divinylbenzene copolymers with high degree of crosslinking, spherical particle shape), porosity 50A (angstroms, Å), 5 μm (microns) (front column), 300x8.0 mm, MZ-Gel SDplus, porosity 50A (angstroms, Å), 5 μm, 300x8.0 mm, MZ-Gelplus, porosity 100A (angstroms, Å), 5 μm, 300x8.0 mm, MZ-gell pump, SDplus, 1310, porosity 1310A (ml), MZ-99G, 500G, 99G, etc. a calibration of a calibration in a manually operated syringe (meter) and a unix 8.0G flow rate measuring a GPC meter calibration instrument.

Determination of the total chloride value:in a bomb-type calorimeter, the reaction vessel is,the silane was decomposed with oxygen and then hydrolyzed with acetic acid and hydrofluoric acid. The chloride content of the resulting solution was determined by titration with silver nitrate.

Determination of hydrolyzable chloride:after hydrolysis with acetic acid, the chloride content was determined by titration with silver nitrate.

SiO ₂ And (3) content determination: a crucible method: determination by fluorination by acid decomposition with concentrated sulfuric acid and subsequent evaporationSiO₂And (4) content.

GC analysis:standard GC assay methods, wherein the monomer content is determined by appropriate calibration and possible internal standards.

Alcohol after hydrolysis: the indicated amount of sample was mixed with sulfuric acid (25% strength). Then the indicated amount of water was added and neutralized with aqueous sodium hydroxide (20% strength). After steam distillation, the alcohol content was determined by GC relative to an internal standard (sec-butanol, HP 5890 with an integrator of HP 3396, 1 ml/min).

Flash point determination: DIN EN ISO 13736(2009.01), DIN EN ISO 2719 (2003.09). The flash point above 40 ℃ was determined by the method of DIN ISO 2719 (= DIN 51758 = EN 22719) and between-30 ℃ and +40 ℃ according to DIN EN ISO 13736 (= DIN 51755).

Water content: Karl-Fischer (DIN 51777)

TGA:In TGA (thermogravimetric analysis), a sample for analysis in a crucible is placed on a balance. During the measurement, the sample itself is located in a heatable oven. The crucible is usually open (no lid, or a hole in the lid). The interior of the oven was flushed with an inert gas (N2) to prevent possible reactions due to oxygen contact.

Equipment: TG 209 from Netzsch, temperature range: room temperature to about 1000 deg.C

Heating rate: 10K/min, initial mass: about 10-12 mg, crucible: the lid was covered with platinum with a hole.

Additional information about TGA analysis is found, for example, in the following internet textbooks: ModernePharmazeutische technology 2009, Cornelia M. Keck, Reiner H. Muller, Section3.5, Thermoanalysis, Lothar Schwabe, FU Berlin, page 76, FIG. 5, http:// Pharmazie-lehrbuch. de/model% 20Pharmazeutische%20 technology. pdf or found in other textbooks on analytical methods.

²⁹ Si NMR spectroscopy: in addition, it is possible to use ²⁹Si NMR spectroscopy, which is also well known to those skilled in the art, determines the monomer content, as well as M, D and T structure.

Determination of dynamic viscosity: the dynamic viscosity was determined in accordance with DIN 53015.

1. Synthesis of the products of the invention

The various methods for reducing the chlorine content, as described above, can also each be combined with the process of the invention independently of one another. For example, a well-defined amount of water can be used in combination with an ion exchanger, and/or in combination with the subsequent addition of a second to sixth specified amount of alcohol to the reaction, and/or in combination with neutralization by a base, and/or in combination with the addition of a reducing agent.

1.1 "VTEO-siloxane oligomer" -silane: Water =1: 1.1-V092

The method comprises the following steps: 380.6 g of VTEO (vinyltriethoxysilane) were charged into a 2 l apparatus. A mixture of ethanol, double distilled water and hydrochloric acid (37%) is then metered in at 35 ℃ and ambient pressure. An exothermic reaction occurs. If the temperature rises above 60 ℃, the metering is interrupted. At the complete metering of H₂After the O/EtOH/HCl mixture, the reaction was started at 77 ℃ and the total reaction time was stirred for 5 hours. After the reaction, the alcohol was distilled on a rotary evaporator at up to 100 ℃ and 100 mbar. After reaching 100 mbar, it was held for 15 minutes, after which the apparatus was allowed to return to normal. The bottom product obtained was a VTEO-siloxane oligomer.

Compound (I)	Initial mass
		Water (W)	39.6 g
Ethanol	181.2 g
		Hydrochloric acid (37% concentration)	0.24 g

Table 1: starting material V092.

1.2 "VTEO-siloxane oligomer" -silane: Water =1: 1.22-V093

The method comprises the following steps: 380.6 g of VTEO were charged into a 2 l apparatus. A mixture of ethanol, double distilled water and hydrochloric acid (37%) is then metered in at 35 ℃ and ambient pressure. An exothermic reaction occurs. If the temperature rises above 60 ℃, the metering is interrupted. At the complete metering of H₂After the O/EtOH/HCl mixture, the reaction was started at 77 ℃ and the total reaction time was stirred for 5 hours. After the reaction, the alcohol was distilled on a rotary evaporator at up to 100 ℃ and 100 mbar. After reaching 100 mbar, it was held for 15 minutes, after which the apparatus was allowed to return to normal. The bottom product obtained is a vinyl siloxane oligomer.

Compound (I)	Initial mass
		Water (W)	43.9 g
Ethanol	181.0 g
		Hydrochloric acid (37% concentration)	0.26 g

Table 2: raw material V093.

1.3 "VTEO-siloxane oligomer" -silane: Water =1: 1.35-V094

The method comprises the following steps: 380.6 g of VTEO were charged into a 2 l apparatus. A mixture of ethanol, double distilled water and hydrochloric acid (37%) is then metered in at 35 ℃ and ambient pressure. An exothermic reaction occurs. If the temperature rises above 60 ℃, the metering is interrupted. At the complete metering of H₂After the O/EtOH/HCl mixture, the reaction was started at 77 ℃ and the total reaction time was stirred for 5 hours. After the reaction, the alcohol was distilled on a rotary evaporator at up to 100 ℃ and 100 mbar. After reaching 100 mbar, it was held for 15 minutes, after which the apparatus was allowed to return to normal. The bottom product obtained is a vinyl siloxane oligomer.

Compound (I)	Initial mass
		Water (W)	49.0 g
Ethanol	181.2 g
		Hydrochloric acid (37% concentration)	0.23 g

Table 3: starting material V094.

1.4 "VTEO-siloxane oligomer" -silane: Water =1: 1.47-V095

The method comprises the following steps: 380.6 g of VTEO were charged into a 2 l apparatus. A mixture of ethanol, double distilled water and hydrochloric acid (37%) is then metered in at 35 ℃ and ambient pressure. An exothermic reaction occurs. If the temperature rises above 60 ℃, the metering is interrupted. At the complete metering of H₂After the O/EtOH/HCl mixture, the reaction was started at 77 ℃ and the total reaction time was stirred for 5 hours. After the reaction, the alcohol was distilled on a rotary evaporator at up to 100 ℃ and 100 mbar. After reaching 100 mbar, it was held for 15 minutes, after which the apparatus was allowed to return to normal. The bottom product obtained is a vinyl siloxane oligomer.

Compound (I)	Initial mass
		Water (W)	53.3 g
Ethanol	181.0 g
		Hydrochloric acid (37% concentration)	0.27 g

Table 4: starting material V095.

1.5 "VTEO/TEOS-siloxane oligomer" -silane: Water = (1+0.1):1.22-V096

The method comprises the following steps: 380.6 g of VTEO and 41.6 g of Tetraethoxysilane (TEOS) were charged into a 2 l apparatus. A mixture of ethanol, double distilled water and hydrochloric acid (37%) is then metered in at 35 ℃ and ambient pressure. An exothermic reaction occurs. If the temperature rises above 60 ℃, the metering is interrupted. At the complete metering of H₂After the O/EtOH/HCl mixture, the reaction was started at 77 ℃ and the total reaction time was stirred for 5 hours. After the reaction, the alcohol was distilled on a rotary evaporator at up to 100 ℃ and 100 mbar. After reaching 100 mbar, it was held for 15 minutes, after which the apparatus was allowed to return to normal. The bottom product obtained is a vinyl-functionalized co-oligomer derived from tetraethoxysilane with condensed Q-structural elements (VTEO/TEOS-siloxane oligomer).

Compound (I)	Initial mass
		Water (W)	44.2 g
Ethanol	181.6 g
		Hydrochloric acid (37% concentration)	0.23 g

Table 5: starting material V096.

1.6 "VTEO/PTEO-siloxane oligomer" -silane: Water =1:1.25-V111

The method comprises the following steps: 190.3 g of VTEO and 206.5 g of PTEO were metered into a 2 l four-neck apparatus having a water condenser and a magnetic stirrer. A mixture of ethanol, double distilled water and hydrochloric acid (37%) is then metered in at 35 ℃ and ambient pressure. An exothermic reaction occurs. If the temperature rises above 60 ℃, the metering is interrupted. At the complete metering of H₂After the O/EtOH/HCl mixture, the reaction was started at 79 ℃ and the total reaction time was taken for 5 hours. After the reaction, the alcohol was distilled on a rotary evaporator at up to 100 ℃ and 100 mbar. After reaching 100 mbar, it was held for 15 minutes, after which the apparatus was allowed to return to normal. The bottom product obtained was a vinyl and propyl functionalized siloxane oligomer formed from VTEO and PTEO.

Compound (I)	Initial mass
		Water (W)	45.2 g
Ethanol	175.0 g
		Hydrochloric acid	0.2 g

Table 6: raw material V111.

1.7 "VTEO/PTEO-siloxane oligomer" -silane: Water =1:1.5-V112

The method comprises the following steps: 190.3 g of VTEO and 206.6 g of PTEO were metered into a 2 l four-neck apparatus having a water condenser and a magnetic stirrer. A mixture of ethanol, double distilled water and hydrochloric acid (37%) is then metered in at 35 ℃ and ambient pressure. An exothermic reaction occurs. If the temperature rises above 60 ℃, the metering is interrupted. At the complete metering of H₂After the O/EtOH/HCl mixture, the reaction was started at 79 ℃ and the total reaction time was taken for 5 hours. After the reaction, the alcohol was distilled on a rotary evaporator at up to 100 ℃ and 100 mbar. After reaching 100 mbar, it was held for 15 minutes, after which the apparatus was allowed to return to normal. The bottom product obtained was a vinyl and propyl functionalized siloxane oligomer formed from VTEO and PTEO.

Compound (I)	Initial mass
		Water (W)	54.3 g
Ethanol	175.0 g
		Hydrochloric acid	0.2 g

Table 7: feedstock V112.

1.8 "VTEO/PTEO/TEOS-siloxane oligomer" -silane: Water = (1+0.1):1.25-V113

The method comprises the following steps: 190.3 g of VTEO and 41.5 g of tetraethoxysilane and 206.4 g of PTEO are metered into a 2 l four-neck apparatus having a water condenser and a magnetic stirrer. A mixture of ethanol, double distilled water and hydrochloric acid (37%) is then metered in at 35 ℃ and ambient pressure. An exothermic reaction occurs. If the temperature rises above 60 ℃, the metering is interrupted. At the complete metering of H₂After the O/EtOH/HCl mixture, the reaction was started at 79 ℃ and the total reaction time was taken for 5 hours. After the reaction, the alcohol was distilled on a rotary evaporator at up to 100 ℃ and 100 mbar. After reaching 100 mbar, it was held for 15 minutes, after which the apparatus was allowed to return to normal. The bottom product obtained is a crosslinked vinyl-and propyl-functionalized siloxane oligomer with Q-structure elements (four-position functionality) formed from VTEO, PTEO and tetraethoxysilane.

Compound (I)	Initial mass
		Water (W)	45.2 g
Ethanol	174.8 g
		Hydrochloric acid	0.19 g

Table 8: feedstock V113.

2. Analysis of

2.1 general analysis

	V092	V093	V094	V095	V096
						Total chloride [ mg/kg]	< 35	< 35	< 35	50	< 35
Hydrolyzed chloride [ mg/kg]	< 3	4	4	6	5
						SiO2[% (by mass)]	50.8	53.6	55.8	58.7	52.2
Free ethanol [% (by mass)]	1.5	1.4	1.5	1.4	0.7
						VTEO [% (by mass)]	0.5	0.2	< 0.1	< 0.1	0.3
Color number [ mg Pt Co/l]	< 5	< 5	10	< 5	10
						Method for harvesting seeds at 20 deg.C]	1.061	1.088	1.108	1.123	1.082
Dynamic viscosity at 20 ℃ mPas]	7.8	13.8	22.9	46.6	11.5

Table 9: analysis results of silicone oligomers of VTEO type.

	V111	V112	V113
				Total chloride [ mg/kg]	55	65	110
Hydrolyzed chloride [ mg/kg]	< 3	4	4
				SiO2[% (by mass)]	50.1	54.5	47.8
Free ethanol [% (by mass)]	0.9	1.2	0.8
				VTEO/PTEO [% (by mass)]	0.1	0.1	0.4
Color number [ mg Pt Co/l]	< 5	< 5	< 5
				Method for harvesting seeds at 20 deg.C]	1.053	1.087	1.044
Dynamic viscosity at 20 ℃ mPas]	17.8	48.1	11.5

Table 10: analysis results of VTEO/PTEO siloxane oligomer.

2.2 NMR analysis

Table 11: results from NMR studies of siloxane oligomers of the VTEO, VTEO/PTEO and VTEO/PTEO/TEOS types [ VS = vinylsilyl, PS = propylsilyl, ES = ethoxysilyl ].

2.3 GPC analysis

Test number	Mn [g/mol]	Mw [g/mol]	D = Mw/Mn
				V092	495.24	564.87	1.1406
V093	538.55	621.30	1.1536
				V094	576.26	679.77	1.1796
V095	624.38	754.87	1.2090
				V096	550.08	710.87	1.2923
V111	581.50	816.27	1.4037
				V112	763.06	1083.40	1.4198
V113	556.68	707.65	1.2735
				V078	275.13	291.11	1.0581
V081	254.06	269.90	1.0624

Table 12 a: evaluation of GPC analysis results.

Like	Mw g/mol	Mn g/mol	M max [ g/mol]
				V092	567.4	504.8	1800
V093	624.3	551.2	2000
				V094	685.3	601.3	2100
V095	783.5	643.7	3000

Table 12 b: evaluation of the results of GPC analysis of the compositions prepared analogously to example 1.1 (V092), example 1.2 (V093), example 1.3 (V094) and analogously to example 1.4 (V095).

Like	Disiloxane + cyclotrisiloxane [% ]]	Trisiloxane + cyclotetrasiloxane [% ]]	Tetrasiloxane + cyclopentasiloxane [% ]]	Pentasiloxane + cyclohexasiloxane [% ]]
					V092	11.6	35.8	26.1	10.2
V093	6	30.2	31.2	9.9
					V094	3.6	26	31.1	10.1
V095	1.2	21.9	31	8.6
					V096	6.3	27.3	28.8	10.4

Table 12 c: evaluation of the results of GPC analysis, the content in% by area of the compositions prepared analogously to example 1.1 (V092), example 1.2 (V093), example 1.3 (V094) and analogously to example 1.4 (V095) amounts to 100% less than disiloxane and greater than hexasiloxane, where less than disiloxane is less than 1.0%, more particularly less than 0.5%.

Like	250-]	500-]	750-]
				V092	46.63	36.85	11.48
V093	35.54	41.7	14.23
				V094	28	42.21	16.34
V095	21.84	40.42	17.38
				V096	32.55	39.41	15.11

Table 12 d: evaluation of the results of the GPC analysis, the content, expressed in% by area, of the compositions prepared analogously to example 1.1 (V092), example 1.2 (V093), example 1.3 (V094) and analogously to example 1.4 (V095) amounts to 100% of less than 250 g/mol and more than 1000 g/mol, where less than 250 g/mol is less than 1.0%, more particularly less than 0.5%.

The molecular weight deviations of the individual siloxane oligomer compositions are interpreted on the one hand as different substitutions of the siloxane oligomers or, in the case of identical substitutions, as customary, slight fluctuations in the individual experiments.

2.4 TGA

Table 13 a: evaluation of the results of TGA analysis

Table 13 b: evaluation of the results of TGA analysis.

3. Comparative examples

Comparative example 1: v078-example from EP0518057B 1-preparation of a cocondensate of vinyltrimethoxysilane and methyltrimethoxysilane with a molar ratio of vinylmethoxymethyl groups of about 1:3

The method comprises the following steps: 397.6 g of Vinyltrimethoxysilane (VTMO) and 244.6 g of methyltrimethoxysilane were charged at 20 ℃ into a 2 l four-neck apparatus having a water condenser and a magnetic stirrer. The mixture was mixed with a solution of 49.9 g of distilled water in 332.8 g of methanol, which solution contained 2400 ppm of hydrogen chloride, using a 500 ml dropping funnel. After a total of 16 hours, all methanol together with HCl was distilled off at about 300 mbar. The resulting oligomer mixture was then distilled to a pressure of about 1 mbar and to a boiling range end point of 113 ℃. 170 g of clear product are obtained in this way.

Table 14: raw material V078.

Comparative example 2: v081-example 6 from EP0518057B1 preparation of condensate of vinyltrimethoxysilane with a molar ratio of vinyl to methoxy groups of about 1:1.75

The method comprises the following steps: 693.83 g of VTMO were charged at 20 ℃ into a 2 l four-necked apparatus with a water condenser and a magnetic stirrer. The mixture was mixed with a solution of 52.82 g of distilled water in 351.53 g of methanol, which solution contained 1100 ppm of hydrogen chloride. This was done using a 500 ml dropping funnel. The temperature was raised to about 36 ℃ in 26 minutes. After a total of 13 hours, all methanol together with hydrochloric acid was distilled off at about 300 mbar over a period of 2-3 hours. The resulting oligomer mixture was then distilled to a pressure of about 1 mbar and to a boiling range end point of 100 ℃. 240 g of clear product are obtained in this way.

Table 15: raw material V081.

The chloride content (total chloride) can be determined by methods known to the person skilled in the art, for example with AgNO₃And (4) measuring the potential. AgNO for hydrolyzable chlorides₃Titration by potentiometric method.

Test No. V078	Total chloride	Hydrolysable chlorides	SiO2	VTMO	Number of colors
							[mg/kg]	[mg/kg]	(mass) [% ]]	(mass) [% ]]	[mg Pt-Co/l]
Distillate (1)	230	16	52.4	< 0.1	< 5

Table 16: the results of the analysis of V078 (comparative example 1), (1) (see example 1 in EP0518057B 1).

Test No. V081	Total chloride	Hydrolysable chlorides	SiO2	VTMO	Number of colors
							[mg/kg]	[mg/kg]	(mass) [% ]]	(mass) [% ]]	[mg Pt-Co/l]
Distillate (2)	50	< 3	48.6	1.7	< 5

Table 17: the results of the analysis of V081 (comparative examples 2), (2) (see example 6 in EP0518057B 1).

Table 18: of products from comparative tests V078 and V081²⁹Results obtained by Si NMR analysis [ VS = vinylsilyl, MS = methylsilyl]。

Comparative examples 3 to 5 are similar to example 6 of EP 0518057:

the process disclosed in example 6 for compound VTMO was replicated separately and carried out for compounds VTEO and VTMO as new variants, as well as for co-oligomers VTMO and Propyltrimethoxysilane (PTMO), and Vinyltriethoxysilane (VTEO) and Propyltriethoxysilane (PTEO). The process here is carried out in equimolar amounts in batches on the 1000 g scale. Each silane was charged at room temperature into a 2 l stirring apparatus (vinyltrimethoxysilane (V074), vinyltriethoxysilane (V075), vinyltrimethoxy-and propyltrimethoxysilane (V076), and vinyltriethoxysilane (V077)). A water/alcohol mixture (examples V074, V076, methanol; examples V075, V077 = ethanol) containing 1100 ppm (0.11%) of hydrogen chloride is metered in. The exothermic temperature curves were observed separately. The temperature here rises to 35-40 ℃ respectively. After a reaction time of 13 hours, the alcohol was stripped off over a period of 3 hours at an absolute pressure of 300 mbar. Finally the oligomer mixture itself is distilled at a pressure <0.1 mbar.

Table 19: analytical results-comparative examples 3 to 5 and the new variants.

Table 20: comparative examples 3 to 5, analysis results, n.r.: no residue, (1.1): individual black dots are on the crucible substrate; (1.2) no significant residue, (1.3) black spots on and at the edge of the crucible base, (2): temperature [ dm/dt ] -first peak at maximum rate of mass decrease.

Table 21: TGA evaluation.

4. Performance testing

Test No. (siloxane oligomer from)	Performance test number
		-	V153 (blank sample)
V092	V119
		V093	V120
V094	V121
		V095	V122
V096	V123
		V111	V124
V112	V125
		V113	V126
V078	V116
		V081	V118

Table 22: specification of performance test.

4.1 kneading test

The following kneading operation was carried out in a HAAKE kneader with a temperature profile of 3 minutes at 140 ℃, increasing from 140 ℃ to 170 ℃ in 2 minutes, and 5 minutes at 170 ℃, at a rotational speed of 30 rpm. Subsequently, each batch was processed by compression to form two slabs at 190 ℃ and a load pressure of 20 t, respectively. To simplify the addition of peroxide, a silane/peroxide solution was prepared.

4.2 preparation of test specimens

The samples prepared were stored in a climate chamber at 23 ℃ and 50% relative atmospheric humidity, after which samples were prepared for tensile testing and for determining the water absorption capacity and for determining the melt index.

Compound (I)	Batch of
		ATH	M56/15
EVA	M56/156
		DCUP	M56/026

Table 23: raw materials and batches for practical applications.

Table 24: peroxide mixture for kneading.

Table 25: initial mass in the kneading test.

4.3 determination of melt index (MFR) and volume flow index (MVR)

The preparation and evaluation were carried out in accordance with DIN ISO 1133 (method B), the content of DIN ISO 1133 (method B) being incorporated in its entirety and being part of the present application. The testing device comprises: zwick 4106 flow tester. Loading of the Plastic melt with the specified load (m) by means of a standard nozzle_nom) At a given temperature (T)_PT) The determination of melt index (MFR) and volume flow index (MVR) was carried out below and at a fixed shear load. The evolution of the mold over time was determined and the MVR and MRF were calculated according to formulas known to those skilled in the art. About 7 g of each sample was pulverized and the melt index ("MFR") was determined at a temperature of 160 ℃ and under a load of 21.6 kg.

Table 26: the MFR and MVR results of the examples were compared.

Test number	V153 (blank sample)
		Siloxane oligomers	-
Test temperature	160℃
		Preheating time	4 minutes
Load(s)	21.6 kg
		MFR [ g min ]]	2.03
MVR [ cm ] Stern in China]	1.50
		High density [ g/cm ] thin strip]	1.349

Table 27: MFR and MVR results for the blank sample.

Table 28: MFR and MVR results for runs V119, V120, V121, V122 and V123.

Table 29: MFR and MVR results for runs V124, V125 and V126.

4.4 Water absorption Capacity

Measurement of Water absorption: test samples of the specified geometry were stored in a water bath under the specified conditions (temperature, time). The results of the weight change of the samples before and during storage and after the drying operation were recorded. After a period of 24 hours, the water absorption capacity was determined by means of a triple determination using the prepared samples which had been stored in a water bath at 70 ℃ for the stated period of time.

Performance test number	Water absorption [ mg/cm ] after 7 days storage2]
		V153	3.81
V116	1.55
		V118	1.40
V119	1.49
		V121	1.48
V122	1.47
		V123	1.39
V124	1.68
		V125	1.55
V126	1.43

Table 30: results of water absorption capacity studies.

4.5 determination of tensile Properties

Tensile properties were determined according to DIN EN ISO 527-1, 527-2, 527-3, the contents of which DIN EN ISO 527-1, 527-2, 527-3 are incorporated in their entirety and are part of the present disclosure. For this purpose, a sample rod of the specified geometry is clamped into a tensile tester and subjected to a uniaxial load until fracture occurs (uniaxial stretching at the specified stretching rate). The change in stress on the sample bar will be recorded by the stretching of the sample and the tensile strength and elongation at break will be determined. Testing equipment: zwick universal tester 4115. The tensile properties (elongation at break and tensile strength) of the prepared sample and tensile bar ("bone") were measured after 24 hours of storage in a climate chamber at 23 ℃ and 50% relative atmospheric humidity, at a tensile rate of 200 mm/min and at a tensile force of 0.2 MPa, for 5 measurements.

Siloxane oligomerizationThe substance is from	Performance test number	Elongation at break [% ]]	Tensile strength [ MPa ]]
				V092	V119	58.26	8.25
V093	V120	65.81	8.43
				V094	V121	102.06	8.16
V095	V122	98.97	8.28
				V096	V123	84.81	8.00
V111	V124	39.61	7.64
				V112	V125	98.39	8.19
V113	V126	58.83	7.69
				V078	V116	80.37	8.66
V081	V118	85.61	9.31

Table 31: results of tensile strength and elongation at break studies.

Claims (42)

1. A composition comprising an ethylenically functional siloxane oligomer having at most one olefinic group on a silicon atom, characterised in that,

-the ethylenically functionalized siloxane oligomer has Si-O-crosslinking structural elements which form linear, cyclic, crosslinked and/or optionally three-dimensionally crosslinked structures, at least one of which corresponds to the general formula I,

(R¹O)[(R¹O)_1-x(R²)_xSi(A)O]_a[Si(Y)₂O]_c[Si(B)(R⁴)_y(OR³)_1-yO]_bR³(I)，

-wherein the structural element is derived from an alkoxysilane, and

-A in the structural elements corresponds to an olefinic group and is selected from linear, branched or cyclic alkenyl-or cycloalkenyl-alkylene-functional groups having 2 to 16C atoms respectively, and

b in said structural element corresponds to a saturated hydrocarbon group and is selected from linear, branched or cyclic alkyl groups having 1 to 16C atoms,

y corresponds to OR³OR, independently of one another, correspond to OR in the crosslinked and optionally three-dimensionally crosslinked structure³Or O_1/2，

-wherein R is¹Independently of one another, linear, branched or cyclic alkyl radicals having 1 to 4C atoms or H,

- R³each independently of the others, corresponds to a linear, branched or cyclic alkyl radical having 1 to 4C atoms or to H, and R²Each independently corresponding to a linear, branched or cyclic alkyl group having 1 to 15C atoms, R⁴Each independently corresponding to a linear, branched or cyclic alkyl group having 1 to 15C atoms,

a, b, c, x and y independently correspond to integers, and 1. ltoreq. a, 0. ltoreq. b, 0. ltoreq. c, x independently of one another is 0 or 1, y independently of one another is 0 or 1, and (a + b + c). gtoreq.2,

-wherein the total chloride content is less than or equal to 250 mg/kg, and

-wherein the structural element in formula I [ (R)¹O)_1-x(R²)_xSi(A)O]_a、[Si(B)(R⁴)_y(OR³)_1-yO]_bAnd [ Si (Y)₂O]_cMore than or equal to 10% of all silicon atoms of formula I are present together as T structure.

2. The composition according to claim 1, wherein the composition,

it is characterized in that the preparation method is characterized in that,

the siloxane oligomer has a structural element derived from at least one alkoxysilane,

(i) derived from an olefinically functionalized alkoxysilane of the formula II,

A-Si(R²)_x(OR¹)_3-x(II)

wherein A corresponds to an olefinic group and is selected from linear, branched or cyclic alkenyl-or cycloalkenyl-alkylene-functional groups each having 2 to 16C atoms, wherein R²Each independently is a linear, branched or cyclic alkyl radical having 1 to 15C atoms, and x is independently of the other 0 or 1, and R¹Independently correspond to methyl, ethyl or propyl, and

(ii) optionally derived from alkoxysilanes of formula III functionalized with saturated hydrocarbon groups,

B-Si(R⁴)_y(OR³)_3-y(III)

wherein B corresponds to an unsubstituted hydrocarbon radical and is selected from linear, branched or cyclic alkyl radicals having 1 to 16C atoms, where R⁴Each independently is a linear, branched or cyclic alkyl radical having 1 to 15C atoms, and y is independently of the other 0 or 1, and R³Independently correspond to a methyl, ethyl or propyl group, and

(iii) optionally derived from Si (OR) of formula IV³)₄Wherein R is³Independently of one another as defined above.

3. The composition according to claim 1 or 2,

characterized in that each is selected independently of the other

(i) Structural element [ (R) in the general formula I¹O)_1-x(R²)_xSi(A)O]_aGreater than or equal to 5% of all silicon atoms of formula I are present as T structures,

(ii) structural element [ (R) in the general formula I¹O)_1-x(R²)_xSi(A)O]_aAnd [ Si (B) (R) ]⁴)_y(OR³)_1-yO]_bAnd [ Si (Y)₂O]_cGreater than or equal to 50% of all silicon atoms of formula I are present together as D structure,

(iii) structural element [ (R) in the general formula I¹O)_1-x(R²)_xSi(A)O]_aLess than or equal to 35% of all silicon atoms of formula I are present as M structures,

(iv) structural element [ Si (B) (R) in general formula I⁴)_y(OR³)_1-yO]_bLess than or equal to 25% based on all silicon atoms of formula I is present as M structure, and

(v) structural element in general formula I [ Si (Y)₂O]_cAt least 20% of structural elements [ Si (Y) ] in the general formula I exist as D structure, or at least 40%₂O]_cExist as a D structure.

4. The composition of claim 3, wherein the structural element of formula I [ (R)¹O)_1-x(R²)_xSi(A)O]_aGreater than or equal to 7.5% of all silicon atoms of formula I are present as T structures.

5. The composition according to claim 1 or 2,

characterized in that in the olefinically functionalized alkoxysilane of the formula II x is 0 and, optionally, in the alkoxysilane of the formula III functionalized with a saturated hydrocarbon radical y is 0.

6. The composition according to claim 1 or 2,

it is characterized in that

-in general formula I and/or II, said olefinic group a is a non-hydrolysable olefinic group selected from vinyl, allyl, butenyl, 3-butenyl, pentenyl, hexenyl, ethylhexenyl, heptenyl, octenyl and cyclohexenyl-C1 to C8-alkylene, cyclohexenyl-2-ethylene, 3' -cyclohexenyl-2-ethylene, cyclohexadienyl-C1 to C8-alkylene, cyclohexadienyl-2-ethylene groups, and thus independently therefrom

-in general formula I and/or III, the unsubstituted hydrocarbon radical B is selected from the group consisting of methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, C₁₃H₂₇、C₁₄H₂₉、C₁₅H₃₁And a hexadecyl group, and

each R independently of the other¹Is methyl, ethyl or propyl and R³Independently methyl, ethyl or propyl.

7. The composition according to claim 1 or 2,

it is characterized in that the preparation method is characterized in that,

-in formula I and/or II, the olefinic group A is vinyl, and is thus independently

-in general formula I and/or III, the unsubstituted hydrocarbon radical B is selected from the group consisting of methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, C₁₃H₂₇、C₁₄H₂₉、C₁₅H₃₁And a hexadecyl group, and

each R independently of the other¹Is methyl, ethyl or propyl and R³Independently methyl, ethyl or propyl.

8. The composition according to claim 1 or 2,

it is characterized in that the preparation method is characterized in that,

the olefinically functionalized siloxane oligomer is present in an amount of greater than or equal to 30 area percent, based on the total composition, as determined by GPC, and has a molecular weight Mw of 500-700 g/mol in the composition.

9. The composition according to claim 1 or 2,

it is characterized in that the preparation method is characterized in that,

the ethylenically functionalized siloxane oligomer is present in the composition as trisiloxane, tetrasiloxane, pentasiloxane, cyclotetrasiloxane, cyclopentasiloxane, and/or cyclohexasiloxane, and also as a mixture comprising at least two of the foregoing siloxanes, at 60% or greater.

10. The composition according to claim 1 or 2,

it is characterized in that the preparation method is characterized in that,

the 50 wt.% mass loss occurs at temperatures above 240 ℃ as determined by TGA.

11. The composition according to claim 1 or 2,

it is characterized in that the preparation method is characterized in that,

the composition has a mass loss of less than 5% by weight at temperatures up to and including 150 ℃ as determined by TGA under conditions of a platinum crucible, a lid with a hole, 10K/min.

12. The composition according to claim 1 or 2,

it is characterized in that the preparation method is characterized in that,

the composition has a mass loss of less than 20% by weight at temperatures up to and including 200 ℃ as determined by TGA under conditions of a platinum crucible, a lid with a hole, 10K/min.

13. The composition according to claim 1 or 2,

it is characterized in that the preparation method is characterized in that,

the alcohol content of the hydrolyzable alkoxy group after complete hydrolysis is 20% by weight or less.

14. The composition of claim 13, wherein the alcohol content of the hydrolyzable alkoxy group after complete hydrolysis is less than or equal to 18 weight percent.

15. The composition of claim 13, wherein the alcohol content of the hydrolyzable alkoxy group after complete hydrolysis is less than or equal to 16 weight percent.

16. The composition of claim 13, wherein the alcohol content of the hydrolyzable alkoxy group after complete hydrolysis is less than or equal to 15 weight percent.

17. The composition of claim 13, wherein the alcohol content of the hydrolyzable alkoxy group after complete hydrolysis is less than or equal to 12 weight percent.

18. The composition according to claim 1 or 2,

it is characterized in that the preparation method is characterized in that,

(i) the ratio of silicon atoms to alkoxy groups in the siloxane oligomer is from 1:0.3 to 1:2.0, said silicon atoms being selected from the group consisting of ethylenically functionalized silicon atoms and silicon atoms functionalized with saturated hydrocarbons, with the proviso that the ethylenically functionalized siloxane oligomer is derived from alkoxysilanes of the formulae II and III, or

(ii) The ratio of silicon atoms to alkoxy groups in the siloxane oligomer is from 1:0.9 to 1:2.5, said silicon atoms being selected from the group consisting of ethylenically functionalized silicon atoms and silicon atoms functionalized with saturated hydrocarbons, with the proviso that the ethylenically functionalized siloxane oligomer is derived from alkoxysilanes of the general formulae II and IV and III.

19. The composition according to claim 1 or 2,

it is characterized in that the preparation method is characterized in that,

wherein the content of silicon atoms in the monomeric alkoxysilanes is less than or equal to 3%, based on all silicon atoms, wherein the monomeric alkoxysilanes are to be regarded as alkoxysilanes of the general formulae II, III and/or IV and also as monomeric hydrolysis products thereof.

20. The composition according to claim 1 or 2,

it is characterized in that the preparation method is characterized in that,

a) the siloxane oligomer and at least one structure of the formula I, respectively derived from an alkoxysilane of the formula II, have a vinyl group as olefinic group A, where R¹Each independently of the others corresponds to a methyl or ethyl group,

b) the siloxane oligomer and at least one structure of formula I, respectively derived from an alkoxysilane of formula II having a vinyl group as the olefinic group A and from an alkoxysilane of formula III having a propyl group as the unsubstituted hydrocarbyl group B, wherein R¹And R³Each independently of the other, corresponds to a methyl or ethyl radical, or

c) The siloxane oligomer and at least one structure of formula I, derived from alkoxysilanes of formula II and formula IV, respectively, and optionally formula III, are selected from a) or b), wherein R is³Derived from formula IV and each independently of the other corresponds to a methyl or ethyl group.

21. The composition according to claim 1 or 2,

it is characterized in that the preparation method is characterized in that,

independently of each other, the siloxane oligomer has a structural element derived from at least one ethylenically functionalized alkoxysilane of the formula II selected from vinyltriethoxysilane, vinyltrimethoxysilane and optionally a structural element derived from the formula III, wherein the alkoxysilane of the formula III is selected from methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, butyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, isobutyltrimethoxysilane, hexyltriethoxysilane, hexyltrimethoxysilane, isohexyltriethoxysilane, isohexyltrimethoxysilane, heptyltriethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilaneTriethoxysilane, octyltrimethoxysilane, isooctyltriethoxysilane, isooctyltrimethoxysilane, undecetyltriethoxysilane, undecetyltrimethoxysilane, decyltriethoxysilane, decyltrimethoxysilane, nonadecyltriethoxysilane, nonadecyltrimethoxysilane, dodecayltriethoxysilane, dodecayltrimethoxysilane, C₁₃H₂₇Triethoxysilane, C₁₃H₂₇Trimethoxy silane, C₁₄H₂₉Triethoxysilane, C₁₄H₂₉Trimethoxy silane, C₁₅H₃₁Trimethoxy silane, C₁₅H₃₁Triethoxysilane, hexadecyltriethoxysilane and hexadecyltrimethoxysilane, and also transesterification products thereof.

22. Composition according to claim 1 or 2, characterized in that the weight-average molecular weight Mw ranges from 564 to 1083 g/mol.

23. A process for preparing a composition as claimed in any one of claims 1 to 22 comprising an ethylenically functionalized siloxane oligomer by at least

(i) An ethylenically functionalized alkoxysilane of the general formula II

A-Si(R²)_x(OR¹)_3-x(II)，

Wherein in formula II A corresponds to an olefinic group selected from linear, branched or cyclic alkenyl-or cycloalkenyl-alkylene-functional groups each having 2 to 16C atoms, R²Independently corresponds to a linear, branched or cyclic alkyl radical having 1 to 15C atoms, and x is 0 or 1, and R¹Independently corresponding to a linear, branched or cyclic alkyl group having 1-4C atoms,

(ii) in the presence of a hydrolysis-and/or condensation catalyst,

(iii) optionally in the presence of a solvent, with a specified amount of water of 1.1 to 1.59mol per mole of silicon atoms in the alkoxysilane used to obtain a siloxane oligomer,

(iv) substantially removing the hydrolysis alcohol and optionally the solvent, and

(v) the total content of chloride in the composition is set to be less than or equal to 250 mg/kg,

(vi) wherein greater than or equal to 10% of the silicon atoms in the ethylenically functionalized siloxane oligomer are present as T structures, based on the total number of silicon atoms in the siloxane oligomer, and

(vii) wherein the composition comprising the ethylenically functionalized siloxane oligomer is obtained as a bottom product.

24. The process according to claim 23, characterized in that (i) the olefinically functionalized alkoxysilane of the formula II (II) is reacted with (i.1) at least one alkoxysilane of the formula III in the presence of a hydrolysis and/or condensation catalyst,

B-Si(R⁴)_y(OR³)_3-y(III)

wherein in formula III B corresponds to a saturated hydrocarbon radical selected from linear, branched or cyclic alkyl radicals having 1 to 16C atoms, R³Each independently of the other corresponds to a linear, branched or cyclic alkyl radical having 1 to 4C atoms, and R⁴Corresponding to a linear, branched or cyclic alkyl group having 1 to 15C atoms, and y is 0 or 1.

25. The process according to claim 23 or 24, characterized in that (i) the olefinically functionalized alkoxysilane of the formula II (II) is reacted with (i.2) at least one tetraalkoxysilane of the formula IV in the presence of a hydrolysis and/or condensation catalyst,

Si(OR³)₄(IV)

wherein in formula IV, R³Each independently of the others, is a linear, branched or cyclic alkyl radical having 1 to 4C atoms.

26. The method according to claim 23 or 24, characterized in that an alcohol is used as solvent.

27. The method according to claim 23 or 24,

it is characterized in that the preparation method is characterized in that,

-in the olefinically functionalized alkoxysilane of the formula II

A-Si(R²)_x(OR¹)_3-x(II)

A is vinyl, allyl, butenyl, pentenyl, hexenyl, ethylhexenyl, heptenyl, octenyl, cyclohexenyl-C1 to C8-alkylene, cyclohexenyl-2-ethylene, 3' -cyclohexenyl-2-ethylene, cyclohexadienyl-C1 to C8-alkylene or cyclohexadienyl-2-ethylene, x is 0 or 1, R is²Independently corresponds to a linear, branched or cyclic alkyl group having 1-15C atoms, and R¹Independently is a methyl, ethyl or propyl group, and independently

Optionally in said alkoxysilane of the formula III

B-Si(R⁴)_y(OR³)_3-y(III)

Unsubstituted hydrocarbon radicals B are methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, C₁₃H₂₇、C₁₄H₂₉、C₁₅H₃₁And hexadecyl, y is 0 or 1, R⁴Corresponds to a linear, branched or cyclic alkyl radical having 1 to 15C atoms, and R³Independently a methyl, ethyl or propyl group.

28. The method according to claim 23 or 24,

it is characterized in that the preparation method is characterized in that,

in the olefinically functionalized alkoxysilanes of the formula II, x is 0 and/or, in the alkoxysilanes of the formula III functionalized with saturated hydrocarbon radicals, y is 0.

29. The method according to claim 23 or 24,

it is characterized in that the first and second electrodes, independently from each other,

-the ethylenically functionalized alkoxysilane of formula II is selected from the group consisting of vinyltriethoxysilane, allyltriethoxysilane, butenyltriethoxysilane, pentenyltriethoxysilane, hexenyltriethoxysilane, ethylhexenyltriethoxysilane, heptenyltriethoxysilane, octenyltriethoxysilane, cyclohexenyl-C1 to C8-alkylenetriethoxysilane, cyclohexenyl-2-ethylenetriethoxysilane, 3' -cyclohexenyl-2-ethylenetriethoxysilane, cyclohexadienyl-C1 to C8-alkylenetriethoxysilane, cyclohexadienyl-2-ethylenetriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, butenyltrimethoxysilane, pentenyltrimethoxysilane, hexenyltrimethoxysilane, ethylhexenyltrimethoxysilane, heptyltrimethoxysilane, octenyltrimethoxysilane, cyclohexenyl-C1 to C8-alkylenetrimethoxysilane, cyclohexenyl-2-ethylenetrimethoxysilane, 3' -cyclohexenyl-2-ethylenetrimethoxysilane, cyclohexadienyl-C1 to C8-alkylenetrimethoxysilane and cyclohexadienyl-2-ethylenetrimethoxysilane, and, independently of each other,

the alkoxysilane of the general formula III is selected from the group consisting of methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, isohexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, isooctyltriethoxysilane, undecyltriethoxysilane, decyltriethoxysilane, nonadecyltriethoxysilane, dodecyltriethoxysilane, C₁₃H₂₇Triethoxysilane, C₁₄H₂₉Triethoxysilane or C₁₅H₃₁Triethoxysilane, hexadecyl triethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, i-propyltrimethoxysilane, butyltrimethoxysilane, i-butyltrimethoxysilaneHexyltrimethoxysilane, isohexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, isooctyltrimethoxysilane, undecyltrimethoxysilane, decyltrimethoxysilane, nonadecyltrimethoxysilane, dodecyltrimethoxysilane, C₁₃H₂₇Trimethoxy silane, C₁₄H₂₉Trimethoxysilanes or C₁₅H₃₁-trimethoxysilane and hexadecyltrimethoxysilane, and, independently of each other,

the alkoxysilane of the general formula IV is selected from tetraethoxysilane and tetramethoxysilane.

30. The method according to claim 23 or 24,

characterized in that a defined amount of water of 1.1 to 1.58 mol per mole of silicon atoms in the alkoxysilane of the formula II and/or III used is added.

31. The method according to claim 30, wherein said step of treating,

characterized in that 1.2 to 1.57 mol of water, 1.25 to 1.56 mol of water, or 1.21, per mole of silicon atom in the alkoxysilane of the formula II and/or III used is added; 1.22; 1.23; 1.24; 1.26; 1.27; 1.28; 1.29; 1.30; 1.31; 1.32; 1.33; 1.34; 1.35; 1.36; 1.37; 1.38; 1.39; 1.40; 1.41; 1.42; 1.43; 1.44; 1.45 of; 1.46; 1.47; 1.48; 1.49; 1.50; 1.51; 1.52; 1.53; 1.54; 1.55 mol of water.

32. The method according to claim 23 or 24,

it is characterized in that the preparation method is characterized in that,

the alkoxysilanes of the general formulae II, III and/or IV are at least partially hydrolyzed and condensed in the presence of an acidic catalyst.

33. The method of claim 32, wherein the acidic catalyst is an acidic catalyst with hydrogen chloride.

34. The method according to claim 23 or 24,

it is characterized in that the preparation method is characterized in that,

substantially complete removal of the alcohol.

35. The method according to claim 23 or 24,

it is characterized in that the preparation method is characterized in that,

(29.i) the amount of water is metered in continuously or at least at intervals over a period of 1 to 1000 minutes and the temperature in the reaction mixture is 5 to 90 ℃ and the pH is 7 or less, the water being optionally added together with a catalyst and/or an alcohol,

(29.ii) the mixture from (29.i) is optionally further reacted at 5 to 80 ℃ for at least 10 minutes to 36 hours.

36. The method according to claim 23 or 24,

it is characterized in that the preparation method is characterized in that,

the hydrolysis alcohol and the optionally present solvent are removed by distillation, and preferably

(30.i) during the distillative removal of the hydrolysis alcohol and optionally of the solvent, the specified amount of alcohol is added at least once, and/or

(30.ii) adding a reducing agent or base in the indicated amounts before or during the distillative removal and subsequently filtering or decanting the olefinically functionalized siloxane oligomer or contacting the olefinically siloxane oligomer with an ion exchanger.

37. The method according to claim 23 or 24,

it is characterized in that the preparation method is characterized in that,

the silanes of the general formula II and the silanes of the general formula III are used in a ratio of from 1:0 to 1:8 and/or the silanes of the general formula II and the silanes of the general formula IV are used in a ratio of from 1:0 to 1: 0.22.

38. A composition comprising an ethylenically functionalized siloxane oligomer obtainable by the process according to any one of claims 23 to 37.

39. Use of a composition according to any of claims 1 to 22 or 38 or a composition prepared according to any of claims 23 to 37 as a binder, as a crosslinking agent by graft polymerization and/or hydrolytic condensation in a conventional manner, for producing polymers, prepolymers and/or mineral-filled polymers grafted with ethylenically functionalized siloxane oligomers, for producing polymers, prepolymers and/or mineral-filled thermoplastics or elastomers grafted with ethylenically functionalized siloxane oligomers, for grafting or for use in the polymerization of thermoplastic polyolefins, as a drying agent for silicone sealants, in crosslinkable polymers for producing cables, for producing crosslinkable polymers, in emulsions and/or together with organosilanes or organopolysiloxanes as oil phase, for filler modification, filler coating, resin modification, resin additive, surface modification, surface functionalization, surface hydrophobization, as a component in coating systems, as a component in sol-gel systems, coating systems or hybrid coating systems, for modifying cathode and anode materials in batteries, as electrolyte liquids, as an additive in electrolyte liquids, for modifying fibers, and for modifying textiles, for modifying fillers for the artificial stone industry, as building protection agents or as a component in building protection agents, as an additive for mineral hardening materials, for modifying wood, wood fibers and cellulose.

40. The use according to claim 39, wherein the modified fibers are modified glass fibers and natural fibers.

41. Use according to claim 39, wherein the use is for the production of mineral-filled thermoplastics, elastomers or prepolymers thereof.

42. The use of claim 39, wherein the desiccant is a water scavenger.