HK1201866B - Composition of olefinically functionalsied siloxane oligomers based on alkoxy silanes - Google Patents

Description

Compositions based on ethylenically functionalized siloxane oligomers of alkoxysilanes

The present invention relates to compositions comprising an ethylenically functionalized siloxane oligomer derived from an ethylenically functionalized alkoxysilane and optionally from an alkoxysilane functionalized with a saturated hydrocarbon, and optionally derived from a tetraalkoxysilane, said ethylenically functionalized siloxane oligomer having at most one olefinic group on a silicon atom and having a reduced total chloride and a weight average molecular weight (Mw) of greater than 315 g/mol.

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 the compounding process are generally above 101 ℃ and for e.g. kneading often occur at 170 ℃. 180 ℃ and thus continue to require VOC-reducing and low-corrosive oligomers which as far as possible no longer contain any acidic compounds, such as formic acid, HCl or chlorine-containing compounds, even very small amounts of these compounds lead to corrosion at the operating temperature and thus wear out of machine elements after a short shutdown period.for stainless steels, nickel-based alloys and copper-based alloys, for example, due to corrosion, they are not resistant to formic acid or HCl (see, for example, Handbuch der Metalbel ä, Witzeman, January 2010, Section 7.2 CorrosionResististance, pp. 200-238.) in the case of Chemische Beständigstaker Niroder-St ä, Thisyssen, Edistan 01/2008. after corrosion of various types of alloy steel, corrosion by the presence of corrosion-induced corrosion at a relatively high temperature and a relatively high corrosion effect of corrosion of alloy steel, such as corrosion at 100% corrosion in the atmospheric corrosion of corrosion²And 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 and US 5,282,998 disclose processes 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 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 more cost-effective and more stable olefinically functionalized siliconesAn alkane oligomer, said ethylenically functionalized siloxane oligomer being low chlorine, preferably chlorine-free, and which is also sufficiently reactive for use as a desiccant in a sealant, while having high temperature stability. Furthermore, the siloxane oligomers should have a very high flash point, or even an approved low VOC at high temperatures, and should be able to be used in the field at elevated temperatures without further safety measures. In addition, their viscosity is also suitable for the application. It is a further object of the present invention to provide an economical process for preparing these ethylenically functionalized siloxane oligomers to allow the preparation of said siloxanes with less energy consumption, wherein said siloxanes have a desired property profile. It is a further object of the present invention to provide mixtures of pure olefinic siloxane oligomers which have a low chlorine content and which can be prepared particularly cost-effectively and which have the abovementioned characteristic profiles, more particularly which are based on alkenylalkoxysilanes, or mixtures of olefinically functionalized and alkyl-functionalized siloxane oligomers, in particular which are based on alkenyl-/alkyl-alkoxysilanes, and to provide a preparation process for such mixtures. The siloxane oligomers show only a small loss of mass even at high temperatures, for example in extruders. Preferably, furthermore, other properties in the actual field are at all retained or enhanced compared to the known systems. It is a further object of the present invention to improve the processability of thermoplastics and elastomers and to improve the properties of the thermoplastics and elastomers produced using them by means of the siloxane oligomers according to the invention. The key points associated with processability are also the rapid dispersibility of the siloxanyl oligomers in thermoplastics, coupled with the very low loss of mass at a given temperature in extruder applications. According to the process, it is also possible to reduce the residual content of the acidic catalyst, more particularly the chlorine content, preferably the total chloride content and/or the content of other hydrolyzable chlorides, considerably further, which is an advantage of the invention. It is a further object of the present invention that the olefinic siloxane oligomers should have good storage stability (even over long storage periods), should minimize the increase in flash point, andpreferably, an increase in viscosity should be avoided, for example, as gelation or flocculation would result by subsequent condensation of the mixture over an extended period of time. Furthermore, the monomer content 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 more economical than the known corresponding processes. Another object is to set simultaneously a defined degree of oligomerization of the siloxanes, the incorporation<A dynamic viscosity of 3000mPa s, preferably less than or equal to 1000 mPa s, more particularly less than or equal to 100 mPa s and greater than or equal to 2 mPa s, to ensure good processability of the silicone. The dynamic viscosity values stated in the present application and in the context of the present invention result from a determination in accordance with DIN 53015.

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

It has surprisingly been found that an ethylenically functionalized alkoxysilane and optionally an alkylalkoxysilane can be reacted in a simple and economical manner to obtain the desired low chlorine composition by reaction with a defined molar amount of water in the presence of a solvent, preferably an alcohol, and an acidic catalyst (but without the use of a metal salt catalyst), the ratio of water to alkoxysilane alkoxy groups being from 1:2 to 1:6, more particularly from 1:2.75 to 1:5.0, wherein the hydrolysis alcohol and any solvent present are substantially separated off and removed; more particularly, the solvent and/or the hydrolyzed alcohol are removed by distillation. According to the invention, an acidic catalyst which is gaseous under standard conditions, more particularly HCl, is used as hydrolysis-and/or condensation catalyst and can be dissolved in the aqueous or alcoholic phase. The reaction thus takes place under homogeneous catalytic conditions. A surprising and surprising advantage is that as a result of the process of the present invention, the gaseous catalyst can be almost completely removed from the composition.

Surprisingly, in this way, it is possible to prepare readily handleable products having good space-time yields>315 g/mol and<molecular weight (M) of 10000 g/mol_w) Excellence inOptionally 320 to 9000 g/mol, more particularly 330 to 5000 g/mol, very particularly 340 to 1000 g/mol, more particularly 350 to 850 g/mol, preferably 350 to 800 g/mol-the molecular weight may further be 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700 and 750 g/mol. Preferred weight average molecular weights are greater than or equal to 350 to 750 g/mol, preferably 350 to 725 g/mol, more particularly 410 to 600 g/mol, still preferably 410 to 590 g/mol, or 410 to 570 g/mol.

Surprisingly, furthermore, the siloxane oligomers obtained in this way already exhibit a very low total chloride content as bottom product. According to the invention, the compositions obtained have a particularly low chloride content or total chloride content, and have the desired profile of properties, since they advantageously exhibit a low content of M structures of less than 80%, more particularly less than 75%, preferably less than or equal to 70%, and have a certain minimum weight-average molecular weight (Mw) of greater than 315 g/mol. It is also surprising that the viscosity is suitable for the desired use, regardless of the molecular weight. Thus, the siloxane oligomer composition of the present invention also has the advantage of low VOC.

Unlike known oligomers, the compositions of the present invention and the siloxane oligomer compositions prepared by the process of the present invention do not require any additional processing, such as final distillation of the siloxane oligomer composition. The compositions prepared, the siloxane oligomer bottoms, show properties equal to or better than known siloxane oligomers which, however, have been purified by distillation and obtained by a slightly different process. Thus, according to the invention, the siloxane oligomer obtained no longer needs to be distilled per se, but instead it can be obtained and used in pure form as a bottom product. Thus, the composition can also be obtained in higher yields, wherein the need for energy is reduced.

The present invention therefore provides compositions comprising an ethylenically functionalized siloxane oligomer having at most one olefinic group on a silicon atom, and having Si-O-cross-linked structural elements forming chain, cyclic, cross-linked and/or optionally three-dimensionally cross-linked structures, wherein at least one structure ideally corresponds to formula I

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

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

b in the structural element corresponds to a saturated hydrocarbon radical, in particular selected from linear, branched or cyclic alkyl radicals having 1 to 16C atoms,

y corresponds to OR³OR, in the crosslinked and optionally three-dimensionally crosslinked structures, independently of one another, correspond to OR³Or O_1/2Y is preferably OR³，

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

- R³independently of one another, corresponds to a linear, branched or cyclic alkyl radical having 1 to 4C atoms, or optionally to H, R²Independently of one another, corresponds to a linear, branched or cyclic alkyl radical having 1 to 15C atoms, and R⁴Independently of one another, corresponds to a linear, branched or cyclic alkyl radical having 1 to 15C atoms,

a, b, c, x and y independently correspond to integers, where 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, more particularly for 1. ltoreq. a, x is 0 or for 1. ltoreq. a, x is 0 and for 1. ltoreq. b, y is 0,

-wherein the structural element in formula I [ (R)¹O)_1-x(R²)_xSi(A)O]_a、[Si(B)(R⁴)_y(OR³)_1-yO]_bAnd/or [ Si (Y)₂O]_cTogether, are present as M structures in less than or equal to 80% to greater than or equal to 30%, more particularly greater than or equal to 35%, based on all the silicon atoms of formula I,

-a weight average molecular weight (Mw) of greater than 315 g/mol, and

-in particular the amount of residue or residues of the acid catalyst used during the preparation, more in particular the amount of chlorine or chlorides, preferably the amount of total chlorides, is less than or equal to 250 mg/kg, more in particular less than or equal to 150mg/kg, preferably less than or equal to 100mg/kg, more preferably less than or equal to 75 mg/kg, further preferably less than or equal to 50mg/kg, down to the limits of the present analytical tests, particularly preferably less than or equal to 35 mg/kg, more in particular down to 0.001 mg/kg of bottom product, as in the composition obtained advantageously as bottom product according to the present invention.

In terms of process, it has been possible to develop a very economical process which can be carried out almost as a one-pot reaction. There is no need for expensive and cumbersome distillation of the bottom product. As a result, a significant increase in product yield can already be achieved relative to the known processes. Surprisingly, as a result of the process, it has been possible to obtain compositions of high purity having a very low content of catalyst or catalyst residues, total chlorides, and a low proportion of high molecular weight siloxanes.

The specific setting of the molecular weight distribution of the compositions according to the invention also leads to a particular thermal stability of the siloxane oligomers and this, in the subsequent practical use in hot extruders, leads to a significantly lower loss of mass, even at high temperatures of 150 to 200 ℃. It is not sufficient to simply prepare compounds having a relatively high molecular weight, since too high a molecular weight of the oligomeric compound leads to entanglement of the oligomers and thus to poor or delayed dispersibility in other products, for example in polymer masses in extruders.

Compositions comprising siloxane oligomers without Q structures are also preferred according to the invention, since Q structures significantly increase the viscosity and thus limit the range of applications. Therefore, c is preferably 0.

According to another alternative, the composition preferably comprises an ethylenically functionalized siloxane oligomer having a weight-average molecular weight (Mw) greater than or equal to 315 g/mol and a number-average molecular weight (Mn) greater than or equal to 300 g/mol, a polydispersity, i.e. a ratio Mw/Mn, ranging from 1.05 to 1.35, limits being included, respectively, preferably ranging from 1.05 to 1.25, more particularly ranging from 1.05 to 1.20, very particularly ranging from 1.05 to 1.18 or from 1.05 to 1.17. In the composition, the siloxane oligomers of the invention therefore exhibit a narrow molar mass distribution, so that small molar mass fractions are obtained together with high-value chains per fraction. Surprisingly, according to the process of the present invention, as a result of controlling the process conditions, such a narrow molar mass distribution in the composition can be obtained even in the form of a bottom product. Another advantage of a narrow molar mass distribution is that it shows very uniform thermal properties over a narrow temperature range.

The present invention preferably provides a composition comprising an ethylenically functionalized siloxane oligomer having a molecular weight in the composition of less than or equal to 1000 g/mol, based on the total composition, present at greater than or equal to 90% (area%, GPC), more particularly greater than or equal to 92% (area%, GPC), preferably greater than or equal to 93%. Wherein, preferably, the polydispersity (Mw/Mn) of the siloxane oligomer is between D = 1.05 and 1.25.

Furthermore, if at the same time more than 80% (area%, GPC), more particularly more than 85% of the total composition has a molecular weight greater than or equal to 250 g/mol; preferably greater than or equal to 85%, more particularly greater than or equal to 90%, with an Mw greater than or equal to 250 g/mol, is preferred. Thus, for greater than or equal to 80%, more particularly greater than or equal to 85% (area%, GPC), preferably greater than or equal to 90%, more preferably greater than or equal to 92%, 93%, 94%, 95% of the siloxane oligomers in the composition, the compositions of the present invention advantageously have a Mw of greater than or equal to 250 to less than or equal to 1000 g/mol, with a variation range that can be plus/minus 5%, preferably plus/minus 2%, more preferably less than or equal to 1%. Such compositions can be obtained by the process of the invention, in particular, without having to pay attention to the specific chloride content or the total chloride content. In particular, linear and branched hexasiloxanes, heptacyclosiloxanes and relatively high molecular weight siloxane oligomers are present in the composition only up to 25 area%, more particularly between 0 and 25 area%, preferably between 10 and 25 area%, more particularly between 11 and 20 area%.

Additionally or independently, greater than or equal to 80%, more particularly greater than or equal to 85% (area%) of a siloxane oligomer, more particularly (a + b + c) ≧ 2 of the siloxane oligomer of the formula I, preferably in combination with 90% (based on the total composition) of less than or equal to 1000 g/mol of siloxane oligomer, is present.

The invention also provides compositions comprising an ethylenically functionalized siloxane oligomer present in the composition as a trisiloxane, tetrasiloxane, cyclotetrasiloxane and/or cyclopentasiloxane to an extent of greater than or equal to 45% (area%, determined by GPC analysis), more particularly greater than or equal to 47.5%, the polydispersity being preferentially between 1.05 and 1.25, more particularly between 1.05 and 1.20, very particularly between 1.05 and 1.17 (limits included). Particularly preferred compositions include an ethylenically functional siloxane oligomer present in the composition to an extent of greater than or equal to 75% (area%, as determined by GPC) as a disiloxane, trisiloxane, tetrasiloxane, pentasiloxane, cyclotrisiloxane, cyclotetrasiloxane, cyclopentasiloxane, and/or cyclohexasiloxane; preferably greater than or equal to 77.5% (area%, GPC), more preferably greater than or equal to 80% of the oligomers are present in these structures, more particularly with a polydispersity of between 1.05 and 1.25, preferably between 1.05 and 1.20, more particularly between 1.05 and 1.17 (limits included). It is generally the case that the designations disiloxane, trisiloxane, tetrasiloxane, pentasiloxane encompass linear and/or branched siloxanes, respectively, and cyclotrisiloxane, cyclotetrasiloxane, cyclopenta-or cyclopentasiloxane encompass cyclic siloxanes.

For compositions comprising ethylenically functionalized oligomers, a high flash point can be set and at the same time good properties at elevated temperatures, due to the higher molecular weight together with a low molar mass distribution and high purity obtained by the process according to the invention. Thus, the compositions of the invention each independently have a flash point at a temperature greater than or equal to 85 ℃, more particularly greater than or equal to 90 ℃. The mass loss of 50 wt.% of the composition, as determined by TGA method, is preferably exhibited only by the composition of the present invention at temperatures above 210 ℃; more particularly, a 50% mass loss is only observed above 220 ℃ (TGA, see the specific examples for the determination), and it is particularly preferred that a 50% mass loss occurs within a very narrow temperature range of about 220 to 250 ℃, in particular also for differently substituted siloxane oligomers, wherein the fluctuation range can lie plus/minus 5 ℃ (heating rate 10K/min, platinum crucible, lid with holes).

According to a further embodiment of the invention, the composition has a mass loss of less than 5% by weight at temperatures up to and including 140 ℃ as determined by TGA (platinum crucible, perforated lid, 10K/min). Alternatively or additionally, the mass loss of the composition at temperatures up to 220 ℃ is 50 wt.% or less. Furthermore, the composition of the invention exhibits a mass loss of only less than 30% by weight at 200 ℃, with a flash point preferably above 90 ℃. The mass loss of the composition of the invention is 10% by weight or less, more particularly 8% by weight or less, at a temperature of 150 ℃. The processing temperature of the polymer to which the siloxane oligomer is added for the purpose of adjusting the properties is typically between 150 and 200 degrees celsius. Within this range, the compositions of the invention exhibit a particularly low mass loss compared to the known siloxane oligomers from the prior art. Of particular note is also the high flash point of the composition above 90 ℃, preferably greater than or equal to 95 ℃, more preferably greater than or equal to 100 ℃. Due to the high purity of the bottom product, these high flash points can also be guaranteed over a long storage period, since little residue of the catalyst remains in the composition.

Also preferred are compositions having an ethylenically functionalized siloxane oligomer in which the weight average molecular weight (Mw) is greater than or equal to 420 g/mol and the number average molecular weight (Mn) is greater than or equal to 400 g/mol, wherein the polydispersity, as the ratio of Mw/Mn, is from 1.05 to 1.35, preferably from 1.05 to 1.25, more particularly from 1.05 to 1.20, more particularly from 1.05 to 1.17. Also preferred are compositions comprising siloxane oligomers having a weight average molecular weight (Mw) of greater than 420 g/mol and a number average molecular weight (Mn) of greater than or equal to 462 g/mol, wherein the polydispersity (D), as the ratio of Mw/Mn, is from 1.10 to 1.20, more particularly from 1.05 to 1.18, or, preferably, the aforementioned values.

According to a further preferred embodiment, the siloxane oligomer in the composition has a weight average molecular weight (Mw) of greater than or equal to 450g/mol to 590 g/mol and a number average molecular weight (Mn) of greater than or equal to 410 g/mol to 510 g/mol, wherein the polydispersity (D), as the ratio of Mw/Mn, is from 1.05 to 1.25, more particularly from 1.05 to 1.22, preferably from 1.05 to 1.20.

Weight average molecular weight (Mw)

And number average molecular weight (Mn)

In each of the cases, the number of the cases,n _i amount of substance (= i-mer) mass]，M _i Molar 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 also be found by the reader from sources including the internet (http:// de. wikipedia. org/wiki/molmassinsenverteilung), or from standard works of mathematics.

In order to guarantee a given characteristic profile in terms of low mass loss at high temperatures, more particularly between 150 and 200 ℃ or between 200 and 230 ℃, and good and rapid dispersibility in polymers, prepolymers or mixtures thereof with monomers (for example in the case of use in extruders), it is extremely important that the composition comprises an olefinic siloxane oligomer having a given molar mass distribution, preferably a relatively narrow molar mass distribution. Too high a content of high molecular weight products such as linear or branched hexa-or heptasiloxanes will hinder dispersibility in the polymer and adversely affect the crosslinking properties. In addition, too high proportions of disiloxanes are also undesirable, since they lead to high quality losses at temperatures between 150 and 200 ℃.

Particularly preferably, 70% or more of the siloxane oligomer in the composition is present in the form of disiloxane, cyclotrisiloxane, trisiloxane, cyclotetrasiloxane, tetrasiloxane, cyclopentasiloxane, pentasiloxane and/or cyclohexasiloxane, preferably 75% or more, more particularly 80% or more, and even more preferably 85% or more. The compositions of the invention therefore preferably comprise an olefinic siloxane oligomer according to the following proportions, which may each independently have a standard deviation of plus/minus 3%, based in each case on the total composition (in 100%): preferably, the amount of monomeric silane is less than 0.5%, the fraction of disiloxanes and cyclotrisiloxanes is preferably less than or equal to 30%, more particularly less than 25%, the fraction of trisiloxanes and cyclotetrasiloxanes is greater than or equal to 20%, preferably greater than or equal to 23%, the fraction of tetrasiloxanes and cyclopentasiloxanes is greater than or equal to 10%, more particularly greater than or equal to 14%, the fraction of pentasiloxanes and cyclohexasiloxanes is greater than or equal to 6% to 40%, preferably 7% to 30%, and in particular the fraction of linear or branched hexasiloxanes, heptacyclosiloxanes and higher molecular weight siloxanes is less than or equal to 30%, more particularly less than or equal to 25%, preferably less than or equal to 20% (area%), respectively independently. Of these, it is particularly preferred that the mass loss as determined by TGA is 50 wt% or less at temperatures up to 210 ℃, preferably below 220 ℃. It is further preferred that the composition also has a flash point greater than or equal to 90 ℃. The fractions in% are each determined as an area percentage by GPC analysis.

The present invention also provides a composition comprising an ethylenically functionalized siloxane oligomer having at most one olefinic group on a silicon atom, and having a Si-O-cross-linking structural element forming a chain, cyclic, cross-linked and/or optionally three-dimensionally cross-linked structure, wherein at least one structure ideally corresponds to formula I, wherein the siloxane oligomer has a structural element derived from at least one alkoxysilane:

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

wherein A is an olefinic group 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 0 or 1, preferably x is 0, and R¹Independently of one another, a methyl, ethyl or propyl group, or optionally a mixture derived from an alkoxysilane of the general formula II, more particularly x is 0, or from a transesterification product thereof, and optionally

(ii) Derived from alkoxysilanes of the general formula III functionalized with saturated hydrocarbon radicals,

wherein B is an unsubstituted hydrocarbon radical selected from linear, branched or cyclic alkyl radicals having 1 to 16C atoms, wherein R is³Independently of one another, methyl, ethyl or propyl, and R⁴Independently of one another, is a linear, branched or cyclic alkyl radical having 1 to 15C atoms, and y is 0 or 1, y preferably being 0, or, optionally, a mixture derived from alkoxysilanes of the formula III or transesterification products thereof, more particularly y = 0, and optionally

(iii) Derived from Si (OR) of the formula IV³)₄Or a transesterification product thereof, wherein R³Independently of one another, methyl, ethyl or propyl,

in particular, in the composition as obtained advantageously as bottom product according to the invention, the amount of residue or residues of the acid catalyst used during the preparation, more particularly the amount of chlorine and/or chloride, preferably the amount of total chloride, is less than or equal to 250 mg/kg, more particularly less than or equal to 150mg/kg, preferably less than or equal to 100mg/kg, more preferably less than or equal to 75 mg/kg, further preferably less than or equal to 50mg/kg down to the limits of the present analytical detection, particularly preferably less than or equal to 35 mg/kg; a weight average molecular weight (Mw) greater than 315 g/mol; in siloxane oligomers, more particularly in idealized formula I, the structural element [ (R) derived from the alkoxysilane by at least partial hydrolysis and condensation¹O)_1-x(R²)_xSi(A)O]_a、[Si(B)(R⁴)_y(OR³)_1-yO]_bAnd/or [ Si (Y)₂O]_cTogether, from less than or equal to 80% to greater than or equal to 30%, more particularly all based on all the silicon atoms of formula IIs greater than or equal to 35% present as an M structure.

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 radical R in the context of the invention²And R⁴Can be independently selected 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 C₁₅H₃₁The radicals or cyclopentyl, cyclohexyl, 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 mixtures of 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 R³They may have methyl or ethyl groups and both, and they may be present in the form of methoxy-and ethoxy-functional oligomers.

In addition to the aforementioned features, the amount of M structures of the siloxane oligomers in the compositions of the invention is significantly reduced with respect to the prior art, which discloses a very high proportion of M and D structures, in which a very major portion is present as M structures.

Furthermore, 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 2% up to as low as the detection limit or 0.0% (based on all silicon atoms), preferably less than 1% to 0.0%, more preferably less than or equal to 0.9% to 0.0%, still more particularly less than or equal to 0.8 to 0.0% by weight. Monomeric alkoxysilanes which come into consideration are alkoxysilanes of the general formulae II, III and/or IV and also their monomeric hydrolysis products. By for example²⁹Method of Si NMR spectroscopy to detect the amount per percent. These monomers lead to post-crosslinking in the siloxane oligomers and impair their characteristic profile. Based on international contracts, such as the OECD definition of polymers, and based on additional specifications, there is a strong need to produce as little monomer as possible in the preparation of polymers.

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 cyclohexadienyl-C1 to C8-alkylene group, preferably a cyclohexadienyl-2-ethylene group.

The unsubstituted hydrocarbon radicals B, also preferably independently in the general formulae I and/or III, can correspond to linear, branched or cyclic alkyl radicals having 1 to 16C atoms, more particularly to methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, octyl, n-octyl, isooctyl or hexadecyl radicals. Preference is also given to the radicalsB may be independently selected from the group consisting of t-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, 3-ethyl-2-methylpentyl, 3-ethyl-3-methylpentyl, 2,3, 3-tetramethylbutyl, 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.

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, less than or equal to 8% to 0.0% based on all silicon atoms of formula I are present as T structures, more particularly less than or equal to 7.8% to 1.00% as T structures, optionally preferably 6.0 to 2.0%.

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. According to one particularly preferred alternative, c is 0 and a is an integer greater than or equal to 1, according to another preferred alternative, c is 0 and a is greater than or equal to 1 and b is greater than or equal to 1, a and b each independently being an integer.

The present invention also provides a composition comprising an ethylenically functionalized siloxane oligomer having at most one olefinic group on a silicon atom, and wherein in particular each is independently selected from:

(i) structural element [ (R) in the general formula I¹O)_1-x(R²)_xSi(A)O]_a0.0 to 8.0, more particularly 0.0 to 7.75%, preferably 1.0% to 7.75%, based on all silicon atoms of the formula I, being present as T structure, and/or the structural element [ Si (B) (R) in the formula I⁴)_y(OR³)_1-yO]_b0.0 to 1.5, preferably 0.0 to 1.0%, and optionally as T structure, based on all 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]_cTogether, less than or equal to 75% to 15% or less than or equal to 75% to 40% based on all silicon atoms of formula I are present as D structure, more particularly 70% to 42%, preferably 65% to 42%, more particularly 65% to 43%, and optionally

(iii) Structural element [ (R) in the general formula I¹O)_1-x(R²)_xSi(A)O]_a25% to 55% based on all silicon atoms of formula I are present as M structures, more particularly 25% to 50%, more particularly 29% to 45%, 35% to 45%, and optionally

(iv) Structural element [ Si (B) (R) in general formula I⁴)_y(OR³)_1-yO]_bLess than or equal to 40% of all the silicon atoms of formula I are present as M structures, more particularly less than or equal to 35%, for example from 30% to 40%, and/or optionally

(v) Structural element in general formula I [ Si (Y)₂O]_cGreater than or equal to 20% of structural element [ Si (Y)₂O]_cPresent as D structure in formula I, more particularly between 20% and 40%, and/or optionally

(vi) Structural element in general formula I [ Si (Y)₂O]_c0.0% to 1% is present as T structure. According to a particularly preferred alternative, in formula I c is 0.

The present invention also provides a composition comprising an ethylenically functional siloxane oligomer having at most one olefinic group on a silicon atom, and wherein each is independently selected from: (i) structural element [ (R) in the general formula I¹O)_1-x(R²)_xSi(A)O]_a0.0 to 8.0, more particularly 0.0 to 7.75%, preferably 1.0% to 7.75%, based on all silicon atoms of the formula I, being present as T structure, and/or the structural element [ Si (B) (R) in the formula I⁴)_y(OR³)_1-yO]_b0.0 to 1.5, preferably 0.0 to 1.0%, based on all silicon atoms of the formula I, being present as a T structure, and (ii) a structural element [ (R) in the formula I¹O)_1-x(R²)_xSi(A)O]_aAnd [ Si (B) (R) ]⁴)_y(OR³)_1-yO]_bAnd [ Si (Y)₂O]_cTogether, less than or equal to 50% to 15% based on all the silicon atoms of formula I are present as D structure, more particularly 50% to 17%, very particularly 50% to 30%, and optionally

(iii) Structural element [ (R) in the general formula I¹O)_1-x(R²)_xSi(A)O]_a28% to 50% based on all silicon atoms of formula I are present as M structure, and optionally

(iv) Structural element [ Si (B) (R) in general formula I⁴)_y(OR³)_1-yO]_bLess than or equal to 40% to 30% based on all silicon atoms of formula I are present as M structures.

Also preferably, the ratio of the M to D structures in the olefinic siloxane oligomer, more particularly the olefinic siloxane oligomer of formula I, is from 1:2 to 10:1, preferably from 1:2 to 3:1, more particularly from 1:2 to 3:1, further preferably from 1:2 to 2.5:1, more particularly from 1:1.2 to 3:1, based on all silicon atoms, additionally particularly in formula I the amount of T structures in all structural elements is from 8.0 to 0.0%, preferably from 8.0 to 0.5%. The composition furthermore has a high flash point of greater than or equal to 85 ℃, more particularly greater than or equal to 90 ℃. The good flash point is attributed to the very high purity of the isolated composition and the very low or no catalyst residues. The invention also provides compositions in which the ratio of M to D structures, based on all silicon atoms, in the ethylenically functionalized siloxane oligomer, or in the at least one siloxane oligomer of formula I, is from 1:1.2 to 3:1, and the flash point of the composition is a temperature greater than or equal to 85 ℃.

The amount of M, D, T or Q structure is generally determined by methods known per se to the person skilled in the art, preferably by²⁹Si-NMR method.

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 mannerFor example, one can construct a vector with D₃、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. The imaginable cross-linked structure 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。

in subsequent applications, compositions exhibiting the aforementioned structure possess high flash points and particularly low VOC contents. One advantage of the compositions of the invention and of the process of the invention which is particularly attractive is that the olefinic siloxane oligomers prepared, in particular vinyl oligomers, or vinyl-/alkyl-siloxane oligomers, unlike the known oligomers, do not require further processing, for example distillation of the siloxane oligomer composition in EP0518057B 1.

Another particular advantage of the olefinically functionalized siloxane oligomers of the invention is that a defined weight average molecular weight, preferably having a defined number average molecular weight, preferably having the ratio of M to D structures according to the invention, directly improves the processability of the siloxane oligomers and polymers, for example during kneading or compounding. The reduction in the amount of water absorbed in particular demonstrates the improved water absorption capacity. The volume flow index is also improved, thus reducing the energy consumption for processing. Furthermore, the corrosion of iron-containing machines is reduced, since a further reduction of the chloride content can already be achieved. The reduced water absorption capacity is beneficial for subsequent application areas, for example in the production of filled cable materials, in particular for cables which are buried in soil and subject to permanent moisture. To avoid slow corrosion of the metal conductor in the cable, the very low chloride or chloride-free composition of the invention contributes.

It may further be preferred that the compositions and/or siloxane oligomers of the invention also have trialkylsilane groups, for example trimethylsilane or triethylsilane groups, for adjusting the degree of oligomerization, for example by adding alkoxytrialkylsilane. In order to adjust the degree of oligomerization during the preparation of the composition, it may therefore be preferred to add an alkoxy trialkylsilane, for example preferably ethoxytrimethylsilane or methoxytrimethylsilane, to the composition to be prepared at the desired point in time for chain termination.

The composition of the invention may comprise at least 20% by weight of siloxane oligomers, wherein the degree of oligomerization 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, in particular the sum of (a + b) is greater than or equal to 6, advantageously the sum of (a + b) is greater than or equal to 8, wherein a is greater than or equal to 1 and b is 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 preferably wherein c is 0 or optionally wherein c is greater than or equal to 1 in (a + b + c).

Additionally or alternatively to one or more of the preceding features, after complete hydrolysis of all alkoxy groups, the composition preferably has an alcohol content of 55% by weight or less, more particularly 50% by weight or less, in the case of methoxysiloxanes, preferably 40% by weight or less, more particularly 35% by weight or less, very particularly 30% by weight or less, and greater than or equal to 5% by weight, preferably greater than or equal to 10% by weight, more particularly greater than or equal to 20% by weight, provided that only the amount of water required for the hydrolysis is added. For the assay, there was no further dilution.

A particular advantage of an alternative of the compositions of the invention comprising an ethylenically functionalized siloxane oligomer is that upon hydrolysis they release up to 55% by weight of the hydrolyzed alcohol from the hydrolyzable alkoxy groups, based on the total composition; preferably less than 45%, more particularly less than 40% VOC (see description of methods section for determination).

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

It is also preferred that the composition comprises an olefinic siloxane oligomer in which the ratio of silicon atoms (selected from the group consisting of olefinically functionalized silicon atoms and from silicon atoms functionalized with saturated hydrocarbons) to alkoxy groups in the siloxane oligomer, or alternatively in formula I, is from 1:0.3 to 1:2.5, preferably from 1:1.0 to 1:2.0, it is also preferred, however, that there is also from 1:1.3 to 1:1.9, particularly preferably from 1:1.3 to 1:1.6, with the proviso that the olefinically functionalized siloxane oligomer is derived from an alkoxysilane of formula II or an alkoxysilane of formulae II and III.

According to one alternative, compositions of purely ethylenically substituted siloxane oligomers are prepared, in particular siloxane oligomers of the formula I in which a is an integer greater than or equal to 2 and b is 0 and c is 0, more particularly having a weight average molecular weight (Mw) of greater than 315 g/mol, more particularly up to 800g/mol, preferably up to 750 g/mol. Advantageously, at least 20% by weight of the siloxane oligomer is present as 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, more particularly having a weight average molecular weight (Mw) of greater than 315 g/mol, more particularly up to 800g/mol, preferably up to 750 g/mol. In particular, at least 20% by weight of the siloxane oligomers have (a + b) greater than or equal to 4, preferably greater than or equal to 8, integers. 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 formula I in which a is greater than or equal to 1 and b is greater than or equal to 1, preferably having a weight average molecular weight (Mw) of greater than 315 g/mol, more particularly up to 800g/mol, preferably up to 750 g/mol. Furthermore, it is preferred that 20% by weight of the siloxane has (a + B) greater than or equal to 4, preferably an integer greater than or equal to 8, preferably a molar ratio of the A groups to the B groups of from 1:0 to 1:8, more particularly a: B of from 1:0 to 1:8, more particularly of from 1:0 or of 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 the weight average molecular weight (Mw) is greater than 315 g/mol, more particularly up to 800g/mol, preferably up to 750 g/mol.

The structural element (monomeric siloxane unit) consistently refers to the individual structural unit M, D, T or Q (see already described embodiments above for the nomenclature of M, D and T and Q structural units), i.e. the structural unit is derived from an alkoxy-substituted silane and is formed by at least partial hydrolysis to optionally complete 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 idealised representation of the possibilities.

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 A as defined aboveOr B, R³Substantially 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 R¹Independently an alkyl group having 1-4C atoms.

The invention also provides a composition comprising

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, and, optionally, the transesterification products thereof,

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 from an alkoxysilane of the formula III having a propyl group as unsubstituted hydrocarbon radical B, wherein R¹And R³Each independently of the others, corresponds to a methyl or ethyl group, and, optionally, a transesterification product thereof, 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, and, optionally, transesterification products thereof.

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.

It is also preferred that the compositions each independently comprise a siloxane oligomer, more particularly having a structural element derived from an alkoxysilane, and optionally at least one structure of formula I is derived from at least one ethylenically functionalized alkoxysilane of formula II selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxysilane, and optionally from an alkoxysilane of formula III, wherein the alkoxysilanes of formula III are each independently selected from the group consisting of methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, butyltriethoxysilane, butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltrimethoxysilane, isobutyl triethoxysilane, isobutyl trimethoxysilane, a mixture thereof, Hexyltriethoxysilane, hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltrimethoxysilane, isohexyltriethoxysilane, isohexyltrimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, isooctyltriethoxysilane, isooctyltrimethoxysilane, undecyltriethoxysilane, undecyltrimethoxysilane, decyltriethoxysilane, decyltrimethoxysilane, nonadecyltriethoxysilane, nonadecyltrimethoxysilane, dodecayltriethoxysilane, dodecasyltrimethoxysilane, C₁₃H₂₇Triethoxysilane, C₁₃H₂₇Trimethoxy silane, C₁₄H₂₉Triethoxysilane, C₁₄H₂₉Trimethoxy silane, C₁₅H₃₁Trimethoxy silane, C₁₅H₃₁Triethoxysilane, hexadecyltriethoxysilane and hexadecyltrimethoxysilane, dimethyldimethoxysilane (DMDMO), dimethyldiethoxysilane, propylmethyldimethoxysilane, propylmethyldiethoxysilane, n-octylmethyldimethoxysilane, n-hexylmethyldimethoxysilane, n-hexylmethyldiethoxysilane, propylmethyldi-xysilaneEthoxysilane, 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 is 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, isobutyltrimethoxysilane, hexyltriethoxysilane, hexyltrimethoxysilane, n-hexyltriethoxysilane, and mixtures thereof, N-hexyltrimethoxysilane, isohexyltriethoxysilane, isohexyltrimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, isooctyltriethoxysilane, isooctyltrimethoxysilane, undecylTriethoxysilane, undecetyltrimethoxysilane, decyltriethoxysilane, decyltrimethoxysilane, nonadecyltriethoxysilane, nonadecyltrimethoxysilane, dodecayltriethoxysilane, dodecamethyltrimethoxysilane, C₁₃H₂₇Triethoxysilane, C₁₃H₂₇Trimethoxy silane, C₁₄H₂₉Triethoxysilane, C₁₄H₂₉Trimethoxy silane, C₁₅H₃₁Trimethoxy silane, C₁₅H₃₁Triethoxysilane, hexadecyltriethoxysilane and hexadecyltrimethoxysilane, and transesterification products thereof.

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 of the invention is that a composition viscosity of <3000 mPa s leads to an advantageously good processability of the respectively processed thermoplastics and elastomers in the extruder.

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, acid-catalyst-free, more particularly total chloride-free siloxane oligomers in the form of bottoms.

By the addition and/or amount of solvent, preferably alcohol, in combination with the amount of water which is strictly specified, the molecular weight and the molecular weight distribution are optimized and in this way the formation of high molecular weight oligomers is maximally avoided. 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 to carry out the process of the invention without using a combination of metal oxide and acid; 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 0.1 ppm 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 0.1 ppm (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 inventive compositions of the ethylenically functionalized siloxane oligomer have an alcohol content (preferably a content of free alcohol) of from less than 2% to 0.0001% by weight, more particularly of less than 1.8% by weight, preferably of less than 1.5% by weight, more particularly of less than 1.0% by weight, very particularly of less than 0.5% by weight, based on the composition, down 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.

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 corresponds to a linear, branched and/or cyclic alkyl group having 1 to 4C atoms, more particularly wherein x is 0,

(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 radical, more particularly a saturated hydrocarbon radical selected from linear, branched or cyclic alkyl radicals having 1 to 16C atoms, 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 group having 1 to 15C atoms and y is 0 or 1, more particularly y is 0, 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) reacting water with a specified molar ratio of water to alkoxy groups of the alkoxysilane to produce the siloxane oligomer, more particularly x = 0 and y = 0 in formulae II and III, optionally in the presence of a solvent, preferably in the presence of (at least) one alcohol as solvent, in a range of from 1:2.75 to 1:5.0, more particularly in a range of from 1:2.75 to 1:4.5, 1:3.0 to 1:4.5 or 1:3.0 to 1:4.25, further preferably in a range of from 1:3.5 to 1:4.25, and more particularly x = 0 and y = 0 in formulae II and III

(iv) Substantially separating off the hydro lyzed alcohol and any solvent present, and more particularly

(v) A composition comprising an ethylenically functionalized siloxane oligomer is obtained as a bottom product after step (iv).

Advantageously, in (iii), water may also be used in the specified molar ratio of water to alkoxy groups of the alkoxysilane from 1:2 to 1:6, more particularly from 1:2.5 to 1: 5.5.

It has surprisingly been found that the hydrolysis alcohols formed during the reaction act as volatile catalysts, for example entrainers of mainly HCl, formic acid and acetic acid, and are thus removed at least partially, preferably almost completely, from the system during the distillative removal of the hydrolysis alcohols, and thus advantageously no additional, expensive and inconvenient, distillation is required in order to recover the end product. This has been achieved with a particularly high purity catalyst which is gaseous at room temperature and highly soluble in a solvent, such as HCl.

Thus, in the process of the present invention, it may be advantageous to obtain or obtain directly in (v), after step (iv), as a bottom product, a composition of the present invention comprising an ethylenically functionalized siloxane oligomer, which is particularly advantageous, the process of the present invention being economical, without the need for costly and inconvenient distillation of additional products, wherein the obtained product still has excellent quality.

More particularly, the compositions comprising siloxane oligomers obtained according to the invention have a content of acid catalyst residues (for example chlorine, more particularly total chlorides) used in the preparation of less than or equal to 250 mg/kg, more particularly less than or equal to 150mg/kg, preferably less than or equal to 100mg/kg, more preferably less than or equal to 75 mg/kg, more preferably less than or equal to 50mg/kg, more particularly less than or equal to 35 mg/kg, wherein the hydrolysable chloride content is preferably less than 8 mg/kg, preferably less than or equal to 5 mg/kg, and/or preferably (vi) silicon atoms, more particularly the total sum of silicon atoms, in the siloxane oligomers, preferably the structural element of formula I [ (R) is the structural element of formula I¹O)_1-x(R²)_xSi(A)O]_a、[Si(B)(R⁴)_y(OR³)_1-yO]_bAnd/or [ Si (Y)₂O]_cTogether, less than or equal to 80% to greater than or equal to 30%, more particularly greater than or equal to 35%, based on all silicon atoms of the formula I, are present as M structures, wherein the siloxane oligomer has a weight-average molecular weight (Mw) of greater than or equal to 315 g/mol, more particularly has a Mw of from 315 to 850 g/mol, preferably a Mw of from 315 to 800g/mol, more particularly a Mw of from 315 to 750 g/mol, wherein the polydispersity is in each case taken as the ratio Mw/Mn, more particularly from 1.05 to 1.25, very particularly from 1.05 to 1.18.

According to one alternative, in (i) at least one alkoxysilane of the general formula II and optionally its transesterification product are reacted in (II) in the presence of an acidic hydrolysis and/or condensation catalyst (iii) with water in the specified molar ratio as described above, (iv) the hydrolysis alcohol and optionally the solvent are substantially separated off and, after step (iv), a composition is obtained as bottom product.

According to a second alternative, in (i) at least one alkoxysilane of the formula II and (i.1) at least one alkoxysilane of the formula III and optionally, independently of one another, the transesterification products thereof are reacted in (II) in the presence of an acidic hydrolysis-and/or condensation catalyst (III) with water in the specified molar ratios as described above, (iv) the hydrolysis alcohol and optionally the solvent are substantially separated off and, after step (iv), a composition is obtained as bottom product.

According to a third alternative, in (i) at least one alkoxysilane of the formula II with (i.2) at least one alkoxysilane of the formula IV and optionally with (i.1) at least one alkoxysilane of the formula III and optionally, respectively independently, (III) in (II) in the presence of an acidic hydrolysis and/or condensation catalyst, is reacted with water in the specified molar ratios as described above, (IV) the hydrolysis alcohol and optionally the solvent are substantially separated off and, after step (IV), a composition is obtained as bottom product.

According to one alternative, it is also possible to react with water in the stated molar ratio of water to alkoxy groups of from 1:2 to 1:6, more particularly from 1:2.5 to 1: 5.5.

Preferably, for siloxane oligomers, the weight average molecular weight (Mw) is greater than or equal to 420 g/mol and the number average molecular weight (Mn) is greater than or equal to 400 g/mol, with a polydispersity, as the ratio Mw/Mn, of from 1.05 to 1.25, more particularly from 1.05 to 1.18. Particularly preferably, greater than or equal to 90% (area%, GPC) has a molecular weight of less than or equal to 1000 g/mol.

Particularly preferably, in the process of the invention, the alkoxysilane of the formula II or the alkoxysilanes of the formulae II and III, respectively, are optionally reacted with water in the presence of the alkoxysilane of the formula IV in a specified water to alkoxysilane alkoxy ratio of from 1:2.5 to 1:5.5, preferably from 1:2.75 to 1:5.0, more particularly from 1:2.75 to 1:4.5, optionally very particularly from 1:3.0 to 1:4, further preferably from 1:3.5 to 1:4.25, to obtain the siloxane oligomer. Further preferably, x and y are 0.

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 0.5 to 2.5 volume units per volume unit of trialkoxysilane.

The solvent used and/or the alcohol used is anhydrous, the solvent or alcohol used having a water content of in particular less than 1 ppm 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, optionally 2 to 6C atoms, more particularly an alkenyl group having one to two double bonds, more particularly an alkenyl group independently selected from vinyl, allyl, butenyl, pentenyl, hexenyl, ethylhexenyl, heptenyl, octenyl and cyclohexenyl-C1 to C8-alkylene, preferably cyclohexenyl-2-ethylene, for example 3' -cyclohexenyl-2-ethylene, or cyclohexadienyl-C1 to C8-alkylene, more particularly a cyclohexadienyl-2-ethylene group, wherein x is in particular 0, and R is¹Independently selected from methyl, ethyl or propyl groups. Particularly preferred are vinyl, cyclohexenyl-2-ethylene, 3' -cyclohexenyl-2-ethylene and cyclohexadienyl-C1 to C8-alkylene groups.

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

the unsubstituted hydrocarbon group B is selected from the group consisting of methyl, ethyl, propyl, isobutyl, octyl, butyl, n-butyl, tert-butyl, pentyl, n-pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl-, 2-dimethylbutyl, 2, 3-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, C₁₃H₂₇-、C₁₄H₂₉-、C₁₅H₃₁And a hexadecyl group, and R³Is a methyl, ethyl or propyl group and y is 0 or 1. Particularly preferably, B is selected from methyl, ethyl, propyl, isobutyl, octyl and hexadecyl groups. And areAnd 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 the aforementioned alkyl groups, 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 6C atoms are used as unsubstituted hydrocarbon groups B.

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 process is carried out batchwise.

The resulting composition is substantially free of solvent, e.g., free of alcohol. For this purpose, 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.

According to the process of the invention, after carrying out steps i, ii, iii and iv and optionally step v, optionally and (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 150mg/kg, preferably less than or equal to 100mg/kg, more preferably less than or equal to 75 mg/kg, still more particularly less than or equal to 50mg/kg, more particularly less than or equal to 35 mg/kg, wherein the hydrolysable chloride content is less than 8 mg/kg, preferably less than or equal to 5 mg/kg, and/or a weight average molecular weight (Mw) of greater than 315 g/mol.

For reactions in which the specified molar ratio of water to alkoxy groups of the alkoxysilane is from 1:2.75 to 1:5.0, all intermediate values to the second decimal place are disclosed as being suitable for the reaction according to the invention, and intermediate values of 1: 2.2; 1: 2.4; 1: 2.6; 1: 2.8; 1: 3.0; 1: 3.2; 1: 3.4; 1: 3.6; 1: 3.8; 1: 4.0; 1: 4.2; 1: 4.4; 1: 4.6; 1: 4.8; 1: 5.0; 1: 5.2; 1: 5.4; 1: 5.6; 1: 5.8; 1:5.8 and all intermediate values from 1:2.0 to 1:6 plus/minus 0.1, preferably from 1:3.0 to 1: 4.5. Advantageously 1:2 to 1: 6.

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 from less than 1 minute to 100 minutes, and the reaction of the alkoxysilane is preferably carried out at a reaction temperature preferably ranging from 20 ℃ to 80 ℃, or from 40 ℃ to 80 ℃, more particularly 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 (iii) of the process of the invention, the amount of water or water can be metered in continuously or at least at one interval over a period of from 1 to 1000 minutes, and a temperature of from 5 to 90 ℃, preferably from 20 to 90 ℃, or from 37 to 90 ℃, preferably from 40 to 90 ℃, more particularly from 50 to 90 ℃, very particularly from 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. The reaction may then take place, preferably the mixture (reaction mixture) is treated and/or the mixture is further reacted 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. 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. The obtained composition of the invention is not distilled by itself.

According to an optional embodiment, in the process according to part iv, the hydrolysis alcohol and the solvent present, more particularly the alcohol added as diluent, are removed by distillation and advantageously the specified amount of alcohol is added during the work-up after distillation at least once, preferably two to six times, and/or between or before the distillative removal of the hydrolysis alcohol and the optional solvent and/or diluent, more particularly the alcohol.

It is useful to add the specified amount of reducing agent, more particularly an inorganic reducing agent, for example an alkali metal, alkaline earth metal, aluminum or metal hydride, or a base, for example preferably HMDS or another amine or alkali metal alkoxide, and then to filter or decant the olefinically functionalized siloxane oligomer in the form of the bottom product, advantageously and/or to contact the olefinically 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 (LAH), or bases which form sparingly soluble precipitates with hydrogen chloride (HCl), which can additionally be used in the process in order to further reduce the chlorine or chloride content of the composition. Bases suitable for this process should not form water in the reaction with a catalyst (e.g. HCl) or with organically bound chlorine (e.g. in chloroalkylsilanes).

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. 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 1.0 wt.%, preferably less than or equal to 0.5 wt.%, or as low as the limit of the current analytical detection 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.

According to the invention, the alcohol, more particularly the hydrolysis alcohol and optionally the added alcohol, is substantially completely removed. The hydrolysis alcohol and/or the added alcohol correspond to the free alcohol. The free alcohol content in the total composition is more preferably less than or equal to 2% to 0.01% by weight, more particularly less than or equal to 1.5% to 0.01% by weight, more preferably less than or equal to 1% to 0.01% by weight, in particular down to the detection limit.

The process of the invention is preferably operated discontinuously, but can also be carried out 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, such as myristic acid and/or polyfunctional organic acids, such as citric acid, fumaric acid, as catalysts or together with HCl as co-catalysts.

In the case of a particularly preferred embodiment of the process of the invention, the silanes of the general formula II and of the general formula III can advantageously be used in the following molar ratios: the molar ratio of silane of the formula II to silane of the formula III is 1:1, in each case plus/minus 0.5, from 0.5:1.5 to 1.5:0.5, and in particular the values lying between them in each case, 0.6; 0.7; 0.8; 0.9; 1.1; 1.2; 1.3 and 1.4 remain explicitly stated.

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.

In the process of the invention, the viscosity of the composition is preferably adjusted to less than or equal to 3000mPa s, more particularly to less than or equal to 1000 mPa s, preferably to less than or equal to 500 mPa s to about 10 mPa s, more preferably to about 1 to 5 mPa s or 3 to 6 mPa s, with a fluctuation range of plus/minus 0.5 mPa s.

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 an ion exchanger, in particular with a basic anion 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 below 100mg/kg, preferably to below 50mg/kg, more particularly to below 25 mg/kg.

In the case of an ethylenically functionalized siloxane oligomer having a chlorine content, 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 polymer with quaternary alkylammonium groups and/or with tertiary dialkylamino groups, in particular the quaternary alkylammonium groups have essentially hydroxide ions as counterions and/or the tertiary dialkylamino groups are in the form of free bases. 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.

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 significantly reduced with respect to the oligomers of the prior art.

The content of solvent (e.g. VOC), more particularly of free alcohol, which is advantageously stable over a period of 6 to 12 months, is preferably below 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, up to the detection limit.

The compounds of formula II that can be used in the process of the invention are as follows: vinyltriethoxysilane, vinyltrimethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, butenyltriethoxysilane, butenyltrimethoxysilane, cyclohexenyl-alkylene-trimethoxysilane, more particularly cyclohexenyl-2-ethylidene-trimethoxysilane, cyclohexadienyl-C1 to C8-alkylenetriethoxysilane or cyclohexadienyl-2-ethylidene-triethoxysilane, cyclohexenyl-2-ethylidene-trimethoxysilane, 3' -cyclohexenyl-2-ethylidene-trimethoxysilane, cyclohexadienyl-C1 to C8-alkylenetrimethoxysilane or cyclohexadienyl-2-ethylidene-trimethoxysilane, cyclohexenyl-2-ethylidene-triethoxysilane, poly (ethylene-co-butylene-2-trimethoxysilane, More particularly 3 '-cyclohexenyl-2-ethylene-triethoxysilane and/or 3' -cyclohexenyl-2-ethylene-trimethoxysilane, cyclohexadienyl-alkylenetriethoxysilane, hexenyltriethoxysilane, hexenyltrimethoxysilane, ethylhexenyltrimethoxysilane, ethylhexenyltriethoxysilane, octenyltriethoxysilane, octenyltrimethoxysilane, with 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, n-octylmethyldimethoxysilane, n-hexylmethyldimethoxysilane, n-hexylmethyldiethoxysilane, propylmethyldiethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, butyltriethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-butyltriethoxysilane, n-butyltrimethoxysilane, hexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, n-butyltriethoxysilane, n-butylmethyldiethoxysilane, n-butyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltrimethoxysilane, Hexyltrimethoxysilane, n-hexyltrimethoxysilane, isohexyltriethoxysilane, isohexyltrimethoxysilane, heptyltrimethoxysilane octyltrimethoxysilane, octyltriethoxysilane, n-octyltrimethoxysilaneN-octyltrimethoxysilane, n-octyltriethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, n-hexyltriethoxysilane, cyclohexyltriethoxysilane, n-propyltri-n-butoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, heptyltrimethoxysilane, n-octyltriethoxysilane, isooctyltriethoxysilane, undecyltriethoxysilane, decyltriethoxysilane, nonadecyltriethoxysilane, dodecyltriethoxysilane, C₁₃H₂₇Triethoxysilane, C₁₄H₂₉Triethoxysilane or C₁₅H₃₁Triethoxysilane, n-octyltrimethoxysilane, isooctyltrimethoxysilane, undecatyltrimethoxysilane, decyltrimethoxysilane, nonadecyltrimethoxysilane, dodecyltrimethoxysilane, C₁₃H₂₇Trimethoxy silane, C₁₄H₂₉Trimethoxysilanes or C₁₅H₃₁-trimethoxysilane, hexadecyltriethoxysilane, hexadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, octadecylmethyldiethoxysilane, octadecylmethyldimethoxysilane, hexadecylmethyldimethoxysilane and/or hexadecylmethyldiethoxysilane, and mixtures of these silanes, or mixtures comprising at least two of these silanes, and transesterification products thereof.

A particularly preferred combination of compounds of formulae II, III and optionally IV for preparing the olefinically functionalized siloxane oligomer, or from which the olefinically functionalized siloxane oligomer is obtainable, is as follows, wherein the siloxane oligomer is preferably prepared without addition of a compound of formula IV: in this list, siloxane oligomers are prepared in a process using compounds separated by a split number, respectively: vinyltriethoxysilane (VTEO); vinyltrimethoxysilane (VTMO); vinyltriethoxysilane and tetraethoxysilane; vinyltrimethoxysilane and tetramethoxysilane; vinyltriethoxysilane and methyltriethoxysilane; vinyltriethoxysilane, methyltriethoxysilane and Tetraethoxysilane (TEOS); 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, it is also possible to use as processing aid in the method at least one silicone oil, for example polydimethylsiloxane, paraffin oil or a mixture comprising one of these processing aids. 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 optionally 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 is added and the specified molar ratio of water to alkoxy groups of the alkoxysilane is set. 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 formulae II, III and optionally IV, optionally with an alcohol in an amount of from 0.2 to 8 times by weight, preferably from 0.2 to 1.0 times, more particularly methanol or ethanol, based on the silanes of the formulae II, III and optionally IV, depending on the alkoxysilane used, and a specified amount of water, in which preferably at least one acidic hydrolysis-and/or condensation catalyst, for example HCl, is dissolved, can be prepared. The pH is set here to preferably less than 7, preferably from 1 to 6, more particularly from 3 to 5.

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 olefinically functionalized alkoxysilane of the formula II and optionally an alkoxysilane of the formula III are introduced as initial charge and, independently of one another, optionally additional and optionally alkoxysilanes of the formula IV, where the alkoxysilanes are preferably introduced as initial charge in the form of a mixture,

2) a mixture comprising a solvent, water and HCl as acidic hydrolysis-and/or condensation catalyst is added, the solvent being an alcohol corresponding to the alcohol to be hydrolyzed, and a specified molar ratio of water to alkoxy groups of the alkoxysilane of 1:2.57 to 1:5.0, preferably 1:3.0 to 1:4.5 is set, preferably the weight of alcohol used is 0.2 to 8 times, preferably 0.2 to 3.0 times, based on the silane of the general formulae II, III and optionally IV. It is further preferred that the weight of alcohol used is from 0.2 to 1.5 times, more particularly from 0.2 to 1.0 times, more particularly from 0.3 to 0.8 times, based on the weight of the silanes of the general formulae II, III and optionally IV.

For this purpose, the alkoxysilane and water are preferably reacted with thorough mixing in an initial charging vessel, for example in a stirred tank. The specified amount of water may be metered in continuously or at least one interval over a period of 1 to 1000 minutes. 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 can be reacted subsequently, preferably while mixing, for example stirring, at a reaction temperature of from 5 to 80 ℃, preferably from 40 to 80 ℃, in a time period of at least 10 minutes to 36 hours, preferably from 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. Compositions of ethylenically functionalized siloxane oligomers according to the present invention are obtained.

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 present invention also provides a composition obtainable by the process of the invention, comprising an ethylenically functionalized siloxane oligomer, more particularly a siloxane oligomer having a weight average molecular weight (Mw) of greater than or equal to 315 g/mol, and preferably having a number average molecular weight (Mn) of greater than or equal to 300 g/mol, wherein the polydispersity, as the ratio Mw/Mn, is more particularly from 1.05 to 1.25, particularly preferably from 1.05 to 1.20. It is further preferred that the weight average molecular weight (Mw) is greater than or equal to 420 g/mol and the number average molecular weight (Mn) is greater than or equal to 400 g/mol, with a polydispersity, as the ratio Mw/Mn, of from 1.05 to 1.25, more particularly from 1.05 to 1.17. It is further preferred according to the invention if the obtainable composition has greater than or equal to 90% (area%, GPC) of siloxane oligomers having a molecular weight of less than or equal to 1000 g/mol. The composition obtained can be simply diluted with a diluent at any time. Depending on the method used, a composition may be obtained which indicates an acidic pH in the presence of moisture. Typically the pH may be between 2 and 6.

At the same time, it is preferred that the total chloride content of these compositions, based on the total composition, is advantageously less than or equal to 250 mg/kg, more particularly less than or equal to 80 mg/kg, still more preferably less than or equal to 50 mg/kg.

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 or dispersibility is a 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 functionalized siloxane oligomers, in particular for producing 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, in silicone sealants, in crosslinkable polymers for producing cables, for producing crosslinkable polymers, in emulsions and/or together with organosilanes or organopolysiloxanes as oil phases. 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 compositions of the invention are advantageously used for filler modification (filler coating), resin modification (additives), surface modification (functionalization, hydrophobization), as a constituent in coating systems (in particular in sol-gel systems or mixed 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-hardened materials, for modifying wood, wood fibers and cellulose. Furthermore, the entire disclosure of DE 102011086862.3, 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.

Example (b):

determination of molecular weight:the molar masses or molecular weights, and also the molar mass distribution, can be determined by Gel Permeation Chromatography (GPC)) To be measured. Including "model Size-Exclusion Liquid Chromatography", Andre Striegel et al, Verlag Wiley&The GPC analysis method is described extensively in the references of Sons, second edition, 2009, for calibrating the method for siloxane analysis, for example, divinyltetramethoxydisiloxane or divinyltetraethoxydisiloxane may be used as standards the percentage of olefinic siloxane oligomers in the present invention corresponds to a number per percent area, which may be determined from the GPC analysis, the MZ-Analysetechnik column used column 50x8.0 mm, MZ-Gel SDplus (styrene/divinylbenzene copolymer with high degree of crosslinking, spherical particle shape), porosity 50A (angstroms, Å), 5 μm (micron) (front column), 300x8.0 mm, MZ-Gel SDplus, porosity 50A (angstroms, Å), 5 μm, 300x8.0 mm, MZ-Gelplus, porosity 100A (angstroms, Å), pump-gelm, 300x8.0 mm, 1310-gell, 1310, A μm, 1000G, 500G, 99G, 500G, a flow rate of a calibration of a test sample in a manually performed on a manually operated reactor, a flow rate of a test tube, a column, a flow rate meter, a manually calibrated test tube, a flow meter, a test tube, a column, a flow meter, a test tube, a.

Determination of the chlorine content or of the total chloride value:the silane was decomposed with oxygen in a bomb calorimeter and then hydrolyzed with acetic acid and hydrofluoric acid. The chloride content of the resulting solution was determined by titration with a well-defined silver nitrate solution.

Determination of chlorine content and hydrolyzable chloride:after hydrolysis with acetic acid, the chloride content was determined by titration with a well-defined silver nitrate solution.

SiO ₂ Determination of content-crucible method: determination by fluorination by acid digestion with concentrated sulfuric acid and subsequent evaporationSiO₂And (4) content.

GC analysis:GC standardQuasi-analytical methods are well known to those skilled in the art, and the monomer content is determined by suitable calibration and optional internal standards.

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.

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 HP 3396 integrator, 1 ml/min).

Flash point determination: DIN EN ISO 13736 (1 month 2009), DIN EN ISO 2719 (9 months 2003). The flash point above 40 ℃ is determined by the method of DIN EN ISO 2719 (= DIN 51758 = EN 22719) and the flash point between-30 ℃ and +40 ℃ is determined according to DIN EN ISO 13736 (= DIN 51755).

Water content: Karl-Fischer (DIN 51777)

TGA：In TGA (thermogravimetric analysis), the sample to be analyzed 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). Inert gas (N) for the interior of the oven₂) Flushing to avoid 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.

Table 1: overview of the raw materials used.

Example 1: ratio of VTMO-siloxane oligomer-water to alkoxy groups 1: 3.7-V087

Vinyl trimethoxy silane oligomer: 220 g of vinyltrimethoxysilane were charged into the reaction flask. 95 g of methanol were mixed with 21 g of water and 0.4 g of 20% strength hydrochloric acid and the mixture was transferred to a dropping funnel. Slowly added dropwise from a dropping funnel to the vinylsilane while stirring at a temperature of about 25 ℃. After the addition was complete, the oil bath was heated to 85 ℃, whereupon the methanol boiled under reflux. After a reaction time of about 3 hours, the methanol was distilled off at the oil bath temperature and under reduced pressure of about 150 to 180 mbar. To remove further methanol, the vacuum was set to below 1 mbar.

Example 2: VTEO-siloxane oligomer-water to alkoxy ratio 1: 3.7-V088

Vinyl triethoxysilane oligomer: 195 g of vinyltriethoxysilane was charged to the reaction flask. 93 g of ethanol were mixed with 14.8 g of water and 0.2 g of 20% strength hydrochloric acid and the mixture was transferred to a dropping funnel. Slowly added dropwise from a dropping funnel to the vinylsilane while stirring at a temperature of about 25 ℃. After the addition was complete, the oil bath was heated to 85 ℃, whereupon the ethanol boiled under reflux. After a reaction time of about 3 hours, ethanol was distilled off at the oil bath temperature and under reduced pressure of about 150 to 180 mbar. To remove further ethanol, the vacuum was set below 1 mbar.

Example 3: ratio of PTEO/VTEO-siloxane oligomer-water to alkoxy 1: 4.0-V089

Co-oligomer of propyltriethoxysilane with vinyltriethoxysilane: 98 g of vinyltriethoxysilane and 100 g of propyltriethoxysilane were charged to the reaction flask. 87 g of ethanol were mixed with 13 g of water and 0.2 g of 20% strength hydrochloric acid and the mixture was transferred into a dropping funnel. Slowly added dropwise from a dropping funnel to the vinylsilane while stirring at a temperature of about 25 ℃. After the addition was complete, the oil bath was heated to 85 ℃, whereupon the ethanol boiled under reflux. After a reaction time of about 3 hours, ethanol was distilled off at the oil bath temperature and under reduced pressure of about 150 to 180 mbar. To remove further ethanol, the vacuum was set below 1 mbar.

Example 4: VTEO/PTEO-siloxane oligomer-water to alkoxy ratio 1:4.8-V097

The method comprises the following steps: 190.3 g of VTEO and 206.2 g of PTEO (propyltriethoxysilane) are charged into a 2 l four-neck apparatus having a water-cooling device 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 allowed to proceed for 5 hours while stirring. After the reaction time, the alcohol was distilled on a rotary evaporator at up to 100 ℃ and 100 mbar. When 100 mbar was reached, the pressure was maintained for 15 minutes, after which the apparatus was allowed to return to normal. The bottom products obtained are vinyl-and of VTEO and PTEOPropyl-functionalized siloxane oligomer (VTEO/PTEO-siloxane).

Compound (I)	Initial mass
		VTEO	190.3 g
PTEO	206.2 g
		Water (W)	22.7 g
Ethanol	174.6 g
		Hydrochloric acid	0.19 g

Table 2: starting material V097.

Example 5: VTEO/PTEO-siloxane oligomer-water to alkoxy ratio 1:4.0-V098

The method comprises the following steps: vinyltrimethoxysilane (VTEO) and Propyltriethoxysilane (PTEO) were charged into a 2 l four-neck apparatus with water cooling and 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 allowed to proceed for 5 hours while stirring. After the reaction time, the alcohol was distilled on a rotary evaporator at up to 100 ℃ and 100 mbar. When 100 mbar was reached, the pressure was maintained for 15 minutes, after which the apparatus was allowed to return to normal. The bottom product obtained is a VTEO-/PTEO-siloxane oligomer.

Compound (I)	Initial mass
		VTEO	190.3
PTEO	206.4 g
		Water (W)	27.2 g
Ethanol	175.1 g
		Hydrochloric acid	0.19 g

Table 3: feedstock V098.

Example 6: VTEO/PTEO/TEOS-siloxane oligomer-water to alkoxy ratio 1:5.0 (5.1) -V099

The method comprises the following steps: 190.3 g of VTEO and 206.4 g of PTEO and 20.9 g of tetraethylThe oxysilane was charged into a 2 l four-necked apparatus with water cooling and 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 allowed to proceed for 5 hours while stirring. After the reaction time, the alcohol was distilled on a rotary evaporator at up to 100 ℃ and 100 mbar. When 100 mbar was reached, the pressure was maintained for 15 minutes, after which the apparatus was allowed to return to normal. The bottom products obtained are vinyl-and propyl-functionalized siloxane oligomers with Q structural elements based on VTEO, PTEO and tetraethoxysilane for controlled hydrolysis and condensation or co-condensation.

Compound (I)	Initial mass
		Water (W)	22.7 g
Ethanol	174.8 g
		Hydrochloric acid	0.19 g

Table 4: additional V099 starting material.

Example 7: VTMO/PTMO-siloxane oligomer-V079

The method comprises the following steps: two monomers, 370.58 g of vinyltrimethoxysilane and 514.20 g of propyltrimethoxysilane, were charged into a 2 l four-necked apparatus with water cooling and magnetic stirring. A mixture of 540.20 g of methanol, 1.02 g of hydrochloric acid (20%) and 80.28 g of demineralized water is then metered in over 10 minutes at room temperature and ambient pressure, and an exothermic process is observed. The temperature was raised to about 40 ℃. The batch was then heated to an oil bath temperature of 100 ℃. The total reaction time was 5 hours. After the reaction time, the alcohol was distilled off at low pressure (<1 mbar) at an oil bath temperature of 100 ℃. 596.30 g of siloxane oligomer were thus obtained.

By the process of the present invention, the yield of examples 1 to 7 can be increased to more than 99%.

Comparative example 1: v078- -example 1 from EP0518057B1 preparation of a cocondensate of vinyltrimethoxysilane and methyltrimethoxysilane with a molar ratio of vinylidene to methoxy 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 using a 500 ml dropping funnel with a solution of 49.9 g of distilled water in 332.8 g of methanol containing 2400 ppm of hydrogen chloride. 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 5: raw material V078.

Comparative example 2: v081-example 6 from EP0518057B1 preparation of condensate of vinyltrimethoxysilane with a molar ratio of vinylidene 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, said solution containing 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 removed by distillation at about 300 mbar over 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.

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

the method disclosed in example 6 for compound VTMO was replicated separately and performed on compounds VTEO and VTMO as new variants, as well as co-oligomer 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 was raised here 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 7: starting materials and yields.

Analysis results

Table 8: 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): DTG 1: temperature of maximum rate of mass decrease [ dm/dt ] -first peak

Table 9: analysis results of siloxane oligomer of VTEO/PTEO type

Table 10: analysis results of siloxane oligomers prepared analogously to V087 to V089 and V079

Test No. V078	Total chloride [ mg/kg]	Hydrolyzable chloride [ mg/kg]	SiO2(mass) [% ]]	VTMO (mass) [% ]]	Color number [ mg Pt-Co/l]
						Distillate (1)	230	16	52.4	< 0.1	< 5

Table 11: analysis results of V078 (comparative example 1), (1) see example 1 in EP0518057B1

Test No. V081	Total chloride [ mg/kg]	Hydrolyzable chloride [ mg/kg]	SiO2(mass) [% ]]	VTMO (mass) [% ]]	Color number [ mg Pt-Co/l]
						Distillate (2)	50	< 3	48.6	1.7	< 5

Table 12: analysis result of V081 (comparative example 2), (2) (see example 6 in EP0518057B 1)

Test number	Mn [g/mol]	Mw [g/mol]	D = Mw/Mn
				V087	461.98	545.00	1.1797
V087 (2)	460.40	538.63	1.1699
				V088	457.84	513.50	1.1606
V088 (2)	416.18	466.50	1.1209
				V089	446.93	510.18	1.1415
V097	369.51	419.02	1.134
				V098	418.20	456.81	1.0923
V099	363.06	411.36	1.1330
				V078	275.13	291.11	1.0581
V081	254.06	269.90	1.0624

Table 13: evaluation of the results of GPC analysis (2) second batch was similar.

The analysis shows good reproducibility of the molar masses and molar mass distributions.

Table 14: of siloxane oligomers of the VTEO, VTMO, VTEO/PTEO and VTEO/PTEO/TEOS type²⁹Results obtained by Si NMR analysis [ VS = vinylsilyl, PS = propylsilyl, ES = ethoxysilyl]

Table 15: the products from comparative tests V078 and V081 were subjected to²⁹Si NMR analysis gave the result that [ VS = vinylsilyl, MS = methylsilyl]

Table 16 a: see 16e

Table 16 b: see 16e, MP = peak of molecular weight

Table 16 c: see 16e

Table 16 d: see 16e

Table 16 e: analysis result of V079 (example 7), (1): DTG 1: temperature of maximum rate of mass decrease [ dm/dt ] -first peak

Table 17: fractions of siloxane oligomers and their proportions in the composition expressed as area%, by GPC of additional siloxane oligomers prepared analogously to examples 1 to 3 and 7, (1) analogously to example 1, V087, (2) analogously to example 2, V088, and (3) analogously to example 3, V089. The figures are the proportions in area% obtained by GPC measurements. See the following explanations

Oligomers from silanes	Mw [g/mol]	Mn [g/mol]	D
				VTMO (1)	543.09	469.25	1.16
VTEO (2)	515.66	450.10	1.15
				VTEO/PTEO (3)	514.59	464.13	1.11
VTMO/PTMO (V079)	374.80	428.99	1.14

Table 18 a: mw, Mn and D of additional siloxane oligomers prepared analogously to examples 1 to 3 and 7, (1) analogously to example 1, V087, (2) analogously to example 2, V088, (3) analogously to example 3, V089

Sample (I)	0-250 relative MW [% ]]	250-]	500–750 rel.MW [%]	750-]	>1000 relative MW [% ]]
						VTMO (1)	3.0	49.6	30.9	11.41	5.06
VTEO (2)	1.1	56.5	28.9	9.1	4.5
						VTEO/PTEO(V079)	0.9	63.3	25.2	7.28	3.37

Table 18 b: mw (relative) of additional siloxane oligomers prepared by analogy to examples 1 to 3 and 7, (1) analogous to example 1, V087, (2) analogous to example 2, V088. The figures are the proportions in area% obtained by GPC measurements. See the explanation below.

Analysis shows that the compositions of the invention having an ethylenically functionalized siloxane oligomer content of disiloxane and/or cyclotrisiloxane of less than or equal to 30% (area%, GPC), preferably less than or equal to 20%, show a particularly low mass loss below 50% by weight in TGA, even at elevated temperatures of greater than 210 to greater than 220 ℃. Of particular advantage are their high flash points of greater than 80 ℃ or up to greater than 90 ℃. It has been found that when the siloxane oligomer content is as follows: the compositions generally exhibit these beneficial properties when less than or equal to 30% of disiloxanes and/or cyclotrisiloxanes, and preferably greater than or equal to 20%, more preferably greater than or equal to 23% (area%, GPC) of linear, branched trisiloxanes and/or cyclotetrasiloxanes, and in particular greater than or equal to 10%, in particular greater than 14% (area%, GPC) of linear, branched tetrasiloxanes and/or cyclopentasiloxanes, and preferably the higher molecular weight fraction is present in as little amount as possible. In the plastics used in practice, in particular during the operation of the extruder, high molecular weight oligomers lead to poor dispersibility, since they cannot be dispersed uniformly and quickly enough. Further preferred are therefore compositions having an ethylenically functionalized siloxane oligomer in which the proportion of linear or branched pentasiloxane and/or cyclohexasiloxane is between 7% and 40% (area%, GPC). Particularly preferably, the compositions have a particularly low content of siloxane oligomers, such as linear, branched hexasiloxanes, cycloheptasiloxanes and higher siloxanes, of less than 30%, more particularly less than 25%. From the point of view of the requirements mentioned, on the one hand the flash point should be very high and the loss of mass should be particularly low in the temperature range between 150 and 200 ℃ and preferably also between 200 and 220 ℃ and, at the same time, effective and rapid dispersibility in the product must be achieved, a highly balanced and narrowly specified ratio of the molecular weights in the composition of the olefinically functionalized siloxane oligomers generally having to be required in order to comply with the required specifications. It has been demonstrated above by a detailed analysis that all the compositions prepared by the process of the invention meet said requirements in terms of purity, low total chloride content, and moreover a high flash point of greater than 90 ℃, together with an effective dispersibility in the polymer, prepolymer or mixture thereof optionally together with the monomers. The above disclosure is not limited to particular embodiments, but applies to all compositions and methods according to the present invention. In view of the low mass loss up to 220 ℃, a further reduction of the VOC content during high temperature conversion has been achieved, for example in an extruder. As demonstrated below in the use examples, it has also been possible to achieve a further reduction in the water uptake of cable materials produced using the siloxane oligomers of the invention.

Remarking: each bottoms product	VTMO oligomer (1)	VTEO oligomer (2)	VTMO-PTMO oligomer (example 7, V079)	VTEO-PTEO oligomer (3)
					Temperature at which 5% mass loss occurs, T =	146℃	149℃	156℃	156℃
Temperature at which 50% mass loss occurs, T =	232℃	228℃	232℃	242℃
					Mass loss at 150 [% ]]	7	6	4	3
Mass loss at 200 [% ]]	28	29	23	23

Table 19: TGA of additional siloxane oligomers prepared by analogy to examples 1 to 3 and 7 of the present invention [ (1) analogously to example 1, V087, (2) analogously to example 2, V088, (3) analogously to example 3, V089]

Note: typical processing temperatures in the plastics and rubber sector are between 150 and 200 ℃.

Kneading operation

Type of Compound	Name (R)
		Polymer and method of making same	EVA (ethylene-vinyl acetate)
Filler material	ATH (aluminium hydroxide)
		Stabilizer	Irganox 1010
Peroxides and their use in the preparation of pharmaceutical preparations	Dicumyl peroxide (DCUP)

Table 20: overview of raw materials used for kneading studies.

Preparation of test samples: after storage in a climatic chamber at 23 ℃ and 50% relative atmospheric humidity, test specimens for the tensile test and for the determination of the water absorption capacity and for the determination of the melt index were prepared from the samples produced.

Table 21: peroxide mixture for kneading.

Kneading study: the kneading operation with a temperature profile of "3 minutes at 140 ℃, increasing from 140 ℃ to 170 ℃ in 2 minutes, 5 minutes at 170 ℃ was carried out in a HAAKE kneading apparatus at a rotational speed of 30 rpm. Subsequently, each batch was processed by compression at 165 ℃ and a load pressure of 20 t to form two plates.

Table 22: initial mass in the kneading study.

And (3) performance testing: after storage in a climatic chamber at 23 ℃ and 50% relative atmospheric humidity, a sample for determining the water absorption capacity was prepared from the sample produced.

Information	Test number	Numerical value [ mg/cm2]Storing for 7 days
			Silane-free	V153	3.81
V078	V116	1.55
			V081	V118	1.40
VTMO-siloxanes, V087	V150	1.22

Table 23: the water absorption capacity is a result.

The compositions of the present invention exhibit lower water absorption in the cable material than known systems.

Claims (39)

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

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

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

-A in said structural element corresponds to an olefinic group selected from linear, branched or cyclic alkenyl-or cycloalkenyl-alkylene-functional groups each having 2 to 16C atoms, and

-B in said structural element corresponds to a saturated hydrocarbon radical selected from linear, branched or cyclic alkyl radicals having 1 to 16C atoms,

y corresponds to OR³OR, in the crosslinked and optionally three-dimensionally crosslinked structures, independently of one another, correspond to OR³Or 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, corresponding to a linear, branched or cyclic alkyl radical having 1 to 4C atoms or to H, R²Each independently corresponding to a linear, branched or cyclic alkyl group having 1 to 15C atoms, and 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 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]_cTogether, less than or equal to 80% and greater than or equal to 30% of all silicon atoms of formula I are present as M structures,

-a weight average molecular weight (Mw) greater than or equal to 315 g/mol, and

-a composition in which the amount of residues of acid catalyst used during the preparation is less than or equal to 250 mg/kg.

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,

wherein A is an olefinic group 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 group having 1 to 15C atoms, and x is 0 or 1, and R¹Each independently being methyl, ethyl or propyl, and optionally

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

wherein B is an unsubstituted hydrocarbon radical selected from linear, branched or cyclic alkyl radicals having 1 to 16C atoms, wherein R is⁴Each independently is a linear, branched or cyclic alkyl group having 1 to 15C atoms, and y is 0 or 1, and R³Each independently being methyl, ethyl or propyl, and optionally

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

3. The composition according to claim 1 or 2,

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 optionally in the alkoxysilanes of the formula III functionalized with saturated hydrocarbon radicals, y is 0.

4. The composition according to claim 1 or 2,

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

the amount of residues of acid catalyst used in the preparation, related to chlorine, chlorides or total chlorides, is less than or equal to 250 mg/kg of composition.

5. The composition according to claim 1 or 2,

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

are selected separately from each other independently of each other,

(i) structural element [ (R) in the general formula I¹O)_1-x(R²)_xSi(A)O]_a0.0% to 8.0% based on all silicon atoms of the formula I is present as T structure,

(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]_cTogether, less than or equal to 75% to 40% based on all silicon atoms of formula I are present as D structures,

(iii) structural element [ (R) in the general formula I¹O)_1-x(R²)_xSi(A)O]_a25% to 55% based on all silicon atoms of the 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 40% of all silicon atoms of formula I are present as M structures,

(v) structural element in general formula I [ Si (Y)₂O]_cMore than 20% are present as D structures,

(vi) structural element in general formula I [ Si (Y)₂O]_c0.0% to 1% is present as T structure.

6. The composition according to claim 1 or 2,

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

the weight average molecular weight (Mw) is greater than or equal to 350 g/mol to 800 g/mol.

7. The composition according to claim 6, wherein the composition,

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

the weight average molecular weight (Mw) is greater than or equal to 350 g/mol to 750 g/mol.

8. The composition according to claim 1 or 2,

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

-in formulae I and/or II, the olefinic groups a are each independently selected from 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 groups, and independently therefrom

In formulae I and/or III, the unsubstituted hydrocarbon radicals B are each independently selected from the group consisting of methyl, ethyl, propyl, isobutyl, octyl or hexadecyl radicals, and

- R¹independently of one another are each a methyl, ethyl or propyl group and R³Independently a methyl, ethyl or propyl group.

9. The composition according to claim 1 or 2,

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

in formulae I and/or II, the olefinic group A is a vinyl group, and independently thereof

In formula I and/or III, the unsubstituted hydrocarbon radical B is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, C₁₃H₂₇-、C₁₄H₂₉-、C₁₅H₃₁-and a hexadecyl group, and

- R¹independently of one another are each a methyl, ethyl or propyl group and R³Independently a methyl, ethyl or propyl group.

10. 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 having a molecular weight of less than or equal to 1000 g/mol is present in the composition at greater than or equal to 90 area percent based on the total composition.

11. The composition according to claim 1 or 2,

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

the weight-average molecular weight (Mw) is greater than 315 g/mol and the number-average molecular weight (Mn) is greater than 300 g/mol, wherein the polydispersity (D), as the ratio Mw/Mn, is from 1.05 to 1.25.

12. The composition according to claim 1 or 2,

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

in formula I c is 0.

13. The composition according to claim 1 or 2,

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

the weight-average molecular weight (Mw) is greater than or equal to 420 g/mol and the number-average molecular weight (Mn) is greater than or equal to 400 g/mol, wherein the polydispersity (D), as the ratio Mw/Mn, is between 1.05 and 1.25.

14. The composition according to claim 1 or 2,

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

the weight-average molecular weight (Mw) is more than 450g/mol to 590 g/mol and the number-average molecular weight (Mn) is more than 410 g/mol to 510 g/mol, wherein the polydispersity (D), as the ratio of Mw/Mn, is from 1.05 to 1.25.

15. The composition according to claim 1 or 2,

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

in the composition, greater than or equal to 45 area percent of the ethylenically functional siloxane oligomer as measured by GPC is present in the composition as trisiloxanes, tetrasiloxanes, cyclotetrasiloxanes, and/or cyclopentasiloxanes.

16. The composition according to claim 1 or 2,

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

at temperatures above 210 ℃, the composition experienced a 50% weight loss of mass as determined by TGA.

17. 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 140 ℃ as measured at 10K/min by TGA using a platinum crucible having a hole in the lid.

18. The composition according to claim 1 or 2,

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

in the siloxane oligomer or in formula I, the ratio of M to D structures is 1:2 to 10:1 based on all silicon atoms.

19. 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 formula I, each derived from an alkoxysilane of formula II, have a vinyl group as the olefinic group A, wherein 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 R is¹And R³Are respectively independent of each otherCorresponding to a methyl or ethyl group, 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, each independently of the others, corresponds to a methyl or ethyl group.

20. 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 is derived from at least one ethylenically functionalized alkoxysilane of the general formula II selected from the group consisting of vinyltriethoxysilane and vinyltrimethoxysilane, and optionally at least one alkoxysilane of the formula III, wherein the alkoxysilane of the formula III is independently selected from the group consisting of methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, butyltriethoxysilane, butyltrimethoxysilane, hexyltriethoxysilane, hexyltrimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, undecyltriethoxysilane, undecyltrimethoxysilane, decyltriethoxysilane, decyltrimethoxysilane, nonadecyltriethoxysilane, nonadecyltrimethoxysilane, vinyltrimethoxysilane, and the like, Dodecyl triethoxysilane, dodecyl trimethoxysilane, C₁₃H₂₇Triethoxysilane, C₁₃H₂₇Trimethoxy silane, C₁₄H₂₉Triethoxysilane, C₁₄H₂₉Trimethoxy silane, C₁₅H₃₁Trimethoxy silane, C₁₅H₃₁Triethoxysilane, hexadecyltriethoxysilane and hexadecyltrimethoxysilane, and transesterification products thereof.

21. A process for preparing a composition comprising an ethylenically functionalized siloxane oligomer according to any one of claims 1 to 20, by at least

(i) An ethylenically functionalized alkoxysilane of the general formula 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 group having 1-15C 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 an acidic hydrolysis-and/or condensation catalyst,

(iii) reacting water with a specified molar ratio of water to alkoxy groups of the alkoxysilane in the presence of a solvent to obtain a siloxane oligomer, and

(iv) substantially separating off the hydrolyzed alcohol and the solvent present, and

(v) after step (iv), a composition comprising an ethylenically functionalized siloxane oligomer is obtained as a bottom product.

22. The method of claim 21, wherein the first and second light sources are selected from the group consisting of,

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

(i) the ethylenically functionalized alkoxysilanes (II) of the general formula II are reacted with (in the presence of) an acidic hydrolysis and/or condensation catalyst

(i.1) reacting at least one alkoxysilane of the formula 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.

23. The method according to claim 21 or 22,

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

(i) an olefinically functionalized alkoxysilane of the general formula II and optionally (i.1) at least one alkoxysilane of the formula III (II) in the presence of an acidic hydrolysis-and/or condensation catalyst

(i.2) reacting at least one tetraalkoxysilane of formula IV,

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

24. The method according to claim 21 or 22,

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

the reaction takes place in the presence of at least one alcohol as solvent.

25. The method according to claim 21 or 22,

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

the at least one alkoxysilane of formula II and optionally the at least one alkoxysilane of formula III are reacted with water in a specified molar ratio of water to alkoxy groups of the alkoxysilane of from 1:3 to 1:4.5 to obtain the siloxane oligomer.

26. The method according to claim 21 or 22,

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

in an olefinically functionalized alkoxysilane of the formula II

A is selected from vinyl and allyl-yl, butenyl, pentenyl, hexenyl, ethylhexenyl, heptenyl, octenyl, cyclohexenyl-C1 to C8-alkylene, cyclohexenyl-2-ethylene, 3' -cyclohexenyl-2-ethylene and cyclohexadienyl-C1 to C8-alkylene, and R¹Independently is a methyl, ethyl or propyl group, and x is 0 or 1, and independently

In the alkoxysilanes of the formula III

The unsubstituted hydrocarbon radical B is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, C₁₃H₂₇、C₁₄H₂₉、C₁₅H₃₁And a hexadecyl group, and R³Is a methyl, ethyl or propyl group and y is 0 or 1.

27. Method according to claim 21 or 22

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

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

28. The method of claim 27, wherein the first and second light sources are selected from the group consisting of,

characterized in that each is independently

-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 or cyclohexadienyl-2-ethylenetriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, butenyltrimethoxysilane, pentenyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, butenyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Hexenyltrimethoxysilane, ethylhexenyltrimethoxysilane, heptyltrimethoxysilane, octenyltrimethoxysilane, cyclohexenyl-C1 to C8-alkylenetrimethoxysilane, cyclohexenyl-2-ethylenetrimethoxysilane, 3' -cyclohexenyl-2-ethylenetrimethoxysilane, cyclohexadienyl-C1 to C8-alkylenetrimethoxysilane, or cyclohexadienyl-2-ethylenetrimethoxysilane, and each independently

The alkoxysilane of the formula III is selected from the group consisting of methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, butyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, undecyltriethoxysilane, decyltriethoxysilane, nonadecyltriethoxysilane, dodecyltriethoxysilane, C₁₃H₂₇Triethoxysilane, C₁₄H₂₉Triethoxysilane or C₁₅H₃₁Triethoxysilane, hexadecyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, undecyltrimethoxysilane, decytrimethoxysilane, nonadecyltrimethoxysilane, dodecayltrimethoxysilane, C₁₃H₂₇Trimethoxy silane, C₁₄H₂₉Trimethoxysilanes or C₁₅H₃₁-trimethoxy silane and hexadecyl trimethoxy silane, and each independently

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

29. The method according to claim 21 or 22,

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

vinyltrimethoxysilane or vinyltriethoxysilane is used.

30. The method according to claim 21 or 22,

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

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

31. The method according to claim 21 or 22,

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

(v) the total chloride content is set to be less than or equal to 250 mg/kg.

32. The method according to claim 21 or 22,

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

(v) in the case where the weight average molecular weight (Mw) is greater than or equal to 315 g/mol, less than or equal to 80% to greater than or equal to 35% of the total number of silicon atoms in the siloxane oligomer are present as M structures.

33. The method according to claim 21 or 22,

characterised in that in said method

a) Vinyl trimethoxysilane was used as the alkoxysilane of the formula II,

b) vinyl triethoxysilane is used as the alkoxysilane of formula II,

c) use of vinyltrimethoxysilane and propyltrimethoxysilane, vinyltriethoxysilane and propyltriethoxysilane, vinyltriethoxysilane and propyltrimethoxysilane or vinyltrimethoxysilane and propyltriethoxysilane as alkoxysilanes of the formulae II and III or use of corresponding methoxy-and ethoxy-mixed functionalized alkoxysilanes in a), b) or c), or

d) Tetraethoxysilane, tetramethoxysilane or mixtures thereof are additionally used in a), b) or c) as alkoxysilanes of the formula IV.

34. The method according to claim 21 or 22,

the method is characterized by comprising the following steps:

1) first introducing at least one (I) olefinically functionalized alkoxysilane of the formula II or at least one (i.1) olefinically functionalized alkoxysilane of the formula I and at least one alkoxysilane of the formula III and optionally in each case at least one (i.2) alkoxysilane of the formula IV,

2) adding a mixture comprising a solvent, water and HCl as acidic hydrolysis-and/or condensation catalyst, wherein the solvent is an alcohol corresponding to the hydrolyzed alcohol, and setting a specified molar ratio of water to alkoxy groups of the alkoxysilane of 1:2.75 to 5.0, wherein the weight of alcohol used is 0.2 to 8 times the weight of the alkoxysilane based on formula II, III and optionally IV.

35. The method of claim 34, wherein said step of selecting said target,

characterized in that the specified molar ratio of water to alkoxy groups of the alkoxysilane is set to 3.0 to 1: 4.5.

36. The method of claim 34, wherein said step of selecting said target,

characterised in that the weight of alcohol used is 0.2 to 1.5 times the weight of the silane of formula II, III and optionally IV.

37. A composition comprising an ethylenically functionalized siloxane oligomer obtainable according to the process of any one of claims 21 to 36.

38. Use of a composition according to any one of claims 1 to 20 or 37, or a composition prepared according to any one of claims 21 to 36, as a binder, as a crosslinking agent by graft polymerization and/or hydrolytic condensation in a manner known per se, 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 or prepolymers thereof grafted with ethylenically functionalized siloxane oligomers, in the grafting or polymerization of thermoplastic polyolefins, as a drying agent, more particularly as a water scavenger, for silicone sealants, in crosslinkable polymers for producing cables, for producing crosslinkable polymers, in emulsions and/or as an oil phase together with organosilanes or organopolysiloxanes, 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 coating systems or mixed coating systems, for modifying cathode and anode materials in batteries, 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 constituent in building protection agents, as an additive for mineral hardening materials, for modifying wood, wood fibers and cellulose.

39. Use according to claim 38 for modifying glass fibres and natural fibres.