DE102011086868A1 - Composition useful e.g. as adhesive, comprises olefinically functionalized siloxane oligomers exhibiting less olefinic group at silicon atom, fatty acid, silyloxy crosslinked structural elements derived from alkoxysilanes, and chloride - Google Patents

Abstract

Composition comprises olefinically functionalized siloxane oligomers (I), which exhibit (a) not > 1 olefinic group at silicon atom, (b) at least one fatty acid (III), (c) silyloxy (Si-O)-crosslinked structural elements, which form chain-like-, cyclic-, crosslinked- or optionally spatially crosslinked structures, and are derived from alkoxysilanes, and (d) chloride. Composition comprises olefinically functionalized siloxane oligomers of formula ((R1O)[(R1O) 1 - x(R2) xSi(A)O] a[Si(Y1) 2O] c[Si(B1)(R4) y(OR3) 1 - yO] bR3) (I), which exhibit (a) not > 1 olefinic group at silicon atom, (b) at least one fatty acid of formula (R5-COOH) (III), (c) silyloxy (Si-O)-crosslinked structural elements, which form chain-like-, cyclic-, crosslinked- or optionally spatially crosslinked structures, and are derived from alkoxysilanes, and (d) chloride, A : olefinic group; B1 : saturated hydrocarbyl, where the ratio of A to B is 1:0-1:8; Y1 : OR3 or O 1 / 2(in crosslinked or optionally spatially crosslinked structures) or OR3; R1, R3 : 1-4C alkyl (optionally branched and/or cyclic) or optionally H or -CO-R5; R2, R4 : 1-15C alkyl (optionally branched or cyclic); R5 : 3-45C hydrocarbyl (optionally substituted); either a : >= 1; and b, c : >= 0; or a+b+c : >= 2; and x, y : 0 or 1. An independent claim is also included for preparing the above composition, comprising reacting an olefinically functionalized alkoxysilane of formula (A-Si(R2) x(OR12) 3 - x) (VI), optionally alkoxysilane (B1-Si(R4) y(OR13) 3 - y) (VII), and/or optionally tetra-alkoxysilane of the formula (Si(OR13) 4) (VIII), with defined amount of water in presence of catalyst (a) comprising hydrochloric acid and chlorosilane, and (b) comprising fatty acid (III) and olefinically functionalized carboxysilane of formula (A-Si(R2) x(OR14) 3 - x) (IX), and optionally in the presence a solvent, preferably alcohol, to obtain oligomer. R12, R13 : 1-4C alkyl (optionally branched and/or cyclic); and R14 : -CO-R5.

Description

The invention relates to a composition containing olefinically functionalized siloxane oligomers derived from olefinically functionalized alkoxysilanes, having at most one olefinic radical per silicon atom and a fatty acid and a very low content of chloride and methods for their preparation and their use.

It is known to react vinyltriethoxysilane, optionally in mixtures with alkyltriethoxysilanes and / or tetraethoxysilane, by acidic HCl-catalyzed hydrolysis and condensation in an alcohol in the presence of a calculated amount of water. Subsequently, the alcohol and the hydrogen chloride (also called hydrochloride or HCl short) must be separated consuming. Other silane hydrolysis and / or condensation catalysts used so far generally belong to the strongly polar inorganic acids, such as H ₃ PO ₄ , or strong organic acids, such as formic acid. The acids used remain in the product or in the case of hydrochloric or hydrochloride (HCl) consuming after the reaction of the organofunctional alkoxysilanes must be removed again from the crude products produced, so as not to contribute to corrosion of the metallic surfaces of the processing machines.

In addition, silane systems are finding increasing interest, which contain fewer and fewer organic solvents and are therefore more environmentally friendly. For this reason, the trend is to provide precondensed VOC poorer silane systems, which then have to be stabilized because they still contain the catalyst or from which the catalyst must be separated consuming.

From the EP 0 518 057 B1 For example, it is known to prepare blends of chain and cyclic vinyl-substituted siloxanes and siloxane oligomers, respectively, which are prepared in a water / alcohol mixture with HCl as a catalyst. The HCl catalyst can not be completely separated by means of the method disclosed therein and a corrosive residual content of HCl remains, even after distillation, in the product produced.

CN 100343311 C describes silanoligomers obtained by catalytic hydrolysis and condensation of vinyltrimethoxysilane. The use of metal salt catalysts, such as copper hydroxide, in combination with acids is mandatory. The separation of the catalysts is complex and it is to be expected that catalyst residues or neutralization products remain in the product and adversely affect many applications. Thus, the separation of the acid by neutralization by means of calcium carbonate and filtration of the resulting calcium salt is sought here.

Siloxanes with high molecular weights in the range of 10,000 g / mol are in JP 10-298289 A wherein these are prepared by hydrolysis and precondensation or condensation of a vinyl- or phenyl-functional alkoxysilane in the presence of an acid catalyst and the catalyst is then removed with the aid of an anhydrous anionic ion exchanger from the product mixture. Such high molecular weight material can not be used in most applications due to high viscosities and low reactivity.

Organosiloxane oligomers having a multiplicity of possible functionalities, an average molecular weight in the range Mn = 350-2500 g / mol and a polydispersity (D = Mw / Mn) of 1.0-1.3 are disclosed in US Pat JP2004-099872 described. The preparation is carried out in the presence of a basic catalyst from a very dilute aqueous solution with a very low, economically not desirable space-time yield; thus 1 ml of product was isolated from 1 liter of solution.

The object of the present invention was to prepare olefinically functionalized oligomers in an economical process with a very low content of hydrochloride as the hydrolysis and / or condensation catalyst. Furthermore, these oligomers should have an improved property profile than the known ones. Another object was to find a catalyst, in particular as a co-catalyst to the hydrochloride, for the hydrolysis and / or condensation of alkoxysilanes, which may remain in the product without having the negative properties mentioned above. Preferably, the content of HCl during the reaction should be lowered so that the chloride does not necessarily have to be removed after the reaction. Another task was to develop a particularly economical and energy-saving process.

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

Surprisingly, it has been found that olefinically functionalized alkoxysilanes, optionally alkyltrialkoxysilanes and optionally tetraalkoxysilane in a simple and economical manner with a fatty acid having a total of 4 to 46 carbon atoms are preferred myristic, caprylic or their carboxysilanes, in the presence of a low content of HCl and hydrolyzed a defined amount of moisture or water and can be condensed to olefinically functionalized oligomers. The HCl content can be adjusted by adding HCl or else by the presence of chlorosilanes which form HCl under the reaction conditions. Such obtainable compositions of olefinically functionalized siloxane oligomers have only very low levels of HCl. According to the invention, the fatty acid used as a catalyst no longer needs to be removed from the oligomer consuming, as was necessary with the sole use of larger amounts of HC as a catalyst. An outstanding advantage of the compositions according to the invention and of the process according to the invention is that the olefinically functionalized oligomers prepared, in particular vinyl oligomers, unlike the known oligomers, require no further workup, such as distillation. The produced oligomeric bottom product shows the same performance as known but purified by distillation siloxane oligomers.

A particular advantage of the olefinically functionalized siloxane oligomers according to the invention is also that the fatty acid-based catalysts directly improve the processability of the siloxane oligomers with polymers, for example in a subsequent kneading or compounding step. Specifically, the melt index improves, so that the energy consumption during processing decreases. Furthermore, the corrosion of ferrous machinery decreases. In addition, the water absorption capacity of the polymers compounded with the siloxane oligomers according to the invention is reduced, and their elongation at break and tensile strength are improved. Another essential advantage of the composition is that it can be prepared and used directly as a bottom product, if appropriate after removal of the hydrolysis alcohol and, if appropriate, added solvent, in an economical manner according to the invention. Since the composition according to the invention no longer has to be distilled, the process for its preparation is considerably more economical. In addition, the properties of the bottom products according to the invention also differ from known olefinic siloxane oligomers, which have been purified by distillation, by their modified ratio of M to D and also to T structures and an optionally higher proportion of higher oligomers.

It was also surprising that the alcohol can be distilled off with less expenditure of energy than in the processes of the prior art, in which far more HCl had to be removed. Particularly surprising was the improvement in the tensile properties or elongation at break of the polymers compounded with the compositions according to the invention, for example elastomers or thermoplastics. In addition, the water absorbency of the polymer compounded with olefinic siloxane oligomers according to the invention could be significantly reduced. Such compounded polymers are particularly suitable for the production of, for example, cable sheaths that are exposed to a humid climate, for example, to be laid under water or in the ground. It was likewise surprising that the hydrolysis and condensation of the polar, olefinically functionalized alkoxysilanes, such as vinyltrimethoxysilane or vinyltriethoxysilane or corresponding allyl-functionalized silanes, with the amphiphilic fatty acids, preferably with HOOC-R ⁵ where R ^{5 is} equal to 7 to 27 C atoms, could be catalyzed.

The olefinic siloxane oligomers prepared in the presence of fatty acid also have a reduced VOC content over the siloxane systems known in the art which have been prepared solely using strong acids. In addition, the oligomers hydrolyzed and condensed with a fatty acid or a fatty acid from a precursor compound such as a carboxy silane preferably have a homogeneous molecular weight distribution which is advantageous for reproducible and homogeneous compounding properties in later fields of application, for example in the production of filled cable compositions.

• – wobei die Strukturelemente aus Alkoxysilanen abgeleitet sind und
• – A in dem Strukturelement ein olefinischer Rest ist, insbesondere abgeleitet aus der allgemeinen Formel II, insbesondere ist A ein nicht hydrolysierbarer olefinischer Kohlenwasserstoffrest, bevorzugt sind lineare, verzweigte oder cyclische, Alkenyl-, Cycloalkenyl-alkylen-funktionelle Gruppen mit jeweils 2 bis 18 C-Atomen, besonders bevorzugt mit 2 bis 8 C-Atomen, und
• – B in dem Strukturelement ein gesättigter Kohlenwasserstoffrest ist, insbesondere abgeleitet aus der allgemeinen Formel IV,
• – Y in dem Strukturelement OR³ entspricht oder in vernetzten und/oder raumvernetzten Strukturen unabhängig voneinander OR³ oder O_1/2 ist, insbesondere abgeleitet aus der allgemeinen Formel V gleich Si(OR³)₄,
• – wobei R¹ unabhängig voneinander einem linearen, verzweigten und/oder cyclischen Alkyl-Rest mit 1 bis 4 C-Atomen entspricht, und gegebenenfalls zu einem geringen Anteil -H und/oder -CO-R⁵ mit R⁵, wie nachstehend definiert; R³ jeweils unabhängig voneinander einem linearen, verzweigten und/oder cyclischen Alkyl-Rest mit 1 bis 4 C-Atomen, und R² und/oder R⁴ jeweils unabhängig einem linearen, verzweigten oder cyclischen Alkyl-Rest mit 1 bis 15 C-Atomen entsprechen,
• – a, b, c, x und y unabhängig voneinander ganzen Zahlen entsprechen; mit 1 ≤ a, 0 ≤ b; insbesondere auch 1 ≤ b; und 0 ≤ c, wie gegebenenfalls 1 ≤ c, vorzugsweise mit a, b, c jeweils unabhängig 0 bzw. 1 bis 35, wobei x unabhängig voneinander 0 oder 1 ist, y unabhängig voneinander 0 oder 1 ist, und (a + b + c) ≥ 2 sind, bevorzugt sind 50 ≥ (a + b + c) ≥ 3, insbesondere 30 ≥ (a + b + c) ≥ 3; 20 ≥ (a + b + c) ≥ 3; besonders bevorzugt 15 ≥ (a + b + c) ≥ 3, weiter bevorzugt 10 ≥ (a + b + c) ≥ 3, jeweils unabhängig mit (i) a größer 1 oder (ii) mit a und b jeweils unabhängig größer 1 oder (iii) mit jeweils unabhängig a, b und c größer gleich 1; und
• – die Fettsäure entspricht der Formel (III) R⁵-COOH (III) mit R⁵ einem unsubstituierten oder substituierten Kohlenwasserstoff-Rest mit 3 bis 45 C-Atomen.

The invention therefore relates to a composition containing olefinically functionalized siloxane oligomers having at most one olefinic radical per silicon atom, the olefinic radical is in particular not hydrolyzable, and the siloxane oligomers are preferably derived from olefinically functionalized alkoxysilanes of general formula II, and contain at least one Fatty acid, in particular of the general formula III, and chloride, the chloride content (total chloride) being, for example, below 200 ppm by weight, in particular below 100 ppm by weight, preferably below 80 ppm by weight, preferably below 50 ppm by weight , more preferably below 25 ppm by weight, preferably below 10% by weight, and the olefinically functionalized siloxane oligomers have Si-O-crosslinked - ie siloxane-crosslinked - structural elements having chain-like, cyclic, crosslinked and / or spatially crosslinked structures, where at least one structure in idealized form corresponds to the general formula I, (R ¹ O) [(R ¹ O) _1-x (R ²⁾ _x Si (A) O] _a [Si (Y) ₂ O] _c [Si (B) (R ⁴⁾ _y (OR ³⁾ _{1 -YO} ] _b R ³ (I),

• - Wherein the structural elements are derived from alkoxysilanes and
• A in the structural element is an olefinic radical, in particular derived from the general formula II, in particular A is a non-hydrolyzable olefinic hydrocarbon radical, preferred are linear, branched or cyclic, alkenyl, cycloalkenyl-alkylene-functional groups each having 2 to 18 C -Atomen, particularly preferably with 2 to 8 C-atoms, and
• B in the structural element is a saturated hydrocarbon radical, in particular derived from the general formula IV,
• - Y in the structural element OR ³ corresponds or in cross-linked and / or spatially crosslinked structures is independently of one another OR ³ or O _1/2 , in particular derived from the general formula V is Si (OR ³ ) ₄ ,
• Wherein R ^{1 is} independently a linear, branched and / or cyclic alkyl radical having 1 to 4 carbon atoms, and optionally to a minor extent -H and / or -CO-R ⁵ with R ⁵ , as defined below; Each R ³ independently of one another is a linear, branched and / or cyclic alkyl radical having 1 to 4 C atoms, and R ² and / or R ^{4 are} each independently a linear, branched or cyclic alkyl radical having 1 to 15 C atoms correspond,
• - a, b, c, x and y independently correspond to integers; with 1 ≤ a, 0 ≤ b; in particular 1 ≤ b; and 0 ≤ c, optionally 1 ≤ c, preferably a, b, c, each independently 0 or 1 to 35, where x is independently 0 or 1, y is independently 0 or 1, and (a + b + c) ≥ 2, preferably 50 ≥ (a + b + c) ≥ 3, in particular 30 ≥ (a + b + c) ≥ 3; 20 ≥ (a + b + c) ≥ 3; particularly preferably 15 ≥ (a + b + c) ≥ 3, more preferably 10 ≥ (a + b + c) ≥ 3, each independently with (i) a greater than 1 or (ii) with a and b each independently greater than 1 or (iii) each independently a, b and c is greater than or equal to 1; and
• - The fatty acid corresponds to the formula (III) R ⁵ -COOH (III) with R ^{5 is} an unsubstituted or substituted hydrocarbon radical having 3 to 45 carbon atoms.

It may be preferred that the composition and / or the siloxane oligomer further comprises trialkylsilane groups, such as trimethylsilane or triethylsilane groups, by the addition of, for example, alkoxytrialkylsilane.

According to the invention, the olefinically functionalized alkoxysilane of the formula II, A-Si (R ² ) _x (OR ¹ ) _3-x (II) with A an olefinic radical, in particular with A is a non-hydrolyzable hydrocarbon radical, with R ² and x as defined above, preferably x = 0, and R ^{1 is} independently a linear, branched and / or cyclic alkyl radical having 1 to 4 C. -Atomen (IIa) or R ^{1 is} a -CO-R ⁵ radical with R ⁵ , as defined below (IIb).

All alkyl radicals having 1 to 4 carbon atoms may always preferably be, independently of one another, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl and / or 2-methylbutyl. Unsaturated carboxylic acid residues are not considered to be an olefinic residue on the silicon atom.

Independently of this, an alkoxysilane according to the invention functionalized with a saturated hydrocarbon radical of the formula IV corresponds to B-Si (R ⁴ ) _y (OR ³ ) _3-y (IV) with B is an unsubstituted hydrocarbon radical, with R ³ , R ⁴ and y as defined above, y is preferably 0.

In general, the siloxane oligomers can be linear and / or cyclic oligomers with M and D structures, or else crosslinked oligomers with M, D and T structures. Only when tetraalkoxysilane is added during the preparation or before processing are siloxane oligomers with M, D, Q and optionally T structures formed.

The content of M, D, T or Q structures is generally determined by a method known per se to the person skilled in the art, preferably by means of ²⁹ Si NMR.

The definition for M, D, T and Q structures usually refers to the number of bound oxygens:

One could also speak of T0, T1, T2 and T3, which in practice, however, is rather uncommon: R-Si (OEt) 3 T0 R-Si (OEt) 2 (OSi) T1 R-Si (OEt) (OSi) 2 T2 R-Si (OSi) 3 T3

Thus, in order to be able to describe silicones and siloxanes or silanoligomers more clearly, it is also possible to use the M, D, T and Q structures instead of an idealized formulaic description. For a more detailed nomenclature of the naming of such siloxane structures, reference should be made to the "Römpp Chemielexikon" - keyword: silicones. For example, from units M only dimers can be formed with M ₂ . For building chains, compositions of units D and M are required, so that trimers (M ₂ D), tetramers (M ₂ D ₂ ) and so on can be built up to linear oligomers with M ₂ D _n . For the formation of cyclic oligomers units D are needed. In this way, for example, rings with D ₃ , D ₄ , D ₅ or higher can be constructed. Branched or crosslinked structural elements, which also include spiro compounds, are obtained if structural units T and / or Q are present together. Conceivable crosslinked structures can be described as T _n (n ≥ 4); D _n T _m (m <n); D _n T _m (n >>m); D ₃ T ₂ ; M ₄ Q; D ₄ Q and so on, to name only a few possible options. Building units M are also referred to as stoppers or regulators, while D units are referred to as chain or ring formers and the T and optionally also the Q units as network formers. Thus, the use of tetraalkoxysilanes due to the four hydrolyzable groups and access of water or moisture units Q and thus the formation of a network (space-crosslinked) effect. In contrast, fully hydrolyzed trialkoxysilanes can cause branching, ie, T units [-Si (-O-) _3/2 ], in one structural element, for example MD ₃ TM ₂ for an oligomer having a degree of oligomerization of n = 7, in which structural representations respective functionalities at the free valences of the silyloxy units are to be defined.

• – „Strukturuntersuchungen von oligomeren und polymeren Siloxanen durch hochauflösende ²⁹Si-Kernresonanz“, H.-G. Horn, H. Ch. Marsmann, Die Markromolekulare Chemie 162 (1972), 255–267 ;
• – „Über die ¹H-, ¹³C- und ²⁹Si-NMR chemischen Verschiebungen einiger linearer, 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 John Wiley & Sons Ltd, 511–533 .

Further details on the understanding of nomenclature of M-, D-, T- and Q-structures as well as related investigation methods are:

• - "Structural Investigations of Oligomeric and Polymeric Siloxanes by High Resolution ²⁹ Si Nuclear Magnetic Resonance", H.-G. Horn, H.C. Marsmann, The Markromolecular Chemistry 162 (1972), 255-267 ;
• "About the ¹ H, ¹³ C, and ²⁹ Si NMR chemical shifts of some linear, branched, and cyclic methyl-siloxane compounds", G. Engelhardt, H. Jancke; J. Organometal. Chem. 28 (1971), 293-300 ;
• - "Chapter 8 - NMR spectroscopy of organosilicone compounds", Elizabeth A. Williams, The Chemistry of Organic Silicon Compounds, 1989 John Wiley & Sons Ltd, 511-533 ,

Compositions according to the invention have siloxane oligomers in which the sum of (a + b) is an integer greater than or equal to 2, in particular from 2 to 30, in particular 2 to 20, preferably 2 to 15, 2 to 10 and c is optionally greater than or equal to 1 , If the degrees of oligomerization are too high, no homogeneous and reproducible product properties can be achieved with the siloxane oligomers. For adjustment of the degree of oligomerization during the preparation of the composition, it may therefore be preferred for a chain termination at a desired time to add an alkoxytrialkylsilane, such as preferably an ethoxytrimethylsilane or methoxytrimethylsilane, to the composition to be prepared.

Furthermore, the composition according to the invention comprising olefinically functionalized siloxane oligomers preferably contains a content of fatty acid, in particular of the formula III, of 0 to 5% by weight, preferably of 0.01 to 3% by weight, relative to the total composition (100% by weight). %), wherein a content of esterified fatty acid according to formula I with R ¹ independently of one another -CO-R ⁵ with R ⁵ , as defined below, can be included here.

The ratio of M structures to D structures in the olefinically functionalized siloxane oligomers is preferably in the range from 5: 1 to 1: 5, in particular from 4: 1 to 1: 4, preferably from 2: 1 to 4: 1, particularly preferably 2: 1 to 3.5: 1, which may optionally be formed in addition T-structures. Alternatively or additionally, preferred compositions contain olefinically functionalized siloxane oligomers having an olefin group to alkoxy group ratio of from 1: 1 to 1: 5, preferably from 1: 1 to 1: 4, with a ratio of 1: 1 in purely olefinically functionalized siloxane oligomers to 1: 2 and in addition alkyl-functionalized siloxane oligomers 1: 1 to 1: 4 are preferred.

Additionally or alternatively, the content of T structures in the compositions of the olefinically functionalized siloxane oligomers determined by ²⁹ Si-NMR is greater than or equal to 5.0%, in particular greater than 7.0%, and contents of greater than 7.5% can be particularly preferred in particular greater than 9.0%. Particularly preferably, the content of T-structures can be greater than 10%, more preferably greater than 12%. Preferably, the content of chloride, such as total chloride, is preferably below 80 ppm by weight, preferably below 50 ppm by weight, more preferably below 25 ppm by weight, preferably below 10% by weight.

Particular preference is given to compositions in which 95% by weight of the siloxane oligomers have a degree of oligomerization of olefinically functionalized siloxane oligomers of from 2 to 10, in particular from 2 to 8.

According to one alternative, compositions of pure olefinically substituted siloxane oligomers are prepared, in particular of the formula I where a is a number from 2 to 30, preferably 2 to 15, particularly preferably 2 to 10 and a fatty acid, in particular of the formula III, in the presence of HCl and / or chlorosilane. The index b is 0 and c can be 0 or greater than 1. Preferred olefinic groups are linear, branched or cyclic, alkenyl, cycloalkenyl-alkylene-functional groups having in each case 2 to 18 C atoms, in particular having 2 to 8 C atoms, particular preference is given to vinyl, allyl, butenyl, in particular 3-butenyl or 2-butenyl; Pentenyl, hexenyl, heptenyl, octenyl or in particular cyclohexenyl-C1 to C8-alkylene, preferably cyclohexenyl-2-ethylene, particularly preferably 3'-cyclohexenyl-2-ethylene or else 2'-cyclohexenyl 2-ethylene and / or cyclohexadienyl-C1 to C8-alkylene, preferably the olefinic group is a cyclohexadienyl-2-ethylene group. Optionally, the composition may be based on a siloxane oligomer prepared in the presence of tetraalkoxysilane.

According to a second preferred alternative, compositions of olefinic- and alkyl-substituted siloxane oligomers are prepared, in particular of the formula I with a greater than or equal to 1 and b greater than or equal to 1, and in particular (a + b) equal to a number from 2 to 30, preferably 2 to 15, more preferably 2 to 10 and a fatty acid, in particular of the formula III, in the presence of HCl and / or chlorosilane. In these compositions it is further preferred if the molar ratio of A radicals to B radicals is 1: 0 to 1: 8, in particular the ratio of a: b is 1: 0 to 1: 8, in particular 1: 0 or 1: 1 to 1: 8. Optionally, the composition may be based on a siloxane oligomer prepared in the presence of tetraalkoxysilane.

According to a specific alternative, compositions of pure vinyl-substituted siloxane oligomers, in particular of the formula I where a is a number from 2 to 30, preferably 2 to 15, particularly preferably 2 to 10 and a fatty acid, in particular of the formula III, in the presence of HCl and / or chlorosilane.

According to a further preferred alternative, compositions of vinyl- and alkyl-substituted siloxane oligomers are prepared, in particular of the formula I with a greater than or equal to 1 and b greater than or equal to 1, and in particular (a + b) equal to a number from 2 to 30, preferably 2 to 15, more preferably 2 to 10 and a fatty acid in the presence of HCl and / or chlorosilane, in particular of the formula III. Here too preferred molar ratios of A radicals to B radicals are 1: 0 to 1: 8, in particular the ratio of a: b is 1: 0 to 1: 8, in particular 1: 0 or 1: 1 to 1: 8. Optionally, the compositions may be based on a siloxane oligomer prepared in the presence of tetraalkoxysilane.

More preferably, the composition comprises siloxane oligomers having structural elements derived from at least one of the alkoxysilanes, from olefinically functionalized alkoxysilanes of the general formula IIa and optionally from a saturated hydrocarbon radical functionalized alkoxysilane of the formula IV, and optionally from a tetraalkoxysilane of the general formula V. Si (OR ³ ) ₄ and optionally structural elements derived from the reaction products of the added, catalytically active chlorosilanes D _n SiCl _4-n (VI) with n = 0 or 1 and the group D in formula VI a saturated or unsaturated hydrocarbon radical Preferably, the group D corresponds to a group A, as defined for the formula I or II, or a group B, as defined for the formula I or IV,

Compositions according to the invention have one or more of the above characteristics and have a molar ratio of the (i) total amount of the Si atoms of the functionalized siloxane oligomers derived from the silanes of general formula IIa, formula IV and / or formula V used (ii) total amount of fatty acid of the general formula III and / or the olefinically functionalized carboxysilane of the formula IIb of preferably 1: 5 × 10 ^-1 to 1: 1 × 10 ^-5 , in particular from 1: 5 × 10 ^-2 to 1: 1 × 10 ^-4 , preferably 1: 3 × 10 ^-2 to 1: 1 × 10 ^-4 , particularly preferably 1: 1 × 10 ^-2 to 1: 1 × 10 ^-4 , more preferably 1: 1 × 10 ^-3 to 1: 1 × 10 ^-4 , according to the invention 1: 5 × 10 ^-3 to 1: 1 × 10 ^-4 , also preferred is a range of 1: 2 × 10 ^-3 to 1: 1 × 10 ^-4 . Alternatively, particularly preferred are also 1: 3 × 10 ^-3 to 1: 1 × 10 ^-4 , preferably 1: 2 × 10 ^-3 to 1: 3 × 10 ^-4 , particularly preferably 1: 2 × 10 ^-3 to 1: 5 × 10 ^-4 . Consequently, the fatty acid has already proven in small doses as a catalyst or as a cocatalyst, ie n _Si : n _{fatty acid / carboxysilane} = (n _{formula IIa} + n _{formula IV} + n _{formula V} ) :( n _{formula III} + n _{formula IIb} )

The silanes of the formulas IIa, IV and / or V and the carboxysilanes of the formula IIb are defined below.

Compositions according to the invention have one or more of the above characteristics, and in addition to the fatty acid, additionally have a chloride content (total chloride content) in the composition of less than or equal to 200 ppm by weight, for example from 200 ppm by weight to 0% by weight . ppm or to the detection limit. In particular, the chloride content is less than or equal to 100 ppm by weight, preferably less than or equal to 80 ppm by weight, more preferably less than or equal to 50 ppm by weight, more preferably less than or equal to 25 ppm by weight, to the detection limit. The chloride content is more preferably less than 30 ppm by weight, less than 20 ppm by weight, less than 15, 10, more preferably less than 5, in particular less than 1 ppm by weight. The content of chloride preferably refers to a composition which is present after preparation of the siloxane oligomers and after removal of the free alcohol as bottom product.

According to the invention, the radical R ⁵ in the fatty acids of the formula III, the precursor compound of a fatty acid of the general formula IIb, d. h in a carboxysilane or in an optionally derived therefrom siloxane, in particular the general formula I, each independently an unsubstituted saturated or unsaturated, optionally polyunsaturated hydrocarbon radical, such as but not limited to a diene, triene, etc. Preferably, the hydrocarbon R ⁵ independently in formula I, II or III 5 to 45 C-atoms, more preferably 7 to 26 C-atoms, preferably 5 to 21, particularly preferably 7 to 21, more preferably 11 to 17, or preferably 7 to 16 carbon atoms or even 11 to 16 carbon atoms, possibly stearyl - with R ⁵ equal to C ₁₇ H ₃₅ - is only appropriate. For if the non-polar alkyl radical of the fatty acid becomes too long, the effect as a catalyst can be impaired by insufficient solubility.

Additionally or alternatively to the abovementioned features, a composition according to the invention in the olefinically functionalized structural elements, in particular as radical A, or the alkoxysilane of general formula IIa or the carboxysilane of formula IIb as olefinic radical A is a linear, branched or cyclic, alkenyl, cycloalkenyl alkylene-functional group having in each case 2 to 18 C atoms, preferably one of the following groups: vinyl, allyl, butenyl, in particular 3-butenyl, or else 2-butenyl; Pentenyl, hexenyl, heptenyl, octenyl, cyclohexenyl-C1 to C8-alkylene, preferably cyclohexenyl-2-ethylene, particularly preferably 3'-cyclohexenyl-2-ethylene or else 2'-cyclohexenyl-2-ethylene - and / or cyclohexadienyl-C1 to C8-alkylene, preferably a cyclohexadienyl-2-ethylene group.

In addition or as an alternative to the abovementioned features, a composition according to the invention in the hydrocarbon-functionalized radicals of the structural elements, in particular as radical B, or the alkoxysilane of general formula IV as unsubstituted hydrocarbon radical B, has a linear, branched or cyclic alkyl radical with 1 to 18 carbon atoms, in particular a methyl, ethyl, propyl and / or octyl group.

In addition or as an alternative to one of the abovementioned features, a composition according to the invention as fatty acid, in particular of formula III, or as carboxy group in a structural element, in particular as radical R ¹ = -CO-R ^{5, has} the carboxy-fatty acid radical of formula III , such as, preferably, caproic acid, enanthic acid, caprylic acid, perlagonic acid, capric acid, lauric acid, myristic acid, palmitic acid, behenic acid, linolenic acid or calendulic acid, or optionally stearic acid or a mixture of at least two of said acids, or the radical R ⁵ is in each case independent in the formulas I, II or III is a monovalent group -C _n H _{2n + 1} , with n = each independently a number of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 or 23, where n = 17 may also be excluded for stearic acid, more preferably, a group C ₁₇ H ₃₁ - the linoleic acid, C ₁₇ H ₂₉ - the alpha-linolenic acid, C ₁₇ H ₂₉ - the Gamma-linolenic acid or Ca lendulic acid.

In general, all fatty acids are considered suitable, provided that they do not interfere with the odor and have more than four carbon atoms, these can be both natural and synthetic fatty acids. The fatty acids caproic acid, enanthic acid, caprylic acid, perlagonic acid, capric acid, lauric acid, myristic acid, palmitic acid, behenic acid, linolenic acid or calendic acid or linoleic acid have proven to be particularly suitable, the caprylic acid, myristic acid or its carboxylates in the carboxysilanes of the formula IIb being particularly preferred have preferably been found. These fatty acids are sufficiently soluble in the reaction mixture and at the same time sufficiently hydrophobic to catalyze the hydrolysis and / or condensation with the olefinic alkoxysilanes of the formula IIa and / or the hydrocarbon-functionalized alkoxysilanes. Depending on the alkoxysilane can be completely dispensed by the use of these catalysts on the addition of a solvent during the reaction, and thereby the efficiency of the process can be significantly improved.

Under a structural element - a monomeric siloxane unit - is consistently understood the single unit M, D, T or Q, i. H. the structural unit derived from an alkoxy-substituted silane, which forms by at least partial hydrolysis to optionally complete hydrolysis and at least partial condensation in a condensate, be it a homo-condensate, a co-condensate, or even block homo- and / or block Co-condensate.

In particular, according to the invention, the siloxane oligomers may be formed, which may comprise the following structural elements, such as preferably:
(R ¹ O) [(R ¹ O) _1-x (R ²⁾ _x Si (A) O] _a R ^1; (R ¹ O) [(R ¹ O) _1-x (R ²⁾ _x Si (A) O] _a; [(R ¹ O) _1-x (R ²⁾ _x Si (A) O] _a; [(R ¹ O) _1-x (R ²⁾ _x Si (A) O] _a R ^1; (R ³ O) [Si (Y) ₂ O] _c ; [Si (Y) ₂ O] _c R ³ , (R ³ O) [Si (Y) ₂ O] _c R ³ ; [Si (Y) ₂ O] _c ; (R ³ O) [Si (B) (R ⁴ ) _y (OR ³ ) _1-y O] _b R ³ ; [Si (B) (R ⁴ ) _y (OR ³ ) _1-y O] _b R ³ , [Si (B) (R ⁴ ) _y (OR ³ ) _1-y O] _b (R ³ O) [Si (B) (R ⁴ ) _y (OR ³ ) _1-y O] _b R ^{3 can form} the chain-like, cyclic and / or crosslinked structures. In the presence of tetraalkoxysilanes or their hydrolysis and / or condensation products, it is also possible to form spatially crosslinked structures. The structural elements with free valencies on the Si atom are covalently over-O-Si and the free valences on the O atom are saturated with - Si bridged bonds of other structural elements, alkyl or carbonyl groups or hydrogen. The structural elements can assume a random or even statistical arrangement in the condensates, which, as one skilled in the art knows, can also be controlled by the order of addition and the hydrolysis and / or condensation conditions. The general formula I does not reflect the actual structure or composition. It corresponds to an idealized representation.

The composition preferably contains siloxane oligomers obtained by random and / or random homo- or co-hydrolysis and / or homo- or co-condensation and / or block condensation of said structural elements, based on the alkoxysilanes of the formulas substituted according to the invention with A or B radicals II (IIa and / or IIb), IV and / or V, arise and / or form under the selected experimental conditions, in particular by the presence of fatty acid and HCl and / or chlorosilane or mixtures thereof.

The substitution pattern of the structural elements applies correspondingly also to the non-idealized chain-shaped, cyclic, crosslinked and / or spatially crosslinked siloxane oligomers in the composition, wherein Y is an OR ³ or in crosslinked and / or spatially crosslinked structures independently of one another OR ³ or O _1/2 - in a siloxane bond - corresponds to residues A and B are as defined, R ³ corresponds to the siloxane oligomers essentially an alkyl radical as defined for R ³ , wherein in crosslinked and / or space-crosslinked structures, siloxane bonds with O _1/2 can also be formed independently of the radicals OR ^{3, in} each case independently of one another as O _{1 / 2} and R ² , R ⁴ independently as defined correspond to an alkyl radical having 1 to 15 carbon atoms, R ¹ can also be defined as an alkyl radical having 1 to 4 carbon atoms or a -CO-R ⁵ Residue as defined correspond or else to a corresponding hydrolysis and / or condensation product of this precursor compound of a silanol hydrolysis and / or condensation catalyst.

The invention also provides a composition containing olefinically functionalized siloxane oligomers, in particular at least one siloxane oligomer according to the idealized formula I, which contains as further component at least one organic solvent, an organic polymer, water, salt, filler, additive, pigment or a mixture of at least two of contains mentioned components. The components may be added to the composition during the preparation of the composition as well as at a later time.

Compositions according to the invention comprising polymers are preferably prepared after the preparation of the olefinically functionalized siloxane oligomers and removal of the free alcohol and optionally removal of HCl, by subsequently reacting the correspondingly prepared siloxane oligomers with an organic polymer, for example a thermoplastic or an elastomer, in each case in the presence of an inorganic polymer Filler be mixed.

A particular advantage of the composition according to the invention is that it has a much lower content of chloride due to its production, preferably the small amount of chloride added could essentially be completely removed during the removal of the hydrolysis alcohol. Thus, when processed in cable compositions, these compositions contribute to a significant improvement in fire protection properties. The fatty acid can remain in the product and does not need to be separated. Another advantage of the compositions of the invention is that they are food safe by the use of fatty acids. When processed in extruders, the fatty acid leads to a cleaning effect and also the corrosion of the extruder screws could be significantly reduced. In addition, the compositions according to the invention have constant flash points based on olefinically functionalized siloxane oligomers and at least one fatty acid and a very low chloride content, preferably up to the detection limit. With corresponding vinyl-functional alkoxysiloxane oligomers from the preparation with HCl as the sole catalyst, the flash point decreases with increasing storage due to constant hydrolysis of the alkoxy groups to hydrolysis alcohol, since in these compositions the chloride content can not be reduced to the necessary extent, in particular not on an industrial scale ,

According to the invention, a composition of the olefinically functionalized siloxane oligomers after removal of the hydrolysis alcohol and optionally solvent itself need not be further purified, such as, for example, distilled, in order to be suitable for the uses according to the invention. Therefore, the inventive method is significantly more economical than known methods in which the oligomer to be suitable for further use, must be purified by distillation.

• (i) ein olefinisch funktionalisiertes Alkoxysilan der allgemeinen Formel IIa, A-Si(R²)_x(OR¹)_3-x (IIa), wobei in Formel IIa A einem olefinischen Rest entspricht, insbesondere wie vor- bzw. nachstehend definiert, R² unabhängig einem linearen, verzweigten oder cyclischen Alkyl-Rest mit 1 bis 15 C-Atomen und x gleich 0 oder 1 ist, bevorzugt x = 0, und R¹ unabhängig einem linearen, verzweigten und/oder cyclischen Alkyl-Rest mit 1 bis 4 C-Atomen entsprechen, insbesondere ist R¹ unabhängig Methyl-, Ethyl, Propyl-, wie iso-Propyl- oder n-Propyl-,
• (ii) in Gegenwart der Katalysatoren a) und b) ausgewählt aus a) HCl und Chlorsilan sowie b) einer Fettsäure der allgemeinen Formel III und einem olefinisch funktionalisierten Carboxysilan der Formel IIb oder einer Mischung von Katalysatoren aus a) und b), R⁵-COOH (III) A-Si(R²)_x(OR¹)_3-x (IIb) mit R¹ gleich R⁵-(C=O)- in Formel IIb, wobei in Formel IIb und III R⁵ unabhängig voneinander einem unsubstituierten oder substituierten Kohlenwasserstoff-Rest mit 3 bis 45 C-Atomen entspricht, in Formel IIb A einem olefinischen Rest, R² einem linearen, verzweigten oder cyclischen Alkyl-Rest mit 1 bis 15 C-Atomen entsprechen, und x gleich 0 oder 1 ist, bevorzugt ist A eine lineare, verzweigte oder cyclische Alkenyl- oder Cycloalkenyl-alkylen-funktionelle Gruppe mit jeweils 2 bis 18 C-Atomen, bevorzugt eine Vinyl-, Allyl-, Butenyl-, insbesondere 3-Butenyl-; Pentenyl-, Hexenyl-, Heptenyl-, Octenyl-, Cyclohexenyl-C1 bis C8-alkylen-, vorzugsweise Cyclohexenyl-2-ethylen-, besonders bevorzugt 3´-Cyclohexenyl-2-ethylen- oder auch 2´-Cyclohexenyl-2-ethylen-; und/oder Cyclohexadienyl-C1 bis C8-alkylen-, vorzugsweise Cyclohexadienyl-2-ethylen-Gruppe, insbesondere mit x = 0, und gegebenenfalls
• (iii) mit einem Alkoxysilan der Formel IV, B-Si(R⁴)_y(OR³)_3-y (IV) mit B einem gesättigten Kohlenwasserstoff-Rest, R³ jeweils unabhängig voneinander einem linearen, verzweigten und/oder cyclischen Alkyl-Rest mit 1 bis 4 C-Atomen und R⁴ einem linearen, verzweigten oder cyclischen Alkyl-Rest mit 1 bis 15 C-Atomen entsprechen und y gleich 0 oder 1 ist, und gegebenenfalls
• (iv) mit einem Tetraalkoxysilan der Formel V, Si(OR³)₄ (V), wobei R³ in Formel V jeweils unabhängig voneinander ein linearer, verzweigter und/oder cyclischer Alkyl-Rest mit 1 bis 4 C-Atomen ist, und
• (v) mit einer definierten Menge Wasser, gegebenenfalls in Gegenwart eines Lösemittels, insbesondere eines Alkohols, zu Oligomeren umgesetzt werden. Das Carboxysilan der Formel IIb wird als Katalysatorvorläufer eingesetzt, der dann unter den Verfahrensbedingungen mindestens eine Fettsäure der Formel II freisetzen kann. Besonders bevorzugte Kombinationen sind HCl und Fettsäure, Carboxysilan und HCl, sowie auch Chlorsilan und Fettsäure oder Chlorsilan und Carboxysilan.

The invention likewise provides a process for preparing a composition, and a composition obtainable by this process, comprising olefinically functionalized siloxane oligomers, by

• (i) an olefinically functionalized alkoxysilane of the general formula IIa, A-Si (R ² ) _x (OR ¹ ) _3-x (IIa), where in formula IIa A corresponds to an olefinic radical, in particular as defined above or below, R ^{2 is} independently a linear, branched or cyclic alkyl radical having 1 to 15 C atoms and x is 0 or 1, preferably x = 0 , and R ¹ independently correspond to a linear, branched and / or cyclic alkyl radical having 1 to 4 C atoms, in particular R ^{1 is} independently methyl, ethyl, propyl, such as iso-propyl or n-propyl,
• (ii) in the presence of the catalysts a) and b) selected from a) HCl and chlorosilane and b) a fatty acid of the general formula III and an olefinically functionalized carboxysilane of the formula IIb or a mixture of catalysts from a) and b), R ⁵ -COOH (III) A-Si (R ² ) _x (OR ¹ ) _3-x (IIb) with R ¹ is R ⁵ - (C = O) - in formula IIb, wherein in formula IIb and III R ^{5 is} independently an unsubstituted or substituted hydrocarbon radical having 3 to 45 carbon atoms, in formula IIb A an olefinic radical , R ² correspond to a linear, branched or cyclic alkyl radical having 1 to 15 C atoms, and x is 0 or 1, A is preferably a linear, branched or cyclic alkenyl or cycloalkenyl-alkylene functional group, each having 2 to 18 carbon atoms, preferably a vinyl, allyl, butenyl, especially 3-butenyl; Pentenyl, hexenyl, heptenyl, octenyl, cyclohexenyl-C1 to C8-alkylene, preferably cyclohexenyl-2-ethylene, particularly preferably 3'-cyclohexenyl-2-ethylene or else 2'-cyclohexenyl-2-ethylene -; and / or cyclohexadienyl-C1 to C8-alkylene, preferably cyclohexadienyl-2-ethylene group, in particular with x = 0, and optionally
• (iii) with an alkoxysilane of the formula IV, B-Si (R ⁴ ) _y (OR ³ ) _3-y (IV) where B is a saturated hydrocarbon radical, R ^{3 are} each independently of one another a linear, branched and / or cyclic alkyl radical having 1 to 4 C atoms and R ^{4 is} a linear, branched or cyclic alkyl radical having 1 to 15 C atoms and y is 0 or 1, and optionally
• (iv) with a tetraalkoxysilane of the formula V, Si (OR ³ ) ₄ (V), wherein R ³ in formula V are each independently a linear, branched and / or cyclic alkyl radical having 1 to 4 carbon atoms, and
• (V) with a defined amount of water, optionally in the presence of a solvent, in particular an alcohol, are reacted to oligomers. The carboxysilane of formula IIb is used as a catalyst precursor, which can then release under the process conditions, at least one fatty acid of formula II. Particularly preferred combinations are HCl and fatty acid, carboxysilane and HCl, as well as chlorosilane and fatty acid or chlorosilane and carboxysilane.

It is preferred if the reaction of olefinic alkoxysilanes in the process according to the invention in the presence of HCl and / or chlorosilane, in particular in the presence of HCl, and the content of HCl and / or chlorosilane below 0.3 wt .-%, preferably smaller is equal to 0.2% by weight, in particular 0.1 to 1 × 10 ^-4 % by weight, with respect to the composition, preferably below 0.05% by weight, particularly preferably below 0.01% by weight. %, more preferably less than 0.005 wt%, even more preferably less than 0.001 wt%, 0.0005 wt%, 0.00025 wt%, 0.00001 wt%. Thus, according to the invention, the content in the reaction mixture before removal of the hydrolysis alcohol or the free alcohol is detected.

The olefinically functionalized siloxane oligomers or the composition containing them is heated only for the removal by distillation of solvents such as alcohol. The siloxane oligomers as such need not be distilled by the process of the invention.

Advantageously, the hydrolysis alcohol can be removed after the reaction, preferably by distillation. In this case, a certain proportion of the added or formed from the chlorosilane HCl is removed from the composition. A particularly gentle distillation takes place under vacuum. Depending on the procedure, a particularly economical process can be carried out without the addition of a solvent with the catalysts according to the invention. Distillation of the olefinic siloxane oligomer is no longer necessary by the process according to the invention. Preferably, the product directly as a bottom product has a property profile that is suitable for the uses mentioned.

At least partially hydrolyzed and, in particular at least partially co-condensed, the condensable, partially hydrolyzed alkoxysilanes are preferably completely condensed. Particular preference is given to partial hydrolysis and condensation only to the extent desired for the preparation of the oligomers of a preferred degree of oligomerization.

The degree of oligomerization can be controlled via the amount of water added as well as by adding a chain terminating agent, such as methoxytrimethylsilane. In general, it may be preferred to add in the process an alkoxytrialkylsilane, in particular alkoxytrimethylsilane. By this measure, at certain times during the process, a chain termination in the oligomerization be carried out to control the degree of oligomerization and optionally also to influence the degree of branching of the oligomers.

R ² and R ⁴ may independently of one another preferably contain in formula IIa and IV methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl and other alkyl groups known to the person skilled in the art the usual structural isomers.

According to one embodiment, a reaction according to the invention of the olefinically functionalized alkoxysilane of the formula IIa, and optionally of the silanes IV and / or V with a fatty acid of the formula III and / or a carboxysilane of the formula IIb in the presence of a defined amount of water and the 0.2 to 8 times the weight of alcohol in relation to the amount by weight of silanes used. Preferably, only a small amount by weight of alcohol of 0.2 to 0.6, particularly preferably from 0.2 to 0.5 in the inventive method with respect to the silanes of the formula IIa, IV and / or V is used.

The reaction according to the invention of the olefinically functionalized alkoxysilane of the formula IIa, and optionally of the silanes IV and / or V can be carried out in the presence of a defined amount of water, optionally without solvent, according to the invention the reaction in a solvent such as preferably alcohol and in the presence of a defined Amount of water is carried. In this way, the process and the degree of oligomerization of the siloxane oligomers produced can be better controlled. Preferred alcohols correspond to the hydrolysis alcohol which is formed by the at least partial hydrolysis and / or condensation. These include ethanol or methanol. Furthermore, the person skilled in the art knows that it uses anhydrous solvents. Alternatively, it is important to consider the water content of the defined amount of water for non-anhydrous solvents. It will be understood by those skilled in the art that the reaction may also be in the presence of another conventional solvent, with those which are easily and preferably completely distilled off being preferred, but may not be, for example, ethers, ketones, hydrocarbons or esters.

The defined amount of water used is preferably 0.1 mol to 100 mol of water per mole of mol of alkoxysilanes of the formulas II, IIa, IIb, IV and / or V used. Preferably, 0.5 to 10 moles of water are used per mole of alkoxysilanes of the formulas II, IIa, IV and / or V, where 0.6 to 5 mol, preferably 0.7 to 2 mol, more preferably 0.75 to 1.5 Mole, and more preferably 0.8 to 1.2 moles of water are added per mole of alkoxysilane. The water is preferably fully desalted.

The invention also provides a process in which the silane of the formula IIa and the silane of the formula IV in a ratio of 1: 0 to 1: 8 are used, preferably in the ratio of 1: 0 to 1: 2, particularly preferably 1: 1 , and / or the silane of the formula IIa in relation to the silane of the formula V in the ratio 1: 0 to 1: 0.5 are used, preferably in the ratio of 1: 0 to 1: 0.05. The siloxane oligomers prepared in the abovementioned ratios show particularly homogeneous properties in terms of performance. The silane of the formula V is preferably used if a stronger crosslinking in the oligomer or as well as the oligomer with a substrate is desired.

In the process according to the invention, the molar ratio of the (i) total amount of silanes used of general formula IIa, formula IV and / or formula V to (ii) total amount of fatty acid of general formula III and / or olefinically functionalized carboxysilane of formula IIb is preferably 1 : 5 x 10 ^-1 to 1: 1 x 10 ^-5 , especially 1: 5 x 10 ^-2 to 1: 1 x 10 ^-4 , preferably 1: 3 x 10 ^-2 to 1: 1 x 10 ^-4 , especially preferably from 1: 1 × 10 ^-2 to 1: 1 × 10 ^-4, more preferably from 1: 1 × 10 ^-3 to 1: 1 × 10 ^-4, according to the invention 1: 5 × 10 ^-3 to 1: 1 x 10 ^{- 4} , preferred is also 1: 2 × 10 ^-3 bis 1: 1 × 10 ^-4 . Alternatively, particularly preferred are also 1: 3 × 10 ^-3 to 1: 1 × 10 ^-4 , preferably 1: 2 × 10 ^-3 to 1: 3 × 10 ^-4 , particularly preferably 1: 2 × 10 ^-3 to 1: 5 × 10 ^-4 . Consequently, the fatty acid has already proven in small doses as a catalyst or co-catalyst, ie n _silane : n _{fatty acid / carboxysilane} = (n _{formula IIa} + n _{formula IV} + n _{formula V} ) :( n _{formula III} + n _{formula IIb} )

It is further preferred if, in the process according to the invention, the reaction of an (i) olefinically functionalized alkoxysilane of the formula IIa (ii) in the presence of the catalysts a) and b) selected from HCl and chlorosilane and selected from b) a fatty acid of the general formula III and an olefinically functionalized carboxysilane of the formula IIb or a mixture of catalysts from a) and b), wherein the molar ratio of the total amount of the catalysts used HCl and / or chlorosilane to the total amount of the fatty acid of formula III and / or of the carboxysilane of the formula IIb is from 8: 1 to 1: 8, in particular from 4: 1 to 1: 4, preferably 3: 1 to 1: 3, more preferably 2: 1 to 1: 2, better by 1: 1 with a fluctuation range of about 0.5 each. According to the invention, HCl and / or chlorosilane is used in the process in approximately equimolar amounts to the fatty acid and / or to the carboxysilane, ie n _Cl-cat : n _{fatty acid / carboxysilane} = (n _HCl + n _chlorosilane ) :( n _{formula III} + n _{formula IIb} )

The invention also provides a composition which is obtainable by this process by (i) and (ii) in the molar ratio of 8: 1 to 1: 8, in particular from 4: 1 to 1: 4, preferably from 3: 1 to 1: 3, more preferably from 2: 1 to 1: 2, more preferably 1: 1 with a fluctuation range of about 0.5 are used, preferably the chloride is substantially completely removed after the reaction.

According to the invention it is further preferred if the alkoxysilanes of the formulas IIa, IV and / or V in the presence of HCl or chlorosilane, which cleaves HCl under the process conditions, and in the presence of a fatty acid of formula III and / or a carboxysilane of formula IIb at least partially be hydrolyzed and condensed and, preferably, the alcohol, in particular both the hydrolysis alcohol and the optionally added alcohol is removed. The hydrolysis and / or the added alcohol correspond to the free alcohol. Particularly preferably, the content of free alcohol in the overall composition is less than 5 wt .-% to 0.01 wt .-%, in particular less than or equal to 2 wt .-% to 0.01 wt .-%, particularly preferably less than 1 wt. -% to 0.01 wt .-% in particular up to the detection limit. It has surprisingly been found that the functional siloxane oligomers obtained in the composition with the two catalysts according to the invention are significantly more stable to hydrolysis than the siloxane oligomers prepared exclusively with a conventional catalyst, ie with only a stronger acid such as formic acid or HCl. As a result, the siloxane oligomers of the invention prove to be more stable than known oligomers and at the same time their VOC content is reduced compared to the oligomers of the prior art.

The stable content over a period of 3 to 6 months of solvents, in particular free alcohol, in relation to the total composition is preferably less than 2 wt .-%, in particular less than or equal to 1 wt .-%, particularly preferably less than or equal to 0, 4 wt .-%, preferably at less than or equal to 0.3 wt .-% up to the detection limit.

According to a preferred process variant, an olefinically functionalized alkoxysilane of general formula IIa is independently in the process according to the invention, A-Si (R ² ) _x (OR ¹ ) _3-x (IIa) A is a linear, branched or cyclic alkenyl or cycloalkenyl-alkylene-functional group having in each case 2 to 18 C atoms, preferably a vinyl, allyl, butenyl, such as 3-butenyl; Pentenyl, hexenyl, heptenyl, octenyl, cyclohexenyl-C1 to C8-alkylene, particularly preferably cyclohexenyl-2-ethylene and / or cyclohexadienyl-C1 to C8-alkylene, likewise preferably a cyclohexadienyl-2-ethylene Group, in particular x is 0, and R ^{1 is} independently a linear, branched and / or cyclic alkyl radical having 1 to 4 C-atoms, in particular a methyl, ethyl or propyl group, and / or independently of an alkoxysilane of formula IV, B-Si (R ⁴ ) _y (OR ³ ) _3-y (IV) with an unsubstituted hydrocarbon radical B, which is a linear, branched or cyclic alkyl radical having 1 to 18 carbon atoms, in particular a methyl, ethyl, propyl, octyl radical used.

Preferred olefinically functionalized alkoxysilane compounds of the formula IIa or olefinically functionalized carboxysilane compounds of the formula IIb are: compounds of the formula IIa / IIb where x = 0 or 1, particularly preferably x = 0, where A is a linear or branched alkenyl radical having 2 to 18 C atoms, in particular having 1 to 8 C atoms, preferably a vinyl, butenyl, cyclohexenyl-2-ethylene, R ^{2 is} a linear, branched or cyclic alkyl radical having 1 to 8 C-atoms, in particular 1 to 4 C atoms, preferably a methyl, ethyl, particularly preferably n-propyl, iso-propyl and / or octyl radical, R ^{1 is} a linear and / or branched alkyl radical having 1 to 3 C atoms in formula IIa, more preferably correspond to a methyl, ethyl and / or iso-propyl or n-propyl radical, and in formula IIb R ^{1 is} a group -CO-R ⁵ having 4 to 45 carbon atoms, preferably 7 to 27 C atoms, particularly preferably having 7 to 22 C atoms.

Compounds of the formula IIa according to the invention are: vinyltriethoxysilane, vinyltrimethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, butenyltriethoxysilane, butenyltrimethoxysilane, cyclohexenylalkylenetrimethoxysilane, in particular cyclohexenyl-2-ethylenetrimethoxysilane, cyclohexenyl-2-ethylenetriethoxysilane, more preferably 3'-cyclohexenyl-2 ethylene-triethoxysilane and / or 3'-cyclohexenyl-2-ethylene-trimethoxysilane; Cyclohexenedienyl-alklyltriethoxysilane, hexenyltriethoxysilane, hexenyltrimethoxysilane, octenyltriethoxysilane, octenyltrimethoxysilane.

Compounds of formula IIb according to the invention are: Vinyltricarboxysilan as Vinyltrimyristatosilan, Vinyltricaprylatosilan, Vinyltripalmitatosilan Allyltrimyristatosilan, Allyltricaprylatosilan, Allyltripalmitatosilan Butenyltrimyristatosilan, Butenyltricaprylatosilan Butenyltripalmitatosilan cyclohexenyl-alkylene-trimyritatosilan, cyclohexenyl-alkylene-tricaprylatosilan, cyclohexenyl-alkylene-tripalmitatosilan. Particularly preferred are cyclohexenyl-2-ethylene-trimyristatosilane, more preferably 3'-cyclohexenyl-2-ethylene-trimyritatosilane, hexenyltrimyristatosilane, octenyltrimyristatosilane, vinyltrimyristatosilane, allyltrimyristatosilane.

Preferred alkylalkoxysilane compounds of the formula IV are: compounds of the formula VI where y = 0 or 1, where B is a linear or branched alkyl radical having 1 to 18 C atoms, in particular having 1 to 8 C atoms, preferably a methyl, Ethyl, particularly preferably n-propyl, iso-propyl, butyl, pentyl, hexyl, heptyl, octyl, hexadecyl or octadecyl radical, R ^{4 is} a linear, branched or cyclic alkyl radical having 1 to 15 C atoms, in particular having 1 to 8 C atoms, preferably a methyl, ethyl, particularly preferably n-propyl, iso-propyl and / or octyl radical, R ^{3 is} a linear and / or branched alkyl radical having 1 to 3 carbon atoms, particularly preferably a methyl, ethyl and / or iso-propyl or n-propyl radical. B is particularly preferably a methyl, ethyl, propyl, octyl, hexadecyl or octadecyl radical and R ^{4 is} a methyl or ethyl radical and R ^{1 is} a methyl or ethyl radical.

Preferred exemplified compounds of the formula IV are: propyltrimethoxysilane (PTMO), dimethyldimethoxysilane (DMDMO), dimethyldiethoxysilane, methyltriethoxysilane (MTES), propylmethyldimethoxysilane, propylmethyldiethoxysilane, n-octylmethyldimethoxysilane, n-hexylmethyldimethoxysilane, n-hexyl- methyldiethoxysilane, propylmethyldiethoxysilane, propylmethyldiethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, n-hexyltriethoxysilane, cyclohexyltriethoxysilane, n-propyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isobutyltriethoxysilane, hexadecyltriethoxysilane, hexadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, octadecylmethyldiethoxysilane, octadecylmethyldimethoxysilane, hexadecylmethyldimethoxysilane and / or hexadecylmethyldiethoxysilane and mixtures of these silanes.

In the process according to the invention, the following combinations are preferably used, such as: vinyltriethoxysilane with caprylic acid in ethanol and a defined amount of water; Vinyltrimethoxysilane with caprylic acid in methanol and a defined amount of water; Vinyltriethoxysilane and Propyltriethoxysilane with caprylic acid in ethanol and a defined amount of water; Vinyltrimethoxysilane and propyltrimethoxysilane with caprylic acid in methanol and a defined amount of water; Vinyltriethoxysilane, propyltriethoxysilane and tetraethoxysilane with caprylic acid in ethanol and a defined amount of water; Vinyltriethoxysilane and propyltriethoxysilane with caprylic acid in ethanol and a defined amount of water; Vinyltrimethoxysilane and iso-butyltrimethoxysilane with caprylic acid in methanol and a defined amount of water; Vinyltriethoxysilane, isobutyltriethoxysilane and tetraethoxysilane with caprylic acid in ethanol and a defined amount of water, vinyltrimethoxysilane, propyltrimethoxysilane and tetramethoxysilane with caprylic acid in methanol and a defined amount of water, vinyltrimethoxysilane, isobutyltrimethoxysilane and tetramethoxysilane with caprylic acid in methanol and a defined amount of water. Vinyltriethoxysilane with vinyltrimyristatosilane in ethanol and a defined amount of water, vinyltrimethoxysilane with vinyltrimyristatosilane in methanol and a defined amount of water, vinyltriethoxysilane and propyltriethoxysilane with vinyltrimyristatosilane in ethanol and a defined amount of water, vinyltrimethoxysilane and propyltrimethoxysilane with vinyltrimyristatosilane in methanol and a defined amount of water; Vinyltriethoxysilane, propyltriethoxysilane and tetraethoxysilane with vinyltrimyristatosilane in ethanol and a defined amount of water; Vinyltrimethoxysilane, propyltrimethoxysilane and tetramethoxysilane with vinyltrimyristatosilane in methanol and a defined amount of water, vinyltriethoxysilane and isobutyltriethoxysilane with vinyltrimyristatosilane in ethanol and a defined amount of water, vinyltrimethoxysilane and isobutyltrimethoxysilane with vinyltrimyristatosilane in methanol and a defined amount of water; Vinyltriethoxysilane, isobutyltriethoxysilane and tetraethoxysilane with vinyltrimyristatosilane in ethanol and a defined amount of water; Vinyltrimethoxysilane, iso-butyltrimethoxysilane and tetramethoxysilane with Vinyltrimyristatosilan in methanol and a defined amounts of water.

Concretely preferred: vinyltriethoxysilane with caprylic acid in ethanol and a defined amount of water; Vinyltrimethoxysilane with caprylic acid in methanol and a defined amount of water; Vinyltriethoxysilane and propyltriethoxysilane with caprylic acid in ethanol and a defined amount of water; Vinyltrimethoxysilane and propyltrimethoxysilane with caprylic acid in methanol and a defined amount of water, vinyltriethoxysilane with vinyltrimyristatosilane in ethanol and a defined amount of water, vinyltrimethoxysilane with vinyltrimyristatosilane in methanol and a defined amount of water, vinyltriethoxysilane and propyltriethoxysilane with vinyltrimyristatosilane in ethanol and a defined amount of water, vinyltrimethoxysilane and Propyltrimethoxysilane with Vinyltrimyristatosilan in methanol and a defined amount of water, vinyltriethoxysilane and propyltriethoxysilane with caprylic acid in ethanol and a defined amount of water; Vinyltrimethoxysilane and iso-butyltrimethoxysilane with caprylic acid in methanol and a defined amount of water; Vinyltriethoxysilane, isobutyltriethoxysilane and tetraethoxysilane with caprylic acid in ethanol and a defined amount of water, vinyltrimethoxysilane, isobutyltrimethoxysilane and tetramethoxysilane with caprylic acid in methanol and a defined amount of water, vinyltriethoxysilane and isobutyltriethoxysilane with vinyltrimyristatosilane in ethanol and a defined amount of water, vinyltrimethoxysilane and iso-butyltrimethoxysilane with vinyltrimyristatosilane in methanol and a defined amount of water.

In the alternative combinations mentioned above, the propyltriethoxysilane can be replaced in each case with butyl or octyltriethoxysilane, or propyltrimethoxysilane also with butyl or octyltrimethoxysilane.

In the above combinations, it is also preferable that vinyltriethoxysilane is cyclohexenyl-2-ethylene triethoxysilane, especially 3'-cyclohexenyl-2-ethylene triethoxysilane, and vinyltrimethoxysilane is cyclohexenyl-2-ethylene trimethoxysilane, especially 3'-cyclohexenyl-2 to replace ethylene-triethoxysilane. Advantages result from the concrete application and the intelligent choice of the remainders, in order to achieve an exact adjustment of the steric hindrance, the desired chain length and the hydrophobia, to give only some hints.

It is clear to the person skilled in the art that, for economic and economic reasons, the solvent used is an alcohol which also forms as a hydrolysis alcohol. Mixtures of alcohols can also be used in principle. Suitable solvents are, in particular, an alcohol selected from the group consisting of methanol, ethanol, propanol and / or a mixture thereof. However, suitable solvents may also be ethyl acetate, THF, ketones, ethers or hydrocarbons. In all processes, the solvent and the alcohol formed during the reaction are preferably removed by distillation from the reaction mixture.

According to a further alternative, the fatty acid used in the process according to the invention as at least one preferred fatty acid of the formula III is selected from caproic acid, enanthic acid, caprylic acid, pergonic acid, capric acid, lauric acid, myristic acid, palmitic acid, behenic acid, linolenic acid, calendulic acid or stearic acid Stearic acid may only be classified as appropriate. Independently of this, alternatively or additionally, at least one carboxysilane of the formula IIb where A is a linear, branched or cyclic alkenyl or cycloalkenyl-alkylene-functional group having in each case 2 to 18 C atoms can be used. Preferably, A in formula IIb is a group selected from: vinyl, allyl, butenyl, such as 3-butenyl; Pentenyl, hexenyl, heptenyl, octenyl, cyclohexenyl-C1 to C8-alkylene group, particularly preferably cyclohexenyl-2-ethylene and / or cyclohexadienyl-C1 to C8-alkylene, particularly preferably cyclohexadienyl-2-ethylene Particularly preferred is 3'-cyclohexadienyl-2-ethylene, wherein in formula IIb is preferably x = 0 and R ¹ is R ⁵ -CO-, with R ^{5 is} independently a monovalent radical -C _n H _{2n + 1} , is, with n = independently a number of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 19, 20, 21, 22 or 23, expediently also n = 17, further preferred radicals are C ₁₇ H ₃₁ - from linoleic acid, C ₁₇ H ₂₉ - from alpha-linolenic acid, C ₁₇ H ₂₉ - from gamma-linolenic acid or calendulic acid, the particularly good properties with respect to the melt flow in a monosil or Sioplasverfahren with thermoplastic base polymers or in the compounding with elastomers show. Depending on the process procedure and the desired properties of the olefinically functionalized siloxane oligomers prepared, it may be preferable to use mixed carboxysilanes of the formula III in the process with regard to the carboxy function. This measure allows a precise control of the product properties of the elastomers compounded with the siloxanes according to the invention and / or thermoplastics, for example with regard to the melt flow properties.

Furthermore, it is preferred that a chlorosilane which corresponds to the general formula VI is used in the process according to the invention, D _n SiCl ₄ -n (VI), in which the group D is a saturated or unsaturated hydrocarbon radical and n is 0 or 1, in particular the group D corresponds independently of a group A or a group B as defined above.

Particularly preferably, the method comprises a step of removing the added or formed from the chlorosilane HCl until the chloride content of 300 ppm by weight and the detection limit is, as well as 200 ppm by weight and the detection limit or of 200 wt. ppm to 0 ppm by weight. Preferably, a chloride content of less than 100 ppm by weight, more preferably less than 50 ppm by weight, more preferably set equal to less than 40 ppm by weight. Alternatively, the following contents are increasingly preferred: less than or equal to 30 ppm by weight, 25 ppm by weight, 20 ppm by weight and less than or equal to 10 ppm by weight, 9, 8, 7, 6, 5, 4, 3, 2 and less than 1 ppm by weight. The chloride content can be lowered, for example, by passing nitrogen through or by adding hexamethyldisilazane.

In addition or as an alternative to one of the abovementioned features, the process may also employ as processing aid at least one silicone oil, such as polydimethylsiloxane, paraffin, paraffin oil or a mixture containing one of these processing aids. A particularly preferred processing aid is polydimethylsiloxane, preferably with a kinematic viscosity of 150 to 400 mm ² / s, in particular from 200 to 400 mm ² / s, preferably by about 350 mm ² / s.

The alcohol already present and / or formed during the reaction is essentially, preferably completely, removed from the reaction mixture in all process variants according to the invention. The distillative removal of the alcohol is preferably carried out under reduced pressure. The distillative removal of the alcohol is preferably carried out until a temperature is reached in the top of the column, which corresponds to the boiling point of the siloxane oligomers. As a rule, the resulting composition according to the invention is then essentially solvent-free, in particular alcohol-free.

• 1) Vorlegen des olefinisch funktionalisierten Alkoxysilans II, dies kann das Alkoxysilan der Formel IIa und gegebenenfalls der Formel IIb sein, gegebenenfalls wird auch ein Verarbeitungshilfsmittel, beispielsweise Silikonöl vorgelegt,
• 2) Herstellen einer Mischung enthaltend mindestens eines der Silane der Formel IIa, IV und/oder V und a) HCl und/oder Chlorsilan sowie gegebenenfalls einen Alkohol in einer Gewichtsmenge von 0,2- bis 8-fach in Bezug auf Silane der Formel IIa, IV und/oder V, insbesondere Methanol oder Ethanol, je nach eingesetztem Alkoxysilan, und eine definierte Menge Wasser. Wurde kein Carboxysilan der Formel IIb vorgelegt, dann wird eine Fettsäure der Formel III der Mischung zugesetzt, andernfalls kann die Fettsäure optional zugesetzt werden. Alternativ kann eine Mischung der Katalysatoren a) HCl und/oder Chlorsilan und b) Fettsäure der Formel III und/oder das Silan der Formel IIb der Mischung in Schritt 2) zugesetzt werden,
• 3) Die Vorlage wird erwärmt, insbesondere auf 20 bis 55 °C, bevorzugt auf 30 bis 40 °C oder auf etwa 35 °C. Die Mischung aus Schritt 2 wird langsam zugetropft. Nach der Zugabe der Mischung wird die Temperatur der gebildeten Reaktionsmischung weiter erhöht, insbesondere wird auf Rückflusstemperatur des Alkohols eingestellt. Beispielsweise durch Erwärmen der Reaktionsmischung auf eine Temperatur von 40 bis 100 °C, bevorzugt 50 bis 95 °C, besonders bevorzugt auf um 55 bis 90 °C, erfindungsgemäß auf etwa Siedetemperatur des Alkohols.

The invention also provides the following process for the preparation of the composition, as well as a composition obtainable by this process, in particular with the following individual steps,

• 1) presentation of the olefinically functionalized alkoxysilane II, this may be the alkoxysilane of the formula IIa and optionally of the formula IIb, optionally also a processing aid, for example silicone oil is initially charged,
• 2) Preparation of a mixture comprising at least one of the silanes of the formula IIa, IV and / or V and a) HCl and / or chlorosilane and optionally an alcohol in an amount by weight of 0.2 to 8 times with respect to silanes of the formula IIa , IV and / or V, in particular methanol or ethanol, depending on the alkoxysilane used, and a defined amount of water. If no carboxysilane of the formula IIb has been introduced, then a fatty acid of the formula III is added to the mixture, otherwise the fatty acid can optionally be added. Alternatively, a mixture of the catalysts a) HCl and / or chlorosilane and b) fatty acid of the formula III and / or the silane of the formula IIb can be added to the mixture in step 2),
• 3) The original is heated, in particular to 20 to 55 ° C, preferably to 30 to 40 ° C or to about 35 ° C. The mixture from step 2 is slowly added dropwise. After the addition of the mixture, the temperature of the reaction mixture formed is further increased, in particular it is adjusted to the reflux temperature of the alcohol. For example, by heating the reaction mixture to a temperature of 40 to 100 ° C, preferably 50 to 95 ° C, more preferably to around 55 to 90 ° C, according to the invention to about boiling point of the alcohol.

After completion of the reaction, the alcohol and volatile compounds such as HCl are separated. Preferably, several hours, for example about 2 to 10 hours, preferably 3 to 5 hours, more preferably heated for 3.5 hours under reflux and then distilled off the alcohol comprising the hydrolysis alcohol and the alcohol used and optionally water, preferably under vacuum and at elevated temperature, preferably until the reaction mixture or the composition obtained is substantially solvent-free, in particular alcohol-free.

It will be understood by those skilled in the art that the functionalized siloxane oligomers so prepared may be diluted with a diluent or may be added or compounded with a polymer such as a thermoplastic base polymer such as PE, PP or an elastomer such as EVA. Other thermoplastic base polymers and elastomers are mentioned below by way of example, the person skilled in the art knows that generally all thermoplastic base polymers or polymers or elastomers are suitable. The skilled worker is familiar with conventional diluents for alkoxysiloxanes, for example, alcohols, ethers, ketones, hydrocarbons, or more preferably also mixtures thereof. The compositions of the functional siloxane oligomers can thus be prepared depending on the desired application as a concentrate or else as a dilute composition of 99.9 to 0.001 wt .-% and all intermediate values, of functional siloxane oligomers in the overall composition. Preferred dilutions contain from 10 to 90% by weight of functional siloxane oligomers, more preferably from 20 to 80% by weight, more preferably from 30 to 70% by weight.

In particular, acrylonitrile-butadiene-styrene (ABS), polyamides (PA), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene (PE), such as LDPE, LLD-PE, m-PE, polypropylene are used as thermoplastic base polymers in the context of the invention (PP), polystyrene (PS), polyvinyl chloride (PVC), chloroprene and the ethylene-based polymers ethylene-vinyl acetate copolymers (EVA), EPDM or EPM and / or celluloid or silane-co-polymerized, for example, from unsaturated functional Monomers including silanes, such as VTMO or VTEO, and monomers such as ethylene and other olefins, polymers understood and as monomers and / or prepolymers, d. H. Precursors of these base polymers, such as ethylene, propylene. Other preferred elastomers may be selected from ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), natural rubber (NR), acrylate copolymer rubber (ACM), acrylonitrile rubber. Butadiene rubber (NBR) and / or polybutadiene rubber (BR).

The invention also relates to compositions comprising olefinically functionalized siloxane oligomers and to a fatty acid of the general formula III obtainable by a process according to any one of claims 10 to 21, in particular the invention provides a composition obtainable from the reaction of an olefinic alkoxysilane of the formula IIa with a fatty acid of Formula III and / or also from the reaction with a carboxysilane of the formula IIb in the presence of a defined amount of water and preferably a solvent such as an alcohol. Suitable solvents are generally all solvents known to those skilled in the art. Alcohols corresponding to the hydrolysis alcohol are economically preferred.

The invention also provides the use of the composition according to the invention as an adhesive, crosslinking agent; in particular by graft polymerization and / or hydrolytic condensation in a conventional manner; for the preparation of olefinically functionalized siloxane oligomers grafted polymers, prepolymers and / or of mineral-filled polymers (compounds), in particular in the production of mineral-filled thermoplastics or elastomers or their prepolymers, for grafting or polymerization of thermoplastic polyolefins, as water scavengers for silicone sealants, in crosslinkable polymers for the production of cables, for the preparation of crosslinkable polymers, as drying agents, as oil phase in an emulsion and / or together with organosilanes or organopolysiloxanes, for filler modification (filler coating), resin modification (additive), surface modification (functionalization, hydrophobing) as an ingredient in coating systems (in particular sol-gel systems or hybrid systems), for modifying cathodes and anode materials in batteries, as an electrolyte fluid, as an additive in electrolyte fluids, for the modification of Fibers, in particular glass fibers and natural fibers, and for modifying textiles, for modifying fillers for the artificial stone industry, as building protection or constituents in building preservatives, as an additive for mineral hardening compositions, for the modification of wood, wood fibers and cellulose. For the joint use of the composition with organosilanes or organosiloxanes according to the invention is fully based on the disclosure of EP 1 205 481 B1 In particular, the disclosure of paragraph [0039] and the list of organosilanes and organosiloxanes disclosed therein.

The invention will be explained in more detail with reference to the following examples without limiting them to these embodiments.

Examples:

Determination of molecular weight:

The determination of molecular weights and the molecular weight distribution can be carried out by means of gel permeation chromatography (GPC). The GPC analysis method is used inter alia in "Modern Size-Exclusion Liquid Chromatography", Andre Striegel et al., Publisher Wiley & Sons, 2nd ed. 2009 , described in detail. For example, divinyltetramethoxydisiloxane can be used as the standard for calibration of the siloxane analysis method. "

und
Zahlenmittel des Molekulargewichts (Mn)

jeweils mit:
n_i = Stoffmenge [Masse] des i-mers
M_i = Molmasse des i-mersWeight average molecular weight (Mw)

and
Number average molecular weight (Mn)

each with:
n _i = amount of substance [mass] of the i-mers
M _i = molar mass of the i-mers

Details on the definition of weight average and number average, which are known per se to the person skilled in the art, but the reader can, inter alia, the Internet under
http://de.wikipedia.org/wiki/Molmassenverteilung
or a standard mathematical work.

Furthermore, the polydispersity (D) is defined as the quotient of Mw / Mn.

Determination of the total chloride value:

In a calorimeter bomb, the silane is digested with oxygen and then hydrolyzed with acetic acid, and hydrofluoric acid. In the resulting solution, the chloride content is determined by titration with silver nitrate.

Determination of hydrolyzable chloride:

After hydrolysis with acetic acid, the chloride content is determined by titration with silver nitrate.

Determination of the SiO ₂ content: crucible method:

The SiO ₂ content is determined by acid digestion with concentrated sulfuric acid and subsequent evaporation by fluorination.

GC analysis:

Standard GC test method in which the monomer content is determined by a suitable calibration and internal standard if necessary.

²⁹ Si NMR spectrometry:

Furthermore, well-known ²⁹ Si NMR spectrometry can also be used to determine the monomer content and of M, D and T structures.

Determination of the dynamic viscosity:

The determination of the dynamic viscosity was according to DIN 53015 carried out.

1.1. syntheses

fuel type description silane Vinyltrimethoxysilane (VTMO) Vinyltriethoxysilane (VTEO) Propyltriethoxysilane (PTEO) methoxytrimethylsilane ethoxytrimethylsilane carboxysilane Vinyltrimyristatosilan alcohol methanol ethanol acid Hydrochloric acid 37% fatty acid caprylic silicone oil AK 350 (Wacker) stabilizer Irganox 1010 peroxide dicumylperoxide Table 1: Overview of the raw materials used.

1.1.1. Siloxane oligomer of vinyltrimethoxysilane

The following solutions were used: description Solution 1 135 Solution 2 136 Solution 3 137 methanol 99.763g (99.76%) 99.800g (99.80%) - VE water - - 98,924g (98.92%) caprylic 0.240g (0.24%) 0.120g (0.12%) - Hydrochloric acid 37% - 0.083g (0.08%) 1.085g (1.08%) Table 2: Weighed Solutions Siloxane oligomers of vinyltrimethoxysilane. description 138 139 140 141 142 153 VTMO 114,766g 114,807g 111,951g 114,344g 112,980g 114,760g methanol - - 71,93g 73,44g 72,59g - VE water 11,35g 11,32g - 11,30g - 11,34g AK 350 - - 5,007g - - - Vinyltrimyristatosilan - - - 0,920g - - methoxytrimethylsilane - - - - 3,21g - Solution 1 73,89g - - - - 73.89 Solution 2 - 73,89g - - - - Solution 3 - - 11,12g - 11,21g - Table 3: Sample siloxane oligomers of vinyltrimethoxysilane.

The vinyltrimethoxysilane is initially charged in the reaction flask. The additives "AK 350" and "Vinyltrimyristatosilan" are also presented in the corresponding experiments in the flask. All other required ingredients are mixed in the dropping funnel. They can also be added separately. At a temperature of about 25 ° C, the contents of the dropping funnel is slowly added dropwise (within about 25 minutes) to the silane or the silane mixture. Following the addition, the oil bath is adjusted to 85 ° C, thus heating the methanol used as solvent to boiling. After a reaction time of around 3 hours, the methanol is distilled off at 85 ° C oil bath temperature and a reduced pressure of 150-180 mbar. The mixture is then stirred for a further hour at 85 ° C oil bath temperature and a pressure of <1 mbar. The olefinically functionalized siloxane is the bottom product.

1.1.2. Siloxane oligomer of vinyltriethoxysilane

The following solutions were used: description Solution 4 127 Solution 5 128 Solution 6 129 ethanol 399.28g (99.82%) 419.36g (99.85%) - VE water - - 100.015g (99.28%) caprylic 0.721g (0.18%) 0.383g (0.09%) - Hydrochloric acid 37% - 0,261g (0.06%) 0.73g (0.72%) Table 4: Weights of the solutions-siloxane oligomers of vinyltriethoxysilane. description 130 131 132 133 VTEO 128,760g 128,756g 125,522g 128,420g ethanol - - 59,79g 61,17g VE water 9,877g 9,864g - 9,882g AK 350 - - 5,002g - Vinyltrimyristatosilan - - - 0,563g ethoxytrimethylsilane - - - - Solution 4 61,426g - - - Solution 5 - 61,410g - - Solution 6 - - 9,67g - Table 5a: Weighed siloxane oligomers of vinyltriethoxysilane. description 134 152 154 Vinyltriethoxysilane (VTEO) 126,715g 128,708g 128,424g ethanol 60,36g - 61,17g VE water - 9,87g 9,85g AK 350 - - - Vinyltrimyristatosilan - - 0,564g ethoxytrimethylsilane 3,17g - - description 134 152 154 Solution 4 - 63,42g - Solution 5 - - - Solution 6 9,76g - - Table 5b: Weighed siloxane oligomers of vinyltriethoxysilane.

To prepare the siloxane oligomers, the vinyltriethoxysilane (VTEO) is initially introduced into the reaction flask. The additives "AK 350" and "Vinyltrimyristatosilan" are also presented in the corresponding experiment in the flask. All other required ingredients are mixed in the dropping funnel. They can also be added separately. At a temperature of about 35 ° C, the contents of the dropping funnel is slowly added dropwise (within about 15 minutes) to the silane or the silane mixture. Following on the Addition, the oil bath is adjusted to 100 ° C and thus the ethanol used as a solvent is heated to boiling. After a reaction time of 3.5 hours, the ethanol is distilled off at 100 ° C oil bath temperature and a reduced pressure of 150-180 mbar. Finally, stirring is continued for a further hour at 100 ° C. oil bath temperature and a pressure of <1 mbar. The olefinically functionalized siloxane oligomer is the bottom product.

1.1.3. Siloxane co-oligomer of vinyltriethoxysilane and propyltriethoxysilane

The following solutions were used: description Solution 7 143 Solution 8 144 Solution 9 145 Solution 10 146 ethanol 79.867g (99.84%) 79.91 g (99.88%) - - VE water - - 89.370g (99.30%) - caprylic 0,127g (0.16%) 0.058g (0.07%) - - description Solution 7 143 Solution 8 144 Solution 9 145 Solution 10 146 Hydrochloric acid 37% - 0.040g (0.05%) 0,628g (0,70g) - Propyltriethoxysilane (PTEO) - - - 394.13g (50.77%) Vinyltriethoxysilane (VTEO) - - - 382.15g (49.23%) Table 6: Weights of the solutions-siloxane oligomers (co-oligomers) from vinyltriethoxysilane and propyltriethoxysilane. description 147 148 149 150 151 ethanol - - 56,88g 58,21g 57,43g VE water 9,16g 9,13g - 9,14g - AK 350 - - 5,000g - - Vinyltrimyristatosilan - - - 0,491g - ethoxytrimethylsilane - - - - 3,12g Solution 7 58,43g - - - - Solution 8 - 58,38g - - - Solution 9 - - 8,96g - 9,04g Solution 10 132,421g 132,481g 129,160g 132,160g 130,403g Table 7: Weights of the co-oligomer syntheses.

For the preparation of co-oligomers vinyltriethoxysilane (VTEO) together with propyltriethoxysilane (PTEO) is placed in a reaction flask. The additives "AK 350" and "Vinyltrimyristatosilan" are also presented in the corresponding experiment in the flask. All other required ingredients are mixed in the dropping funnel. At a temperature of about 35 ° C, the contents of the dropping funnel are slowly added dropwise (within about 15 minutes) to the silane. Following the addition, the oil bath is adjusted to 100 ° C and thus the ethanol used as solvent heated to boiling. After a reaction time of about 3.5 hours, the ethanol is distilled off at 100 ° C oil bath temperature and a reduced pressure of 150-180 mbar. Finally, a further hour at 100 ° C oil bath temperature and a pressure of <1 mbar is stirred. The olefinically functionalized siloxane oligomer is the bottom product.

1.1.4. Siloxane oligomer of vinyltrimethoxysilane

The amount of caprylic acid is adjusted stoichiometrically to the amount of hydrochloric acid customary in the art.

Execution:

In a 2-l four-necked apparatus with water cooling and magnetic stirrer VTMO be weighed. Subsequently, a mixture of methanol, bi-dist-water and hydrochloric acid (37%) at 25 ° C and ambient pressure is added. There is an exothermic reaction. Should the temperature rise above 45 ° C, the dosage will be interrupted. The total reaction time is 5 working days starting with the metering of the H ₂ O / HCl / methanol mixture. After the reaction time, the alcohol is distilled at up to 90 ° C and 100 mbar on a rotary evaporator. After reaching the 100 mbar this is held for 15 minutes before the system is relieved. The resulting bottoms are vinyltrimethoxysiloxane oligomer. material supplier weighing VTMO Evonik Degussa GmbH 286,4g methanol ROTH 187,0g caprylic Merck 0.25 g Water Bi-Dest Evonik Degussa GmbH 28,35g Hydrochloric acid (37%) MERCK 0.15 g Table 8: Raw materials for production 115

The evaluation of the NMR analyzes shows that oligomerization took place on product 115. The structures formed, in contrast to the previous methods, i. The prior art synthesized VTMO siloxane oligomer has about 100% more T-structures. GPC analysis also showed changes compared to the prior art synthesized VTMO siloxane oligomer. The reaction time was five working days.

1.2. analytics

1.2.1. GC analysis

Experiment no. used catalyst components and optionally additive Proportions in the siloxane oligomer composition [wt%] VTMO MeOH EtOH VTEO PTEO 139 Caprylic acid + HCl <0.1 0.1 - - - 140 AK 350 (2.5% by weight) <0.1 <0.1 - - - 141 Vinyltrimyristatosilan <0.1 4.2 - - - 142 methoxytrimethylsilane <0.1 0.2 - - - 153 caprylic 1.2 10.3 - - - 131 Caprylic acid + HCl - - 0.1 <0.1 - 132 AK 350 (2.5% by weight) - - 0.1 0.1 - 133 Vinyltrimyristatosilan - - 8.2 0.3 - 134 ethoxytrimethylsilane - - 0.2 <0.1 - 152 caprylic - - 0.3 92.9 - 154 Vinyltrimyristatosilan - - 4.0 43.9 - 147 caprylic - - 0.1 46 52 148 Caprylic acid + HCl - - 0.2 0.2 4.8 149 AK 350 (2.5% by weight) - - 0.1 0.1 2.7 150 Vinyltrimyristatosilan - - 2.9 15.2 33.4 151 ethoxytrimethylsilane - 0.1 0.1 3.7 Table 9: Results of the GC evaluations.

1.3.2. GPC analysis

Experiment no. used catalyst components and optionally additive Mn [g / mol] Mw [g / mol] Poly dispersity 139 Caprylic acid + HCl 4,5150E + 02 5,5107E + 02 1.2205 140 AK 350 (2.5% by weight) 5,2423E + 02 1,0723E + 03 2.0455 141 Vinyltrimyristatosilan 4,0094E + 02 5,4147E + 02 1.3505 142 methoxytrimethylsilane 4,5755E + 02 5,3219E + 02 1.1631 153 caprylic 6,4096E + 02 9,4887E + 02 1.4804 131 Caprylic acid + HCl 4,5608E + 02 1,0679E + 03 2.3415 132 AK 350 (2.5% by weight) 4,2763E + 02 6,3281E + 02 1.4798 133 Vinyltrimyristatosilan 7,1096E + 02 1,5434E + 03 2.1709 134 ethoxytrimethylsilane 4,3111E + 02 7,1118E + 02 1.6496 152 caprylic 3,5322E + 02 1,8590E + 03 5.2630 154 Vinyltrimyristatosilan 3,1931E + 02 5,0283E + 02 1.5747 147 caprylic 1,9235E + 02 3,2093E + 02 1.6685 148 Caprylic acid + HCl 4,0356E + 02 6,3805E + 02 1.5811 149 AK 350 (2.5% by weight) 4,1769E + 02 6,9357E + 02 1.6605 150 Vinyltrimyristatosilan 2,7636E + 02 3,9962E + 02 1.4460 151 ethoxytrimethylsilane 3,9759E + 02 4,8267E + 02 1.2140 Table 10: Results of the GPC evaluations.

1.3.3. NMR analysis

Based on the GC and GPC results, a structural analysis by NMR was additionally performed on the test products listed below: Vers. No. ¹ H and ¹³ C NMR ²⁹ Si NMR analyzes - proportions in the composition [mol%] silane monomer M-structure D structure T structure Other 139 1.3 moles of SiOMe / mol vinyl, no free MeOH VTMO - 40.9% Si 50.7% Si 8.4% Si 140 1.2 mol SiOMe / mol vinyl, No free MeOH, signal for AK 350 VTMO - 34.0% Si 51.9% Si 10.6% Si 3.5% Si AK 350 141 1.2mol SiOMe // mol vinyl, little free MeOH VTMO - 50.7% Si 39.6% Si 9.7% Si 142 1.3 mol of SiOMe / mol vinyl, no free MeOH, 0.017 mol of methoxytrimethylsilane / mol of VTMO VTMO - 40.3% Si 48.5% Si 9.4% Si 1.8% Si methoxy-trimethylsilane 131 1.5 moles of SiOEt / mole vinyl, a little free EtOH, indicating silicone compound. VTEO - 58.0% Si 38.8% Si 2.5% Si 0.7% Si probably silicone oil 132 1.5 mol SiOEt / mol vinyl, little free tOH, signal for AK 350 VTEO - 55.2% Si 33.8% Si 2.4% Si 8.6% Si AK 350 134 1.5 mol SiOEt / mol vinyl, a little free EtOH, 0.03 mol ethoxytrimethylsilane / mol VTEO VTEO - 60.1% Si 34.0% Si 2.5% Si 3.2% Si ethoxytri methyl silane, 0.2% Si silicone oil 148 1.0 moles of propylsilyl + 3.1 moles SiOEt / mole vinylsilyl, slightly free EtOH PTEO: 3.2% Si 36.7% Si 9.9% Si - Cocondensate: PTEO: 49.8% VTEO: 50.2% VTEO: - 35.1% Si 14.3% Si 0.8% Si 149 1.0 moles of propylsilyl + 3.1 moles SiOEt / mole vinylsilyl, slightly free EtOH PTEO: 1.6% Si 33.0% Si 10.0% Si - Co-condensate PTEO: 49.4% VTEO: 50.6% VTEO - 31.1% Si 13.6% Si 0.9% Si 151 1.0 moles of propylsilyl + 3.2 moles of SiOEt / mole of vinylsilyl, low in free EtOH, 0.08 moles of ethoxytrimethylsilane PTEO: 2.3% Si 34.7% Si 11.6% Si - Co-condensate PTEO: 50.1% VTEO: 49.9% 2.7% Si Ethoxytri methyl silane, 0.3% Si Silicone oil VTEO - 34.6% Si 13.2% Si 0.6% Si

1.3.4. Evaluation 115

VTMO siloxane oligomer: water 115 Total chloride: mg / kg 40 Hydrol. Chloride: mg / kg 10 SiO 2:% (mass) 55.1 Free methanol:% (mass) 0.1 VTMO:% (mass) 2.9 VTMO siloxane oligomer: water 115 mg Pt-Co / l <5 Density: g / cm3 1,106 Viscosity: mPas 8.2 GPC: Mn g / mol 593.37 GPC: Mw g / mol 745.04 D 1.2556 Table 15: Wet chemical analysis results Experiment no. ¹ H and ¹³ C NMR ²⁹ Si NMR analyzes - proportions in the composition [mol%] monomer M-structure D structure T structure 115 1.3 moles of SiOMe 0.1 moles MeOH 2.10 (VTMO) 37.50 47,20 13,20 Table 16: NMR analysis results

2. Comparative experiments

Comparative Example 1

V078 - Example 1 off EP 0 518 057 B1 - Preparation of a cocondensate of vinyltrimethoxysilane and methyltrimethoxysilane having a molar ratio of vinyl: methoxy groups of approx. 1: 3

Execution:

397.6 g of vinyltrimethoxysilane (VTMO) and 244.6 g of methyltrimethoxysilane were initially charged at 20 ° C. in a 2 l four-necked apparatus with a water cooler and magnetic stirrer. To the mixture was added a solution of 49.9 g of distilled water containing 2400 ppm of hydrogen chloride in 332.8 g of methanol. to a 500 ml dropping funnel was used. After a total of 16 hours, the entire methanol was HCl distilled off at about 300 mbar. Thereafter, the resulting oligomer mixture was distilled to a pressure of about 1 mbar and a boiling interval up to 113 ° C. Thus, 170 g of clear product were recovered. material supplier weighing VTMO Evonik Degussa GmbH 397.6 g MTMS Evonik Degussa GmbH 244.6 g Hydrochloric acid 2400ppm Merck (HCl 37%) water Bidest 49.9 g methanol ROTH 332.8 g Table 17: Raw materials V078

Comparative Example 2:

V081 - Example 6 off EP 0 518 057 B1 - Preparation of a condensate of vinyltrimethoxysilane having a molar ratio of vinyl: methoxy groups of about 1: 1.75

Execution:

693.83 g of VTMO were initially charged at 20.degree. C. in a 2 l four-necked apparatus with water cooler and magnetic stirrer. To the mixture was added a solution of 52.82 g of distilled water containing 1100 ppm of hydrogen chloride in 351.53 g of methanol. Served with a 500ml dropping funnel. The temperature increased within 26 minutes to about 36 ° C. After a total of 13 hours, the entire methanol was hydrochloric acid distilled off within 2-3 hours at about 300 mbar. Thereafter, the oligomer mixture thus obtained was distilled to a pressure of about 1 mbar and a boiling interval to 100 ° C. Thus, 240 g of clear product were recovered. material supplier weighing VTMO Evonik Degussa GmbH 693.7 g methanol 351.5 g Hydrochloric acid 1100ppm Merck (HCl 37%) water Bidest 52.8 g Table 18: Raw materials V081

The analytical results of the comparative experiments are summarized in Tables 19 to 22:
The determination of the chloride content (total chloride) can be carried out by the methods known to the person skilled in the art, such as the potentiometric determination with AgNO ₃ . The hydrolyzable chloride is titrated potentiographically with AgNO ₃ . Experiment no. V078 total Chloride hydrolyzable chloride SiO ₂ VTMO color number [Mg / kg] [Mg / kg] (Dimensions) [%] (Dimensions) [%] [mg Pt-Co / l] Distillate (see Example 1 in EP0518057B1 ) 230 16 52.4 <0.1 <5 Table 19: Analysis results for V078 (Comparative Example 1) Experiment no. V081 total Chloride Hydrolyzable. chloride SiO2 VTMO color number [Mg / kg] [Mg / kg] (Dimensions) [%] (Dimensions) [%] [mg Pt-Co / l] Distillate (see Example 6 in EP0518057B1 ) 50 <3 48.6 1.7 <5 Table 20: Analysis results of V081 (Comparative Example 2) Test-number Mn [g / mol] Mw [g / mol] D = Mw / Mn V078 275.13 291.11 1.0581 V081 254.06 269.90 1.0624 Table 21: Evaluation of the GPC analysis results Comparative experiment no. Proportions in the siloxane oligomer compositions M structure [mol%] D structure [mol%] T structure [mol%] Silane monomer [mol%] 078 52.1 (VS) 9.1 (VS) - (VS) 0.9 (VTMO) 29.3 (MS) 8.6 (MS) - (MS) - (MTMS) 081 91.8 (VS) 6.8 (VS) - (VS) 1.2 (VTMO) Table 22: Results from the ²⁹ Si NMR analyzes on the products from the comparative experiments V078 and V081 [VS = vinylsilyl, MS = methylsilyl]

3.1. Application engineering investigations

3.1.1 Input materials used

fuel type description polymer EVA (ethylene vinyl acetate) filler ATH (aluminum trihydroxide) stabilizer Irganox 1010 peroxide Dicumyl peroxide (DCUP) Table 23: Overview of the feed materials used for the kneading study.

To simplify the weighing of the peroxide, the following solutions were used: Experiment no. Weighing DCUP Weighing silane Silane batch comment 172 0,184g 9,817g 139 VTMO siloxane oligomer, cat .: caprylic acid + HCl 173 0,184g 9,818g 140 VTMO siloxane oligomer, additive: AK350 (lower silane content) 174 0,184g 10,356g 140 VTMO siloxane oligomer, additive: AK350 175 0,184g 9,822g 142 VTMO siloxane oligomer, additive: methoxytrimethylsilane 177 0,184g 9,821g 131 VTEO siloxane oligomer, cat .: caprylic acid + HCl 178 0,184g 9,823g 132 VTEO siloxane oligomer, additive: AK350 (lower silane content) 179 0,184g 10,457g 132 VTEO siloxane oligomer, additive: AK350 180 0,184g 9,818g 134 VTEO siloxane oligomer, additive: ethoxytrimethylsilane 182 0,184g 9,826g 148 VTEO / PTEO siloxane co-oligomer, cat .: caprylic acid + HCl 183 0,184g 9,821g 149 VTEO / PTEO siloxane co-oligomer, additive: AK350 (lower silane content) 184 0,184g 10,339g 149 VTEO / PTEO siloxane co-oligomer, additive: AK350 185 0,184g 9,817g 151 VTEO / PTEO siloxane co-oligomer, additive: ethoxytrimethylsilane

3.1.2 kneading experiments

The following kneading was processed with a temp. Profile of "3 min at 140 ° C, from 140 ° C to 170 ° C in 2 min, 5 min at 170 ° C" at a speed of 30 U / min in HAAKE kneader , From each batch, two plates were then pressed each at 165 ° C and a load pressure of 20t. Experiment no. Weighing EVA Weighing ATH Weighing Irganox 1010 Weighed silane DCUP solution. Silane DCUP solution. Batch Silane designation 19, 038g 30,461g 0,190g VTMO siloxane oligomer 156 0.310 g 172 157 0.310 g 173 158 0,327g 174 159 0.310 g 175 19,038g 30,461g 0,190g VTEO siloxane oligomer 161 0.310 g 177 162 0.310 g 178 163 0,327g 179 164 0.310 g 180 167 19,038g 30,461g 0,190g 0.310 g 183 VTEO / PTEO siloxane co-oligomer 168 0,327g 184 169 0.310 g 185 170 19,038g 30,461g 0,190g - - blank value

3.2. Application technical tests

Of the samples prepared, after storage at 23 ° C and 50% r.H. (relative humidity) in the climatic chamber, test specimens for tensile tests and determination of the water absorption capacity or determination of the melt index.

3.2.1 Determination of water absorption capacity

The water absorption capacity was determined after a period of 24 h and 7 d by a triple determination by storing them for the said period in a water bath at 70 ° C.

Tabelle 26: Ergebnisse Wasseraufnahmefähigkeits-Bestimmung.

Table 26: Results of water absorbency determination.

The 1 graphically shows the results of the water absorption test. Graphical representation of the results of the water absorption test (storage for 7 days at 70 ° C in a water bath).

3.2.2 Determination of melt flow rate (MFR)

The processing and evaluation took place in accordance with the DIN ISO 1133 (Method B), the content of which is fully incorporated by reference and made the subject of the application. Testing device: Zwick flow tester 4106. The melt index (MFR) or volume flow index determination (MVR) is carried out under defined shear load and defined temperature (T _PT ) and defined load (m _nom ) of a plastic melt through a standard nozzle. The way change of the stamp is determined over time and according to the formulas MVR and MRF known to the person skilled in the art.

Tabelle 27: Ergebnisse der Schmelzindex-Bestimmung. In the kneading experiments 3.1.2, ~ 7 g of the individual samples were cut into small pieces and the melt index ("MFR") was determined at a temperature of 160 ° C. and a load of 21.6 kg.

Table 27: Results of Melt Index Determination.

The 2 additionally graphically shows the results of the melt index determination (vinyl-functional siloxane oligomers,> 16 hours at 23 ° C. and 50% rH stored, MFR measured at 21.6 kg and 160 ° C.).

3.2.3. Determination of tensile properties

The determination of the characteristic sheep took place on the basis of the DIN EN ISO 527-1, 527-2, 527-3 , the contents of which are referred to in their entirety and made the content of the application. For this purpose, a sample rod of defined geometry is clamped in the tensile testing machine and loaded uniaxially until breakage (uniaxial elongation at a defined strain rate). The change in stress on the sample rod is recorded by way of the elongation of the specimen and the tensile strength and the elongation at break. Tester Zwick Universal Tester 4115.

By means of the specimens or tensile bars ("bones") prepared under "3.1.2 Preparation", the tensile properties (elongation at break and tensile strength) of the samples after ~ 40 days of storage in a climate chamber at 23 ° C and 50% RH (relative humidity) , with a test speed of 200mm / min and a pre-load of 0.2 MPa, determined by a five-fold determination. Experiment no. means median Tensile strength [MPa] Elongation at break [%] Tensile strength [MPa] Elongation at break [%] 156 12.1 132 12.2 130 157 11.2 118 11.1 114 158 10.0 69 10.0 83 159 12.1 98 12.1 97 161 10.7 103 10.8 99 162 9.8 68 9.7 65 163 10.1 84 10.2 95 164 9.8 71 9.9 69 167 8.8 59 8.9 55 168 8.9 127 8.9 129 169 8.9 115 8.9 127 170 10.0 68 10.1 66 Table 28: Results of the train characteristic provisions.

3 additionally graphically represents the median of the results of the tensile strength determinations (vinyl-functional siloxane oligomers, stored for 40 days at 23 ° C. and 50% RH).

4 additionally graphically represents the mean values of the results of elongation at break.

The results of the performance tests clearly show improved properties of the olefinically functionalized siloxane oligomers prepared from the two catalysts caprylic acid and hydrochloric acid, ie. from VTMO, VTEO and the co-condensate of VTEO and PTEO, as the reference formulations of the prior art (Comparative Examples). This is particularly evident in the melt index, the improved tensile strength and the improved elongation at break. Furthermore, the results show that the examples according to the invention even show improved properties in comparison with reference formulations to which silicone oil has been added. Thus, the product 166 has a significantly improved elongation at break than the reference product. Overall, Example 156 exhibits improved water-receptivity, elongation-at-break, and tensile strength properties, and product 161 also has improved elongation at break, tensile strength, and improved melt index than the reference product.

3.3 Kneading tests with products from V078, V081 and 115

The following kneading was processed with a temp. Profile of "3 min at 140 ° C, from 140 ° C to 170 ° C in 2 min, 5 min at 170 ° C" at a speed of 30 U / min in HAAKE kneader , From the batch was then pressed a plate at 190 ° C and a load pressure of 20 t. To simplify the addition of the peroxide, silane / peroxide solutions were prepared.

Preparation of the measuring body:

Of the samples prepared, after storage at 23 ° C and 50% RH in the climatic chamber, specimens for tensile tests and determination of water absorbency or determination of melt index were made. Silane DCUP soln. charge Weighing DCUP Weighing silane For trial no. comment V078 9,81g 0.19 g V116 Examples V081 9,81g 0.19 g V118 Table 29: Weights of the prepared dicumyl peroxide solution. Silane sol. charge weighing weighing For trial no. Silane designation comment DCUP silane 115 0.19 g 9,81g 154 VTMO siloxane oligomer 115 Table 30: Weights of the prepared dicumyl peroxide solution Experiment no. weighing weighing weighing Silane-DCUP solution. Charge comment EVA ATH DCUP silane soln V116 27,72g 61,61g 0.45 g V078 Examples V118 0.44 g V081 Table 31: Weighing AT experiments. Experiment no. EVA ATH DCUP soln. Silane DCUP solution. charge Silane designation Irganox VTMO siloxane oligomer 154 27,72g 61,60g 0.44 g 115 0,28g Table 32: Weighing AT experiments.

Melt Flow Index (MFR) and Volume Flow Index (MVR) Determinations ~ 7g of the individual samples were chopped and melt index ("MFR") determined at a temperature of 160 ° C and a load of 21.6 kg. Examples test number V116 V118 raw material V078 V081 Type VTMO / MTMS VTMO test temperature 160 ° C preheating 4min loading weight 21.6 kg MFR g min 3.19 3.39 MVR ccm min 2.36 2.51 Density g / ccm 1,352 1,348 Table 33: Application techniques MFR and MVR of the patent examples VTMO siloxane oligomer test number 153 154 raw material 115 Type blank test temperature 160 ° C preheating 4min loading weight 21.6 kg MFR g / 10min 2.03 3.39 MVR ccm / 10min 1.50 2.51 Density g / ccm 1,349 1,349 Table 34: Results of MFR and MVR determination

Determination of water absorption capacity

The water absorption capacity was determined by means of the test specimens after a period of 24 hours by a triple determination by storing them in the water bath at 70 ° C. for the said period of time. info test number Value [mg / cm2] 7d storage Without silane 153 3.81 Experiment with fatty acid and HCl as catalyst 154 1.24 Table 35: Results of water absorbency info test number Value [mg / cm2] 7d storage VTMO / MTMS siloxane V116 1.55 VTMO siloxane V118 1.40 Table 36: Results of water absorbency

Determination of tensile properties

The processing and evaluation took place as in point 3.2.3. explained. After 24 hours of storage in a climatic room at 23 ° C and 50% RH, the tensile properties (elongation at break and tensile strength) of the samples, with a test speed of 200 mm / min and an initial force of 0.2 MPa has been determined by a five-fold determination. AT test number V153 154 UN Commodity 115 comparison calculation blank Elongation at break [%] εB median 71,30 80.37 Tensile strength [MPa] σM median 8.91 8.66 Table 37: Determination of tensile properties Type Commodity AT ID Experimental NR AT elongation Tensile strenght [%] [MPa] Examples EP0518057 B1 V078 VTMO / MTMS Vorl.3 V116 80.37 8.66 EP0518057 B1 V081 VTMO V118 85.61 9.31 Table 38: Overall results Results Tensile properties and elongation at break

3.4 Determination of the gel content from experiment 154

Sample preparation:

Tubular baskets with a diameter of about 10 mm and a length of about 70 mm were produced from the wire mesh. The baskets are marked with a pencil according to the sample order. The chips were removed from the cross-linked plastic with the aid of a sharp knife. The sample weight was about 200 mg.

Extraction:

After eight hours of extraction at 160 ° C, the baskets were removed from the extraction constructions and dried at about 140 ° C for three hours. test number Uncrosslinked gel content Crosslinked gel content 154 2.15% 34.94% Table 39 Gel content 154

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 0518057 B1 [0004, 0114, 0116, 0118, 0118, 0137, 0137]
• CN 100343311 C [0005]
• JP 10-298289A [0006]
• JP 2004-099872 [0007]
• EP 1205481 B1 [0088]

Cited non-patent literature

• H.-G. Horn, H.C. Marsmann, The Markromolecular Chemistry 162 (1972), 255-267 [0024]
• G. Engelhardt, H. Jancke; J. Organometal. Chem. 28 (1971), 293-300 [0024]
• Elizabeth A. Williams, The Chemistry of Organic Silicon Compounds, 1989 John Wiley & Sons Ltd, 511-533 [0024]
• "Modern Size Exclusion Liquid Chromatography", Andre Striegel et al., Published by Wiley & Sons, 2nd Ed. 2009 [0090]
• http://en.wikipedia.org/wiki/Mol mass distribution [0092]
• DIN 53015 [0099]
• DIN ISO 1133 [0125]
• DIN EN ISO 527-1, 527-2, 527-3 [0128]

Claims (23)

Composition containing olefinically functionalized siloxane oligomers having at most one olefinic radical on the silicon atom, characterized in that - it contains at least one fatty acid of general formula III and chloride and - the olefinically functionalized siloxane oligomers Si-O-crosslinked structural elements, the chain-like, cyclic form crosslinked and / or spatially crosslinked structures, wherein at least one structure in idealized form corresponds to the general formula I, (R ¹ O) [(R ¹ O) _1-x (R ²⁾ _x Si (A) O] _a [Si (Y) ₂ O] _c [Si (B) (R ⁴⁾ _y (OR ³⁾ _{1 -YO} ] _b R ³ (I), where the structural elements are derived from alkoxysilanes and - A in the structural element corresponds to an olefinic radical and - B in the structural element corresponds to a saturated hydrocarbon radical, - Y corresponds to OR ³ or in crosslinked and / or spatially crosslinked structures independently of one another OR ³ or O _{1 / 2,} - wherein R 1 is independently a linear, branched and / or cyclic alkyl radical having 1 to 4 carbon atoms, and optionally H and / or -CO-R ⁵ with R ⁵ as defined below, equal, - R3 each independently of one another represent a linear, branched and / or cyclic alkyl radical having 1 to 4 C atoms, and R ² and / or R ⁵ each independently correspond to a linear, branched or cyclic alkyl radical having 1 to 15 C atoms, a, b, c, x and y are independently integers with 1 ≤ a, 0 ≤ b, 0 ≤ c, x is independently 0 or 1, y is independently 0 or 1, and (a + b + c) ≥ 2, - the fatty acid entspric ht R ⁵ -COOH (III) with R ^{5 is} an unsubstituted or substituted hydrocarbon radical having 3 to 45 carbon atoms. A composition according to claim 1, characterized in that the siloxane oligomers have derived structural elements from at least one of the alkoxysilanes, (i) from olefinically functionalized alkoxysilanes of the general formula II, A-Si (R ² ) _x (OR ¹ ) _3-x (II) with A an olefinic radical, with R ² and x as defined above, preferably x is 0, and R ^{1 is} independently a linear, branched and / or cyclic alkyl radical having 1 to 4 C atoms (IIa) or R ^{1 is} a -CO R ⁵ radical with R ⁵ as defined below (IIb), and optionally (ii) with a saturated hydrocarbon radical functionalized alkoxysilane of formula IV, B-Si (R ⁴ ) _y (OR ³ ) _3-y (IV) with B is an unsubstituted hydrocarbon radical, with R ³ , R ⁴ and y as defined above, y is preferably 0, and optionally (iii) of a tetraalkoxysilane of the general formula V is Si (OR ³ ) ₄ with R ³ independently of one another defined above. A composition according to claim 1 or 2, characterized in that R ^{5 is} independently an unsubstituted saturated or unsaturated hydrocarbon radical and independently in formula I, IIb or III has 5 to 45 C-atoms, preferably 7 to 26 C-atoms. Composition according to any one of Claims 1 to 3, characterized in that In formulas I and / or II, the olefinic radical A is a nonhydrolyzable olefinic radical, in particular a linear, branched or cyclic, alkenyl or cycloalkenyl-alkylene-functional group having in each case 2 to 18 C atoms, preferably a vinyl, Allyl, butenyl, such as 3-butenyl, pentenyl, hexenyl, heptenyl, octenyl, cyclohexenyl, C1 to C8 alkylene, preferably cyclohexenyl, 2-ethylene, such as 3'-cyclohexenyl-2-ethylene - and / or cyclohexadienyl-C1 to C8-alkylene, preferably cyclohexadienyl-2-ethylene group, and / or independently thereof - in formulas I and / or IV, the unsubstituted hydrocarbon radical B is a linear, branched or cyclic alkyl radical with 1 to 18 carbon atoms, in particular a methyl, ethyl, propyl, octyl group, and / or independently - the fatty acid of the formula III caproic acid, enanthic acid, caprylic acid, pergonic acid, capric acid, lauric acid, myristic acid, palmitic acid, Behenic acid, linolenic acid, calendulic acid and / or r is stearic acid, or R ^{5 is} independently in formulas I, II or III a monovalent radical -C _n H _{2n + 1} , with n = independently a number from 5 to 23, or a radical selected from C ₁₇ H ₃₁ -, C ₁₇ H ₂₉ - and C ₁₇ H ₂₉ - is. Composition according to any one of Claims 1 to 4, characterized in that the sum of (a + b) is an integer from 2 to 10 and c is optionally greater than or equal to 1. Composition according to any one of Claims 1 to 5, characterized in that the molar ratio of A residues to B residues is 1: 0 to 1: 8. Composition according to one of claims 1 to 6, characterized in that b is greater than or equal to 1. A composition according to any one of claims 1 to 7, characterized in that it contains as further component at least one organic solvent, an organic polymer, water, salt, filler, additive, pigment or a mixture of at least two of said components. Composition according to any one of Claims 1 to 9, characterized in that the molar ratio of the (i) total amount of Si atoms of the functionalized siloxane oligomers derived from the silanes of general formula IIa, formula IV and / or formula V used is ( ii) total amount of fatty acid used of the general formula III and / or the olefinically functionalized carboxysilane of the formula IIb is preferably 1: 5 × 10 ^-1 to 1: 1 × 10 ^-5 , in particular 1: 5 × 10 ^-2 to 1: 1 × 10 ^-4 , preferably 1: 3 × 10 ^-2 to 1: 1 × 10 ^-4 , particularly preferably 1: 1 × 10 ^-2 to 1: 1 × 10 ^-4 . Process for the preparation of a composition containing olefinically functionalized siloxane oligomers, by (i) an olefinically functionalized alkoxysilane of general formula IIa, A-Si (R ² ) _x (OR ¹ ) _3-x (IIa), wherein in formula IIa A is an olefinic radical, R ^{2 is} independently a linear, branched or cyclic alkyl radical having 1 to 15 C atoms and x is 0 or 1 and R ^{1 is} independently a linear, branched and / or cyclic alkyl radical (B) a fatty acid of general formula (III) and an olefinically functionalized carboxysilane of formula (IIb) or a mixture of Catalysts from a) and b), R ⁵ -COOH (III) A-Si (R ² ) _x (OR ¹ ) _3-x (IIb) where R ¹ is R ⁵ -CO- in formula IIb, where in formula IIb and III R ⁵ independently of one another corresponds to an unsubstituted or substituted hydrocarbon radical having 3 to 45 C atoms, and in formula IIb A to an olefinic radical, R ² a linear, branched or cyclic alkyl radical having 1 to 15 carbon atoms, where x is 0 or 1, and optionally (iii) with an alkoxysilane of the formula IV, B-Si (R ⁴ ) y (OR ³ ) _3-y (IV) where B is a saturated hydrocarbon radical, R ^{3 are} each independently of one another a linear, branched and / or cyclic alkyl radical having 1 to 4 C atoms, R ^{4 is} a linear, branched or cyclic alkyl radical having 1 to 15 C atoms and y is 0 or 1, and optionally (iv) with a tetraalkoxysilane of the formula V, Si (OR ³ ) ₄ (V), wherein R ³ in formula V are each independently a linear, branched and / or cyclic alkyl radical having 1 to 4 carbon atoms, and (v) with a defined amount of water, optionally in the presence of a solvent, preferably alcohol, to oligomers be implemented. A method according to claim 10, characterized in that - in the olefinically functionalized alkoxysilane of general formula IIa, A-Si (R ² ) _x (OR ¹ ) _3-x (IIa), A is a linear, branched or cyclic alkenyl or cycloalkenyl-alkylene-functional group having in each case 2 to 18 C atoms, preferably a vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl or cyclohexenyl -C1 to C8-alkylene, preferably cyclohexenyl-2-ethylene, such as 3'-cyclohexenyl-2-ethylene and / or cyclohexadienyl-C1 to C8-alkylene, particularly preferably a cyclohexadienyl-2-ethylene group, in particular x is 0 and R ^{1 is} independently a linear, branched and / or cyclic alkyl radical having 1 to 4 C atoms, in particular a methyl, ethyl or propyl group, and / or independently - in the alkoxysilane of the formula IV . B-Si (R ⁴ ) _y (OR ³ ) _3-y (IV), the unsubstituted hydrocarbon radical B is a linear, branched or cyclic alkyl radical having 1 to 18 C atoms, in particular a methyl, ethyl, propyl or octyl radical. A method according to claim 10 or 11, characterized in that - the fatty acid of formula III is selected from caproic acid, enanthic acid, caprylic acid, pergonic acid, capric acid, lauric acid, myristic acid, palmitic acid, behenic acid, linolenic acid, calendulic acid and / or stearic acid, and / or independently In the carboxysilane of the formula IIb A is a linear, branched or cyclic alkenyl or cycloalkenyl-alkylene-functional group having in each case 2 to 18 C atoms, preferably a vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl -, octenyl, cyclohexenyl-C1 to C8-alkylene, preferably cyclohexenyl-2-ethylene and / or cyclohexadienyl-C1 to C8-alkylene, particularly preferably cyclohexadienyl-2-ethylene group, in particular when x is 0; or R ¹ is R ⁵ -CO- is independently a monovalent radical -C _n H _{2n + 1} with R ⁵ , with n = independently a number from 5 to 23 or a radical selected from C ₁₇ H ₃₁ -, C ₁₇ H ₂₉ - and C ₁₇ H ₂₉ - is. Method according to one of claims 10 to 12, characterized in that the chlorosilane of the general formula VI corresponds to D _n SiCl ₄ -n (VI), in which the group D is a saturated or unsaturated hydrocarbon radical and n is 0 or 1, in particular the group D corresponds independently of a group A or a group B as defined above. Process according to one of Claims 10 to 13, characterized in that the alkoxysilanes of the formulas IIa, IV and / or V are at least partially hydrolyzed in the presence of a fatty acid of the formula III or of a carboxysilane of the formula IIb and in the presence of HCl and / or a chlorosilane and condensed, preferably the free alcohol is removed. Method according to one of claims 10 to 14, characterized in that alkoxytrialkylsilane, in particular alkoxytrimethylsilane is added. Method according to one of claims 10 to 15, characterized in that the molar ratio of the (i) total amount of silanes used of the general formula IIa, formula IV and / or formula V, all as defined above, to (ii) total amount of fatty acid used general formula III and / or the olefinically functionalized carboxysilane of formula IIb, both as defined above, 1: 5 × 10 ^-2 to 1: 1 × 10 ^-4 , in particular 1: 3 × 10 ^-2 to 1: 1 × 10 ^-4 , preferably 1: 1 × 10 ^-2 to 1: 1 × 10 ^-4 , particularly preferably 1: 1 × 10 ^-3 to 1: 1 × 10 ^-4 . Method according to one of claims 9 to 16, characterized in that the molar ratio of the total amount of the catalysts used HCl and / or chlorosilane to the total amount of the fatty acid of the formula III and / or the carboxysilane of the formula IIb of 8: 1 to 1: 8 is, in particular from 4: 1 to 1: 4, preferably from 3: 1 to 1: 3, particularly preferably 2: 1 to 1: 2, in particular by 1: 1 with a fluctuation range of about 0.5 each. Method according to one of claims 10 to 17, characterized in that the HCl is removed until the chloride content is less than or equal to 200 ppm by weight in the total composition, in particular less than or equal to 100 ppm by weight, preferably below 20 ppm by weight . Method according to one of claims 10 to 18, characterized in that is used as a processing aid silicone oil, such as polydimethylsiloxane, paraffin, paraffin oil or a mixture containing one of these processing aids. Process according to one of Claims 10 to 19, characterized in that the silane of the formula IIa and the silane of the formula IV in the ratio 1: 0 to 1: 8 are used and / or the silane of the formula IIa in relation to the silane of the formula V in the ratio 1: 0 to 1: 0.5 is used. Method according to one of claims 10 to 20, characterized in that the oligomers are diluted with a diluent. Composition comprising olefinically functionalized siloxane oligomers and a fatty acid of general formula III obtainable by a process according to one of Claims 10 to 21. Use of a composition according to any one of claims 1 to 22 as an adhesive, as a crosslinking agent by graft polymerization and / or hydrolytic condensation in a conventional manner, for the preparation of olefinically functionalized siloxane oligomers grafted polymers, prepolymers and / or mineral-filled polymers (Compounds ), in particular in the production of thermoplastics or elastomers, preferably of mineral-filled thermoplastics, elastomers or prepolymers thereof, for grafting or in the polymerization of thermoplastic polyolefins, as drying agents, in particular as water scavengers for silicone sealants, in crosslinkable polymers for the production of cables for the preparation of crosslinkable polymers, as an oil phase in an emulsion and / or together with organosilanes or organopolysiloxanes, for filler modification (filler coating), resin modification (additive), surface modification (functionalization, Hydroph bierung), as a component in coating systems (in particular sol-gel systems or hybrid systems), for modifying cathodes and anode materials in batteries, as an electrolyte fluid, as an additive in electrolyte fluids, for the modification of fibers, especially glass fibers and natural fibers, as well as for the modification of textiles , for modification of fillers for the artificial stone industry, as building protection or component in building protection, as an additive for mineral hardening materials, for the modification of wood, wood fibers and cellulose.

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