DE102011086867A1 - Composition useful e.g. as adhesive, comprises olefinically functionalized siloxane oligomers exhibiting less olefinic group at silicon atom, fatty acid, and silyloxy crosslinked structural elements derived from alkoxysilanes - Google Patents

Abstract

Composition comprises olefinically functionalized siloxane oligomer (I), which exhibit (a) not > 1 olefinic group at silicon atom, (b) at least one fatty acid (II), and (c) silyloxy (Si-O)-crosslinked structural elements, which form chain-like-, cyclic-, crosslinked- or optionally spatially crosslinked structures, and are derived from alkoxysilanes. Composition comprises olefinically functionalized siloxane oligomer 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) (II), and (c) silyloxy (Si-O)-crosslinked structural elements, which form chain-like-, cyclic-, crosslinked- or optionally spatially crosslinked structures, and are derived from alkoxysilanes. 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 : 1-4C alkyl (optionally branched and/or cyclic), optionally H, and/or -CO-R5; R3 : 1-4C alkyl (optionally branched and/or cyclic); R2, R4 : 1-15C alkyl (optionally branched or cyclic); R5 : optionally substituted 3-45C hydrocarbon; 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 olefinically functionalized alkoxysilane compound of formula (A-Si(R2) x(OR11) 3 - x) (III), optionally alkoxysilane compound of formula (B1-Si(R4) y(OR13) 3 - y) (IV) and optionally tetraalkoxysilane compound of formula (Si(OR13) 4) (V) with a defined amount of water, in presence of fatty acid compound of formula (II), and/or olefinically functionalized carboxy silane compound of formula (A-Si(R2) x(OR14) 3 - x) (VI), and optionally in presence of a solvent, preferably alcohol, to obtain siloxane oligomers. R11, R13 : 1-4C alkyl (optionally branched and/or cyclic); and R14 : -CO-R5.

Description

The invention relates to a composition comprising olefinically functionalized siloxane oligomers derived from olefinically-functionalized alkoxysilanes, having at most one olefinic radical per silicon atom and containing a fatty acid, and processes 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 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 the method disclosed therein, and a residual corrosive content of about 50 to about 230 ppm HCl remains even in products that are distilled in accordance with the disclosed process.

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 JP 2004-099872 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 without hydrochloride as a hydrolysis and / or condensation catalyst. Another object was to find a catalyst for the hydrolysis and / or condensation of alkoxysilanes, which can remain in the product without having the negative properties mentioned above. Another object was to find a particularly economical process for this catalyst.

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 alkylalkoxysilanes and optionally tetraalkoxysilane, can be prepared in a simple and economical manner with a fatty acid, which has a total of 4 to 46 carbon atoms, preferably myristic, caprylic or carboxy silanes, and hydrolyzed a defined amount of moisture or water and can be condensed to olefinically functionalized oligomers. Such available compositions are free of HCl. According to the invention, the catalyst used no longer needs to be removed from the oligomer consuming, as it was necessary for HCl as a catalyst. An outstanding advantage of the compositions according to the invention and of the process according to the invention is that the vinyl oligomers prepared, unlike the known oligomers, do not require any further workup, such as distillation of the compositions of the siloxane oligomers. 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 kneading or compounding. 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. 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 HCl also had to be removed.

It was also 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 with R ⁵ is 7 to 27 carbon atoms catalyzed could be.

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 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, 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 im Wesentlichen 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 bis 35 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, 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 comprising 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 the general formula II, and contain at least a fatty acid, in particular of the general formula III, and the olefinically functionalized siloxane oligomers have Si-O-crosslinked siloxane-crosslinked structural elements having chain-like, cyclic, crosslinked and / or spatially crosslinked structures, where at least one structure in an idealized form of the general formula I corresponds, (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 nonhydrolyzable olefinic hydrocarbon radical, 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 independently of one another substantially corresponds to a linear, branched and / or cyclic alkyl radical having 1 to 4 C atoms, and optionally - to a small extent -H and / or -CO-R ⁵ with R ⁵ , such 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 to atoms,
• - 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 with a, b, c each independently 0 to 35 and 1 to 35, respectively, where x is independently 0 or 1, y is independently 0 or 1, and (a + b + c) ≥ 2, preferably 50 ≥ (a + b + c) ≥ 3, 30 ≥ (a + b + c) ≥ 3; 20 ≥ (a + b + c) ≥ 3; particularly preferred 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 having independently a, b and c is greater than or equal to 1; and
• The fatty acid corresponds to the formula (III), R ^{5 is} -COOH (III), with R ^{5 is} an unsubstituted or substituted hydrocarbon radical having 3 to 45 carbon atoms.

According to the invention, the composition is chloride-free and is prepared in particular without the addition of chloride-containing compounds, so that the process according to the invention also manages without the addition of chloride-containing compounds. As a result, the composition according to the invention does not have the disadvantages of the chloride-containing compositions known from the prior art. Even a complicated distillation of the prepared composition can also be omitted. The chloride content of the composition is thus practically 0 ppm or mg / kg, in particular of the hydrolyzable chloride, unless chlorinated by contaminated starting materials or equipment parts. Thus, preferably the subject of the invention is a composition containing olefinically functionalized siloxane oligomers, wherein the composition is substantially free of hydrolyzable chloride. In particular, a composition is considered to be free of hydrolyzable chloride if the content of hydrolyzable chloride is less than or equal to 5 ppm, preferably less than or equal to 3 ppm. 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 to 3% by weight, relative to the total composition (100% by weight) in which a content of esterified fatty acid according to formula I with R ¹ independently of one another can be included here -CO-R ⁵ with R ⁵ , as defined below.

It may be preferred that the composition and / or the siloxane oligomer additionally contain trialkylsilane groups, such as trimethylsilane or triethylsilane groups, for example by the addition of 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. Atoms (IIa) or with R ¹ 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 the oligomers are processed 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 Si-Kernresonanz“, H.-G. Horn, H. Ch. Marsmann, Die Markromolekulare Chemie 162 (1972), 255–267 ;
• – „Über die H-, C- und Si-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 Si nuclear resonance", H.-G. Horn, H.C. Marsmann, The Markromolecular Chemistry 162 (1972), 255-267 ;
• - "On the H, C and 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 advantageously 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, and from 2 to 20, preferably from 2 to 15, in particular from 2 to 10, and c is optionally greater than or equal to 1, such as, for example, 1 to 20, in particular 2 to 15. 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 to add an alkoxytrialkylsilane, such as preferably an ethoxytrimethylsilane or methoxytrimethylsilane, to the composition to be prepared for chain termination at a desired time.

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.

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, especially preferably from 2.1: 1 to 3.5: 1, it being possible where appropriate for additional T structures to be formed.

Alternatively or additionally, preferred compositions contain olefinically-functionalized siloxane oligomers having an olefin group to alkoxy group ratio of 1: 1 to 1: 5, preferably 1: 1 to 1: 4, wherein in purely olefinically-functionalized siloxane oligomers, a ratio of 1 : 1 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 according to the invention The content of T-structures can also be over 9.0%.

According to an 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 or else 4 to 30, preferably from 2 to 15, particularly preferably from 2 to 10 and a fatty acid, in particular the Formula III. 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. Also preferred are olefinic, unsubstituted groups having 2 to 8 carbon atoms. 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 or even 4 to 30, preferably from 2 to 15, particularly preferably from 2 to 10 and a fatty acid, in particular of the formula III. 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 equal to a number from 2 to 30, preferably from 2 to 15, particularly preferably from 2 to 10 and a fatty acid are prepared, in particular of the formula III.

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 or even 4 to 30, preferably from 2 to 15, particularly preferably from 2 to 10 and a fatty acid, 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 which are obtainable or 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 one Tetraalkoxysilane of the general formula V equal Si (OR ³ ) ₄ , and have been reacted in the presence of at least one fatty acid, in particular of the formula (III).

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 a siloxane oligomer derived therefrom, in particular of the general formula I, in each case independently of an unsubstituted, saturated or unsaturated, optionally polyunsaturated hydrocarbon radical, such as, but not limited to, a diene, triene, etc. Preferably, the hydrocarbon radical R ^{5 is} 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 especially 7 to 16 C-atoms or 11 to 16 C atoms, with possibly stearyl with R ⁵ equal to C ₁₇ H ₃₅ - 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; 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, linoleic acid have proved 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. The use of a co-catalyst in addition to the fatty acid can be dispensed with.

Under a structural element - a monomeric siloxane unit - is consistently understood the single unit M, D, T or Q, i. H. the derived from an alkoxy-substituted silane structural unit 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.

According to the invention, in particular the siloxane oligomers may form with 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 ⁴ ) _1-y O] _b R ^{3 can form} the chain-like, cyclic and / or crosslinked structures, and in the presence of tetraalkoxysilanes or their hydrolysis and / or condensation products, spatially crosslinked structures can also form. The structural elements with free valencies on the Si atom are covalently saturated via -O-Si and the free valences on the O atom 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.

The substitution pattern of the structural elements applies correspondingly also to the non-idealized chain-form, cyclic, crosslinked and / or spatially crosslinked siloxane oligomers in the composition, wherein the silyl groups of the siloxane oligomers may independently be substituted as follows: Y is an OR ³ or crosslinked and / or spatially crosslinked structures independently of one another corresponds to OR ³ or O _1/2 - in a siloxane bond - with radicals A and / or B as defined, R ³ in the siloxane oligomers essentially corresponds to an alkyl radical as defined for R ³ , wherein in crosslinked and / or space-crosslinked structures, it is also possible independently of each other to form siloxane bonds with O _1/2 from the radicals OR ³ , or these radicals can be present independently of one another as O _1/2 and optionally independently with R ² and / or R ⁴ and which, as defined, correspond to an alkyl radical having 1 to 15 C atoms, with -OR ¹ , R ¹ may also be as defined t is an alkyl radical having 1 to 4 C atoms or else a -CO-R ⁵ radical as defined corresponding to or else 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 in which 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 of the general formula III and / or the olefinically-functionalized carboxysilane of the formula IIb, both as defined above, 1: 5 × 10 ^-1 to 1: 1 × 10 ^-5 or 1: 5 × 10 ^-2 to 1: 1 × 10 ^-5 , It is preferably 1: 1 × 10 ^-1 to 1: 1 × 10 ^-3 or 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 , more preferably 1: 5 × 10 ^-3 to 1: 1 × 10 ^-4 . Alternatively preferred are also 1: 2 × 10 ^-3 to 1: 1 × 10 ^-4 , more preferably 1: 2 × 10 ^-3 to 1: 1 × 10 ^-4 , particularly preferably 1: 2 × 10 ^-3 to 1: 5 × 10 ^-4 , more preferably 1: 2 × 10 ^-3 to 1: 1 × 10 ^-3 . Compositions having particularly good properties are obtained when the molar ratio of (i) the total amount of silane used to (ii) total amount of fatty acid is about 1: 1 x 10 ^-1 to 1: 1 x 10 ^-3 or 1: 1 x 10 ^{- 2} to 1: 1 × 10 ^-3 , in particular from 1: 1 × 10 ^-2 to 1: 5 × 10 ^-3 , preferably by 1: 8 × 10 ^-3 plus / minus 1 × 10 ^-2 .

The invention also relates to a composition comprising olefinically functionalized siloxane oligomers, in particular at least one siloxane oligomer according to the idealized formula I, which as further components 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.

A particular advantage of the composition according to the invention is that it is completely free of chloride due to the production process and thus leads to a considerable improvement in the fire protection properties when processed in cable compositions. The fatty acid can remain in the product and does not need to be separated. Thus, a significant advantage of the composition is that it can be used as bottom product, optionally after separation of the hydrolysis alcohol and optionally added solvent, directly in an economical manner according to the invention. Another advantage of the compositions of the invention is that they are food safe by the use of fatty acids, in the processing in extruding the fatty acid leads to a cleaning effect and also the corrosion of the screws, as it was caused by HCl, 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. In the case of corresponding vinyl-functional alkoxysiloxane oligomers from the preparation with HCl as catalyst, the flashpoint is reduced with increasing storage by continuous hydrolysis of the alkoxy groups to form hydrolysis alcohol.

• (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 einer Fettsäure der allgemeinen Formel III und/oder einem olefinisch-funktionalisiertem Carboxysilan der Formel IIb, R⁵-COOH (III) A-Si(R²)_x(OR¹)_3-x (IIb) mit R¹ gleich R⁵-CO- 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) mit 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.

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 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 a fatty acid of general formula III and / or an olefinically-functionalized carboxysilane of formula IIb, 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 is} independently an unsubstituted or substituted hydrocarbon radical having 3 to 45 carbon atoms, in formula IIb A an olefinic radical, R ² a linear, branched or cyclic alkyl radical having 1 to 15 carbon atoms and x is 0 or 1, preferably A is a linear, branched or cyclic alkenyl or cycloalkenyl-alkylene functional group having in each case 2 to 18 C atoms 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) with 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.

According to the invention, the hydrolysis alcohol is removed, preferably by distillation. 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. According to the invention, the composition thus prepared, 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.

At least partially hydrolyzed and, in particular at least partially co-condensed, preferably the condensable, partially hydrolyzed alkoxysilanes are substantially 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, a chain termination in the oligomerization can take place at certain times during the process in order to control the degree of oligomerization and, if appropriate, 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 out. 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. 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. These include ethanol or methanol. 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 0.7 mol to 5.0 mol of water per mole of mol of alkoxysilanes of the formulas II, IIa, IIb, IV and / or V used; it is particularly preferable to use 0.75 to 1.5 mol of water , Further preferred are 0.8 to 1.4, alternatively 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1, 3 and 1.35 moles of water. 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 for a stronger crosslinking in the oligomer or as well as the oligomer with a substrate.

In the process according to the invention, the molar ratio of the (i) total amount of silanes used is of general formula IIa, formula IV and / or formula V to (ii) total amount of fatty acid used of general formula III and / or the olefinically-functionalized carboxysilane of formula IIb preferably 1: 5 × 10 ^-1 to 1: 1 × 10 ^-5 , in particular 1: 1 × 10 ^-1 to 1: 1 × 10 ^-3 or 1: 5 × 10 ^-2 to 1: 1 × 10 ^-4 , preferably 1: 3 × 10 ^-2 to 1: 1 × 10 ^-4 , more 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 , preferably 1: 2 × 10 ^-3 to 1: 1 × 10 ^-4 .

Alternatively preferred are also 1: 2 × 10 ^-3 to 1: 1 × 10 ^-4 , preferably 1: 2 × 10 ^-3 to 1: 5 × 10 ^-4 , particularly preferably 1: 2 × 10 ^-3 to 1: 1 × 10 ^-3 . In the process according to the invention, a molar ratio of (i) the total amount of silane used to (ii) total amount of fatty acid is particularly preferably about 1: 1 × 10 ^-1 to 1: 1 × 10 ^-3 or else 1: 1 × 10 ^-2 to 1: 1 × 10 ^-3 , in particular from 1: 1 × 10 ^-2 to 1: 5 × 10 ^-3 , preferably by 1: 8 × 10 ^-3 plus / minus 1 × 10 ^-2 . Consequently, the fatty acid has already proven to be a catalyst in low dosage, ie n _silane : n _{fatty acid / carboxysilane} = (n _{formula IIa} + n _{formula IV} + n _{formula V} ) :( n _{formula III} + n _{formula IIb} )

According to the invention, it is further preferred if the alkoxysilanes of the formulas IIa, IV and / or V are at least partially hydrolyzed and condensed in the presence of a fatty acid of the formula III and / or of a carboxysilane of the formula IIb, and preferably the alcohol, in particular both the hydrolysis alcohol and also the optionally added alcohol is removed. The hydrolysis and / or the added alcohol correspond to the free alcohol. The content of free alcohol in the overall composition is particularly preferably less than 5% by weight to 0.01% by weight, in particular less than 2% by weight to 0.01% by weight, particularly preferably less than 1% by weight. % to 0.01 wt .-% in particular up to the detection limit. It has surprisingly been found that the functional siloxane oligomers obtained with the catalyst according to the invention are significantly more stable to hydrolysis than the siloxane oligomers prepared with a conventional catalyst, ie a stronger acid such as formic acid or HCl. As a result, the siloxane oligomers according to the invention are 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 less than or equal to 0.3 wt .-%.

• – unabhängig davon ein Alkoxysilan der Formel IV, B-Si(R⁴)_y(OR³)_3-y (IV)

mit einem unsubstituierten Kohlenwasserstoff-Rest B, der ein linearer, verzweigter oder cyclischer Alkyl-Rest mit 1 bis 18 C-Atomen ist, insbesondere ein Methyl-, Ethyl-, Propyl-, Octyl-Rest, eingesetzt.According to a preferred process variant, an olefinically-functionalized alkoxysilane of the 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-C 1 -C 8 -alkylene, particularly preferably cyclohexenyl-2-ethylene and / or cyclohexadienyl-C 1 to C 8 -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

• Regardless 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 II where x = 0 or 1, particularly preferably x = 0, where A is a linear or branched alkenyl radical having 2 to 18 carbon atoms. Atoms, in particular having 2 to 8 carbon atoms, preferably a vinyl, butenyl, cyclohexenyl-2-ethylene, R ^{2 is} a linear, branched or cyclic alkyl radical having 1 to 8 carbon atoms, especially 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, particularly preferably correspond to a methyl, ethyl and / or iso-propyl or n-propyl radical, and in formula IIb R ^{1 of} a group -CO-R having 4 to 45 C atoms, preferably having 7 to 27 C Atoms, more preferably having 7 to 22 carbon atoms.

Compounds of the formula IIa which can be used 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, the methoxy-substituted ones being particularly preferred.

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 preferably 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 1 up 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 C 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, the methoxy-substituted radicals being particularly preferred ,

Preferred exemplified compounds of formula IV are:
Propyltrimethoxysilane (PTMO), dimethyldimethoxysilane (DMDMO), dimethyldiethoxysilane, methyltriethoxysilane (MTES), propylmethyldimethoxysilane, propylmethyldiethoxysilane, n-octylmethyldimethoxysilane, n-hexylmethyldimethoxysilane, n-hexylmethyldiethoxysilane, propylmethyldiethoxysilane , Propylmethyldiethoxysilane, propytriethoxysilane (PTEO), isobutyltrimethoxysilane (IBTMO), isobutyltriethoxysilane (IBTEO), octyltrimethoxysilane, octyltriethoxysilane (OCTEO), 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 Vinyltrimyristatosilan 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 iso-butyltriethoxysilane with vinyltrimyristatosilane in ethanol and a defined amount of water; Vinyltrimethoxysilane and iso-butyltrimethoxysilane 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 are: 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 Vinyltrimyristatosilan 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 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, iso-butyltrimethoxysilane and tetramethoxysilane with caprylic acid in methanol and a defined amount of water; Vinyltriethoxysilane and iso-butyltriethoxysilane with vinyltrimyristatosilane in ethanol and a defined amount of water; Vinyltrimethoxysilane and iso-butyltrimethoxysilane with Vinyltrimyristatosilan 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 with propyltrimethoxysilane or else 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 a precise adjustment of the steric hindrance, the desired chain length and the hydrophobicity, in order to give 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 therefore also be used in principle.

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, more preferably Cyclohexenyl-2-ethylene and / or cyclohexadienyl-C 1 -C 8 -alkylene, particularly preferably cyclohexadienyl-2-ethylene group, more preferably 3'-cyclohexadienyl-2-ethylene, wherein in formula IIb preferably x = 0 and R ^{1 is} equal to R ⁵ -CO-, with R ⁵ independently being a monovalent radical -C _n H _{2n + 1} , with n = independently being 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, which show particularly good properties with respect to the melt flow in the subsequent kneading or compounding with thermoplastic base polymers or with elastomers. Depending on the process procedure and the desired properties of the olefinically functionalized siloxane oligomers prepared, it may be preferred 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 siloxanes containing elastomers and / or thermoplastics produced, for example with respect to the melt flow properties.

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 having a kinematic viscosity of about 150-400 mm ² / s, particularly preferred alternatives have a kinematic viscosity of about 200 mm ² / s or 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. The composition thus obtained preferably corresponds directly to the composition according to the invention, and preferably does not itself have to be further purified.

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, tetrahydrofuran (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.

• 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 gegebenenfalls einen Alkohol in einer Gewichtsmenge von 0,2 bis 8fach 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.
• 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 von 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 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.
• 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 from 50 to 95 ° C, more preferably to around 55 to 90 ° C, according to the invention to about boiling point of the alcohol.

After the reaction, the alcohol is 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 person skilled in the usual diluents for alkoxysiloxanes are known, for example, alcohols, ethers, ketones, hydrocarbons, or mixtures thereof are mentioned here. 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, as well as the ethylene-based polymers ethylene-vinyl acetate copolymers (EVA), EPDM or EPM and / or celluloid or silane-co-polymerized polymers understood and example from unsaturated functional monomers including silanes, such as VTMO, VTEO, and monomers such as ethylene and other olefins prepared base polymers, monomers and / or prepolymers 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 a fatty acid of general formula III obtainable by a process according to any one of claims 9 to 16, in particular the subject matter of the invention is a composition obtainable from the reaction of an olefinic alkoxysilane of 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 relates to compositions containing olefinically functionalized siloxane oligomers and a catalyst selected from a fatty acid of general formula III or a compound of the formula IIb, releases this catalyst, obtainable by a process according to one of claims 9 to 16 or 17.

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 a drying agent, as an oil phase in an emulsion, together with organosilanes or organopolysiloxanes. 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-mers

Weight average molecular weight (Mw)

and
Number average molecular weight (Mn)

each with:

_i

= Amount of substance [mass] of the i-mers

M _i

= Molar mass of the i-mer

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 of inventive products 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) Table 1: Overview of the raw materials used.

1.1.1 Siloxane oligomer of vinyltrimethoxysilane

The following solutions were used: description Solution 1 135 methanol 99.763g (99.76%) VE water - caprylic 0.240g (0.24%) Table 2: Weights of required solutions for the preparation of the siloxane oligomers of vinyltrimethoxysilane. description 141 153 vinyltrimethoxysilane 114,344g 114,760g methanol 73,44g - VE water 11,30g 11,34g description 141 153 Vinyltrimyristatosilan 0,920g - methoxytrimethylsilane - - Solution 1 - 73.89 Table 3: Weighings for the preparation of the siloxane oligomers of vinyltrimethoxysilane.

The vinyltrimethoxysilane is initially charged in the reaction flask. The additives "AK 350" and "Vinyltrimyristatosilan" are also presented in 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 3 hours, the methanol is distilled off at 85 ° C oil bath temperature and a reduced pressure of 150-180mbar. The mixture is then stirred for a further hour at 85 ° C oil bath temperature and a pressure of <1 mbar.

Designation 141:

114.344 g vinyltrimethoxysilane and 0.920 g Vinyltrimyristatosilan be submitted in a reaction flask. 73.44 g of methanol and 11.30 g of water are transferred to a dropping funnel. At a temperature of about 25 ° C, the methanol / water mixture is slowly added dropwise with stirring to the vinylsilanes. When the addition is complete, the oil bath is heated to 85 ° C, so that the methanol boils under reflux. After about three hours of reaction, the methanol is distilled off at the said oil bath temperature and a reduced pressure of about 150 to 180 mbar. For further separation methanol and possibly water, the vacuum is adjusted to less than 1 mbar.

1.1.2 Siloxane oligomer of vinyltriethoxysilane

For easier dosing of some starting materials, the solution 4 was prepared: description Solution 4 127 ethanol 399.28g (99.82%) VE water - caprylic 0.721g (0.18%) Table 4: Weights of the solutions for the preparation of the siloxane oligomers of vinyltriethoxysilane. description 130 133 152 154 Vinyltriethoxysilane (VTEO) 128,760g 128,420g 128,708g 128,424g ethanol - 61,17g - 61,17g VE water 9,877g 9,882g 9,87g 9,85g Vinyltrimyristatosilan - 0,563g - 0,564g Solution 4 61,426g - 63,42g - Table 5: Weights for the preparation of the 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 starting materials 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 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 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.

1.1.3 siloxane oligomer: co-oligomer of vinyltriethoxysilane and

propyltriethoxysilane

To simplify the dosage of some starting materials, the following solutions were used: description Solution 7 143 Solution 10 146 ethanol 79.867g (99.84%) - water caprylic 0,127g (0.16%) - Propyltriethoxysilane (PTEO) - 394.13g (50.77%) Vinyltriethoxysilane (VTEO) - 382.15g (49.23%) Table 6: Weights of the solutions for the preparation of siloxane oligomers (co-oligomers) from vinyltriethoxysilane and propyltriethoxysilane. description 147 150 ethanol - 58,21g VE water 9,16g 9,14g AK 350 - - Vinyltrimyristatosilan - 0,491g ethoxytrimethylsilane - - Solution 7 58,43g - Solution 10 132,421g 132,160g 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 150-180mbar. Finally, a further hour at 100 ° C oil bath temperature and a pressure of <1 mbar is stirred.

1.1.4 Siloxane oligomer of vinyltrimethoxysilane - 114

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

Procedure: Vinyltrimethoxysilane (VTMO) is weighed in a 2 l four-necked apparatus with water cooling and magnetic stirrer. Subsequently, a mixture of methanol, bi-dist-water and caprylic acid at 25 ° C and ambient pressure is metered. 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 from the dosage of the H ₂ O / caprylic acid / 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 a composition with VTMO siloxane oligomer and caprylic acid. material weighing VTMO 285,9g methanol 183,3g caprylic 2.3g Water Bi-Dest 28,5g Table 8: Raw materials 114

The NMR results show that oligomerization of the VTMO took place. 1.3 Analysis 1.3.1. GC analysis Experiment no. used catalyst component Proportions in the siloxane oligomer composition [wt%] VTMO MeOH EtOH VTEO PTEO 141 Vinyltrimyristatosilan <0.1 4.2 - - - 153 caprylic 1.2 10.3 - - - 133 Vinyltrimyristatosilan - - 8.2 0.3 - 150 Vinyltrimyristatosilan - - 2.9 15.2 33.4 Table 8: Results of the GC evaluations. 1.3.2. GPC analysis Experiment no. used catalyst component Mn [g / mol] Mw [g / mol] Poly dispersity 141 Vinyltrimyristatosilan 4,0094E + 02 5,4147E + 02 1.3505 153 caprylic 6,4096E + 02 9,4887E + 02 1.4804 130 Caprylic acid (template) 1,8384E + 02 1,9834E + 02 1.0789 133 Vinyltrimyristatosilan 7,1096E + 02 1,5434E + 03 2.1709 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 150 Vinyltrimyristatosilan 2,7636E + 02 3,9962E + 02 1.4460 Table 10: Results of the GPC evaluations.

1.3.3. NMR analysis

In addition, a structure determination by NMR was carried out on the following test product: Insurance no ¹ H and ¹³ C NMR analyzes ²⁹ Si NMR analyzes - proportions in the composition [mol%] monomer M-structure D structure T structure 141 1.2 mol of SiOMe / mol vinyl, little free MeOH - (VTEO) 50.7 39.6 9.7 Table 11: Results of the NMR evaluations 141. Experiment no. ¹ H and ¹³ C NMR analyzes ²⁹ Si NMR analyzes - proportions in the composition [mol%] monomer M-structure D structure T structure 1.3 mol of SiOMe 0.5 mol of MeOH 0.1 mol of caprylic acid 114 0.30 (VTMO) 50,10 42.0 7.60 Table 12: NMR results 114 1.3.4. Wet chemical analysis results Silane: water V114 Total chloride mg / kg 45 Hydrol. Chloride mg / kg <3 SiO2% (mass) 54.1 Free methanol% (mass) 2.4 VTMO% (mass) 0.6 Appearance color number 1 Mg Pt-Co / l <5 Density g / cm3 1,105 Viscosity mPa s 8.2 GPC Mn g / mol 561.56 Mw g / mol 802.31 D 1.4287 Table 13: Wet chemical analysis results

2. Comparative Examples

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 to 11 3 ° 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 14: 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. A 500 ml dropping funnel was used for this purpose. 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 Merck (HCl 37%) 52.8 g material supplier weighing 1100ppm Water Bidest Table 15: Raw materials V081

The analytical results for the comparative experiments are summarized in Tables 16 to 19:
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 16: Analysis results for V078 (Comparative Example 1) Experiment no. V081 total Chloride Hydrolyzable. chloride SiO ₂ 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 17: Analysis results for 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 18: 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) ²⁹ Table 19: Results from the Si NMR analyzes on the products from the comparative experiments V078 and V081 [VS = vinylsilyl, MS = methylsilyl]

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, 0107, 0109, 0111, 0111]
• CN 100343311 C [0005]
• JP 10-298289A [0006]
• JP 2004-099872 [0007]
• EP 1205481 B1 [0080]

Cited non-patent literature

• "Structural investigations of oligomeric and polymeric siloxanes by high-resolution Si nuclear resonance", H.-G. Horn, H.C. Marsmann, The Markromolecular Chemistry 162 (1972), 255-267 [0024]
• "On the H, C and Si NMR chemical shifts of some linear, branched and cyclic methyl-siloxane compounds", G. Engelhardt, H. Jancke; J. Organometal. Chem. 28 (1971), 293-300 [0024]
• "Chapter 8 - NMR spectroscopy of organosilicone compounds", 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., Publisher Wiley & Sons, 2nd Ed. 2009 [0082]
• http://en.wikipedia.org/wiki/Mol mass distribution [0084]
• DIN 53015 [0090]

Claims (19)

Composition comprising 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 - the olefinically functionalized siloxane oligomers Si-O-crosslinked structural elements, the chain-like, cyclic, crosslinked and / or form spatially crosslinked structures, where at least one structure corresponds in an idealized form 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 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 C-atoms, and optionally H and / or -CO-R ⁵ with R ⁵ as defined below, corresponds, - R ³ each independently of one another correspond to a linear, branched and / or cyclic alkyl radical having 1 to 4 carbon atoms, and R ² and / or R ⁴ are each independently a linear, branched or cyclic alkyl radical having 1 to 15 carbon atoms - a, b, c, x and y are independently integers corresponding to 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 ents MPLIANCEWITH 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 an R ¹ a Radical -CO-R ⁵ with R ⁵ as defined below (IIb) corresponds, and optionally (ii) from with a saturated hydrocarbon radical functionalized alkoxysilane of the 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. A 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 non-hydrolyzable olefinic radical, in particular a linear, branched or cyclic, alkenyl or cycloalkenyl-alkylene functional group in each case 2 to 18 C atoms, preferably a vinyl, allyl, butenyl, such as 3-butenyl, pentenyl, hexenyl, heptenyl, Octenyl, cyclohexenyl-C 1 -C 8 -alkylene, preferably cyclohexenyl-2-ethylene, such as 3'-cyclohexenyl-2-ethylene and / or cyclohexadienyl-C 1 -C 8 -alkylene, preferably cyclohexadienyl-2-ethylene, and / or independently of this, in formulas I and / or 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, octyl group, and or independently - the fatty acid of the formula III is caproic acid, enanthic acid, caprylic acid, perlagonic acid, capric acid, lauric acid, myristic acid, palmitic acid, behenic acid, linolenic acid, calendic acid and / or stearic acid, or R ^{5 is} independently a monovalent radical in formulas I, II or III -C _n H _{2n + 1} , is, with n = independently a number from 5 to 23, or a residue 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 30, with a greater than or equal to 1 and b equal to 0 or greater than 1, preferably independently 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 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 ^-1 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 , more preferably 1: 5 × 10 ^-3 to 1: 1 × 10 ^-4 , particularly preferably 1: 2 × 10 ^-3 to 1 : 1 × 10 ^-4 , also preferably 1: 1 × 10 ^-3 to 1: 1 × 10 ^-4 , further preferred is a molar ratio of 1: 1 × 10 ^-1 to 1: 1 × 10 ^-3 , more preferably from 1: 1 x 10 to 1: 5 x 10 ^-3 . A process for preparing a composition containing olefinically functionalized siloxane oligomers by (i) preparing 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 1 to 4 carbon atoms, (ii) in the presence of fatty acid of general formula III and / or an olefinically-functionalized carboxysilane of formula IIb, R ⁵ -COOH (III) A-Si (R ² ) _x (OR ¹ ) _3-x (IIb) where R ¹ is R ⁵ -CO- in formula IIb, wherein in formulas IIb and III R ^{5 is} independently an unsubstituted or substituted hydrocarbon radical having 3 to 45 carbon atoms, and in formula IIb A is an olefinic radical, R ^{2 is} a linear, branched or cyclic alkyl radical having 1 to 15 C atoms correspond to x being 0 or 1, and optionally (iii) to 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) with 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 9, 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 -C 1 to C 8 -alkylene, preferably cyclohexenyl-2-ethylene, such as 3'-cyclohexenyl-2-ethylene and / or cyclohexadienyl-C 1 to C 8 -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-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 9 or 10, characterized in that - the fatty acid of the formula III is selected from caproic acid, enanthic acid, caprylic acid, perlagonic 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-C 1 -C 8 -alkylene, preferably cyclohexenyl-2-ethylene and / or cyclohexadienyl-C 1 -C 8 -alkylene, particularly preferably cyclohexadienyl-2-ethylene, 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 9 to 11, characterized in that the alkoxysilanes of formulas IIa, IV and / or V are at least partially hydrolyzed and condensed in the presence of a fatty acid of formula III or a carboxysilane of formula IIb, and preferably the alcohol is removed , Method according to one of claims 9 to 12, characterized in that Alkoxytrialkylsilan, in particular alkoxytrimethylsilane is added. Method according to one of claims 9 to 13, 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. Method according to one of claims 9 to 14, characterized in that the silane of the formula IIa and the silane of the formula IV in the ratio 1: 0 to 1: 8 is 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 9 to 15, characterized in that the molar ratio of (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 the formula IIb, both as defined above, 1: 5 × 10 ^-1 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 , also preferably 1: 5 × 10 ^-3 to 1: 1 x 10 ^-4 , more preferably 1: 2 x 10 ^-3 to 1: 1 x 10 ^-4 , also preferably 1: 1 x 10 ^-3 to 1: 1 x 10 ^-4 , more preferably is a molar ratio of 1: 1 x 10 ^-2 to 1: 1 x 10 ^-3 , more preferably from 1: 1 x 10 ^-2 to 1: 5 x 10 ^-3 . Method according to one of claims 9 to 16, 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 9 to 17. Use of a composition according to any one of claims 1 to 18 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.