DE102011086869A1 - Polymer composition useful e.g. as adhesive, comprises olefinically functionalized siloxane oligomers exhibiting less olefinic group at silicon atom and silyloxy-crosslinked structural elements, organic polymer and inorganic solid material - Google Patents

Abstract

Polymer composition comprises olefinically functionalized siloxane oligomers of (I), at least one organic polymer, and an inorganic solid material, where the siloxane oligomers exhibit (a) not > 1 olefinic group at silicon atom, (b) at least one fatty acid (III), and (c) silyloxy (Si-O)-crosslinked structural elements, which form chain-like-, cyclic-, crosslinked- or optionally spatially crosslinked structures, and are derived from alkoxysilanes, and the siloxane oligomers are optionally chemically bonded to the inorganic solid material. Polymer composition comprises olefinically functionalized siloxane oligomers of formula ((R1O)[(R1O) 1 - x(R2) xSi(A)O] a[Si(Y1) 2O] c[Si(B1)(R4) y(OR3) 1 - yO] bR3) (I), at least one organic polymer, and an inorganic solid material, where the siloxane oligomers exhibit (a) not > 1 olefinic group at silicon atom, (b) at least one fatty acid of the formula (R5-COOH) (III), and (c) silyloxy (Si-O)-crosslinked structural elements, which form chain-like-, cyclic-, crosslinked- or optionally spatially crosslinked structures, and are derived from alkoxysilanes, and the siloxane oligomers are optionally chemically bonded to the inorganic solid material. A : olefinic group; B1 : saturated hydrocarbyl; Y1 : OR3 or O 1 / 2(in crosslinked or optionally spatially crosslinked structures) or OR3; R1, R3 : 1-4C alkyl (optionally branched and/or cyclic) or optionally H, and/or -CO-R5; R2, R4 : 1-15C alkyl (optionally branched or cyclic); either a : >= 1; and b, c : >= 0; or a+b+c : >= 2; x, y : 0 or 1; and R5 : 3-45C hydrocarbyl (optionally substituted). An independent claim is also included for: preparing the above composition, comprising reacting olefinically functionalized siloxane oligomers comprising at least one fatty acid of (III) with the organic polymer and the inorganic solid material in a compounding apparatus.

Description

The invention relates to a polymer composition comprising olefinically functionalized siloxane oligomers having at most one olefinic radical on the silicon atom, at least one organic polymer, an inorganic solid and a fatty acid and also processes for their preparation and their use for the preparation of, for example, cables.

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 hydrochloride 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 the catalyst. The HCl catalyst can not be completely separated by means of the method disclosed therein and a corrosive residual content of HCl remains even after distillation in the product produced.

In the case of known siloxane oligomers, therefore, the chloride content had to be reduced or the associated property profile of the siloxane oligomers had to be accepted for these reasons by means of complicated processes.

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 with a large number of possible functionalities, an average molecular weight in the range Mn = 350-2500 g / mol and a polydispersity (D = Mw / Mn) of 1.0-3.3 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 provide a chloride-free polymer composition of olefinically functionalized oligomers as well as a polymer composition with a very low chloride content of olefinically functionalized oligomers and processes for their preparation. This polymer composition should have an improved property profile than the known ones. Another object was to use a catalyst as a hydrolysis and / or condensation catalyst, which can remain in the product without having the negative properties mentioned above.

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 polymer compositions of olefinically functionalized siloxane oligomers containing a fatty acid, in particular from the hydrolysis and / or condensation of corresponding olefinic alkoxysilanes, can be prepared in a simple and economical manner with at least one polymer and an inorganic solid and have significantly improved properties than known polymer compositions , The property profile of compositions according to the invention shows improved values for elongation at break, tensile strength, water absorbency and / or melt index. It is true that the melt index should indeed have a certain value but at the same time must not be too high.

For the preparation of the olefinically functionalized siloxane oligomers, olefinically functionalized alkoxysilanes, optionally alkylalkoxysilanes and optionally tetraethoxysilane in a simple and economical manner with a fatty acid having a total of 4 to 46 carbon atoms are preferred myristic, caprylic or carboxy silanes, optionally in the presence of a small Content of HCl and a defined amount of moisture or water is hydrolyzed and condensed to olefinically functionalized oligomeric alkoxysiloxanes. The HCl content can be adjusted by adding HCl or else by the presence of chlorosilanes which form HCl under the reaction conditions. Such available olefinically functionalized siloxane oligomers have only very low levels of HCl. The fatty acid used as catalyst can remain in the product. If only larger amounts of HC are used as a catalyst, it would first have to be removed in an energy-consuming manner. The vinylsiloxane oligomers produced require no further work-up. 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 used according to the invention in the polymer compositions is also that the fatty acid-based catalysts directly improve the processability of the siloxane oligomers with the polymers and at the same time can be used as crosslinking catalyst, for example in a subsequent kneading or compounding step. The fatty acid can thus be used in different process steps as a catalyst and thus reduces the total amount of catalyst required.

Particularly surprising was the improvement in the tensile properties or elongation at break of the compositions according to the invention which are prepared from organic polymers, more preferably from elastomers or thermoplastics or mixtures thereof, with the olefinic siloxane oligomers containing at least one fatty acid. In addition, the water absorption capacity of this polymer composition could be significantly reduced. Such compounded polymers are particularly well suited for the production of, for example, cable sheaths, which are exposed, for example, to a humid climate, which are laid under water or in the ground.

The olefinic siloxane oligomers prepared according to the invention in the presence of fatty acid in the polymer composition also have a permanently reduced VOC content compared with the siloxane systems known from the prior 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/oder ggf. ein Polymerisationsprodukt eines olefinischen Restes, insbesondere ein Polymerisationsprodukt A eines A´ = olefinischer Rest, und
• – B in dem Strukturelement ein gesättigter Kohlenwasserstoffrest ist, insbesondere abgeleitet aus der allgemeinen Formel IV,
• – Y in dem Strukturelement OR³ entspricht oder in vernetzten und/oder raumvernetzten Strukturen unabhängig voneinander OR³ oder O_1/2 ist, insbesondere abgeleitet aus der allgemeinen Formel V gleich Si(OR³)₄,
• – wobei R¹ unabhängig voneinander einem linearen, verzweigten und/oder cyclischen Alkyl-Rest mit 1 bis 4 C-Atomen entspricht, und gegebenenfalls – zu einem geringen Anteil – H und/oder -CO-R⁵ mit R⁵, wie nachstehend definiert; R³ jeweils unabhängig voneinander einem linearen, verzweigten und/oder cyclischen Alkyl-Rest mit 1 bis 4 C-Atomen, und R² und/oder R⁴ jeweils unabhängig einem linearen, verzweigten oder cyclischen Alkyl-Rest mit 1 bis 15 C-Atomen entsprechen,
• – a, b, c, x und y unabhängig voneinander ganzen Zahlen entsprechen; mit 1 ≤ a, 0 ≤ b; insbesondere auch 1 ≤ b; und 0 ≤ c, wie gegebenenfalls 1 ≤ c, vorzugsweise mit a, b, c jeweils unabhängig 0 bzw. 1 bis 35, wobei x unabhängig voneinander 0 oder 1 ist, y unabhängig voneinander 0 oder 1 ist, und (a + b + c) ≥ 2 sind, bevorzugt sind 50 ≥ (a + b + c) ≥ 2, weiter bevorzugt 50 ≥ (a + b + c) ≥ 3, vorzugsweise 30 ≥ (a + b + c) ≥ 3; 20 ≥ (a + b + c) ≥ 3; besonders bevorzugt 15 ≥ (a + b + c) ≥ 3, ebenfalls 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 der Formel (III) R⁵-COOH (III) entspricht, mit R⁵ einem unsubstituierten oder substituierten Kohlenwasserstoff-Rest mit 3 bis 45 C-Atomen und die Siloxanoligomere gegebenenfalls an den anorganischen Feststoff gebunden sind.

The invention therefore relates to a polymer composition comprising olefinically functionalized siloxane oligomers, at least one organic polymer and an inorganic solid, wherein the siloxane oligomers have at most one olefinic radical per silicon atom, the olefinic radical is in particular not hydrolyzable, and the siloxane oligomers are preferably from olefinically functionalized Derived alkoxysilanes of the general formula II, and contain at least one fatty acid, in particular the general formula III, and the olefinically functionalized siloxane oligomers have Si-O-crosslinked - siloxane-crosslinked - structural elements, with chain-like, cyclic, crosslinked and / or spatially crosslinked structures, where at least one structure in idealized form corresponds to the general formula I, (R ¹ O) [(R ¹ O) _1-x (R ²⁾ _x Si (A) O] _a [Si (Y) ₂ O] _c [Si (B) (R ⁴⁾ _y (OR ³⁾ _{1 -YO} ] _b R ³ (I),

• - Wherein the structural elements are derived from alkoxysilanes and
• A in the structural element is an olefinic radical, in particular derived from the general formula II, in particular A is a nonhydrolyzable olefinic hydrocarbon radical and / or optionally a polymerization product of an olefinic radical, in particular a polymerization product A of an A'= olefinic 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 is} independently a linear, branched and / or cyclic alkyl radical having 1 to 4 carbon atoms, and optionally - to a small extent - H and / or -CO-R ⁵ with R ⁵ , as defined below ; Each R ³ independently of one another is a linear, branched and / or cyclic alkyl radical having 1 to 4 C atoms, and R ² and / or R ^{4 are} each independently a linear, branched or cyclic alkyl radical having 1 to 15 C atoms correspond,
• - a, b, c, x and y independently correspond to integers; with 1 ≤ a, 0 ≤ b; in particular 1 ≤ b; and 0 ≤ c, optionally 1 ≤ c, preferably a, b, c, each independently 0 or 1 to 35, where x is independently 0 or 1, y is independently 0 or 1, and (a + b + c) ≥ 2, preferably 50 ≥ (a + b + c) ≥ 2, more preferably 50 ≥ (a + b + c) ≥ 3, preferably 30 ≥ (a + b + c) ≥ 3; 20 ≥ (a + b + c) ≥ 3; more preferably 15 ≥ (a + b + c) ≥ 3, also preferably 10 ≥ (a + b + c) ≥ 3, each independently with (i) a greater than 1 or (ii) with a and b each independently greater than 1 or (iii) each independently a, b and c is greater than or equal to 1; and
• - The fatty acid of formula (III) R ⁵ -COOH (III) corresponds, with R ^{5 is} an unsubstituted or substituted hydrocarbon radical having 3 to 45 carbon atoms and the siloxane oligomers are optionally bonded to the inorganic solid.

The invention is also a composition in which the sum of (a + b) with a greater than or equal to 1, and b is 0 or b is greater than or equal to 1, an integer greater than or equal to 2, in particular from 2 to 50 and c optionally greater than or equal to 1. Preferably, a and b are each independently an integer from 2 to 10.

Furthermore, the polymer composition preferably comprises as further components at least one radical generator or its degradation products or reaction products, auxiliaries, additives, processing aids and / or a pigment. The composition according to the invention particularly preferably comprises a free-radical generator and / or its reaction products. Therefore, after addition of the radical generator, the polymer composition contains Group A polymerization products with the organic polymer. Particular preference is given to using dicumyl peroxide as free-radical initiator. In general, all radical formers which appear suitable to the person skilled in the art can be used; preference is given to selecting from: organic peroxide and / or an organic perester, in particular tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, dicumyl peroxide, di-tert-butyl peroxide and / or tert-butylcumyl peroxide, 1,3-di (2-tert-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexine (3), di-tert. amyl peroxide, 1,3,5-tris (2-tert-butylperoxy-isopropyl) benzene, 1-phenyl-1-tert-butyl peroxyphthalide, alpha, alpha'-bis (tertiarybutylperoxy) diisopropylbenzene, 2 , 5-Dimethyl-2,5-di-tert-butylperoxyhexane, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (tert. Butyl peroxy) valerate, ethyl-3,3-di (tert-butylperoxy) butytate, 3,3,6,9,9-hexamethyl-1,2,4,5-tetraoxa-cyclononane or a mixture of at least two free-radical initiators.

As inorganic solid it is generally possible to use any mineral solid or synthetically produced inorganic solid. Preferred inorganic solids are selected from the group of phosphates, metal hydroxides or metal oxide (hydroxide) s, silicates, carbonates and sulfates.

Further, the solid may be a flame retardant filler. The solid is then preferably selected from the group of ammonium orthophosphates, ammonium diphosphates, ammonium polyphosphates, melamine orthophosphates, melamine diphosphates, melamine polyphosphates, melamine borophosphates. Other alternative solids are selected from aluminum hydroxides, aluminum trihydroxide (ATH), alumina hydroxide (AlOOH.aq), magnesium dihydroxide (MDH), brucite, huntite, hydromagnesite, mica, montmorillonite, calcium carbonate, talc, silicates, kaolin, bentonite, silicic acid, clay, quartz , Wollastonite, titanium dioxide, calcium carbonate (chalk, dolomite), SiO ₂ , precipitated silica, fumed silica, aluminum oxides such as alpha and / or gamma alumina, alumina hydroxides; Boehmite, barite, barium sulfate, lime, silicates, aluminates, aluminum silicates, calcium silicate and / or ZnO or mixtures thereof.

The following flame retardants are preferably used according to the invention as solid a): ammonium orthophosphates, eg. NH4H2PO4, (NH4) 2HPO4 or mixtures thereof (eg FR CROS ™ 282, FABUTIT ™ 747S), ammonium diphosphates, e.g. NH4H3P2O7, (NH4) 2H2P2O7, (NH4) 3HP2O7, (NH4) 4P2O7, or mixtures thereof (e.g., FR CROS ™ 134), ammonium polyphosphates, as particularly, but not exclusively, J. Am. Chem. Soc. 91, 62 (1969) emerge, z. For example, those having crystal structure phase 1 (e.g., FR CROS ™ 480), crystal structure phase 2 (e.g., FR CROS ™ 484) or mixtures thereof (e.g., FR CROS ™ 485), melamine orthophosphates, e.g. C3H6N6.H3PO4, 2C3H6N6.H3PO4, 3C3H6N6.2H3PO4, C3H6N6.H3PO4, melamine diphosphates, e.g. C3H6N6.H4P2O7, 2C3H6N6.H4P2O7 3C3H6N6.H4P2O7 or 4C3H6N6.H4P2O7, melamine polyphosphates, melamine borates, e.g. B. BUDIT ™ 313, melamine borophosphates.

As the solid b) also inorganic or mineral materials are preferably used, as they are not exhaustively enumerated below. They can act in an advantageous manner reinforcing, stretching and flame retardant. They carry at least on their surfaces groups which can react with the alkoxy groups, the hydroxy groups of the siloxanols or the unsaturated silane compound. As a result, the silicon atom having the functional group bonded thereto can be chemically fixed on the surface. Such groups on the surface of the filler are especially hydroxyl groups. Accordingly, preferably used fillers are metal hydroxides with a stoichiometric proportion or, in their different dehydration stages, with a substoichiometric proportion of hydroxyl groups up to oxides with comparatively few remaining, but detectable by DRIFT-IR spectroscopy or NIR spectroscopy hydroxyl groups.

Thus, calcium carbonate, talc and glass fibers can be used as the inorganic solid. Furthermore, so-called "char former", such as ammonium polyphosphate, stannates, borates, talc, or such can be used in combination with other fillers. Preferably, the solids are powdery, particulate, porous, swellable or optionally foamy. For example. may also include foamed glass as a solid, as well as calcined, precipitated, milled or spray-dried variants thereof. Specifically mentioned as preferred solids such as ATH (aluminum trihydroxide, Al (OH) ₃ ), magnesium hydroxide (Mg (OH) ₂ ) or fumed silica (The particle size is usually in the range of a few nanometers, the specific surface area is therefore large and im Generally from 50 to 600 m ² / g), precipitated silica (a largely amorphous silica which generally has a specific surface area of from 50 to 150 m ² / g.) Precipitated silica, in contrast to fumed silica, has a certain porosity, for example about 10 Vol .-%) or a calcium silicate. In addition to a content of inorganic solid may also be present carbon black or preferably carbon black.

An organic polymer is understood as meaning a polymer having a hydrocarbon-based backbone, which may also contain oxygen, nitrogen or sulfur. The siloxane oligomer is based on a Si-O-linked skeleton of its structural elements. The organic polymer in the polymer composition or the organic polymer used in the method of the present invention is an elastomer or a thermoplastic according to the present invention. It is particularly preferred that at least one polymer is selected from the following polymers: acrylonitrile-butadiene-styrene (ABS), polyamides (PA), polymethylmethacrylate (PMMA), polycarbonate (PC), polyethylene (PE), such as LDPE, LLD-PE, m -PE; Polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), chloroprene, and an ethylene-based co-polymer such as ethylene-vinyl acetate (EVA), ethylene-propylene rubber (EPR), ethylene-propylene-diene Rubber (EPDM); Styrene-butadiene rubber (SBR), natural rubber (NR), acrylate copolymer rubber (ACM), acrylonitrile-butadiene rubber (NBR), polybutadiene rubber (BR), celluloid, silane-co-polymerized polymer, silane-grafted polymer, polyvinyl chloride , a derivative of these polymers or a mixture containing at least one of the polymers and, for example, also from unsaturated functional monomers including silanes, such as VTMO, VTEO, and monomers such as ethylene and other olefins prepared base polymers, Therefore, the inventive polymer composition also comprises olefinically functionalized siloxane oligomers grafted polymers or prepolymers, silane-modified PE, silane-modified PP, and / or polymers (compounds) filled with inorganic solids filled with olefinically functionalized siloxane oligomers, especially thermoplastics filled with inorganic solids or elastomers comprising olefinic siloxane oligomers.

Furthermore, the olefinically functionalized siloxane oligomers used may preferably contain from 0 to 5% by weight, preferably from 0.1 to 3% by weight, of fatty acid, in particular of the formula III, ie in relation to the total composition of olefinically functionalized siloxane oligomers at least one fatty acid (100 wt .-%), wherein a content of esterified fatty acid according to formula I with R ¹ independently of one another -CO-R ⁵ with R ⁵ , as defined below, here may be included.

The invention also provides a polymer composition in which the molar ratio of the (i) total amount of the Si atoms of the functionalized siloxane oligomers, in particular of the formula I, to (ii) total amount of fatty acid of the general formula III is 1: 5 × 10 ^-1 to 1: 1 × 1 ^-5 , in particular 1: 5 × 10 ^-2 to 1: 1 × 10 ^-4 , preferably 1: 3 × 10 ^-2 to 1: 1 × 10 ^-4 , particularly preferably 1: 1 × 10 ^-2 to 1: 1 × 10 ^-4 , more preferably 1: 1 × 10 to 1: 1 × 10, according to the invention 1: 5 × 10 ^-3 to 1: 1 × 10 ^-4 , preferably also a range of 1: 2 × 10 ^-3 to 1: 1 x 10 ^-4 . Alternatively, particularly preferred are also 1: 3 × 10 ^-3 to 1: 1 × 10 ^-4 , preferably 1: 2 × 10 ^-3 to 1: 3 × 10 ^-4 , particularly preferably 1: 2 × 10 ^-3 to 1: 5 × 10 ^-4 . Consequently, the fatty acid has already proven itself in small doses as a catalyst or as a cocatalyst for hydrolysis, condensation and / or crosslinking, ie n _Si : n _{fatty acid} = (n _{formula IIa} + n _{formula IV} + n _{formula V} + n _{Si formula IIb} + n _{formula VI} ): (n _{formula III} + (x _{formula IIIIb} n _{formula IIb} ).

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

x _{Formula IIIIIb} , means number of fatty acid molecules of formula III from a formula IIb.

Since the siloxane oligomers used according to the invention themselves did not have to be distilled, the properties of these as bottom products also differ from known olefinic siloxane oligomers which have been purified by distillation. This can be expressed by an altered ratio of M, to D and also to T structures and an optionally higher proportion of higher oligomers.

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 networked Structural elements, which also include spiro compounds, are obtained if structural units T and / or Q are present together. Conceivable crosslinked structures can be described as T _n (n ≥ 4); D _n T _m (m <n); D _n T _m (n >>m); D ₃ T ₂ ; M ₄ Q; D ₄ Q and so on, to name only a few possible options. Building units M are also referred to as stoppers or regulators, while D units are referred to as chain or ring formers and the T and optionally also the Q units as network formers. Thus, the use of tetraalkoxysilanes due to the four hydrolyzable groups and access of water or moisture units Q and thus the formation of a network (space-crosslinked) effect. In contrast, fully hydrolyzed trialkoxysilanes can cause branching, ie, T units [-Si (-O-) _3/2 ], in one structural element, for example MD ₃ TM ₂ for an oligomer having a degree of oligomerization of n = 7, in which structural representations respective functionalities at the free valences of the silyloxy units are to be defined.

• – „Strukturuntersuchungen von oligomeren und polymeren Siloxanen durch hochauflösende 29Si-Kernresonanz“, H.-G. Horn, H. Ch. Marsmann, Die Markromolekulare Chemie 162 (1972), 255–267 ;
• – „Über die 1H-, 13C- und 29Si-NMR chemischen Verschiebungen einiger linearer, verzweigter und cyclischer Methyl-Siloxan-Verbindungen“, G. Engelhardt, H. Jancke; J. Organometal. Chem. 28 (1971), 293–300 ;
• – „Chapter 8 – NMR spectroscopy of organosilicon compounds“, Elizabeth A. Williams, The Chemistry of Organic Silicon Compounds, 1989 John Wiley & Sons Ltd., 511–533 .

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

• - "Structural investigations of oligomeric and polymeric siloxanes by high-resolution 29Si nuclear resonance", H.-G. Horn, H.C. Marsmann, The Markromolecular Chemistry 162 (1972), 255-267 ;
• - "About the 1H, 13C, and 29Si 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 ,

According to the invention, the fatty acid of the formula III can be used in the form of the fatty acid or can also be released from the carboxysilane of the formula IIb, as defined below. According to the invention, the fatty acid is used as a hydrolysis, condensation and / or crosslinking catalyst.

• (i) olefinisch funktionalisierte Siloxanoligomere umfassend mindestens eine Fettsäure der allgemeinen Formel III, wobei die Siloxanoligomere höchstens einen olefinischen Rest am Silizium-Atom aufweisen und Si-O-vernetzte Strukturelemente aufweisen, die kettenförmige, cyclische, vernetzte und/oder raumvernetzte Strukturen bilden, wobei mindestens eine Struktur in idealisierter Form der allgemeinen Formel I entspricht, (R¹O)[(R¹O)_1-x(R²)_xSi(A)O]_a[Si(Y)₂O]_c[Si(B)(R⁴)_y(OR³)_1-yO]_bR³ (I), – wobei die Strukturelemente aus Alkoxysilanen abgeleitet sind und – A in dem Strukturelement einem olefinischen Rest und – B in dem Strukturelement einem gesättigten Kohlenwasserstoff-Rest entsprechen, – Y entspricht OR³ oder in vernetzten und/oder raumvernetzten Strukturen unabhängig voneinander OR³ oder O_1/2, – wobei R¹ unabhängig voneinander einem linearen, verzweigten und/oder cyclischen Alkyl-Rest mit 1 bis 4 C-Atomen, und gegebenenfalls H und/oder -CO-R⁵ mit R⁵, wie nachstehend definiert, entspricht, – 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 ganzen Zahlen entsprechen mit 1 ≤ a, 0 ≤ b; 0 ≤ c, x unabhängig voneinander 0 oder 1 ist, y unabhängig voneinander 0 oder 1 ist, und (a + b + c) ≥ 2, – die Fettsäure entspricht der Formel R⁵-COOH (III) mit R⁵ einem unsubstituierten oder substituierten Kohlenwasserstoff-Rest mit 3 bis 45 C-Atomen, und
• (ii) mit einem organischen Polymer, insbesondere ausgewählt aus einem Elastomer oder Thermoplast, wie vorstehend definiert,
• (iii) mit einem anorganischen Feststoff in einer Compoundierapparatur umgesetzt werden, insbesondere wird in (iii) a) mit einem anorganischen Feststoff, gegebenenfalls einem Radikalbildner und gegebenenfalls einem Antioxidationsmittel in einer Compoundierapparatur umgesetzt werden oder b) in einem ersten Schritt mit einem Radikalbildner und gegebenenfalls einem Antioxidationsmittel und einem anorganischen Feststoff gemischt werden, und in einem nachfolgenden Schritt gegebenenfalls unter Zusatz eines Vernetzungskatalysators in Form gebracht werden und unter Einwirkung von Feuchtigkeit vernetzt werden oder c) mit einem Radikalbildner und gegebenenfalls einem Antioxidationsmittel, einem anorganischen Feststoff und gegebenenfalls unter Zusatz eines Vernetzungskatalysators gemischt werden, in Form gebracht werden und unter Einwirkung von Feuchtigkeit vernetzt werden.

The invention also provides a process for the preparation of a polymer composition containing olefinically functionalized siloxane oligomers, by

• (i) olefinically functionalized siloxane oligomers comprising at least one fatty acid of the general formula III, wherein the siloxane oligomers have at most one olefinic radical on the silicon atom and Si-O-crosslinked structural elements which form chain-like, cyclic, crosslinked and / or spatially crosslinked structures, wherein at least one structure in 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 corresponds to an olefinic radical and B in the structural element corresponds to a saturated hydrocarbon radical, Y corresponds to OR ³ or in crosslinked and / or spatially crosslinked structures independently of one another OR ³ or O _{1 / 2} , - wherein R ^{1 is} independently a linear, branched and / or cyclic alkyl radical having 1 to 4 carbon atoms, and optionally H and / or -CO-R ⁵ with R ⁵ , as defined below, 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 - a, b, c, x and y are independently integers with 1 ≤ a, 0 ≤ b; 0 ≤ c, x is independently 0 or 1, y is independently 0 or 1, and (a + b + c) ≥ 2, - the fatty acid is of the formula R ⁵ -COOH (III) with R ⁵ an unsubstituted or substituted hydrocarbon radical having 3 to 45 carbon atoms, and
• (ii) with an organic polymer, in particular selected from an elastomer or thermoplastic, as defined above,
• (iii) are reacted with an inorganic solid in a compounding apparatus, in particular (iii) a) is reacted with an inorganic solid, optionally a free radical generator and optionally an antioxidant in a compounding apparatus or b) in a first step with a free radical generator and optionally an antioxidant and an inorganic solid, and optionally in a subsequent step Addition of a crosslinking catalyst are brought into shape and crosslinked under the action of moisture or c) are mixed with a free radical generator and optionally an antioxidant, an inorganic solid and optionally with the addition of a crosslinking catalyst, are brought into shape and crosslinked under the action of moisture.

According to an alternative, in the process in (iii) b) in the first step a mixture comprising a free radical generator and optionally an antioxidant and an inorganic solid can be prepared, and in a subsequent step optionally with the addition of a crosslinking catalyst, fed to an extrusion unit, the extrusion, optionally with the introduction of a metallic conductor or conductor bundle, and the extrudate is crosslinked in the presence of moisture.

As antioxidants and / or stabilizers, the following can be used: tetrakis (methylene (3,5-di- (tert.) -Butyl-4-hydrocinnamate)) methane, 2,6-di-tert-butyl-4- methylphenol, 6,6'-di-tert-butyl-2,2'-thiodiprene-cresol, 2 ', 3-bis - [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] ] propionohydrazide, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, octadecyl-3- (3,5-di-tert-butyl 4-hydroxyphenyl) propionates, thiodiethylenebis bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,6-bis (octylthiomethyl) -o-cresol, 2,2'-oxamino-bis [ ethyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (2-tert-butyl-4-thio (-2'-methyl-4-hydroxy-5'-tert .butyl) phenyl-5-methyl) phenyl phosphite, pentaerythrityl tetrakis [3- (3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) propionate], 4,4-bis- (1,1-dimethylbenzyl ) -diphenylamine, 2,2,4-trimethyl-1,2-dihydroquinoline, 2-hydroxy-4-octoxybenzophenone, poly (4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1 , 4-butanedioic acid), tris (2,4-di- (t ert) butylphenyl) phosphate. A compounding apparatus is preferably an extruder or kneader.

Preferred metal deactivators are, for example, N, N'-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine and tris (2-tert-butyl-4-thio (2'-butyl) methyl-4-hydroxy-5'-tert.butyl) phenyl-5-methyl) phenylphosphite.

Another object of the invention is the use of a polymer composition according to the invention for the production of moldings, as water scavengers, in sealants, as drying agents, adhesives, in flame retardant equipment, particularly preferably for the production of moldings, preferably of cables, pipes, hoses, water pipes, medical products.

The following are preferred polymer compositions as well as siloxane oligomers to be used containing at least one fatty acid of the general formula III as well as general preparation examples for their representation. The olefinically functionalized alkoxysilane used for the preparation of the olefinic siloxane oligomers corresponds to 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 (as formula IIa) or a -CO-R ⁵ radical with R ⁵ (as formula IIb), as defined below. 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. The olefinically and optionally saturated hydrocarbon-substituted siloxane oligomer used to prepare the polymer composition is obtained by the reaction of a silane of the formula II and optionally a alkoxysilane of the formula IV functionalized with a saturated hydrocarbon radical, 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. By adding tetraalkoxysilane during the preparation of the siloxane oligomers or before processing, siloxane oligomers having M, D, Q and optionally T structures are formed.

The ratio of M structures to D structures in the present olefinically functionalized siloxane oligomers is preferably in the range from 5: 1 to 1: 5, especially from 4: 1 to 1: 4, preferably from 2: 1 to 4: 1, especially preferably from 2: 1 to 3.5: 1, it being possible where appropriate to additionally form T structures. Alternatively or additionally, preferred compositions contain olefinically functionalized siloxane oligomers having an olefin group to alkoxy group ratio of from 1: 1 to 1: 5, preferably from 1: 1 to 1: 4, with a ratio of 1: 1 in purely olefinically functionalized siloxane oligomers to 1: 2 and in addition alkyl-functionalized siloxane oligomers 1: 1 to 1: 4 are preferred.

Additionally or alternatively, the content of T-structures in the compositions of the olefinically functionalized siloxane oligomers determined by means of ²⁹ Si-NMR is greater than or equal to 5%, 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 more than 9.0%. At the same time, the content of chloride in the siloxane oligomers is particularly low, as stated below.

If the degrees of oligomerization are too high, homogeneous and reproducible product properties can not be achieved with the siloxane oligomers. For adjustment of the degree of oligomerization during the preparation of the composition, it may therefore be preferred for a chain termination at a desired time to use an alkoxytrialkylsilane, such as preferably an ethoxytrimethylsilane or methoxytrimethylsilane, in the composition to be prepared. The siloxane oligomers thus prepared have preferred degrees of oligomerization and thus particularly reproducible property profiles. The degree of oligomerization of the siloxane oligomers can be controlled via the amount of water added as well as by adding a chain stopper.

Siloxane oligomers 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, are particularly preferred.

The chloride content (total chloride) of the siloxane oligomers used is preferably less than or equal to 200 ppm by weight, in particular less than or equal to 100 ppm by weight, preferably less than or equal to 80 ppm by weight, preferably less than or equal to 50 ppm by weight, more preferably less equal to 25 ppm by weight, less than or equal to 20 ppm by weight, less than or equal to 15 ppm by weight, more preferably less than or equal to 10 ppm by weight, more preferably less than or equal to 5, especially less than or equal to 1 ppm by weight, with respect to to the oligomers comprising the fatty acid.

According to an alternative, for the preparation of the polymer composition, the pure olefinically substituted siloxane oligomers with a fatty acid, in particular oligomers of the formula I where a is a number from 2 to 30, preferably 2 to 15, particularly preferably 2 to 10 and a fatty acid, in particular of the formula III used. Preferred olefinic groups or A groups (formula I, II, IIa or IIb) are linear, branched or cyclic, alkenyl, cycloalkenyl-alkylene-functional groups having in each case 2 to 18 C atoms, in particular 2 to 8 C atoms. Atoms, particularly preferred are vinyl, allyl, butenyl, especially 3-butenyl or 2-butenyl; Pentenyl, hexenyl, heptenyl, octenyl, or in particular cyclohexenyl-C1 to C8-alkylene groups, preferably cyclohexenyl-2-ethylene, particularly preferably 3'-cyclohexenyl-2-ethylene or else 2'-cyclohexenyl -2-ethylene; and / or cyclohexadienyl-C1 to C8-alkylene, preferably the olefinic group is a cyclohexadienyl-2-ethylene group. Optionally, the composition may be based on a siloxane oligomer prepared in the presence of tetraalkoxysilane.

According to a second preferred alternative, olefinic and alkyl-substituted siloxane oligomers with a fatty acid, in particular of the formula I with a greater than or equal to 1 and b greater than or equal to 1, and in particular (a + b) equal to a number from 2 to 30, preferably 2 to 15, particularly preferably 2 to 10 and a fatty acid, used for the preparation of a polymer composition. In the case of these siloxane oligomers, 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, a siloxane oligomer prepared in the presence of tetraalkoxysilane can also be used.

According to a concrete alternative, purely vinyl-substituted siloxane oligomers, in particular of the formula I where a is a number from 2 to 30, preferably 2 to 15, particularly preferably 2 to 10 and a fatty acid, in particular of the formula III, are used for the preparation of the polymer composition. According to a further preferred alternative, vinyl- and alkyl-substituted siloxane oligomers, in particular of the formula I with a greater than or equal to 1 and b greater than or equal to 1, and in particular (a + b) equal to a number from 2 to 30, preferably 2 to 15, especially preferably 2 to 10 and containing a fatty acid of formula III used. Also Here, 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.

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

Siloxane oligomers having olefinic and saturated hydrocarbon groups or correspondingly functionalized radicals of the structural elements, in particular as radical B, or the educt (alkoxysilane of general formula IV) as unsubstituted hydrocarbon radical B, preferably have a linear, branched or cyclic alkyl radical 1 to 18 carbon atoms, in particular a methyl, ethyl, propyl and / or octyl group.

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

According to the invention in the olefinic siloxane oligomers and / or in the polymer composition contained fatty acids, in particular of formula III are caproic, enanthic, caprylic, pergonic, capric, lauric, myristic, palmitic, behenic, linolenic or calendic acid, or optionally stearic acid or a mixture of at least two said acids on or correspondingly derived therefrom carboxy groups in a structural element, in particular as the radical R ¹ = -CO-R ^5, the carboxy-fatty acid radical of the formula III. The radical R ⁵ is in each case independently in the formulas I, II or III 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 - of linoleic acid, C ₁₇ H ₂₉ - The alpha-linolenic acid, C ₁₇ H ₂₉ - the gamma-linolenic acid or calendulic acid, which show particularly good properties with respect to the melt flow in a kneading or compounding step with thermoplastic base polymers or in the compounding with elastomers. Depending on the process procedure and the desired properties of the olefinically functionalized siloxane oligomers prepared, it may be preferable to use carboxy-silanes of the formula IIb or mixtures of the formulas III mixed with the carboxy function in the process. This measure allows a precise control of the product properties of the elastomers compounded with the siloxanes according to the invention and / or thermoplastics, for example with regard to the melt flow properties.

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 selected from caprylic acid, myristic acid or their carboxylates in the carboxysilanes of the formula IIb have proven to be particularly suitable. These fatty acids are sufficiently soluble in the reaction mixture and at the same time sufficiently hydrophobic to catalyze the hydrolysis and / or condensation with the olefinic alkoxysilanes of the formula IIa and / or the hydrocarbon-functionalized alkoxysilanes. Depending on the alkoxysilane can be completely dispensed by the use of these catalysts on the addition of a solvent during the reaction, and thereby the efficiency of the process can be significantly improved.

Under a structural element - a monomeric siloxane unit - is consistently understood the single unit M, D, T or Q, ie derived from an alkoxy-substituted silane unit, the is formed 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, siloxane oligomers can be used in the process according to the invention or can be present in the polymer composition comprising the following structural elements, such as preferably:
(R ¹ O) [(R ¹ O) _1-x (R ²⁾ _x Si (A) O] _a R ^1; (R ¹ O) [(R ¹ O) _1-x (R ²⁾ _x Si (A) O] _a; [(R ¹ O) _1-x (R ²⁾ _x Si (A) O] _a; [(R ¹ O) _1-x (R ²⁾ _x Si (A) O] _a R ^1; (R ³ O) [Si (Y) ₂ O] _c ; [Si (Y) ₂ O] _c R ³ , (R ³ O) [Si (Y) ₂ O] _c R ³ ; [Si (Y) ₂ O] _c ; (R ³ O) [Si (B) (R ⁴ ) _y (OR ³ ) _1-y O] _b R ³ ; [Si (B) (R ⁴ ) _y (OR ³ ) _1-y O] _b R ³ , [Si (B) (R ⁴ ) _y (OR ³ ) _1-y O] _b (R ³ O) [Si (B) (R ⁴ ) _y (OR ³ ) _1-y O] _b R ^{3 can form} the chain-like, cyclic and / or crosslinked structures, and in the presence of tetraalkoxysilanes or their hydrolysis and / or condensation products, it is also possible to form spatially crosslinked structures. The structural elements with free valencies on the Si atom are covalently above -O-Si and the free valences on the O atom are saturated with -Si bridged bonds of other structural elements, alkyl or carbonyl groups or hydrogen. The structural elements can assume a random or even statistical arrangement in the condensates, which, as one skilled in the art knows, can also be controlled by the order of addition and the hydrolysis and / or condensation conditions. The general formula I does not reflect the actual structure or composition. It corresponds to an idealized representation. The siloxane oligomers generally comprise 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 substituted with A or B radicals alkoxysilanes of Formulas II (IIa and / or IIb), IV and / or V, arise and / or form under the selected experimental conditions, in particular by the presence of fatty acid and HCl and / or chlorosilane or mixtures thereof.

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

The invention also provides a polymer composition which contains as further component at least one processing aid, organic solvent, water, salt, organic filler, additive, pigment or a mixture of at least two of said components. The components may be added to the composition during the preparation of the composition as well as at a later time.

A particular advantage of the siloxane oligomers used in the polymer composition according to the invention is that they have a much lower content of chloride, preferably the small amount of chloride added during the removal of the hydrolysis alcohol could be reduced or removed for example by passage of nitrogen or use of hexamethyldisilazane , Thus, when processed in cable compositions, these compositions contribute to a significant improvement in fire protection properties. The fatty acid can remain in the product and does not need to be separated. A further advantage of the compositions according to the invention is that they are suitable for food 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 extruder screws could be considerably reduced. Another essential advantage of the olefinically functionalized siloxane oligomers is that they can be used directly as the bottom product, if appropriate after separation of the hydrolysis alcohol and any added solvent, in an economical manner according to the invention.

• (i) ein olefinisch funktionalisiertes Alkoxysilan der allgemeinen Formel IIa, A-Si(R²)_x(OR¹)_3-x (IIa), insbesondere wie vor- bzw. nachstehend definiert, insbesondere ist R¹ unabhängig Methyl-, Ethyl, Propyl-, wie iso-Propyl- oder n-Propyl-,
• (ii) in Gegenwart des Katalysators b) einer Fettsäure der allgemeinen Formel III und einem olefinisch funktionalisierten Carboxysilan der Formel IIb oder einer Mischung dieser; oder alternativ in Gegenwart der Katalysatoren a) und b) ausgewählt aus a) HCl und Chlorsilan sowie b) einer Fettsäure der allgemeinen Formel III und einem olefinisch funktionalisierten Carboxysilan der Formel IIb oder einer Mischung von Katalysatoren aus a) und b), R⁵-COOH (III) A-Si(R²)_x(OR¹)_3-x (IIb), beide unabhängig wie definiert, insbesondere mit x=0, und gegebenenfalls
• (iii) mit einem Alkoxysilan der Formel IV, B-Si(R⁴)_y(OR³)_3-y (IV), wie definiert, insbesondere mit y = 0, und gegebenenfalls
• (iv) mit einem Tetraalkoxysilan der Formel V, Si(OR³)₄ (V), wie definiert, insbesondere mit R³ Methyl oder Ethyl, und
• (v) mit einer definierten Menge Wasser, gegebenenfalls in Gegenwart eines Lösemittels, insbesondere eines Alkohols, zu Oligomeren umgesetzt werden. Der freie Alkohol umfassend den zugesetzten Alkohol und den Hydrolysealkohol wird abdestilliert.

The olefinically functionalized siloxane oligomers are prepared by

• (i) an olefinically functionalized alkoxysilane of the general formula IIa, A-Si (R ² ) _x (OR ¹ ) _3-x (IIa), in particular as defined above or below, in particular R ^{1 is} independently methyl, ethyl, propyl, such as iso-propyl or n-propyl,
• (ii) in the presence of the catalyst b) a fatty acid of general formula III and an olefinically functionalized carboxysilane of formula IIb or a mixture thereof; or alternatively in the presence of the catalysts a) and b) selected from a) HCl and chlorosilane and b) a fatty acid of the general formula III and an olefinically functionalized carboxysilane of the formula IIb or a mixture of catalysts from a) and b), R ⁵ -COOH (III) A-Si (R ² ) _x (OR ¹ ) _3-x (IIb), both independently as defined, 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), as defined, in particular with y = 0, and optionally
• (iv) with a tetraalkoxysilane of the formula V, Si (OR ³ ) ₄ (V), as defined, in particular with R ^{3 is} methyl or ethyl, and
• (V) with a defined amount of water, optionally in the presence of a solvent, in particular an alcohol, are reacted to oligomers. The free alcohol comprising the added alcohol and the hydrolysis alcohol is distilled off.

It may be preferred if the reaction of olefinic alkoxysilanes in the presence of HCl and / or chlorosilane, especially in the presence of HCl, and the content of HCl and / or chlorosilane preferably less than or equal to 0.3 wt .-%, further smaller is equal to 0.1% by weight, in particular from 0.1 to 1 × 10 ^-4 % by weight, with respect to the composition or reaction mixture, preferably less than or equal to 0.05% by weight, more preferably less than or equal to 0.01 wt%, more preferably less than or equal to 0.005 wt%, even more preferably less than or equal to 0.001 wt%, 0.0005 wt%, 0.00025 wt%, 0.00001 wt% %, wherein the content in the reaction mixture is before removal of the hydrolysis alcohol or the free alcohol. Distillation of the olefinic siloxane oligomer as such is no longer necessary. Only the alcohol and / or the hydrolysis alcohol are removed. Preferably, the product directly as the bottom product has a property profile that is suitable for the inventions mentioned inventions. 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.

Preferred alcohols in the preparation of the siloxane oligomers correspond to the hydrolysis alcohol which is formed by the at least partial hydrolysis and / or condensation. These include ethanol or methanol.

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

In the preparation of the olefinic siloxanes is preferably the molar ratio of the (i) total amount of Si atoms of the silanes used of the general formula IIa, formula IV and / or formula V to (ii) total amount of fatty acid used of the general formula III and / or olefinically functionalized carboxysilane of the formula IIb of preferably in the range of 1: 5 × 10 ^-1 to 1: 1 × 10 ^-5 , in particular 1: 5 × 10 ^-2 to 1: 1 × 10 ^-4 , preferably 1: 3 × 10 ^-2 to 1: 1 x 10 ^-4 , more preferably 1: 1 x 10 ^-2 to 1: 1 x 10 ^-4 , further preferably 1: 1 × 10 ^-3 to 1: 1 × 10 ^-4 , according to the invention 1: 5 × 10 ^-3 to 1: 1 × 10 ^-4 , preferably also a range of 1: 2 × 10 to 1: 1 × 10. Alternatively, particularly preferred are also 1: 3 × 10 ^-3 to 1: 1 × 10 ^-4 , preferably 1: 2 × 10 ^-3 to 1: 3 × 10 ^-4 , particularly preferably 1: 2 × 10 ^-3 bis 1: 5 × 10 ^-4 . Consequently, the fatty acid has already proven itself in low doses as a hydrolysis and / or condensation catalyst in the preparation of the siloxanes or as a co-catalyst, ie n _Si : n _{fatty acid / carboxysilane} = (n _{formula IIa} + n _{formula IV} + n _{formula V} ) :( n _{formula III} + n _{formula IIb} )

Consequently, the siloxanes produced have a corresponding molar ratio to the fatty acids used. The Si atoms from formula IIb are considered only if their proportion becomes significant. The silanes of the formulas IIa, IV and / or V and the carboxysilanes of the formula IIb are defined below.

It is further preferred if, in the process for preparing the olefinically functionalized siloxane oligomers, the reaction is carried out by reacting an (i) olefinically functionalized alkoxysilane of the formula IIa (ii) in the presence of the catalysts a) and b) selected from HCl and chlorosilane and selected from b) a fatty acid of the general formula III and an olefinically functionalized carboxysilane of the formula IIb or a mixture of catalysts from a) and b) are reacted, wherein the molar ratio of the total amount of the catalysts used HCl and / or chlorosilane to the total amount of the fatty acid Formula III and / or the carboxysilane of the formula IIb of 8: 1 to 1: 8, in particular 4: 1 to 1: 4, preferably 3: 1 to 1: 3, particularly preferably 2: 1 to 1: 2, and 1: 1 with a fluctuation range of about 0.5 each. According to the invention, HCl and / or chlorosilane is used in the process in approximately equimolar amounts to the fatty acid and / or to the carboxysilane, preferably the chloride is substantially completely removed after the reaction. n _Cl-cat : n _{fatty acid / carboxysilane} = (n _HCl + n _{chlorosilaneVI} ) :( 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 in the presence of HCl or chlorosilane, which cleaves HCl under the process conditions, and in the presence of a fatty acid of formula III and / or a carboxysilane of formula IIb at least partially be hydrolyzed and condensed and, preferably, the alcohol, in particular both the hydrolysis alcohol and the optionally added alcohol is removed. The hydrolysis and / or the added alcohol correspond to the free alcohol. 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 .-% and up to the detection limit.

According to the invention, the olefinically functionalized siloxane oligomers prepared in this way need not be further purified, for example distilled, after removal of the hydrolysis alcohol and optionally solvent itself 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 application, must be purified by distillation.

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

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

Compounds of the formula IIb according to the invention are: vinyltricarboxysilane, such as vinyltrimyristatosilane, vinyltricaprylatosilane, vinyltripalmitatosilane, allyltrimyristatosilane, allyltricaprylatosilane, Allyltripalmitatosilan, Butenyltrimyristatosilan, Butenyltricaprylatosilan Butenyltripalmitatosilan, cyclohexenyl-alkylene-trimyritatosilan, cyclohexenyl-alkylene-tricaprylatosilan, cyclohexenyl-alkylene-tripalmitatosilan, particularly preferably cyclohexenyl-2-ethylene-trimyristatosilan, more preferably 3 cyclohexenyl-2-ethylene-trimyritatosilan, Hexenyltrimyristatosilan, Octenyltrimyristatosilan , Vinyltrimyristatosilane, allyltrimyristatosilane.

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

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

Preferably used olefinic siloxane oligomers were prepared from the following - not final - combinations: 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, iso-Butyltriethoxysilane 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 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, propyltriethoxysilane and tetraethoxysilane with vinyltrimyristatosilane in ethanol and a defined amount of water; Vinyltrimethoxysilane, propyltrimethoxysilane and tetramethoxysilane with vinyltrimyristatosilane in methanol and a defined amount of water, vinyltriethoxysilane and isobutyltriethoxysilane with vinyltrimyristatosilane in ethanol and a defined amount of water, vinyltrimethoxysilane and isobutyltrimethoxysilane with vinyltrimyristatosilane in methanol and a defined amount of water; Vinyltriethoxysilane, isobutyltriethoxysilane and tetraethoxysilane with vinyltrimyristatosilane in ethanol and a defined amount of water; Vinyltrimethoxysilane, iso-butyltrimethoxysilane and tetramethoxysilane with Vinyltrimyristatosilan in methanol and a defined amounts of water.

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

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

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

Preferably, A in formula IIb is a group selected from: vinyl, allyl, butenyl, such as 3-butenyl; Pentenyl, hexenyl, heptenyl, octenyl, cyclohexenyl-C1 to C8-alkylene group, particularly preferably cyclohexenyl-2-ethylene and / or cyclohexadienyl-C1 to C8-alkylene, particularly preferably cyclohexadienyl-2-ethylene Group, particularly preferred is 3'-cyclohexadienyl-2-ethylene, wherein in formula IIb is preferably x = 0 and R ¹ is R ⁵ -CO-, with R ⁵ as defined above.

In addition or as an alternative to one of the abovementioned features, at least one silicone oil, such as polydimethylsiloxane, paraffin, paraffin oil or a mixture comprising one of these processing aids, may be added in the process for the preparation of the siloxane oligomers or subsequently as siloxane oligomers as processing aids. A particularly preferred processing aid is polydimethylsiloxane, preferably having a kinematic viscosity of 200 to 400 mm ² / s, in particular about 350 mm ² / s.

Depending on the desired properties of the siloxane oligomers, it may be expedient to add the inorganic solid already during their preparation, such as preferably the abovementioned inorganic solids. It may also be dyes, pigments or neutral or basic silica sols or silica gels. As auxiliaries and as further components, nanoscale fillers or generally customary fillers can be added to the siloxane oligomers or the polymer composition, for example organic fillers, such as cellulose-containing fillers. Flow aids can also be added.

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 in the art per se, but the reader u. a. the Internet at http://de.wikipedia.org/wiki/Molmassenverteilung or a standard mathematical work. Furthermore, the polydispersity (D) is defined as the quotient of Mw / Mn.

Determination of the total chloride value:

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

Determination of hydrolyzable chloride:

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

Determination of the SiO ₂ content: crucible method:

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

GC analysis:

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

²⁹ Si NMR spectrometry:

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

Determination of the dynamic viscosity:

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

1.1. syntheses

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

1.1.1 Siloxane oligomer of vinyltrimethoxysilane

Only for easier dosing of some starting materials, the following solutions were used: description Solution 1 135 Solution 2 136 Solution 3 137 methanol 99.763g (99.76%) 99.800g (99.80%) - VE water - - 98,924g (98.92%) caprylic 0.240g (0.24%) 0.120g (0.12%) - Hydrochloric acid 37% - 0.083g (0.08%) 1.085g (1.08%) Table 2: Weights of required solutions for the siloxane oligomers of vinyltrimethoxysilane. description 139 140 141 142 153 Vinyl trimethoxy silane 114,807g 111,951g 114,344g 112,980g 114,760g methanol - 71,93g 73,44g 72,59g - VE water 11,32g - 11,30g - 11,34g AK 350 - 5,007g - - - Vinyltrimyristato silane - - 0,920g - - Methoxytrimethyl silane - - - 3,21g - Solution 1 - - - - 73.89 Solution 2 73,89g - - - - Solution 3 - 11,12g - 11,21g - 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 the corresponding experiments in the flask. All other required ingredients are mixed in the dropping funnel. They can also be added separately. At a temperature of about 25 ° C, the contents of the dropping funnel is slowly added dropwise (within about 25 minutes) to the silane or the silane mixture. Following the addition, the oil bath is adjusted to 85 ° C, thus heating the methanol used as solvent to boiling. After a reaction time of 3 hours, the methanol is distilled off at 85 ° C oil bath temperature and a reduced pressure of 150-180 mbar.

The mixture is then stirred for a further hour at 85 ° C oil bath temperature and a pressure of <1 mbar.

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 of methanol and possibly water, the vacuum is adjusted to less than 1 mbar. The bottoms product is the olefinically functionalized siloxane.

1.1.2 Siloxane oligomer of vinyltriethoxysilane

For simpler dosing of some starting materials, the following solutions 4 to 6 were prepared: description Solution 4 127 Solution 5 128 Solution 6 129 ethanol 399.28g (99.82%) 419.36g (99.85%) - VE water - - 100.015g (99.28%) caprylic 0.721g (0.18%) 0.383g (0.09%) - Hydrochloric acid 37% - 0,261g (0.06%) 0.73g (0.72%) Table 4: Weights of the solutions for the preparation of the siloxane oligomers of vinyltriethoxysilane. description 130 131 132 133 vinyltriethoxysilane 128,760g 128,756g 125,522g 128,420g (VTEO) ethanol - - 59,79g 61,17g VE water 9,877g 9,864g - 9,882g AK 350 - - 5,002g - Vinyltrimyristatosilan - - - 0,563g ethoxytrimethylsilane - - - - Solution 4 61,426g - - - Solution 5 - 61,410g - - Solution 6 - - 9,67g - Table 5a: Weights for the preparation of the siloxane oligomers of vinyltriethoxysilane. description 134 152 154 Vinyltriethoxysilane (VTEO) 126,715g 128,708g 128,424g ethanol 60,36g - 61,17g VE water - 9,87g 9,85g AK 350 - - - Vinyltrimyristatosilan - - 0,564g ethoxytrimethylsilane 3,17g - - Solution 4 - 63,42g - Solution 5 - - - Solution 6 9,76g - - Table 5b: Weighers 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 required ingredients are mixed in the dropping funnel. They can also be added separately. At a temperature of about 35 ° C, the contents of the dropping funnel is slowly added dropwise (within about 15 minutes) to the silane or the silane mixture. Following 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, a further hour at 100 ° C oil bath temperature and a pressure of <1 mbar is stirred.

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

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

1.1.4 Siloxane oligomer of vinyltrimethoxysilane

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

Implementation (115):

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

The evaluation of the NMR analyzes shows that an oligomerization in sample 115 has taken place. The structures formed, in contrast to the conventional methods, d. H. normally synthesized VTMO siloxane oligomer about 100% more T structures. GPC analysis also showed changes compared to normal synthesized VTMO siloxane oligomer. The reaction time was five working days.

1.2. analytics

1.2.1. GC analysis

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

1.3.2. GPC analysis

Experiment no. used catalyst components and optionally additive Mn [g / mol] Mw [g / mol] polydispersity 139 Caprylic acid + HCl 4,5150E + 02 5,5107E + 02 1.2205 140 AK 350 (2.5% by weight) 5,2423E + 02 1.0723E + 03 2.0455 141 Vinyltrimyristatosilan 4,0094E + 02 5,4147E + 02 1.3505 142 methoxytrimethylsilane 4,5755E + 02 5,3219E + 02 1.1631 153 caprylic 6,4096E + 02 9,4887E + 02 1.4804 131 Caprylic acid + HCl 4,5608E + 02 1.0679E + 03 2.3415 132 AK 350 (2.5% by weight) 4,2763E + 02 6,3281E + 02 1.4798 133 Vinyltrimyristatosilan 7,1096E + 02 1,5434E + 03 2.1709 134 ethoxytrimethylsilane 4,3111E + 02 7,1118E + 02 1.6496 152 caprylic 3,5322E + 02 1,8590E + 03 5.2630 154 Vinyltrimyristatosilan 3,1931E + 02 5.0283E + 02 1.5747 148 Caprylic acid + HCl 4.0356E + 02 6,3805E + 02 1.5811 149 AK 350 (2.5% by weight) 4,1769E + 02 6,9357E + 02 1.6605 150 Vinyltrimyristatosilan 2,7636E + 02 3,9962E + 02 1.4460 151 ethoxytrimethylsilane 3,9759E + 02 4,8267E + 02 1.2140 Table 10: Results of the GPC evaluations.

1.3.3. NMR analysis

Based on the GC and GPC results, a structural analysis by NMR was additionally performed by the test products listed below: Vers ¹ H and ¹³ C NMR ²⁹ Si NMR analyzes - proportions in the composition [mol%] silane monomer M-structure D structure T structure Other 139 1.3 mol of SiOMe / mol vinyl, no free MeOH VTMO - 40.9% Si 50.7% Si 8.4% Si 140 1.2 mol SiOMe / mol vinyl, no free MeOH, signal for AK 350 VTMO - 34.0% Si 51.9% Si 10.6% Si 3.5% Si AK 350 141 1.2 mol SiOMe // mol vinyl, a little free MeOH VTMO - 50.7% Si 39.6% Si 9.7% Si 142 1.3 mol SiOMe / mol vinyl, no free MeOH, 0.017 mol methoxytrimethyl silane / mol VTMO VTMO - 40.3% Si 48.5% Si 9.4% Si 1.8% Si methoxytrimethylsilane 131 1.5 moles of SiOEt / mole vinyl, a little free EtOH, indicating silicone compound. VTEO - 58.0% Si 38.8% Si 2.5% Si 0.7% Si probably silicone oil 132 1.5 mol SiOEt / mol vinyl, low free EtOH, signal for AK 350 VTEO - 55.2% Si 33.8% Si 2.4% Si 8.6% Si AK350 134 1.5 mol SiOEt / mol vinyl, a little free EtOH, 0.03 mol ethoxytrimethylsilane / mol VTEO VTEO - 60.1% Si 34.0% Si 2.5% Si 3.2% Si ethoxy trimethylsilane, 0.2% Si silicone oil 148 1.0 moles of propylsilyl + 3.1 moles SiOEt / mole vinylsilyl, slightly free EtOH PTEO: VTEO: 3.2% Si - 36.7% Si 35.1% Si 9.9% Si 14.3% Si - 0.8% Si Co-condensate: PTEO: 49.8% VTEO: 50.2% 149 1.0 moles of propylsilyl + 3.1 moles SiOEt / mole vinylsilyl, slightly free EtOH PTEO: VTEO: 1.6% Si - 33.0% Si 31.1% Si 10.0% Si 13.6% Si - 0.9% Si Co-condensate PTEO: 49.4% VTEO: 50.6% 151 1.0 mol of propylsilyl + 3.2 mol of SiOEt / mol of vinylsilyl, a little free of EtOH, 0.08 mol of ethoxytrimethysilane VTEO: PTEO: 2.3% Si - 34.7% Si 34.6% Si 11.6% Si 13.2% Si - 0.6% Si Co-condensate PTEO: 50.1% VTEO: 49.9% 2.7% Si ethoxytrimethylsilane, 0.3% Si silicone oil Table 11: Results of the NMR evaluations.

2. Application engineering experiments

2.1 Uses used

fuel type description polymer EVA (ethylene vinyl acetate) filler ATH (aluminum trihydroxide) stabilizer Irganox 1010 peroxide Dicumyl peroxide (DCUP) Table 8: Overview of the feedstocks used for the kneading tests.

To simplify the weighing of the peroxide, the following solutions were used: Experiment no. Weighing DCUP Weighed siloxane oligomer Siloxane oligomer charge comment 172 0,184g 9,817g 139 VTMO siloxane oligomer, cat .: caprylic acid + HCl 173 0,184g 9,818g 140 VTMO siloxane oligomer, additive: AK350 (lower silane content) 174 0,184g 10,356g 140 VTMO siloxane oligomer, additive: AK350 175 0,184g 9,822g 142 VTMO siloxane oligomer, additive: methoxytrimethylsilane 177 0,184g 9,821g 131 VTEO siloxane oligomer, cat .: caprylic acid + HCl 178 0,184g 9,823g 132 VTEO siloxane oligomer, additive: AK350 (lower silane content) 179 0,184g 10,457g 132 VTEO siloxane oligomer, additive: AK350 180 0,184g 9,818g 134 VTEO siloxane oligomer, additive: ethoxytrimethylsilane 182 0,184g 9,826g 148 VTEO / PTEO siloxane co-oligomer, cat .: caprylic acid + HCl 183 0,184g 9,821g 149 VTEO / PTEO siloxane co-oligomer, additive: AK350 (lower silane content) 184 0,184g 10,339g 149 VTEO / PTEO siloxane co-oligomer, additive: AK350 185 0,184g 9,817g 151 VTEO / PTEO siloxane co-oligomer, additive: ethoxytrimethylsilane Table 13: Weighing tests for kneading tests

2.2 kneading experiments

The following kneading was processed with a temp. Profile of "3 min at 140 ° C, from 140 ° C to 170 ° C in 2 min, 5 min at 170 ° C" at a speed of 30 U / min in HAAKE kneader , From each batch, two plates were pressed at 165 ° C and a load pressure of 20 t. Experiment no. Weighing EVA Weighing ATH Weighing Irganox 1010 Initial weight of siloxane oligomer DCUP solution. Siloxane oligomer DCUP sol. charge Silane designation 19,038g 30,461g 0,190g VTMO siloxane oligomer 156 0.310 g 172 157 0.310 g 173 158 0,327g 174 159 0.310 g 175 161 19,038g 30,461g 0,190g 0.310 g 177 VTEO siloxane oligomer 162 0.310 g 178 163 0,327g 179 164 0.310 g 180 166 19,038g 30,461g 0,190g 0.310 g 182 VTEO / PTEO siloxane co-oligomer 167 0.310 g 183 168 0,327g 184 169 0.310 g 185 170 19,038g 30,461g 0,190g - - blank value Table 14: Weighing weights of the kneading.

2.3 Technical tests

After storage at 23 ° C. and 50% R.H. (relative humidity) in the climatic chamber, specimens for tensile tests and the determination of the water absorption capacity or determination of the melt index were made from the samples prepared.

2.4 Determination of water absorption capacity

The water absorption capacity (see above) was determined after a period of 24 hours and 7 days by a triple determination by storing them for the said period in a water bath at 70 ° C.

Table 15: Results of water absorbency determination.

The 1 Graphically shows the results of the water absorption test. Graphical representation of the results of the water absorption tests (storage 7 d at 70 ° C in a water bath).

2.5 Determination of melt flow rate (MFR)

The processing and evaluation took place in accordance with the DIN ISO 1133 (Method B), the content of which is fully incorporated by reference and made the subject of the application. Testing device: Zwick flow tester 4106. Melt flow index (MFR) or volume flow index determination (MVR) is determined under Shear load and defined temperature (T _PT ) and defined load (m _nom ) of a plastic melt through a standard nozzle. The way change of the stamp is determined over time and according to the formulas MVR and MRF known to the person skilled in the art. In kneading, ~ 7 g of the individual samples were cut into small pieces and, at a temperature of 160 ° C. and a load of 21.6 kg, the melt index ("MFR") was determined.

Table 16: Results of melt index determination.

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

2.6. Determination of tensile properties

The determination of the characteristic sheep took place on the basis of the DIN EN ISO 527-1 . 527-2 . 527-3 , the contents of which are referred to in their entirety and made the content of the application. For this purpose, a sample rod of defined geometry is clamped in the tensile testing machine and loaded uniaxially until breakage (uniaxial elongation at a defined strain rate). The change in stress on the sample rod is recorded by way of the elongation of the specimen and the tensile strength and the elongation at break. Zwick Universal Tester 4115. The tensile properties (elongation at break and tensile strength) after ~ 40 days of storage in a climate chamber at 23 ° C and 50% RH (tensile strength) are determined by means of the test pieces or tensile bars ("bones") produced under "kneading". The samples, with a test speed of 200mm / min and a pre-load of 0.2 MPa, have been determined by a five-fold determination. Experiment no. means median Tensile strength [MPa] Elongation at break [%] Tensile strength [MPa] Elongation at break [%] 156 12.1 132 12.2 130 157 11.2 118 11.1 114 158 10.0 69 10.0 83 159 12.1 98 12.1 97 161 10.7 103 10.8 99 162 9.8 68 9.7 65 163 10.1 84 10.2 95 164 9.8 71 9.9 69 166 9.1 111 9.1 134 167 8.8 59 8.9 55 168 8.9 127 8.9 129 169 8.9 115 8.9 127 170 10.0 68 10.1 66 Table 17: Results of the train characteristic provisions.

3 graphically represents the median of the tensile strength results (vinyl-functional siloxane oligomers stored at 23 ° C and 50% RH for 40 days). 4 graphically represents the mean values of the results of elongation at break.

The results of the performance tests clearly show improved properties of the olefinically functionalized siloxane oligomers prepared with the two catalysts caprylic acid and hydrochloric acid, ie. H. from VTMO, VTEO and the co-condensate of VTEO and PTEO, as the reference formulations of the prior art (Comparative Examples). This is particularly evident in the melt index, the improved tensile strength and the improved elongation at break. Furthermore, the results show that the inventive examples show improved properties in comparison with reference formulations to which silicone oil has been added.

3. Comparative Experiments:

Comparative Example 1

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

Execution:

397.6 g of vinyltrimethoxysilane (VTMO) and 244.6 g of methyltrimethoxysilane were initially charged at 20 ° C. in a 2 l four-necked apparatus with a water cooler and magnetic stirrer. To the mixture was added a solution of 49.9 g of distilled water containing 2400 ppm of hydrogen chloride in 332.8 g of methanol. to a 500 ml dropping funnel was used. After a total of 16 hours, the entire methanol was HCl distilled off at about 300 mbar. Thereafter, the resulting oligomer mixture was distilled to a pressure of about 1 mbar and a boiling interval up to 113 ° C. Thus, 170 g of clear product were recovered. material supplier weighing VTMO Evonik Degussa GmbH 397.6 g MTMS Evonik Degussa GmbH 244.6 g Hydrochloric acid 2400ppm Merck (HCl 37%) water Bidest 49.9 g methanol ROTH 332.8 g Table 18: Raw materials V078

Comparative Example 2:

V081 - Example 6 off EP 0518057 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. The mixture was treated with a solution of 52.82 g containing 1100 ppm of hydrogen chloride distilled water in 351.53 g of methanol. Served with a 500ml dropping funnel. The temperature increased within 26 minutes to about 36 ° C. After a total of 13 hours, the entire methanol was hydrochloric acid distilled off within 2-3 hours at about 300 mbar. Thereafter, the oligomer mixture thus obtained was distilled to a pressure of about 1 mbar and a boiling interval to 100 ° C. Thus, 240 g of clear product were recovered. material supplier weighing VTMO Evonik Degussa GmbH 693.7 g methanol 351.5 g Hydrochloric acid 1100ppm Merck (HCl 37%) water Bidest 52.8 g Table 19: Raw materials V081

The analytical results for the comparative experiments are summarized in Tables 20 to 23:
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 EP 0518057 B1 ) 230 16 52.4 <0.1 <5 Table 20: Analysis results of 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 EP 0518057 B1) 50 <3 48.6 1.7 <5 Table 21: 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 22: Evaluation of GPC analysis results Comparative Experiment no. Proportions in the siloxane oligomer compositions M structure [mol%] D structure [mol%] T structure [mol%] Silane monomer [mol%] 078 52.1 (VS) 9.1 (VS) - (VS) 0.9 (VTMO) 29.3 (MS) 8.6 (MS) - (MS) - (MTMS) 081 91.8 (VS) 6.8 (VS) - (VS) 1.2 (VTMO) Table 23: Results from the ²⁹ Si NMR analyzes on the products from the comparative experiments V078 and V081 [VS = vinylsilyl, MS = methylsilyl]

3.1. Evaluation of the analysis results regarding experiment 115

VTMO-siloxane from experiment 115 Total chloride: mg / kg 40 Hydrol. Chloride: mg / kg 10 SiO 2:% (mass) 55.1 Free methanol:% (mass) 0.1 VTMO:% (mass) 2.9 GPC: Mn g / mol 593.37 GPC: Mw g / mol 745.04 D 1.2556 Table 24: Wet chemical analysis results Experiment no. ¹ H and ¹³ C NMR ²⁹ Si NMR analyzes - proportions in the composition [mol%] monomer M-structure D structure T structure 115 1.3 mol SiOMe, 0.1 mol MeOH 2.10 (VTMO) 37.50 47,20 13,20 Table 25: Results from NMR studies

4. Comparative kneading tests with product from V078, V081 and 115

The following kneading was processed with a temp. Profile of "3min at 140 ° C, from 140 ° C to 170 ° C in 2min, 5min at 170 ° C" at a speed of 30 rpm in the HAAKE kneader. From the batch was then pressed a plate at 190 ° C and a load pressure of 20t. To simplify the addition of the peroxide, silane / peroxide solutions were prepared. Preparation of the measuring bodies: Test specimens for tensile tests and the determination of the water absorption capacity or determination of the melt index were made from the samples prepared after storage at 23 ° C. and 50% RH in a climatic chamber. Siloxane-DCUP-sol. charge Weighing DCUP Weighed siloxane oligomer For trial no. comment V078 9,81g 0.19 g V116 Examples V081 9,81g 0.19 g V118 Table 26: Weighers of the prepared dicumyl peroxide solution. Siloxane soln. charge weighing weighing for trial no. Siloxane oligomer designation comment DCUP siloxane 115 0.19 g 9,81g 154 VTMO siloxane oligomer 115 Table 27: Weights of the prepared dicumyl peroxide solution. Experiment no. weighing weighing weighing Siloxane oligomeric DCUP solution. Batch comment EVA ATH DCUP silane sol. V116 0.45 g V078 V118 27,72g 61,61g 0.44 g V081 Examples Experiment no. EVA ATH DCUP soln. Siloxane oligomer DCUP sol. charge Siloxanol monomer designation Irganox VTMO siloxane oligomer 154 27,72g 61,60g 0.44 g 115 0,28g Table 28: Weighing AT experiments.

Melt Flow Index (MFR) and Volume Flow Index (MVR) Determinations ~7 g of the individual samples were chopped and melt index ("MFR") determined at a temperature of 160 ° C and a load of 21.6 kg. Examples test number V116 V118 raw material V078 V081 Type VTMO / MTMS VTMO test temperature 160 ° C preheating 4min loading weight 21.6 kg MFR g min 3.19 3.39 MVR ccm min 2.36 2.51 Density g / ccm 1,352 1,348 Table 29: Application techniques MFR and MVR of the patent examples VTMO siloxane oligomer test number 153 154 raw material 115 Type blank test temperature 160 ° C preheating 4 min loading weight 21.6 kg MFR g / 10min 2.03 3.39 MVR ccm / 10min 1.50 2.51 Density g / ccm 1,349 1,349 Table 30: Results of MFR and MVR determination

Determination of water absorption capacity

The water absorption capacity was determined by means of the test specimens after a period of 24 hours by a triple determination by storing them in the water bath at 70 ° C. for the said period of time. info test number Value [mg / cm2] 7d storage Without silane 153 3.81 Experiment with fatty acid and HCl as catalyst 154 1.24 Table 31: Results of water absorbency

Determination of tensile properties

The processing and evaluation took place as in point 3.2.3. explained. After 24 hours of storage in a climatic room at 23 ° C and 50% RH, the tensile properties (elongation at break and tensile strength) of the samples, with a test speed of 200 mm / min and an initial force of 0.2 MPa has been determined by a five-fold determination. AT test number V153 154 UN Commodity 115 comparison calculation blank Elongation at break [%] εB median 71,30 80.37 Tensile strength [MPa] σM median 8.91 8.66 Table 32: Determination of tensile properties

4.1 Determination of gel content 154

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

Extraction:

After eight hours of extraction at 160 ° C, the baskets were removed from the extraction constructions and dried at about 140 ° C for three hours. test number Uncrosslinked gel content Crosslinked gel content 154 2.15% 34.94% Table 33: Gel content 154

QUOTES INCLUDE IN THE DESCRIPTION

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

Cited patent literature

• EP 0518057 B1 [0004, 0118, 0120, 0122]
• CN 100343311 C [0006]
• JP 10-298289A [0007]
• JP 2004-099872 [0008]

Cited non-patent literature

• J. Am. Chem. Soc. 91, 62 (1969) [0021]
• "Structural investigations of oligomeric and polymeric siloxanes by high-resolution 29Si nuclear resonance", H.-G. Horn, H.C. Marsmann, The Markromolecular Chemistry 162 (1972), 255-267 [0034]
• "About the 1H, 13C, and 29Si NMR chemical shifts of some linear, branched, and cyclic methyl siloxane compounds", G. Engelhardt, H. Jancke; J. Organometal. Chem. 28 (1971), 293-300 [0034]
• "Chapter 8 - NMR spectroscopy of organosilicone compounds", Elizabeth A. Williams, The Chemistry of Organic Silicon Compounds, 1989 John Wiley & Sons Ltd., 511-533 [0034]
• "Modern Size Exclusion Liquid Chromatography", Andre Striegel et al., Published by Wiley & Sons, 2nd Ed. 2009 [0083]
• DIN 53015 [0091]
• DIN ISO 1133 [0113]
• DIN EN ISO 527-1 [0115]
• 527-2 [0115]
• 527-3 [0115]

Claims (17)

A polymer composition comprising olefinically functionalized siloxane oligomers, at least one organic polymer and an inorganic solid, wherein the siloxane oligomers have 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 Have O-crosslinked structural elements which form chain-like, cyclic, crosslinked and / or spatially crosslinked structures, wherein 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 carbon atoms, and optionally H and / or -CO-R ⁵ with R ⁵ , as defined below, Each R ³ independently of one another is a linear, branched and / or cyclic alkyl radical having 1 to 4 C atoms, and R ² and / or R ^{4 are} each independently a linear, branched or cyclic alkyl radical having 1 to 15 C atoms - a, b, c, x and y are independently integers with 1 ≤ a, 0 ≤ b, 0 ≤ c, x is independently 0 or 1, y is independently 0 or 1, and (a + b + c) ≥ 2, - the fatty acid corresponds maybe R ⁵ -COOH (III) with R ⁵ an unsubstituted or substituted hydrocarbon radical having 3 to 45 carbon atoms, and the siloxane oligomers are optionally chemically bonded to the inorganic solid. A composition according to claim 1, characterized in that it comprises as further components at least one radical generator or its degradation products, auxiliaries, additives, processing aids and / or a pigment. A composition according to claim 1 or 2, characterized in that the radical generator is an organic peroxide and / or an organic perester, in particular tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, dicumyl peroxide, di-tert-butyl peroxide and / or tert-butylcumyl peroxide, 1,3-di (2-tert-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexine (3), di-tert-amyl peroxide , 1,3,5-tris (2-tert-butylperoxy-isopropyl) benzene, 1-phenyl-1-tert-butylperoxyphthalide, alpha, alpha'-bis (tert-butylperoxy) -diisopropylbenzene, 2, 5-dimethyl-2,5-di-tert-butylperoxyhexane, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (tert. butylperoxy) valerate, ethyl 3,3-di (tert-butylperoxy) butytate, 3,3,6,9,9-hexamethyl-1,2,4,5-tetraoxa-cyclononane or a mixture of at least two free radical generators. Composition according to one of claims 1 to 3, characterized in that the inorganic solid is selected from the group of metal hydroxides, metal oxide (hydroxide) s, phosphates, silicates, carbonates and sulfates. Composition according to Claims 1 to 4, characterized in that the solid is selected from the group of ammonium orthophosphates, ammonium diphosphates, ammonium polyphosphates, melamine orthophosphates, melamine diphosphates, melamine polyphosphates, melamine borophosphates, aluminum hydroxides, aluminum trihydroxide (ATH), aluminum oxide hydroxide (AlOOH.aq), magnesium dihydroxide (MDH). , Brucite, huntite, hydromagnesite, mica, montmorillonite, calcium carbonate, talc, silicates, kaolin, bentonite, silicic acid, clay, quartz, wollastonite, titanium dioxide, calcium carbonate (chalk, dolomite), SiO ₂ , precipitated silica, fumed silica, aluminum oxides, such as alpha and / or gamma-alumina, alumina hydroxides; Boehmite, barite, barium sulfate, lime, silicates, aluminates, aluminum silicates, calcium silicate and / or ZnO or mixtures thereof. Composition according to one of claims 1 to 5, characterized in that - R ⁵ in formula III or I preferably 7 to 26 carbon atoms, - in formula I, the olefinic radical A is a non-hydrolyzable olefinic radical, in particular a linear, branched or cyclic, alkenyl or cycloalkenyl-alkylene-functional group having in each case 2 to 18 C atoms, preferably a vinyl, allyl, butenyl, such as 3-butenyl, pentenyl, hexenyl, heptenyl, octenyl, Cyclohexenyl-C1 to C8-alkylene group, preferably cyclohexenyl-2-ethylene, such as 3'-cyclohexenyl-2-ethylene and / or cyclohexadienyl-C1 to C8-alkylene, preferably a cyclohexadienyl-2-ethylene group, and / or its polymerization product; and / or independently thereof - in formulas I 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, optionally R ^{5 is} independently in formulas I or III a monovalent radical -C _n H _{2n + 1} , where 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 -. Composition according to any one of Claims 1 to 6, characterized in that the polymer is an elastomer or a thermoplastic. Composition according to any one of Claims 1 to 7, characterized in that the polymer comprises at least one acrylonitrile-butadiene-styrene (ABS), polyamides (PA), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene (PE), such as LDPE, LLD -PE, m-PE; Polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC) and an ethylene unit-based co-polymer such as ethylene-vinyl acetate (EVA), ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber ( EPDM); Styrene-butadiene rubber (SBR), natural rubber (NR), acrylate copolymer rubber (ACM), acrylonitrile-butadiene rubber (NBR), polybutadiene rubber (BR), celluloid, silane-co-polymerized polymer, silane-grafted polymer, silane modified PE, silane-modified PP, a derivative of these polymers, or a mixture containing at least one of the polymers. Composition according to any one of Claims 1 to 8, 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 9, characterized in that b is greater than or equal to 1. A composition according to any one of claims 1 to 10, characterized in that the molar ratio of the (i) total amount of Si atoms of the functionalized siloxane oligomers, in particular of the formula I to (ii) total amount of fatty acid of the general formula III 1: 5 × 10 ^-1 to 1: 1 × 10 ^-5 , in particular 1: 5 × 10 ^-2 to 1: 1 × 10 ^-4 , preferably 1: 3 × 10 ^-2 to 1: 1 × 10 ^-4 , particularly preferably 1: 1 × 10 ^-2 to 1: 1 x 10 ^-4 . Process for the preparation of a polymer composition containing olefinically functionalized siloxane oligomers, comprising (i) olefinically functionalized siloxane oligomers comprising at least one fatty acid of general formula III, wherein the siloxane oligomers have at most one olefinic radical on the silicon atom and Si-O-crosslinked structural elements which form the chain-like, form cyclic, crosslinked and / or spatially crosslinked structures, where at least one structure in idealized form corresponds to the general formula I, (R ¹ O) [(R ¹ O) _1-x (R ²⁾ _x Si (A) O] _a [Si (Y) ₂ O] _c [Si (B) (R ⁴⁾ _y (OR ³⁾ _{1 -YO} ] _b R ³ (I), Wherein the structural elements are derived from alkoxysilanes and A in the structural element 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 to 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 independently correspond to integers with 1 ≤ a, 0 ≤ b; 0 ≤ c, x is independently 0 or 1, y is independently 0 or 1, and (a + b + c) ≥ 2, - corresponds to the fatty acid R ⁵ -COOH (III) R ^{5 is} an unsubstituted or substituted hydrocarbon radical having 3 to 45 C atoms, and (ii) reacted with an organic polymer and (iii) with an inorganic solid in a compounding apparatus. A method according to claim 13, characterized in that the organic polymer is selected from an elastomer or thermoplastic. Method according to claim 12 or 13, characterized, that according to (iii) a) is reacted with an inorganic solid, a radical generator and optionally an antioxidant in a compounding apparatus, or b) is mixed in a first step with a free radical generator and optionally an antioxidant and an inorganic solid, and in a subsequent step, optionally with the addition of a crosslinking catalyst is shaped and crosslinked under the action of moisture, or c) is mixed with a free radical generator and optionally an antioxidant, an inorganic solid and optionally with the addition of a crosslinking catalyst, is brought into shape and is crosslinked under the action of moisture. A method according to claim 14, characterized in that in (iii) b) in the first step, a mixture comprising a free radical generator and optionally an antioxidant and an inorganic solid is prepared, and in a subsequent step, optionally with the addition of a crosslinking catalyst is fed to an extrusion unit, the Extrusion, optionally with the introduction of a metallic conductor or conductor bundle, carried out and the extrudate is crosslinked in the presence of moisture. Polymer composition of organic polymers comprising at least one fatty acid and inorganic solids obtainable by a process according to claims 12 to 15. Use of a composition according to any one of claims 1 to 15 as water scavengers, in sealing compounds, in flameproofing equipment, as a desiccant, for the production of moldings, of cables, pipes, hoses, as adhesives, in medical products.

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