Process for manufacturing organic silicon compounds

The invention relates to a process for the addition of silanes or siloxanes which have SiH groups to compounds having olefinic double bonds in the presence of a dissolved platinum⁽⁰⁾complex catalyst and with an activating amount of at least one unsaturated hydrocarbon.

SiC-linked, organomodified siloxanes, especially polyether siloxanes, are an industrially very important class of substances with their widely adjustable surfactant behavior. The established route for the production of these substances lies in the platinum metal-catalyzed addition of siloxanes and silanes carrying SiH groups to olefinically functionalized compounds, such as eg on allyl polyether.

The use of platinum catalysts for the addition of silanes or siloxanes with SiH groups to compounds having one or more olefinic double bonds is known (hydrosilylation) and, for example, in the book "Chemistry and Technology of Silicones", Verlag Chemie, 1960, page 43, and in the patent literature, for example in DE-A-26 46 726, EP-A-0 075 703 and US-A-3 775 452. In today's operational practice, mainly hexachloroplatinic acid and cis-diamminoplatin (II) chloride have become established.

As simple as this reaction principle can be described, its reproducible implementation on an industrial scale is often complicated.

On the one hand, this addition reaction only proceeds without any appreciable formation of by-products if the compounds which have olefinic double bonds are free of groups which can react with the SiH group in competition with the addition reaction. For this, the hydroxyl group bound to carbon must be taken into account in particular.

On the other hand, the amounts of platinum metal required in parts by weight per million parts by weight of the hydrosilylation mixture in order to obtain useful results are often so high that these processes become economically uninteresting.

In particular, however, a lack of SiH conversions leads to an undesirable increase in molecular weight due to the re-formation of SiOSi bonds. As a result of this cross-linking, the viscosity of these products cannot be kept within the specified ranges.

Even active catalyst systems, such as, for example, those of the Karstedt type (US Pat. No. 3,814,730), tend to deactivate and shutdown phenomena in the production of organomodified siloxanes, in particular allyl polyether siloxanes, so that there is often a need for post-catalysis and / or the drastic temperature increase results in the addition reaction.

It has also been found in some cases that it is detrimental to the hydrosilylation if the known platinum catalysts are used above the normal catalyst weight fractions and / or at high temperatures. These stricter reaction conditions accelerate the formation of rearranged by-products.

WO-A-98/00463 describes defined solid compounds with high decomposition temperatures (144.3 ° C. and 138.4 ° C.) which, starting from the Karstedt catalyst, provide an active and at the same time stable catalyst system by adding selected electron-poor olefins for homogeneous hydrosilylation. The increased activity is attributed to the introduction of strong π-acid ligands, such as, in particular, methyl naphthoquinone or tetraethyl tetracarboxylatoethylene.

In the examples given, triethylsilane is added to vinyltrimethylsilane, the olefin component being used in a 100% excess. Despite this high excess and taking into account that the vinyl group, unlike the allyl group, is not isomerization-active, the catalysis switches off after 2 hours at 50 ° C., with the SiH conversion only reaching 68%. At 73 ° C, this catalyst system decomposes immediately and only leads to 18% SiH conversion (P Steffanut et al., Chem. Eur. J. 1998, 4, No. 10, page 2014).

All of the measures mentioned at the outset for increasing the SiH conversion have so far only had a disadvantageous effect on the achievable product qualities with regard to sensory and technical properties.

The usability of products resulting from the platinum metal-catalyzed addition reaction of siloxanes bearing SiH groups to compounds having olefinic double bonds is in particular directly linked to the conversion achieved in hydrosilylation; that is, minimizing remaining SiH functions. Residual SiH leads to uncontrollable hydrolysis and crosslinking processes, which in particular in the case of addition compounds of high molecular weight lead to gelling and render the products unusable.

In practice, there has been no lack of effort, especially in the case of the alkylsiloxane-polyether siloxane copolymers used as emulsifiers, which are produced in the course of a three-stage addition reaction, residual SiH functions by applying excess ethylene as an SiH-binding auxiliary olefin to the reaction matrix intercept.

However, this measure does not have the desired efficiency, so that about 2 to 3% of unreacted silicon hydrogen (based on the starting siloxane) remains. Experience has shown that such a product is not stable in storage and suffers gelling.

Particularly sensitive indicators of deviations from the quality level are, for example, those allyl polyether siloxanes which are used as foam stabilizers in the production of flexible PU foams. The activity and cell fineness are criteria for assessing the stabilizer quality as application parameters. Process changes in stabilizer manufacture, such as the change in the catalytic conditions during the SiC coupling reaction has an influence on the foam quality.

There is therefore a need for a catalyst which overcomes the disadvantages of the prior art and on the one hand has a high activity with regard to the attachment of the SiH groups to olefinic double bonds and on the other hand leads to fewer side reactions, in addition to the aforementioned rearrangement reaction, competition reactions in the form of the reaction of the SiH groups with OH groups of the polyethers and also disproportionation reactions within the silane or siloxane compounds used should be avoided. This is to be understood as a redistribution of the SiH groups in the silane or siloxane usually present in the mixture. The technical problem to be solved is also defined, in particular, in being able to carry out the SiC linkage reaction at low temperatures as quantitatively and reliably as possible, even in conventional steel reactors.

Surprisingly, it has now been found that all of the difficulties discussed at the outset and familiar to the person skilled in the art in the SiC coupling reaction can be remedied if the auxiliary olefins are not added to the reaction mixture after the addition reaction has ended, but before the addition of platinum⁽⁰⁾ -Complex catalyst solutions, in particular commercially available Karstedt complexes, these with effective amounts of activating C_2-6Acted on olefins, added to the reaction mixture and the hydrosilylation at moderate temperatures, preferably between about 20 ° C to about 150 ° C, but especially below about 60 ° C. In this way, a highly active and safe-to-use platinum catalyst is obtained, which leads the desired reaction to the quantitative SiH conversion without further measures.

The invention therefore relates to a process for the preparation of high purity polyorganosiloxanes and polyorganosilanes by the addition of siloxanes and / or silanes which contain at least one H - Si group to compounds with olefinic double bonds in the presence of a platinum catalyst and, if appropriate, further additional components, is characterized in that you can implement in the presence of a platinum⁽⁰⁾-Complex catalyst, which was dissolved in a solvent before the addition to the reaction medium and the solution of which was mixed with an effective amount of at least one unsaturated hydrocarbon having 2 to 6 carbon atoms.

Another object of the invention is a method for activating platinum⁽⁰⁾ -Complex catalysts, characterized in that solutions of these catalysts at temperatures which are preferably in the range from about 0 ° C to about 30 ° C, with an effective amount of at least one unsaturated hydrocarbon having 1 to 6 carbon atoms, which is preferably free of electron-withdrawing substituents.

According to the invention, the effective minimum amount is defined as the amount of olefin, which significantly improves the activity of the catalyst used and also allows the reaction to be carried out in practical times. Activity is understood to be the combination of a low light-off temperature and the ability to completely convert the SiH compounds.

The amounts of activating olefins are advantageously such that the starting temperature of the hydrosilylation reaction intended according to the invention is approx. 20 to 30 ° C. below the starting temperature of the hydrosilylation reaction, which is the use of the non-activated platinum⁽⁰⁾complex catalyst itself allows. In particular, however, the amounts are such that the reaction (addition) temperatures are in the range from approximately 20 to 50 ° C., quantities which bring about starting temperatures of the catalyst below approximately 25 to 30 ° C. being very particularly preferred. This is usually ensured at the saturation concentration of the activating olefin in the respective solvent.

The platinum which can also be used according to the invention for the activation ⁽⁰⁾ Complex catalysts are the catalysts belonging to the prior art, in particular the known platinum complexes of siloxanes, silanes, organopolysiloxanes and organosilanes with unsaturated hydrocarbon radicals.

According to the invention, Karstedt complexes are particularly preferred as catalysts. Reference is made to US Pat. No. 3,775,452 as a reference for these compounds and the processes for their preparation. Complexes with divinyl-tetramethyl-disiloxane radicals are particularly preferred according to the invention.

In addition, other stable zero-valent platinum-olefin complexes such as bis-1,5-cyclooctadiene-platinum are also suitable⁽⁰⁾ and tris-norbornene platinum⁽⁰⁾, Di-platinum-tris (heptadiene-1.6), platinum (η2, η2-1.2.6.7-heptadiene-1.6) (η2-1.2-heptadiene-1.6) and platinum - (η2-ethylene) (η2, η2-1,2,6,7-heptadiene-1,6).

The activation of the catalysts according to the invention is preferably carried out in such a way that a 0.1 to 10%, preferably 0.5 to 5%, solution of the catalyst in a solvent or solvent mixture is initially taken, and an activating olefin is preferably applied at room temperature and the mixture is introduced into the reactant mixture of the hydrosilylation immediately or, if appropriate, after preferably cooled storage, without any further treatment.

According to the invention, propene, butene-1, butene-2, pentenes, hexenes, cyclohexene and in particular ethylene are preferably used as activating olefins. In addition, such substituted ethylenes are suitable as activating ligands whose substituents correspond to Houk's definition of X substituents (electron donor substituents) (Ian Fleming, Grenz Orbitals and Reactions of Organic Compounds, Verlag Chemie, Weinheim 1979, p. 137 and KN Houk, J Am. Chem. Soc. 95, 4092 (1973)).

This finding is completely unexpected for the person skilled in the art, since this is in contrast to the experience and teachings of the prior art. WO-A-98/00463 teaches that electron-deficient olefins should be used as exchange ligands to activate the Karstedt complex. However, these substituted ethylenes correspond to Houk's definition of Z substituents (electron acceptor substituents) (loc.cit.).

It is assumed that the clearly demonstrable increase in activity in the context of the process according to the invention, which is evident in particular from a drastic reduction in the light-off temperatures in the hydrosilylation and also in an increased selectivity and in quantitative SiH conversions, is caused by one with which Olefin loading triggered, cascade of dissociation and association processes, the novel platinum⁽⁰⁾- spawn species. This new kind of platinum⁽⁰⁾-Complexes act as astonishingly active catalysts and open up possibilities for the technical implementation of hydrosilylation reactions in a way which is not foreseeable for the person skilled in the art.

The amount of activating olefin ligand added, based on the solution of the catalyst, is chosen such that it lies in the solution of the catalyst complex from the minimum effective concentration to the saturation concentration of the olefin or beyond. It has been found that the saturation concentration of the olefin in the respective solvent that can be set in the system under normal pressure at room temperature certainly leads to sufficient activation of the catalyst system.

The ratio of the catalyst originally used to the catalyst according to the invention results from the respective concentration / saturation concentration. The saturation concentration of ethylene in various organic solvents is described, for example, by A. Saghal, HM La and W. Hayduk in "Solubility of Ethylene in several Polar and Non-Polar-Solvents", The Canadian Journal of Chemical Engineering, Vol. 56, June 1978, p. 354-357.

The respective minimum effective concentration can be determined in the catalyst system under consideration by means of a few simple orientation tests.

It is essential to the invention to treat the known catalysts of the prior art with a sufficient amount of an activating olefin. The manner, the time and the temperature of the treatment are not critical and can be varied within wide limits.

If desired or required for operational or technical reasons, the preferred procedure outlined above can be modified to the respective technical or operational concerns. For example, activating olefin can also be initially introduced into the reactor together with small amounts of the reactant system and, if appropriate, with one or more solvents, and the catalyst can then be added. This in-situ activation can take place either in one step or by controlled dosing of the catalyst precursor. However, the procedure described here is not preferred since it requires increasing amounts of activating olefins.

Mixtures of two or more of the activating olefins can also be used to adjust the desired catalytic activity and selectivity. According to the invention, activity and selectivity relate to the system to be catalyzed in each case.

Suitable solvents according to the invention are all organic solvents which are inert under the reaction conditions, in particular hydrocarbons, such as, for example, aliphatic, cycloaliphatic and optionally substituted aromatic hydrocarbons such as, for example, pentane, hexane, heptane, cyclohexane, methylcyclohexane, decalin, toluene, xylene, etc. Educts can also be used as solvents, provided they are suitable for keeping sufficient amounts of the catalyst in a homogeneous solution.

The catalyst solutions activated according to the invention are used in the system-dependent concentrations customary for hydrosilylation reactions.

The amount of platinum catalyst to be used depends essentially on the reactivity and the molecular weight of the reactants. Generally 10 is used^-2 until 10^-8 Moles, preferably 10^-3 until 10^-6 Mol of the catalysts per 1 mol of SiH groups in the silane or siloxane.

The catalysts activated according to the invention can be used over a wide temperature range. In order to avoid the product-damaging side reactions described in the prior art, the temperature range is preferably chosen to be so low that it represents an acceptable compromise between the desired product purity and the production output. The ethylene-activated systems preferred according to the invention surprisingly catalyze very satisfactorily even from 20 ° C. under weak exothermic conditions. To achieve higher throughput rates, the reaction temperature can also be increased considerably (up to approx. 150 ° C) without deactivation and switch-off phenomena.

The optimal reaction temperatures are in some cases considerably below the temperatures required in the prior art when using the known technical catalyst systems. According to the prior art, for example, a polysiloxane-polyoxyalkylene block copolymer is used in a one-step process at approx. 100 ° C using cis-diamminoplatin (II) chloride as a catalyst (10 ppm platinum based on the total batch), while the catalyst system claimed according to the invention enables the production of this PU soft foam stabilizer even at reaction temperatures ≤ 36 ° C (Example 1).

According to the invention, the process is preferably carried out at normal pressure, but deviating pressure ranges are also possible, if desired.

The reactants, ie the silanes or siloxanes containing SiH groups and the organic compounds having olefinic double bonds, and processes for their preparation are known. The silanes or siloxanes are described, for example, in the book "Chemistry and Technology of Silicones", Verlag Chemie, 1960.

Examples of suitable organosilicon compounds with SiH groups are:<ul id="ul0001" list-style="dash" compact="compact"><li>monomeric silanes, such as R₃SiH; R₂SiH₂; RSiH₃;</li><li>cyclic silanes, such as (RHSiO}₄; (RHSiO}₃;</li><li>linear or branched oligomeric or polymeric siloxanes such as R₃SiO- (R₂SiO-)_a (RSi (H) O-) _bSiR₃ where a ≥ 0 and b ≥ 1; MR₂SiO- (R₂SiO-)_c(RSi (H) O-)_dSiR₂H, where c and d ≥ O;<chemistry id="chem0001" num="0001"><img file="EP1520870B1_D0001.tif" /></chemistry></li></ul>wherein<ul id="ul0002" list-style="none" compact="compact"><li>e ≥ 0,</li><li>f ≥ 1 and</li><li>g ≥ 1</li></ul>is.

In the above formulas, R denotes groups which do not hinder the addition reaction, such as alkyl groups having 1 to 8 carbon atoms; substituted alkyl groups having 1 to 8 carbon atoms, such as the 3-chloropropyl, 1-chloromethyl, 3-cyanopropyl group; Aryl groups such as the phenyl group; Aralkyl groups such as the benzyl group; Alkoxy or alkoxyalkyl groups, such as the ethoxy or ethoxypropyl group. Here, R can also have different meanings within a molecule. However, preference is given to compounds in which all the radicals R or their predominant number have the meaning of a methyl radical.

Examples of suitable organic carbon compounds with olefinic double bonds are compounds of the formulas         CH₂= CH-CH₂-O- (CH₂-CH₂O-)_x-CH₂-CH (R ') O-)_y(SO)_e.g.-R "         CH₂= CH-O- (CH₂-CH₂O-)_x-CH₂-CH (R ') O-)_y-R "         CH₂= CH-CH₂-R^IV        CH₂= CH- (O)_{x '} -R^IVwherein<ul id="ul0003" list-style="none" compact="compact"><li>x = 0 to 100,</li><li>x '= 0 or 1,</li><li>y = 0 to 100,</li><li>z = 0 to 100,</li></ul><dl id="dl0001" compact="compact"><dt>R '</dt><dd>is an optionally substituted alkyl group having 1 to 4 carbon atoms and</dd><dt>R "</dt><dd>a hydrogen radical or an alkyl group with 1 to 4 carbon atoms; the group -C (O) -R '"with R'" = alkyl radical; the group -CH₂-O-R '; an alkylaryl group such as the benzyl group; the group means -C (O) NH-R '.</dd><dt>R^IV</dt><dd>an optionally substituted hydrocarbon radical having 7 to 47, preferably 13 to 37, carbon atoms,</dd><dt>SO</dt><dd>the rest C₆H₅-CH (-) -CH₂-O-</dd></dl>means.

Furthermore, there are, for example, compounds of the formulas<chemistry id="chem0002" num="0002"><img file="EP1520870B1_D0002.tif" /></chemistry><chemistry id="chem0003" num="0003"><img file="EP1520870B1_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP1520870B1_D0004.tif" /></chemistry>suitable.

The catalysts activated according to the invention have the following advantages in particular over the catalyst systems described in the prior art:<ul id="ul0004" list-style="none" compact="compact"><li>a) The activated catalyst already shows a catalytic activity from a temperature of 20 ° C, as is observed with other hydrosilylation catalysts only at significantly higher temperatures. This characteristic is of particular importance for operational practice, since long and costly heating and cooling phases can be dispensed with when carrying out production approaches. This time saving decisively increases the system capacity, thus the productivity and thus the economy.</li><li>b) Along with the comparatively low reaction temperatures which the use of the catalyst activated according to the invention permits, thermodynamically favored side reactions are strongly suppressed, which is reflected in the quality of the reaction products obtained. For example, in reaction systems which are susceptible to an allyl-propenyl rearrangement, a greatly reduced formation of the degradation product propionaldehyde is observed. This reduced side reaction not only improves the olfactory quality of the products obtained (avoidance of the pungent odor sometimes caused by the aldehyde content), but also helps, for example in the case of the hydroxy-functional silicone polyethers, to prevent undesired molecular weight build-up by acetal formation on the aldehyde. This ensures the viscosity stability of the products and thus their rheological behavior in the respective application.</li><li>c) The catalyst activated according to the invention can be used successfully over a very wide temperature range without registering a loss of activity or switch-off phenomena. This flexibility with regard to the reaction temperature to be selected also permits the addition of compounds bearing SiH groups to conventionally kinetically inhibited olefinic substrates. For the production of sophisticated SiC linkage products on an industrial scale, in which 2 or more olefinic substrates are added in a multi-stage process, it is also essential that reaction batches carried out in the metering process show no undesirable build-up of reactant concentrations (reactant accumulation) in the boiler. Uncontrollable, sudden exotherms, especially in the case of the SiH-rich systems, can otherwise trigger critical operating conditions that endanger product quality and occupational safety. The use of the catalyst claimed according to the invention therefore increases operational safety.</li><li>d) In order to ensure the storage stability of silicone-polyether copolymers, in particular of alkylsiloxane-polyether siloxane copolymers, in addition to the avoidance of acetal structures already discussed, it is imperative to achieve a quantitative SiH conversion. Otherwise, uncontrollable hydrolysis and condensation reactions on the originally SiH-functional molecules lead to a rapid increase in molecular weight, which produces gelated products relatively quickly and sometimes causes considerable economic damage. The catalyst according to the invention performs this quantitative SiC linkage even in a 3-stage hydrosilylation process (without the excesses of compounds with olefinic double bonds which are customary and mandatory when using the unactivated catalysts of the prior art), as set out in Example 5.</li><li>e) After the addition reaction through the catalyst entry has ended, the products produced with the catalyst activated according to the invention show no undesired intrinsic coloration caused by the catalyst.</li><li>f) In the production of the complex silicone polyethers used as flexible polyurethane foam stabilizers, the catalyst activated according to the invention demonstrates its unusual performance in that, in direct comparison with catalysts of the prior art, in addition to a rapid addition reaction at low temperatures, it also has very good product properties with regard to Ensures activity and cell structure (Examples 1 to 3).</li></ul>

The method claimed according to the invention is suitable for the production of SiC-linked systems, which are used in the field of polyurethane foam stabilizers (for example: soft flexible foam, rigid foam, cold foam, ester foam, etc.) and are used as release agents (silicone waxes, radiation-curing systems such as, for example) Silicone acrylates, etc.), are used in paint additives as defoamers, deaerators, slip and leveling additives, in applications of wetting agents, in cosmetic formulations for thickeners, emulsifiers, etc.

The process according to the invention is explained in more detail by the following examples. The percent SiH conversions mentioned in the examples are determined indirectly by treating the reaction product obtained with sodium butoxide in n-butanol and volumetrically determining the amount of hydrogen which can still be eliminated.

Examples:

Activation of a Commercial Catalyst According to the Invention:

10th ml of a 1% toluene solution commercially available Karstedt catalyst [H₂C = CH-Si (CH₃)₂-O-Si (CH₃)₂-CH = CH₂]₃Pt₂ are saturated with ethylene at 25 ° C. over a period of 5 minutes by introduction.

Example 1

Preparation of a polysiloxane-polyoxyalkylene block copolymer (PU flexible foam stabilizer):

In an argon-inertized flask equipped with a stirrer, thermometer and reflux condenser, 80.2 g of a polyether with the middle formula:         CH₂= CH-CH₂O- (C₂H₄O)₃ (C.₃H₆O)₂₉-CH₃15.1 g of a polyether with the average formula:         CH₂= CH-CH₂O- (C₂H₄O)₁₁ (C.₃H₆O)₁₆-CH₃40.5 g of a polyether with the middle formula:         CH₂= CH-CH₂O- (C₂H₄O) ₃₁ (C.₃H₆O) -CH₃115.8 g of a polyether with the middle formula:         CH₂= CH-CH₂O- (C₂H₄O) ₃₁ (C.₃H₆O) ₄₂-OH together with 60 g of a siloxane with the average formula:         (CH₃) ₃SiO- [(CH₃) ₂SiO-]₇₀- [(CH₃) HSiO-] ₇- Themselves₃) ₃submitted at 25 ° C with stirring and mixed with 0.35 ml (8 ppm platinum) in the form of the catalyst prepared according to the invention above. The reaction matrix consisting of polyethers and hydrogen siloxane is initially two-phase and cloudy.

The temperature of the reaction mixture rises to 36 ° C. within a few minutes. After approx. 35 minutes, the previously cloudy reaction mixture reaches the clear point, which indicates the end of the reaction in a manner that is easily visible. In addition, a gas volumetric SiH determination (decomposition of a weighed sample on the gas burette using a sodium butylate solution) confirms quantitative conversion.

Example 2 (comparative example):

Preparation of a polysiloxane-polyoxyalkylene block copolymer (PU flexible foam stabilizer):

Using the starting materials of Example 1, 80.2 g of a polyether with the average formula are in an argon-inertized flask equipped with a stirrer, thermometer and reflux condenser:         CH₂= CH-CH₂O- (C₂H₄O) ₃ (C.₃H₆O) ₂₉-CH₃15.1 g of a polyether with the average formula:         CH₂= CH-CH₂O- (C₂H₄O) ₁₁ (C.₃H₆O)₁₆-CH₃40.5 g of a polyether with the middle formula:         CH₂= CH-CH₂O- (C₂H₄O) ₃₁ (C.₃H₆O) -CH₃115.8 g of a polyether with the middle formula:         CH₂= CH-CH₂O- (C₂H₄O) ₃₁ (C.₃H₆O) ₄₂-OH together with 60 g of a siloxane with the average formula:         (CH₃)₃SiO- [(CH₃)₂SiO-]₇₀- [(CH₃) HSiO-]₇- Themselves₃)₃submitted at 25 ° C with stirring and with 0.43 ml (12 ppm platinum) in the form of the Karstedt catalyst [H₂C = CH-Si (CH₃)₂-O-Si (CH₃)₂-CH = CH₂]₃Pt₂ transferred. After 110 minutes (temperature increase 7 ° C.) the clear point of the reaction mixture is reached and after 120 minutes total reaction time a gas volumetric SiH conversion of 98% is found.

Example 3 (comparative example):

Preparation of a polysiloxane-polyoxyalkylene block polymer (PU flexible foam stabilizer):

In analogy to Examples 1 and 2, the reaction mixture described there with 0.47 ml (13 ppm Pt) in the form of 2-methylnaphtoquinone-divinyltetramethyldisiloxane-platinum⁽⁰⁾complex (preparation according to WO-A-98/00463, pp. 15 to 17 above) added. After 140 minutes, with only a temperature increase of 3 ° C being recorded, the reaction batch achieves quantitative conversion by passing through the clear point.

The foam stabilizers produced are tested in the following way using a foam formulation:

In each case 300 parts of a commercially available polyether for the production of flexible polyurethane foams, which has three hydroxyl groups in the middle molecule and a molecular weight of 3,500, is 0.33 with 15 parts of water, 15 parts of a conventional physical blowing agent, the corresponding amount of the foam stabilizer to be investigated Parts of diethylene triamine and 0.69 parts of tin octoate are mixed with good stirring. After adding 189 parts of toluene diisocyanate (isomer mixture 2.4 and 2.6 in a ratio of 4: 1), the mixture is stirred for 7 seconds at 2,500 rpm with a smooth stirrer. stirred and the mixture poured into a box open at the top. A fine-pored foam is created, which is characterized by the following parameters:<ul id="ul0005" list-style="none" compact="compact"><li>1. the sagging of the foam at the end of the climbing phase (the so-called "fallback"),</li><li>2nd the number of cells per centimeter of foam, which is determined microscopically.</li></ul>

The following table provides an overview of the synthesis parameters of the stabilizers obtained according to the two noninventive and the stabilizers obtained according to embodiment 1 and compares the measured values ​​of the relapse for 2 different concentrations (1.8 parts / 1.5 parts):<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="7" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="34mm" colsep="1" /><colspec colnum="2" colname="col2" colwidth="19mm" colsep="1" /><colspec colnum="3" colname="col3" colwidth="24mm" colsep="1" /><colspec colnum="4" colname="col4" colwidth="16mm" colsep="1" /><colspec colnum="5" colname="col5" colwidth="21mm" colsep="1" /><colspec colnum="6" colname="col6" colwidth="24mm" colsep="1" /><colspec colnum="7" colname="col7" colwidth="31mm" colsep="1" /><thead><row><entry namest="col1" nameend="col1" align="center" valign="top" /><entry namest="col2" nameend="col2" align="center" valign="top">C._Pt [ppm]</entry><entry namest="col3" nameend="col3" align="center" valign="top">t_{Clear point} [min]</entry><entry namest="col4" nameend="col4" align="center" valign="top">ΔT [° C]</entry><entry namest="col5" nameend="col5" align="center" valign="top">Sales [%]</entry><entry namest="col6" nameend="col6" align="center" valign="top">Relapse [cm]</entry><entry namest="col7" nameend="col7" align="center" valign="top">Cells per centimeter</entry></row></thead><tbody><row><entry namest="col1" nameend="col1" align="left" valign="top">Embodiment 1</entry><entry namest="col2" nameend="col2" align="center" valign="top">8</entry><entry namest="col3" nameend="col3" align="center" valign="top">35</entry><entry namest="col4" nameend="col4" align="center" valign="top">11</entry><entry namest="col5" nameend="col5" align="center" valign="top">100</entry><entry namest="col6" nameend="col6" align="center" valign="top">0,5/1,5</entry><entry namest="col7" nameend="col7" align="center" valign="top">14</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Comparative Example 2</entry><entry namest="col2" nameend="col2" align="center" valign="top">12</entry><entry namest="col3" nameend="col3" align="center" valign="top">110</entry><entry namest="col4" nameend="col4" align="center" valign="top">7</entry><entry namest="col5" nameend="col5" align="center" valign="top">98</entry><entry namest="col6" nameend="col6" align="center" valign="top">0,9/2,7</entry><entry namest="col7" nameend="col7" align="center" valign="top">8</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Comparative Example 3</entry><entry namest="col2" nameend="col2" align="center" valign="top">13</entry><entry namest="col3" nameend="col3" align="center" valign="top">140</entry><entry namest="col4" nameend="col4" align="center" valign="top">3</entry><entry namest="col5" nameend="col5" align="center" valign="top">100</entry><entry namest="col6" nameend="col6" align="center" valign="top">0,7/1,7</entry><entry namest="col7" nameend="col7" align="center" valign="top">12</entry></row></tbody></tgroup></table></tables>

The determination of the number of cells in the case of flexible polyurethane foam, which is stabilized with the silicone polyether obtained according to the teaching of the invention, is remarkable and surprising for the person skilled in the art. The morphology of the cells is so uniform here that one can do without the otherwise required averaging to determine the number of cells per centimeter.

Example 4:

Preparation of a polydimethylsiloxane-allyl glycidyl ether addition product:

Analogously to Example 1, 238.4 g of a linear α, ω-dihydrogen polydimethylsiloxane (chain length N = 80) with 11.6 g of allyl glycidyl ether are placed in a round-bottom flask with stirring at 25 ° C. and with 0.25 ml (9 ppm Pt) of the catalyst prepared according to the invention. The temperature of the reaction matrix rose to 40 ° C. after only 15 minutes. Gas volumetric SiH determination confirms quantitative conversion. A batch run under operational practical conditions (catalyst: cis-diamminoplatinum (II) chloride (10 ppm platinum based on the total batch), 120 ° C. reaction temperature) takes 1 to 3 hours to complete the reaction.

Example 5:

Preparation of an alkylsiloxane-polyether siloxane copolymer:

60 g of a siloxane of the medium composition MD containing lateral SiH groups are placed in an argon-inertized multi-necked flask equipped with KPG stirrer, dropping funnel and reflux condenser₇₅D^H₂₅M (SiH content: 3.6 Val / kg) with 0.18 ml of the catalyst solution prepared according to the invention (12 ppm Pt) at 25 ° C. 21 g of hexadecene are added dropwise in the course of 18 minutes, so that the heat of reaction causes the batch temperature to rise to 64.degree. 35.6 g of a polyether with the average composition CH₂= CH-CH₂O- (C₂H₄O)₈-OH (iodine number: 62 g iodine / 100 g) was quickly added dropwise, the reaction temperature dropping to 50.degree. After the addition has ended, a further 10.9 g of hexadecene are added within 10 minutes. Gas volumetric SiH determination on a sample of the cooled reaction batch shows quantitative conversion.

Example 6:

Preparation of a trisiloxane wetting agent:

142.9 g of a polyether of the middle composition CH are in an inertized multi-necked round bottom flask equipped with KPG stirrer, reflux condenser and dropping funnel₂= CH-CH₂O- (C₂H₄O)₈-Oh₃ (Iodine number: 62 g iodine / 100 g) at 23 ° C. with stirring and mixed with 0.23 ml (10 ppm) of the catalyst prepared according to the invention. 60 g of an approximately 74% heptamethyltrisiloxane (the remainder consists of higher homologues) are added dropwise over the course of 30 minutes, so that the temperature of the reaction mixture reaches 38 ° C. After the metering has ended, stirring is continued for about 1 hour and a gas volumetric SiH conversion&gt; 99% is determined from a sample of the cooled batch.

Example 7:

Production of a silicone release wax:

Analogously to Example 1, 337.5 g of α-olefin C30 + with 28.9 g of 1-hexadecene in 337.5 g of the isoparaffin Cobersol © B56 are placed in a round bottom flask with stirring at 57 ° C. and mixed with 0.6 ml (10 ppm Pt) of the catalyst prepared according to the invention. Over a period of 15 min, 150 g of a siloxane of the middle formula MD which laterally contains SiH groups are added to this mixture_1,75D^H_1,25M was added dropwise, the temperature of the reaction matrix rising to 69 ° C. Gas volumetric SiH determination gives a conversion of 93.7% after 2 h, 97.2% after 3 h and 98.8% after 4 h.