Composition containing platinum

Abstract

The invention provides for a composition comprising elemental platinum and/or at least one platinum-containing compound, where said platinum has a positive oxidation state, and one or more organic compounds comprising carbon atoms, hydrogen atoms and at least two oxygen atoms, wherein at least one of said compounds comprises at least one olefinic unsaturation, characterized in that said composition comprises a proportion of organic compounds comprising carbon atoms, hydrogen atoms and at least two oxygen atoms of from 50.0 to 99.9 wt % and a proportion of the sum of elemental platinum and platinum-containing compounds of from 0.1 to 50.0 wt % in each case based on the composition, with the proviso that the proportions of organic compounds comprising carbon atoms, hydrogen atoms and at least two oxygen atoms and of elemental platinum and platinum-containing compounds sum to at least 90 wt % based on the composition and the proviso that the olefinic unsaturation content is at least 0.1 g of iodine/100 g of the organic compounds comprising carbon atoms, hydrogen atoms and at least two oxygen atoms, corresponding to at least 0.004 meq/g, for a process for preparing said composition and for the use thereof.

Claims

1. A composition comprising elemental platinum or platinum(II)-containing compound, wherein said platinum(II) has a positive oxidation state, and an organic compound is vinyl 4-hydroxy butyl ether wherein said composition comprises from 50.0 to 99.9 wt % of the organic compound and from 0.1 to 50.0 wt % of elemental platinum or platinum(II)-containing compound in each case based on the composition, wherein the organic compound and elemental platinum or platinum(II)-containing compound sum to at least 90 wt % based on the composition, wherein the organic compound have an olefinic unsaturation content of at least 0.1 g of iodine/100 g of the organic compound, corresponding to at least 0.004 meq/g, and wherein the platinum(II)-containing compound comprises from more than 95 mol % of cis-(NH.sub.3).sub.2PtCl.sub.2.

2. The composition according to claim 1, wherein the composition comprises at least one platinum(II) compound, wherein the platinum(II)-containing compound comprises from more than 99.5 mol % of cis-(NH.sub.3).sub.2PtCl.sub.2, and the composition comprises no detectable amounts of elemental platinum or platinum (0) compounds.

3. The composition according to claim 1, wherein the platinum(II)-containing compound comprises more than 99.5 mol % of cis-(NH.sub.3).sub.2PtCl.sub.2 as platinum(II)-containing compound, and the organic compound and elemental platinum or platinum(II)-containing compound sum to at least 99 wt % based on the composition.

4. The composition according to claim 1, wherein the composition comprises di--chlorobis(1,2-n)cyclohexene platinum(II) chloride as platinum(II)-containing compound.

5. The composition according to claim 1, wherein the elemental platinum or platinum(II)-containing compounds is from 0.3 to 1 wt % based on the composition.

6. A process for preparing a composition according to claim 1, wherein the elemental platinum or the platinum(II)-containing compound are washed into the vessel with the vinyl 4-hydroxy butyl ether.

7. The process according to claim 6, wherein the addition of the elemental platinum or the platinum(II)-containing compound is effected at a temperature in the vessel of from 30 C. to 75 C.

8. The process according to claim 6, wherein the vessel employed is a spherical vessel fitted with a lateral port by means of which the elemental platinum(II) or the platinum(II)-containing compound are added.

9. The process according to claim 6, wherein the vessel comprises a lateral port with a rotatable connection with which a container containing the elemental platinum(II) or the platinum(II)-containing compound can be connected and, for emptying, rotated such that the contents can feed into the vessel under gravity.

Description

EXAMPLE 1 (INVENTIVE)

(1) Preparation of a cis-diamminedichloroplatinum(II) catalyst preparation in an allyl alcohol-started methyl-end-capped polyether, molecular weight (calculated according to iodine number): 1449 g/mol, 12 wt % ethylene oxide, 88 wt % propylene oxide, statistical structure. 15.36 mg of cis-PtCl.sub.2(NH.sub.3).sub.2 are homogeneously incorporated into 2.0 g of the polyether described here for about 30 seconds at 25 C. using a Xenox 40e microstirrer (from Proxxon) rotating at 20 000 revolutions per minute.

EXAMPLE 2 (INVENTIVE)

(2) In a RC1e reaction calorimeter (Mettler-Toledo), 250 g of a hydrosiloxane having the average formula:
(CH.sub.3).sub.3Si(OSi(CH.sub.3).sub.2).sub.78(OSiH(CH.sub.3)).sub.10OSi(CH.sub.3).sub.3,

(3) SiH value: 1.52 val/kg,

(4) and 748.47 g of an allyl alcohol-started methyl-end-capped polyether having a statistical structure (allyl polyether) having a molar mass of 1459 g/mol (according to iodine number) are heated to 90 C. with stirring and then admixed with 76.80 mg of the cis-PtCl.sub.2(NH.sub.3).sub.2 paste prepared in Example 1 (10 ppm Pt based on total batch). Alongside measurement of the thermal conversion, samples are taken after 2.5, 3.5, 5.5, and 6.5 hours and said samples are weighed into a glass burette and subsequently decomposed by addition of a sodium butoxide solution. The gas-volumetric determination, which accompanies the reaction, of SiH value via the volume of liberated hydrogen gas permits additional conversion monitoring.

EXAMPLE 3 (INVENTIVE)

(5) While maintaining all other parameters cited in Example 2, the reaction mixture consisting of hydrosiloxane and allyl polyether is admixed, at 90 C. with stirring, with the cis-PtCl.sub.2(NH.sub.3).sub.2 allyl polyether preparation prepared in Example 1 (10 ppm Pt based on total batch). Thermal conversion and gas-volumetric conversion are determined as described in Example 2.

EXAMPLE 4 (NON-INVENTIVE)

(6) Similarly to, and while maintaining all other parameters from, Examples 2 and 3, the reactants are heated to 90 C. with stirring in the reaction calorimeter and subsequently admixed with 15.36 mg of pulverulent cis-PtCl.sub.2(NH.sub.3).sub.2. Thermal conversion and gas-volumetric conversion are determined as described in Example 2.

(7) FIG. 1 summarizes the thermal conversions measured by the reaction calorimeter in Examples 2, 3 and 4, normalized to 100%, as a function of reaction time. The conversion curves for the reaction batches catalysed with the inventive cis-PtCl.sub.2(NH.sub.3).sub.2-polyether preparations (Examples 2 and 3) show a steeper curve in the initial phase of the reaction than the conversion curve characterizing the non-inventive use of the pulverulent cis-PtCl.sub.2(NH.sub.3).sub.2 complex and thus denote a spontaneous exotherm.

(8) The shapes of the gas-volumetrically determined SiH conversion curves in FIG. 2 (Examples 2 and 3) likewise underscore the enhanced catalytic activity of the inventive polyether preparations of cis-PtCl.sub.2(NH.sub.3).sub.2 compared to cis-PtCl.sub.2(NH.sub.3).sub.2 employed in pulverulent form.

EXAMPLE 5 (INVENTIVE)

(9) Preparation of a cis-diamminedichloroplatinum(II) catalyst preparation in a mixture consisting of an ally alcohol-started polyetherol and a butanol-started polyetherol whose mixed molecular weight (calculated according to OH number) is 2018 g/mol and which comprises 90 wt % of ethylene oxide and 10 wt % of propylene oxide in a statistical structure and whose olefinic unsaturation content according to high-resolution .sup.1H NMR spectroscopy is 0.04 mol % allyl, corresponding to 0.004 meq/g.

(10) The preparation was prepared using a Getzmann Dispermat dissolver provided with a dispersing disc of 2 cm in diameter, said dissolver rotating at a rotational speed of 5500 revolutions per minute. 12 g of the polyether described hereinabove were initially charged at a temperature in the range of from 40 C. to 50 C. under the above dispersing conditions and 3.0 g of cis-PtCl.sub.2(NH.sub.3).sub.2 were added. The resulting mixture was dispersed for a total of 15 minutes and the mass was then allowed to cool down with additional manual stirring using a spatula. A very evenly yellow-coloured homogeneous paste was obtained.

EXAMPLE 6 (INVENTIVE)

(11) Preparation of a flexible polyurethane foam stabilizer using the cis-PtCl.sub.2(NH.sub.3).sub.2 polyether preparation prepared in Example 5.

(12) A 500 ml 4-necked flask equipped with a stirrer, thermometer and reflux condenser is initially charged, at 25 C. and with stirring, with a reaction mixture having the following composition:

(13) 198 g of a mixture of different ally polyethers having molecular weights of from 600 g/mol to 3800 g/mol and PO proportions of from 0 to 88 wt % based on the respective polyethers where the (weight-)average formula of the polyether mixture is
CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.16(C.sub.3H.sub.6O).sub.19R,

(14) where R=89 mol % Me and 11 mol % H, and 60 g of a siloxane having the average formula:
(CH.sub.3).sub.3SiO[(CH.sub.3).sub.3SiO].sub.60.5[(CH.sub.3)HSiO].sub.6.5Si(CH.sub.3).sub.3

(15) (SiH value: 1.263 val/kg).

(16) The reaction matrix consisting of polyethers and hydrosiloxane is initially biphasic and cloudy.

(17) The reaction mixture is heated to 90 C. and then admixed with 20 mg of the inventive catalyst preparation prepared in Example 5 (10 ppm Pt based on total batch). According to gas-volumetric SiH determination (decomposition of an aliquot sample using sodium butoxide in a gas burette), quantitative conversion is achieved after about 2.5 hours. The clear and slightly yellow-coloured polyether siloxane has a viscosity of 1424 mPas. The viscosity was determined on a Haake Viscotester VT550 at 25.00 C. using a Rotor NV measuring spindle. This instrument is a Searle rotational viscometer in which the flow resistance of the test substance is measured at a predefined rotational speed. The torque, rotational speed and geometry of the measuring device are used to calculate viscosity, shear stress and shear rate.

(18) The performance testing of the foam stabilizer thus prepared is carried out with a foam formulation in the following way:

(19) 300 parts of a commercially available polyether for preparing flexible polyurethane, an average molecule of which comprises three hydroxyl groups and has a moleular weight of 3500, is in each case mixed with 15 parts of water, 15 parts of a customary physical blowing agent, the appropriate amount of the foam stabilizer to be analysed, 0.33 parts of diethylenetriamine and 0.69 parts of tin octoate with vigorous stirring. Addition of 189 parts of toluene diisocyanate (mixture of 2,4 and 2,6 isomers in a 4:1 ratio) is followed by stirring for 7 seconds at 2500 rpm with a Glatt stirrer and pouring of the mixture into an open-topped box. This affords a fine-pored foam which is characterized by the following parameters:

(20) 1. the degree to which the foam settles at the end of the rise phase (known as collapse),

(21) 2. the number of cells per centimetre of foam, determined by microscopy.

(22) The measured collapse values for 2 different concentrations (1.8 parts/1.5 parts) are reported below:

(23) Collapse: 1.0/1.5 in cm

(24) Porosity: 11/8

(25) Density: 17.95/18.05 kg/m.sup.3

(26) Number of cells per centimetre: 13/13

EXAMPLE 7 (NON-INVENTIVE)

(27) Preparation of a Rigid Polyurethane Foam Stabilizer

(28) A 500 ml 4-necked flask equipped with a stirrer, thermometer and reflux condenser is initially charged, at 25 C. and with stirring, with a reaction mixture having the following composition:

(29) 161.3 g of a polyether A having the average formula:

(30) CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.13.5(C.sub.3H.sub.6O).sub.3.6H (molecular mass according to iodine number: 824 g/mol) and

(31) 60 g of a hydrosiloxane having the general formula:
(CH.sub.3).sub.3Si(OSi(CH.sub.3).sub.20.5(OSiH(CH.sub.3)).sub.5OSi(CH.sub.3).sub.3, SiH value 2.51 val/kg.

(32) This reaction matrix is rapidly heated to 70 C. and 1.6 mg of solid di--chlorobis[chloro(cyclohexene)platinum(II)] (Pt 92), corresponding to 4 ppm Pt based on the reaction batch, are added at 50 C. The reaction batch is held at 70 C. for two hours and the reaction temperature is subsequently elevated to 90 C. Addition of the platinum complex is followed by the appearance of initial black platinum agglomerates pervading through the liquid phase. The gas-volumetrically determined SiH conversion achieved is 80.3% after 3 hours and 99.0% after 4 hours. Once cooled down, a very cloudy polyethersiloxane interspersed with black flocular platinum precipitate is obtained.

EXAMPLE 8 (INVENTIVE)

(33) Preparation of a Rigid Polyurethane Foam Stabilizer

(34) A 500 ml 4-necked flask equipped with a stirrer, thermometer and reflux condenser is initially charged, at 25 C. and with stirring, with a reaction mixture having the following composition:

(35) 161.3 g of a polyether A having the average formula:

(36) CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.13.5(C.sub.3H.sub.6O).sub.3.6H (molecular mass according to iodine number: 824 g/mol) and

(37) 60 g of a hydrosiloxane having the general formula:
(CH.sub.3).sub.3Si(OSi(CH.sub.3).sub.2).sub.20.5(OSiH(CH.sub.3)).sub.5OSi(CH.sub.3).sub.3, SiH value: 2.51 val/kg.

(38) This reaction matrix is rapidly heated to 70 C. and 0.161 mg of a previously prepared 1 wt % solution of di--chlorobis[chloro(cyclohexene)platinum(II)] (Pt 92 dissolved in polyether A) solution, corresponding to 4 ppm Pt based on the reaction batch, are added at 50 C. After 2 hours at 70 C. and a further hour at a reaction temperature of 90 C., the gas-volumetrically determined SiH conversion achieved is quantitative (100%). Once cooled down, a colourless, clear polyethersiloxane showing no trace of platinum precipitate is obtained.

EXAMPLE 9 (STORAGE STABILITY TESTING)

(39) The experiment according to Example 2 was repeated using as catalyst a catalyst according to Example 5 which, however, had first been stored at 22 C. for 3 months. The result of this experiment is reported in Table 1.

(40) TABLE-US-00001 TABLE 1 Hydrosilylation results as gas-volumetric SiH conversion in mol % SiH conversion Example 2 Example 9 Example 4 after inventive inventive non-inventive 2.5 h 70.2% 70.7% 39.7% 3.5 h 81.6% 75.1% 49.1% 4.5 h 87.1% 81.3% 59.1% 5.5 h 92.6% 86.4% 60.9% 6.5 h 96.8% 90.5% 66.9% Clearing point 57 min 46 min 200 min

(41) Clearing Point

(42) Introducing the composition according to the invention into a hydrosilylation system consisting of addition-capable unsaturated polyethers and a siloxane bearing SiH groups leads to the formation of a silicone polyether which acts as a surfactant and thus influences the further course of the reaction. All solvent-free hydrosilylations targeting the SiC bond forming reaction between SiH siloxanes and unsaturated polyethers are initially biphasic due to the incompatibility of SiH siloxane and polyethers. The increase in product concentration over the course of the reaction is accompanied by a decrease in the concentration of incompatible reactants, the silicone polyether copolymer simultaneously acting as a surfactant which, at the phase interface, promotes the dispersal of remaining incompatible reactant droplets, specifically of SiH siloxanes and also of partially reacted SiH siloxanes, in the polyether matrix. The clearing point observable in the SiC bond forming preparation of silicone polyethers is an indicator and consequence of this increasing phase dispersal occurring in the reaction system. At the clearing point, the diameter of the individual droplets of the incompatible dispersed phase has fallen below the wavelength of visible light and the previously cloudy reaction matrix appears to the naked eye to be a single clear phase.

(43) As is apparent from Table 1, the best conversions are achieved when the catalyst is employed in the form of the composition according to the invention. Even storage at room temperature for 3 months (Example 9) shows no significant effect on catalyst activity.

EXAMPLE 10 (INVENTIVE)

(44) Pilot plant preparation of a coatings additive

(45) In a 120 l pilot plant reactor, 50.00 kg of an ,-dihydropolydimethylsiloxane having an average total chain length N=30 and a SiH content of 0.87 val/kg are heated to 80 C. with N.sub.2 inertization and stirring. 973.8 mg of solid di--chlorobis[chloro(cyclohexene)platinum(II)] (Pt 92) (corresponding to 10 ppm Pt based on the total batch) are initially stirred into 60.6 g of vinyl 4-hydroxybutyl ether and this Pt composition is then added, along with 553.1 g of Na.sub.2CO.sub.3, to the siloxane initially charged with stirring. 5 minutes after this addition, 5.246 kg of vinyl 4-hydroxybutyl ether are added dropwise over 20 minutes and the incipient SiC bond forming reaction causes the temperature of the reaction mixture to rise to 98 C.

(46) After 2.5 hours of total reaction time, the gas-volumetrically determined SiH conversion achieved is 99.4%. 1.125 kg of volatiles are removed by distillation at 140 C. with application of an auxiliary vacuum of 22 mbar, the bottoms, once cooled down, are admixed with 55.3 g of butylethanolamine and 0.5% of bentonite and stirred for a further 30 minutes before being filtered through a K 300 filter sheet. This affords a clear, virtually colourless product having a viscosity of 82.1 mPas at 25 C.