MXPA01006391A - Porous polymethylsilsesquioxane with adsorbent properties - Google Patents

Abstract

The invention concerns a porous polymethylsilsesquioxane (PMS) having a specific surface area ranging between about 50 and 500 m2/g, a porous volume ranging between about 0.1 and 0.8 cm3/g, a monolayer volume ranging between about 10 and 60 cm3/g, a pore radius less than 1 mn of 90%of the pores and insoluble in water and organic solvents. The inventive PMS is prepared by precipitating a polymethylsiliconate of general formula (I) wherein n is an integer between about 20 and 100 and M is an alkaline or alkaline-earth metal or NH4+.

Description

POLIMETILSILSESQUIOX- \ NO POROUS WITH ADSORPENT PROPERTIES Technical Field The present application refers to the field of materials. More particularly, it relates to a porous, hydrophobic polymethyl silsesquioxane which has remarkable adsorption properties of the organic molecules.

Background of the Invention The use in the industry of adsorbent materials such as activated carbons, silicas, aluminas or zeolites is already known for applications as varied as purification of water or air to prevent contamination, separation of liquids or gases by chromatography, the support of the catalysts or the encapsulation of the active substances, just to point out some examples. The adsorbent properties of the materials depend on a certain number of physical parameters such as the apparent density, the specific surface area, the particle size, the volume of the pores and the distribution of the pores, indicating their microporosity Ref.130032 (<2 nm), its mesoporosity (between 2 nm and 50 nm) or its acroporosity (> 50 nm). A support will also be characterized by its thermal stability, its regenerability, the reversibility of its adsorbent capacities, its hydrophobicity, its flammability and its absence of toxicity. At present, the most commonly used hydrophobic adsorbent is activated carbon. However, this has the disadvantage that it is flammable or combustible and that it forms explosive mixtures with air. It is also difficult to regenerate and has a limited adsorption capacity. Another class of commonly used adsorbents are silicas. They exist in a wide range of specific surface areas and particle sizes and, as. result, they have variable adsorbent properties.

Description of the invention The present invention relates to a hydrophobic material which belongs to the family of polymethylsilsesquioxanes, hereinafter abbreviated as PMS, which are thermally stable and have the capacity to adsorb several times their own weight in the organic substance.

More precisely, the present application describes a porous polymethyl isosquioxane in a powdered form containing the units Ends of the Material Chain Units characterized by a specific surface area of between about 50 m2 / g and 500 m2 / g, a pore radius smaller than 1 nm for 90% of the pores, and insolubility in water and in organic solvents. In the preferred embodiments, the polymethylsiloquoisxane according to the invention has a pore volume of between 0.1 cm 3 / g and 0.8 cm 3 / g and / or a volume of the monolayer of between about 10 cm 3 / g and 60 cm 3 / g. The polimetilsilsesquioxane. according to the invention may also contain the units Unpolymerized silanols They may be present due to incomplete polymerization during the preparation reaction described hereinafter or due to the treatment which leads to partial hydrolysis of the PMS. The present invention also relates to a process for the preparation of said polymethyl siloxane. The polymethylsilyesquioxanes according to the invention are obtained by the acid precipitation of an aqueous solution of a polymethyl siliconate, followed by filtration and drying. The reaction for the preparation of the polymethylsilsquioxanes according to the invention is illustrated hereinafter in the schematic equation (1), in which the formula (I) is representative of a polymethyl siliconate suitable for use in the invention and the formula (II) ) is representative of a precipitate which is formed after the addition of a suitable acid by means of a condensation reaction of the polymethylsiliconate. + rviA- + H20 (i) ?? ± ration ^ [CHaSiOt sk (1) Washing Drying PMS M = alkaline / alkaline earth metal, NH 4 +; n = total number from 20 to 100 The polymethylsilyquioxane obtained by the reaction shown schematically above and forming the subject of the invention, can be described approximately by the empirical formula (CH3SiO? .5) x. However, it is not possible to specify the value x, that is to say, to provide the exact molecular weight of the polymethylsilyesquioxane, since the latter is insoluble in all known solvents in view of its very high molecular weight.

In equation (1), the letter M represents an alkali metal such as Li, Na, K, an alkaline earth metal such as Mg, Ca, or an NH 4 + group, preferably it is for Na and K. The value n in the formula (I), which represents the number of the units of [MoSi (0) CH3J repeated, is an integer between 20 and 100, preferably between 30 and 80. The siliconates characterized by the formula (I) are soluble in water and can be purchased in the market as aqueous solutions. It has been found that good results are obtained if the product known by the name of Rhodorsil® Siliconate 51T, marketed by Rhone-Poulenc, is used as the siliconate. This product is an aqueous solution of potassium polymethylsiliconate at about 46% by weight, with a pH of about 13 and a density of about 1.34. However, it is also possible to prepare the polymethyl siliconates used in the synthesis of PMS from the polymethylhydrosiloxane known by the name of PMHS and represented by the following formula (III): CH3 CH3 CH3- Si-O Si-0 S- CH3 (I) + n / 2 H2 (2) M + OH "CH3 CH-, CH3 (III) In this formula (III), n has the same value as specified here above for polymethylsilicontes, especially between about 20 and 100, preferably between about 30 and 80. The desired polymethylsilicontes are obtained by converting the Si-H bond to a Si-0 + M ~ bond, M represents an alkali metal, an alkaline earth metal or NH4 +. This conversion can be carried out for example by alkaline hydrolysis using a base such as NaOH, KOH, Ca (0H) 2, or by the action of an alcohol followed by alkaline hydrolysis. It is also possible to use the polymethylsilicontes obtained by the reduction of a carbonyl substrate using PMHS and a catalyst, with a metal salt, preferably zinc, followed by alkaline hydrolysis. Such a process forms the subject of the international application WO 96/12694 in the name of Firmenich SA. The content of this application with respect to the preparation of the PMHS polymethyl siliconates forms part of the present application and is incorporated herein by reference. In the preparation of said polyimethylsiliconatos, used as the starting materials, the best results are obtained, from the point of view of the properties of the PMS obtained as the final product, when it has been necessary to resort to a PMHS with a viscosity of between 15 cSt and 50 cSt, preferably between 25 cSt and 35 cSt, and a density between 0.95 and 1.02. As is evident from equation (1), the polymethylsiliconatos (I) undergo a condensation reaction when they are neutralized by a suitable acid. The acid is added until a pH of about at least 11, preferably about 7, is reached. The acid can still be added until the pH of about 1 is reached. The acid used can be a mineral acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, perchloric acid or fluoroboric acid. The acid may also be an organic acid such as acetic acid, propionic acid, butyric acid, valeric acid, 2-ethylhexanoic acid, chloroacetic acid, dichloroacetic acid or trichloroacetic acid. You can also use carbon dioxide gas. Preferred acids are acetic acid, sulfuric acid or phosphoric acid, the latter being the most advantageous acid according to the invention. Then, the precipitate formed during the neutralization of the polymethylsiliconate is filtered or centrifuged, then washed one or more times with water to remove the alkali salts and, if necessary, with a solvent miscible with water, such as methanol, ethanol, isopropanol or acetone, to allow the best drying of the obtained PMS. The preparation of the PMS ends with drying under the conditions which allow the removal of the water and / or the washing with solvents. The drying can be carried out at temperatures between 80 ° C and 400 ° C at ambient pressure or under vacuum. The drying temperature will preferably be between 90 ° C and 150 ° C, and a vacuum of 1 hPa to 100 hPa will preferably be used. The drying process will be carried out under the usual conditions known to the person skilled in the art, using for example a rotary dryer, mentioned here as a non-limiting example. As a result of the drying process, a porous PMS will be obtained which contains less than about 8%, preferably less than about 5% by weight of water. According to an even more preferred embodiment, a PMS containing about 1% or less by weight of water will be obtained. As mentioned hereinabove, this PMS is insoluble in hydrophilic or hydrophobic solvents or in water. The porous PMS, as obtained by the process described hereinabove, is a fine powder capable of adsorbing a large number of hydrophobic substances. The apparent density of this powder is between approximately 0. 04 g / cm3 and 0.8 g / cm3, depending on the preparation method. It has been established that powders having a density between approximately 0.08 g / cm3 and 0.4 g / cm3 have the best adsorbent capacity, these capacities increase when the density is reduced. The characteristic data of these materials, determined by the physical adsorption of nitrogen (carried out on a Sorptomatic 1900 machine manufactured by Cario Erba) and evaluated based on the Brunauer-Emmett-Teller equation (BET) were as follows: specific surface area of between 50 m2 / g and 500 m2 / g, preferably between 75 m2 / g and 375 m2 / g; 90% of the pores having a radius smaller than 10 angstroms (1 nm), preferably smaller than 9 angstroms (0.9 nm). In a preferred embodiment, the pore volume of the PMS according to the invention is between 0.1 cm 3 / g and 0.8 cm 3 / g. It is even more preferred if this volume is between 0.2 cm3 / g and 0.7 cm3 / g. In another preferred embodiment, the volume of the PMS monolayer according to the invention is between 10 cm 3 / g and 60 cm 3 / g, and it is even more preferred if this volume is between 15 cm 3 / g and 50 cm 3 / g.

In addition, the average particle size of the PMS (which, of course, varies depending on the preparation method) is between 1 μm and 200 μm, as measured by laser powder diffraction and in suspension in water in the presence of an agent surfactant. The surfactant can be, for example, the polyoxyethylene (20) sorbitan monooleate, sold under the name Tween® 80 (origin: ICI, England). The gravimetric measurements have shown that the porous PMS according to the invention is thermally stable up to a temperature of about 400 ° C or slightly above. Beyond this, chemical conversions can be carried out and, at approximately 500 ° C, EMS loses its methyl groups and is converted into silica. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the result of the differential calorimetry carried out on the PMS according to the invention under the indicated conditions, which well illustrates the thermal behavior of the polymethyl silsquioxane according to the invention. Another feature of the PMS according to the invention is its essentially amorphous nature. Figure 2 shows the two adsorption bands (halos) centered around 10 ° and 22 ° theta and obtained by X-ray diffraction. These two bands mentioned above are typical of the PMS according to the invention and demonstrate that the PMS is a amorphous powder with a low degree of crystallinity. Finally, the PMS according to the invention is in the form of nanoparticle conglomerates of a porous nature and with particle sizes between about 1 μm and 200 μm. A particle size of between about 2 μm and 50 μm is preferred. This size varies according to the conditions of the preparation. A remarkable characteristic of the PMS according to the invention is its hydrophobic nature due to the fact that the PMS floats on the water and remains completely dry. In contrast, due to its lipophilic nature, the PMS according to the invention associates itself intimately with any organic molecule and is able to adsorb more than five times its own weight in the organic substance, as will be shown in the following examples . Due to its lipophilicity, its specific surface area and its high pore volume, the PMS according to the invention tends by itself to multiple applications as a solid support for a wide variety of materials used in the chemical, perfumery and / or of the cosmetics. Among the large number of possible applications, the use of a solid support for the enzymes has proven to be highly advantageous. Enzymes fixed to a solid support such as silica, clays or polyolefins are commonly used in the pharmaceutical or condiments industries, just to point out two examples. The immobilization of the enzyme facilitates the separation thereof from the reaction medium and frequently increases the conversion of the substrate in relation to the use of the same non-immobilized enzyme. Thus, the PMS according to the invention can advantageously replace the supports known in the field of immobilization of the enzymes. The non-limiting examples of the enzymes which can be fixed to the PMS according to the invention are lipases, peroxidases, hydrogenases, lyases, proteases and isomerases. For use as a support for the enzyme, PMS can be used as such or suffer a treatment which facilitates the fixation of the enzyme, for example the thermal, acid or basic treatment, or the modification of its surface by the organosiloxanes. The modifications that can be made to a support to achieve a good immobilization of the enzyme are known to the person skilled in the art. A specific example of a reaction in which the PMS according to the invention is used as a support for the enzyme is the optical resolution of a mixture of enantiomers of an ester or an alcohol. In the case of an ester, this term is taken to mean hydrolysis or enantioselective transesterification, ie of a single enantiomer, of an enantiomer mixture of a chiral ester. In the case of an alcohol, this term means the enantioselective esterification of a mixture of the enantiomers of a chiral alcohol. The enzyme which will be generally used in this resolution reaction is a lipase, examples of which are Candida antárctica, Pseudomonas fluorescens, Pseudomonas amano, Humicola lang. , Candida cylindracea, Mucor miehei, Chromabacterium viscosum, Aspergillus niger, Mucor javanicus and Rhisopus arrhizus. The PMS according to the invention can also be used as a support for transition metals or derivatives thereof, thereby making it possible to obtain homogeneous or heterogeneous catalysts. Another application of the PMS according to the invention, which is appropriate to point out here, is the use as a solid receptor to activate substances such as perfumes, seasonings, insect repellents or antimicrobial agents, for example with the object of obtaining a lasting effect of these substances due to the slow restitution of these active substances in air or water. For example, the PMS according to the invention, which contains odoriferous compounds adsorbed on its surface, can be used as air fresheners. Another example is the use of PMS in soaps as a support for perfumes incorporated in soaps. We had the ability to find out that the smells diffused by the soaps containing the PMS are preferred over those of the soap that does not contain the PMS. The presence of PMS allows a lasting effect of the perfume, and often the process of deterioration of the perfume due to the acidic or basic medium in the soaps is gradually reduced. Additional applications of this type include shampoos and other hair products, such as conditioners, lacquers and drying shampoos, and also "leave on site" products, ie products for hair treatment and hair cleaning which remain in the hair after application. Actually, it has been found that the PMS was a very effective support for the perfumes proposed to be incorporated in these hair care products, the perfume is released in a controlled and more durable way than when they are used together as they exist , that is, not supported on the PMS. The concentrations at which PMS can be used in these applications can vary within a fairly wide range of values. Concentrations in the order of 0.05% to 0.5% by weight, in relation to the weight of the product in which it is incorporated, can be indicated as an example. Naturally, this concentration depends on the amount of perfume added to the product and can easily be adjusted as a function of this amount. The PMS has therefore proven to be highly advantageous as a support for perfume in all applications for body care or hair care, cosmetic, traditionally perfumed, and also in other applications in functional perfumery, for example detergents or softeners of tissues. It can also be used in the extraction of organic substances in solution or suspension in water, as in the case, for example, of fruit juices, infusions of vegetable substances, wines or other maceration products, or perfumes or ingredients. to perfumed washed away by water vapor. The adsorbent properties of the PMS according to the invention can also be used in the purification of fumes or gases, such as in gas masks or cigar filters, for example. PMS has proven very useful in non-scented soaps, in which it can advantageously adsorb unpleasant odors diffused by the bases used in these soaps. PMS is also useful in the separation of molecules by chromatography due to a lower adsorption of polar substances in relation to polar substances. This has resulted in that the PMS according to the invention is particularly well adapted to the separation of the molecules by reverse chromatography. For example, it was possible to find out that it was possible to separate the chlorophyll extract from the carotene on a PMS column according to the invention by elution with, initially, a 50:50 mixture of water and methanol and, by increasing of the proportion of methanol, pure methanol, whereby the elution of the dyes is possible. The PMS according to the invention is also suitable for use in spherical exclusion chromatography. Naturally, the applications noted hereinabove do not constitute an exhaustive list of the potential uses of the PMS according to the invention, and many other applications are possible in which the adsorbing properties of the PMS will be advantageously used. The invention will now be illustrated by means of the following examples, in which the abbreviations have the usual meaning in the art and the temperatures are given in degrees Celsius.

Examples Examples 1 to 4 Preparation of polimetilsilsesquioxano (PMS) 1500 g of the potassium polymethylsiliconate in 46% solution in water are diluted with 6000 g of water. Maintaining the temperature below 30 ° C, the neutralization is then carried out with 486 g of acetic acid until a pH of 7 is reached. A white precipitate is immediately formed which is filtered, then washed twice with water. The precipitate is then dried at 120 ° in an oven under a vacuum of 10 mbar for 12 hours. 400 g of a dry porous PMS containing 1% residual water (Karl Fischer analysis) and. which has a density of 0.08. This PMS (referred to as PMS 1) has a specific surface area of 191 m2 / g, a pore volume of 0.32 cm3 / g and a monomolecular layer volume of 44 cm3 / g (measurements determined by the physical adsorption of nitrogen by the BET method). The average particle size was 7 μm (measured by laser beam diffraction). To determine its adsorbent capacity with respect to the organic substances, the limonene contained in a burette was measured on 2 g of the PMS 1 contained in a rotary notch until the PMS 1 became slightly sticky. The volume withdrawn from the run was then measured: 11 ml, ie 5.5 ml of limonene adsorbed per g of the PMS 1. Proceeding as described above for example 1, but replacing the acetic acid with the 10% sulfuric acid en- weight (eg 2), 20% phosphoric acid (eg 3) or a gas stream of carbon dioxide (eg 4), at a pH of 10, formed a white precipitate which was filtered, washed twice with water and drying at 120 ° C at 10 mbar for 12 hours. The properties of the PMS obtained after drying are described in Table 1 (PMS 1 to 4). It was found that the PMS obtained had different surface areas and different pore volumes and that in all cases they adsorbed more than 3 ml of limonene per g of PMS.

Table 1: Comparison of the adsorbent properties of the porous PMS obtained by the methods used in Examples 1 to 4 Examples 5 to 9 Extraction of organic substances from water Solutions or suspensions containing 10 g of the organic substance in 1 liter of water were stirred at 20 ° C with 5 g of the pulverized PMS obtained in Example 1 (PMS 1) for 10 minutes. The solid was then filtered and weighed, then the residual aqueous phase, which was extracted with diethyl ether, was weighed. In this way, the amount of organic substance extracted by the adsorbent in the water was determined. As shown in Table 2, the porous PMS has the remarkable property of very effectively extracting the organic substances from the water. Products that have a poor solubility, such as toluene (example 5) or citral (item 6), are completely extracted, while highly soluble substances such as butanol (example 7), methyl ethyl ketone (eg 8) or diethyl ether of ethylene glycol (eg 9) are extracted at least 70%. As the porous PMS is hydrophobic, it only contains small amounts of water when it is filtered using an organic solvent such as methanol, ethanol, acetone or methylene chloride.

Table 2: Percentage of the product extracted by 5 g of the adsorbent support starting from a solution containing 10 g of the organic substance in 1 liter of water Example 10 Enantioselective saponification of 2-pentyl-l-cyclopenten-1-yl acetate using a lipase fixed to a support derived from the PMS A. Preparation of fixed lipase A suspension of the polymethylsilsquioxane according to the invention in a 9: 1 mixture of propan-2-ol and H20 was prepared in a proportion of 5 ml of liquid per g of the support. The suspension was stirred for 1 hour at 50 °. Then it was cooled to room temperature and stirred for an additional 10 h before being diluted in water in a ratio of 1: 2. After being stirred for 1 h, the suspension was filtered. The product can be stored wet. To fix the lipase to this pretreated support, 1 g of an adsorbate of Pseudomonas fl orescens on clay (origin: Biocatalysts, Great Britain) was suspended in 4 ml of a phosphate buffer at pH 7 and 0o. After being stirred for 1 h, the suspension was filtered and the extract was diluted 1: 1 with a 1: 4 mixture of propan-2-ol and the phosphate buffer (0.5 M, pH 7.1 m) before the addition of the pre-treated support as described here above (0.5 g up to 2 g of the equivalent based on dry weight). The suspension was stirred at 50 ° for 15 h before isolation of the immobilized enzyme by filtration, washing with cold acetone and with pentane. The product is dried with air at room temperature. The thus obtained lipase immobilized on the PMS according to the invention can be used as such. It can also be used in the preparation of a biocomposite of the lipase-PMS-silicone type. For this purpose, 10 g of the adsorbed material obtained as described here above were dispersed in a mixture containing 7 g of the polymethyldisiloxane having silanol termini with high functionality (0.9% to 1.2% functionality).; origin: ABCR GmbH, Germany) and 21 g of the polydimethyldisiloxane having the silanol endings with lower functionality (0.1% functionality, origin: ABCR GmbH, Germany). After the addition of a crosslinking agent comprising 12 g of a polydiethylsilicate containing 45% by weight of silica solids (origin: ABCR GmbH &Co., Germany) and 0.6 g of tin 2-ethylhexanoate (origin: ABCR GmbH &Co., Germany), the mixture obtained is poured on aluminum. The gel time in the air and at room temperature was about 30 minutes, the ripening time from about 1 h to 2 h. An elastic material was obtained which, after grinding, is used in the enantioselective hydrolysis reaction as described hereinafter.

B. Saponification reaction 0. 4 g of a racemic mixture of 2-pentyl-1-cyclopenten-1-yl acetate (obtained as described for example in the European application EP-A-841 331 in the name of Firmenich SA) in the form of a suspension in a mixture containing 0.2 g of ethanol, 0.2 g of isopropanol and 0.1 g of a triethanolamine buffer solution at pH 7.5 was hydrolysed using 50 mg of immobilized Pseudomonas fl uorescens, obtained by the two preparation methods described under A and corresponding to approximately 15 g of the enzyme. The temperature was maintained at 25 ° during a reaction time of 40 h. The mixture was then extracted with methyl tert-butyl ether. The extract was analyzed by gas chromatography on a 25 m long Megadex 5 chiral column (100 ° to 150 ° to 3 ° / minute). An enantiomeric excess (ee) of approximately 93% and a conversion of almost 100% were obtained.

Example 11 Use of the PMS that contains the perfume adsorbed in the products for the care of the body A. Baby powder 0. 3 g of the PMS obtained in Example 1 were mixed with 0.5 g of a standard perfuming base to obtain a dry powder. This was mixed with 95.7 g of sterilized talc (cosmetic quality) and 3.5 g of crumbled zinc oxide. The product thus obtained was then sieved to remove the agglomerates and obtain a baby powder of the desired quality.

B. Powdered deodorant 1. 0 g of the PMS obtained in Example 1 is mixed with 1.5 g of a standard perfuming base. The dry powder which is formed was mixed with 97.0 g of the sterilized talc and 0.5 g of Triclosan (for example the Irgasan® DP-300 product made by Biba SC, Basle, Switzerland). A powder was thus obtained which is suitable as a perfumed deodorant.

Example 12 Preparation of a scented composition for an air freshener A perfumed composition for an air freshener was prepared from the following ingredients: Ingredients% by weight Dolomite 5. . 0 PMS 2. . 0 Perfume 13. . 0 Tween® 20 X) 0. , 2 II. Water 49.4 Tylosa MHB 30, 000 2) 0.4 III. Plaster (molding) 30.0 Total 100.0 1) polyoxyethylene sorbitan monolaurate; origin: ICI, Great Britain 2) carboxymethyl cellulose; Origin: Hoechst AG, Germany Parts I and II were mixed completely separately and then together. The mixture thus obtained is poured into plaster molds previously prepared in various decorative forms.

Example 13 Preparation of perfumed compositions for air fresheners The perfumed compositions for the air freshening gels were prepared from the following ingredients: Compositions A B Ingredients% by weight Satiagel K6 X) 1.3 1.3 Glycerin 3.0 3.0 Water 87.4 86.4 Glydant II 2) 0.1 0.1 Tylose MHB 30,000 3) 0.2 0.2 II. Magnesium carbonate - 2.5 Si02 3.0 1.5 Perfume 5.0 5.0 Total 100.0 100.0 1) carrageenan, origin: Kelco Int. Ltd., USA 2) condom, origin: Lonza Ind., Switzerland 3) see example 12 Parts I and II were completely mixed separately. After heating Part I to 75 ° C, part II was added thereto and the entire mixture was completely blended to obtain a homogeneous mixture. The compositions thus obtained were then molded in various ways in a known manner to produce air freshening products.

Example 14 Preparation of unscented soaps containing PMS A soap with a non-synthetic base was prepared from the following ingredients: Ingredients% by weight Sodium salt of tallow fatty acid or other natural fatty acid * 88.95 Water 10.00 Sodium chloride 0.50 Glycerin 0.50 Free alkaline substance 0.05 (or 100.00 free fatty acids 0.5% -1.0%) * palm, stearin palm , olive, etc.

The soaps were then prepared without any additive and with the addition of 1.5% by weight of the PMS, with this base having a strongly unpleasant odor. After the preparation, a panel of evaluators did not notice any difference between these two soaps. The soaps were then stored at 40 ° for 30 days, after which the panel largely preferred the soap containing the PMS due to a reduced odor level. The result was confirmed by the same panel that evaluated the smell of these soaps again after storage for two months at room temperature. All evaluations were carried out blindfolded.

Example 15 Preparation of a conditioner to be left on the site A conditioner to be left on the site, ie not proposed to be removed by rinsing, was prepared from the following ingredients: Ingredients% by weight A) Phytantriol® 1) 0.10 Renex® 690 2) 0.20 Propylene glycol 1.00 D-Panthenol 1} 0.20 Deionized Water 94.85 Ethoquad® 0/12 3) 0.70 Liquid Crosilk 4) 0.05 Mackpro NSP 5) 0.10 Arginine Hydrochloride 0.10 Kathon® CG 6) 0.05 Glydant® 7) 0.20 Germall II 8) 0.20 Sodium Phosphate, Triassic (12H20) 0.25 Phosphoric acid (aqueous solution at 0.40 42%) Cationic emulsion Dow Corning 929 9) 1. . 00 B) PMS 10) 0., 30 Perfume 10) 0.. 30 Total 100,. 00 ) Origin: Hoffmann-La Roche) Nonoxynol-10; origin: ICI Surfactants) Isopropyl alcohol (and) PEG-2 oleammonium chloride; origin: Akzo Nobel) Silk powder; origin: Croda) Hydrolyzed Silk Quarternium-79; origin: Mclntyre) Methylchloroisothiazoline and methylisothiazoline; Origin: Rohm & Haas) DMDM hydantoin; origin: Lonza) Diazolidinil Urea; origin: ISP) Amodimethicone (and) Nonoxynol-10 (and) Tallowtrimonium; origin: Dow Corning 0) Origin: Firmenich SA Phytanthiol® was thoroughly mixed with Renex® 690, and the other ingredients of part A were added. Next, the PMS according to the invention was completely mixed with the perfume and left overnight for the complete absorption of the perfume. Part B thus prepared was added to part A and the entire mixture was thoroughly homogenized, whereby a conditioner is produced which is to be stirred before use and is proposed to be applied to wet hair without subsequent rinsing. Alternatively, a thickener can also be added to this product to prevent separation of the perfumed PMS particles. If necessary, the pH is adjusted to 4 - 4.5 using phosphoric acid. When this product was applied to the hair and compared in a test with the eyes closed with a similar product, but containing the perfume without being supported on the PMS, it was found out that the hair treated with the first one released the fragrance of the perfume during a much longer time than when the conventionally perfumed conditioner was used.

Example 16 Preparation of shampoos A liquid shampoo was prepared from the following ingredients: Ingredients% by weight Deionized water 64.38 Kathon® 1) CG 0.10 Comperlan® 2) KD 1.50 Texapon® 3 > NSO IS 32.00 Citric acid 0.02 Perfume 4) 0.50 Sodium chloride 1.50 Total 100.00 The ingredients were thoroughly mixed to obtain a homogeneous shampoo base from which the following compositions were prepared: Composition Ingredients A Base + 0.5% by weight of PMS B Base + 0.5% by weight of Luviquat Hold 5) C Base + 0.5% of Luviquat Hold 5) + 0.5% PMS D Base + 0. 5% of Jaguar Exel 6) E Base + 0.5% of Jaguar Exel 6 > + 0.5% PMS 1) see example 15 2) cocamide DEA; origin: Henkel 3) sodium sulfate and laureth; origin: Henkel 4) origin: Firmenich SA 5) cationic polymer; origin: BASF 6) cationic polymer; Origin: Rhodia In the preparation of the compositions C and E, the perfume was first mixed with the PMS, as described in the preceding example, before the incorporation of this mixture into the base. Compositions A and E were compared with blindfolded by a panel of assessors who were asked to assign a value, on the ascending scale of 1 to 10, which corresponds to the intensity of the perceived fragrance on dry and wet hair. . The results of these evaluations are summarized in the following table: Composition Intensity of Fragrance BASE 3 A 6 B 5 C 6 D 6 E 8 It is clearly evident from this table that, when the perfume is added to the shampoo on a PMS support in accordance with the. invention, the latter distinctly improves the deposition of perfume on the hair. In addition, it has been found that the hair remained perfumed for longer than when the perfume was added as such to the shampoo base.

Example 17 Preparation of a conditioner to be removed by rinsing A conditioner that is to be removed by rinsing was prepared from. of the following ingredients: Ingredients% by weight A) Deionized water 91.60 Aqueous 20% solution of chlorhexidine digluconate 1.}. 0.25 Nipagin® MNa '0.10 Nicotinamide 3) 98% 0.05 Genamin® KSL 4) 3.00 Lactic Acid L (+) 85% -90% 0.30 D-Panthenol 5) 0.30 Dow Corning Q2-5200 6) 0.20 Ethyl Alcohol 1.30 Ultra Lanolin 7) 0.20 B) Jaguar C-162 8) 1.00 Natrosol 250 H 9) 0.70 C) PMS 10) 0.50 Perfume 10) 0.50 Total 100.00 ) origin: ICN Biochemicals) Sodium methylparaben; origin: ÑIPA) Niacinamide; origin: Acros Organics) PEG-5 Stearil Ammonium Lactate; origin: Clariant) origin: Hoffmann-La Roche) Copolyol from Laurylmeticone; origin: Dow Corning) origin: Westbrook Lanolin) Hydroxypropyl Chloride Hydroxypropyltrimonium; origin: Rhone-Poulenc 9) Hydroxyethyl cellulose; Origin: Hercules 10) Origin: Firmenich SA Part A was heated to about 60 ° C until the cetyl alcohol solution was supplemented. Part B, which has been previously mixed, was then added. The homogenization was then carried out until the cream thus formed had cooled to room temperature. The PMS was completely mixed with the perfume, and the mixture was allowed to stand overnight for a good absorption. This perfumed PMS was then added to the cream previously prepared to obtain the desired conditioner. The pH of the latter can be adjusted around 4 if necessary, using lactic acid.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (32)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. A porous polymethyl isosquioxane in a powdered form containing the units
2. Ends of Units of the Material Chain characterized by a specific surface area between about 50 m2 / g and 500 m2 / g, a pore radius smaller than 1 nm for 90% of the pores, and insolubility in water and organic solvents. 2. A polimetilsilsesquioxane according to claim 1, characterized by a pore volume between about 0.1 cm3 / g and 0.8 cm3 / g.
3. 3. A polymethylsiloquoisxane according to claim 1 or 2, characterized by a volume of monocoat of between about 10 cm3 / g and 60 cm3 / g.
4. 4. A polimetilsilsesquioxane according to any of claims 1 to 3, characterized by two adsorption bands around 10 ° and 22 ° obtained by X-ray diffraction.
5. 5. A polymethyl silsesquioxane according to any of claims 1 to 4, characterized by an average particle size between 1 μm and 200 μm.
6. 6. A polymethylsilyquioxane according to any of claims 1 to 5, characterized by a thermal stability of up to about 400 ° C and a decomposition temperature of about 500 ° C, as determined by calorimetry and differential thermogravimetry.
7. 7. A polymethyl silsesquioxane according to any of claims 1 to 6, characterized by a powder density of about 0.04 g / cm3 and 0.8 g / cm3.
8. 8. A polimetilsilsesquioxane according to any of claims 1 to 7, characterized in that it is a conglomerate of. porous nanoparticles with a particle size between about 1 μm and 200 μm.
9. 9. A polimetilsilsesquioxane according to any of claims 1 to 8, characterized in that it also contains the units Unpolymerized silanols
10. 10. A polymethylsilyquioxane according to any of claims 1 to 9, characterized by a specific surface area of between about 75 m2 / g and 375 m2 / g, a pore volume of between about 0.2 cm3 / g and 0.7 cm3 / g, a volume of the monolayer of between about 15 cm3 / g and 50 cm3 / g and a pore radius smaller than 0.9 nm for 90% of the pores.
11. 11. A process for the preparation of a porous polymethyl isosquioxane in the pulverized form, this process comprises the precipitation, by means of an acid, of an aqueous solution containing a polymethyl-siliconate of the general formula CH 3 0 CH 3 I CH 3 - Si - O - Si - o - Si - CH 3 (I) CH 3 CH 3 CH 3 in which n is an integer between about 20 and 100 and M is an alkali metal or an alkaline earth metal or NH 4 +.
12. 12. A process according to claim 11, characterized in that the acid is added to the solution until a pH of about at least 11 is reached.
13. 13. A process according to claim 11, characterized in that the acid is added to the solution until a pH of at least about 7 is reached.
14. 14. A process according to any of claims 11 to 13, characterized in that M is sodium or potassium.
15. 15. A process according to any of claims 11 to 14, characterized in that the acid used is sulfuric acid, phosphoric acid or acetic acid.
16. 16. A process according to any of claims 11 to 15, characterized in that the polymethyl- silsquioxane is isolated from the solution and washed and dried at temperatures between about 80 ° C and 400 ° C.
17. 17. A process according to any of claims 11 to 16, characterized in that the polymethylsiliconate of the formula (I) is prepared from a polymethylhydrosiloxane of the general formula CH3 H CH3 I CH3- S? -0- Si- O- S? -CH3 (III) CH3 CH3 CH3 wherein n is an integer between about 20 and 100.
18. 18. A process according to claim 17, characterized in that the polymethylsiliconate is prepared by the cleavage of the Si-H bond by means of an aqueous base or by the reaction with a carbonyl substrate catalyzed by a suitable metal derivative followed by hydrolysis.
19. 19. A porous polymethyl isosquioxane in the powdered form obtainable by a process according to any of claims 11 to 18.
20. 20. The use of the polymethyl silsesquioxane according to any of claims 1 to 10 and 19 as a support for the immobilization of the enzymes or for the preparation of such support.
21. 21. The use according to claim 20, wherein the support is prepared from the polymethyl siloxane by the reaction with an organosiloxane.
22. 22. The use according to claim 20 or 21, wherein the enzyme is a lipase, a peroxidase, a hydrogenase, a lyase, a protease or an isomerase.
23. 23. The use according to claim 20 or 21, wherein the enzyme is a lipase capable of effecting optical resolution of a mixture of enantiomers of an ester or an alcohol.
24. 24. The use according to any of claims 1 to 10 and 19 as a support for transition metals or derivatives thereof.
25. 25. The use according to any of claims 1 to 10 and 19 as an adsorbent for the extraction of the organic molecules.
26. 26. The use according to any of claims 1 to 10 and 19 in the purification of gases and water or in the preparation of the molecules by chromatography.
27. 27. The use according to any of claims 1 to 10 and 19 as an adsorbent for odoriferous compounds.
28. 28. The use according to claim 27, characterized in that the polymethyl-silsesquioxane containing the odoriferous compounds is used as a refresher for the air, a soap, a shampoo or another hair care product.
29. 29. The use according to claim 27, characterized in that the polymethyl-silsesquioxane is used in a non-scented soap to adsorb the unpleasant odors diffused by the soap.
30. 30. The use according to any of claims 1 to 10 and 19 as a support for a perfume, for the preparation of soaps, gels for bathing or for showering,. shampoos, conditioners, lacquers, cosmetic compositions, detergents or fabric softeners.
31. 31. A perfumed or perfuming composition, characterized in that it contains a. polimetilsilsesquioxane according to claim 9.
32. 32. A composition according to claim 31, characterized in that it is in the form of a soap, a shampoo or other hair care product.