EP2580173A2 - Procédé de production d'une substance à base de sol de silice - Google Patents

Procédé de production d'une substance à base de sol de silice

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Publication number
EP2580173A2
EP2580173A2 EP11725672.7A EP11725672A EP2580173A2 EP 2580173 A2 EP2580173 A2 EP 2580173A2 EP 11725672 A EP11725672 A EP 11725672A EP 2580173 A2 EP2580173 A2 EP 2580173A2
Authority
EP
European Patent Office
Prior art keywords
silica sol
reaction
sol material
temperature
carried out
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11725672.7A
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German (de)
English (en)
Inventor
Ekkehard Barth
Rolf Bachmann
Arne Braun
Maren Heinemann
Sebastian Schmidt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Innovation GmbH
Original Assignee
Bayer Innovation GmbH
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Filing date
Publication date
Application filed by Bayer Innovation GmbH filed Critical Bayer Innovation GmbH
Publication of EP2580173A2 publication Critical patent/EP2580173A2/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/141—Preparation of hydrosols or aqueous dispersions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/146—After-treatment of sols
    • C01B33/148—Concentration; Drying; Dehydration; Stabilisation; Purification
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/6224—Fibres based on silica
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/624—Sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/62635—Mixing details
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62685—Treating the starting powders individually or as mixtures characterised by the order of addition of constituents or additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/441—Alkoxides, e.g. methoxide, tert-butoxide

Definitions

  • the present invention relates to a process for the preparation of a biodegradable and / or resorbable silica sol material, which is particularly advantageous in terms of the reproducibility of the material, the rate of synthesis and the ability to produce the silica sol material on an industrial scale.
  • Another object of the invention relates to a biodegradable and / or resorbable silica sol material which can be prepared by the inventive synthesis method.
  • biodegradable and / or resorbable silica sol materials and their preparation are described in the prior art.
  • misting may occur in the reaction vessel.
  • the particles that are in such a mist can subsequently be removed only via a filtration step. If the particles are not removed via a filtration step, they can, for example, in the further processing of the silica sol material to a silica gel fiber by means of a spinning system, clog the spinning nozzles of the spinning plant. The spinning process must then be interrupted and the nozzles must be cleaned. On the other hand, an additional filtration step is to be avoided if possible, since the filtration loses synthesis material which can no longer be converted to the silica sol material. , -
  • WO2008 / 086970A1 relates to a similar silica sol material but in which the hydrolysis-condensation step is carried out over a period of at least 16 hours.
  • the hydrolysis-condensation reaction is preferably carried out batchwise in a stirred tank.
  • the Si compound and the solvent are preferably charged. This is followed by the rapid addition of an acid, preferably in the form of HNO 3 . It is described that the hydrolysis-condensation reaction proceeds rapidly due to the acid strength and the contents of the container heat up by about 40 ° C.
  • the subsequent removal of the solvent occurs to a viscosity of the mixture of 0.5 to 2 Pa ⁇ s at a shear rate of 10 s -1 at 4 ° C.
  • filtration is not required, followed by ripening at a temperature of preferably 2 ° C to 4 ° C to effect further condensation under kinetically controlled conditions to suppress formation of a three-dimensional polymeric gel network
  • the product of ripening preferably has a viscosity of 35 to 45 Pa ⁇ s (shear rate 10 s -1 at 4 ° C) at a loss factor (at 4 ° C, 10 s -1 , 1% deformation) of 2.5 to 3.5.
  • WO2008 / 148384A1 relates to a similar silica sol material.
  • a gas-diffusion-tight container preferably a rotary evaporator, is used during evaporation.
  • the hydrolysis-condensation step involves the immediate addition of a mixture of H 2 O and HNO 3 to a mixture of TEOS and ethanol.
  • the kinetically controlled ripening is carried out in particular by vibration-free storage of the reaction mixture in a closed gas-diffusion-tight vessel.
  • WO2009 / 077104A relates to a similar silica sol material, in which, compared to WO2008 / 148384A1, evaporation in a closed apparatus is optionally carried out by continuously supplying a chemically inert drag gas stream.
  • All of the above-mentioned prior art processes comprise at least three steps: hydrolysis-condensation, solvent-removal and maturation. The steps are obviously carried out in different vessels. The times for the individual steps sometimes vary considerably. The individual steps are completed when a preferred viscosity has been set; that is, it is obviously necessary to follow the viscosity of the reaction mixtures in order to complete one step in the presence of the desired (intermediate) product.
  • the end of the silica sol material production process at the beginning of the preparation can only be predicted within a range of ⁇ 2 days.
  • the above-described imponderables counteract a meaningful economic planning and production.
  • the object of the present invention was therefore to address the disadvantages of the prior art and to provide an improved process for the preparation of silica sol materials.
  • the method should allow a reproducible production of silica sol materials.
  • the method should be scalable to an industrial scale and allow a more accurate prediction of the end of the reaction.
  • the change of reaction vessels between the individual steps should be avoided.
  • the object is achieved by a method for producing a silica sol material, which comprises the following steps:
  • step (c) ripening the single-phase solution obtained in step (b) into a silica sol material having a viscosity between 30 and 100 Pa ⁇ s at a shear rate of 10 s -1 at 4 ° C and a loss factor of 2 to 5.
  • the combination preferably takes place over a period of at least 15 minutes, more preferably at least 30 minutes, and even more preferably at least 1 hour. The shorter the period of time for metering, the more likely additional equipment will be required to remove the heat generated during the reaction and maintain the temperature of the reaction mixture within a predetermined range.
  • controlled pooling has significant advantages, particularly with regard to a process operated on an industrial scale, for example in the compliance with safety regulations, in the process control and in the reproducibility. It is conceivable to carry out the combination in step (a) of the method according to the invention at a constant rate. It is also conceivable to carry out the combination in such a way that the temperature of the reaction mixture develops within a predetermined range. In the latter case, therefore, there is a control loop in which the combination of the components is controlled by the temperature and / or temperature change in the reaction mixture. In a preferred embodiment of the process according to the invention, the combination in step (a) takes place under quasi-isothermal conditions.
  • the reaction under quasi-isothermal conditions would preferably be within a sump temperature range (ie, measured within the reaction mixture) of ⁇ 5 ° C, preferably from ⁇ 2 ° C, particularly preferably run from ⁇ 0.5 ° C.
  • the components are combined in step (a) so that the heat released by the hydrolysis-condensation reaction is used to heat up the synthesis approach. It can thus be avoided overheating of the synthesis approach, for example, to low-performance or inert heat exchangers and the hydrolysis-condensation reaction can be performed in a controlled manner at the desired temperature.
  • step (a) The hydrolysis-condensation reaction in step (a) is preferably carried out with stirring.
  • hydrolyzable silicon compound preferably refers to a Si compound of the formula (I) SA, (I) wherein the radicals X are the same or different and are hydroxy, hydrogen, halogen, amino, alkoxy, acyloxy, acylcarbonyl and or alkoxycarbonyl and derived from alkyl radicals which optionally represent substituted straight-chain, branched or cyclic radicals having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, and by oxygen or sulfur atoms or by amino
  • X in the formula (I) is an optionally substituted straight-chain, branched and / or cyclic alkoxy radical having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms
  • X in the formula (I) is an optionally substituted straight-chain and / or branched C 1 -C 5 -alkoxy radical preferred are substituted, but preferably unsubstituted, straight-chain and / or
  • aqueous acid solution describes mixtures and / or solutions which have a pH of from 0 to ⁇ 7, preferably from 0 to 2.
  • the aqueous acid solution may comprise one or more further substances which Preferably, a water-soluble solvent is added, particularly preferably ethanol,
  • a water-soluble solvent is added, particularly preferably ethanol
  • the aqueous acid solution preferably comprises water and ethanol in a molar ratio of 1 to 1.27 to 1 to 1.59, particularly preferably in a molar ratio of 1 to 1.41.
  • Nitric acid is preferably used as proton donor. - -
  • aqueous or alcoholic preferably an aqueous dilute ethanolic solution of a physiologically tolerated acid (eg citric, succinic, acetic or ascorbic acid) and at least one essential (eg L-arginine), particularly preferred; L-valine, L-leucine, L-isoleucine, L-phenylalanine, L-thyroxine, L-methionine, L-lycin or L-tryptophan) or non-essential amino acid (eg L-glutamine, L-glutamic acid, L-asparagine, L-aspartic acid, L-cysteine, L-glycine, L-alanine, L-proline, L-histidine, L-tyrosine).
  • a physiologically tolerated acid eg citric, succinic, acetic or ascorbic acid
  • essential eg L-arginine
  • non-essential amino acid eg L-glutamine, L-glutamic acid
  • Such mixtures and / or solutions form in a physiological environment with molecular oxygen enzymatically (by means of a nitroxide synthase, NOS) nitric oxide (NO).
  • NOS nitroxide synthase
  • organic nitrates or nitrate esters such as. Ethyl nitrate, which form NO with the help of an organic nitrate reductase, are used.
  • Thiol groups (cysteine) are required for this enzymatic release of NO.
  • the molar ratio of S1X 4 water in the range of 1: 1, 5 to 1: 2.5, preferably in the range of 1: 1, 7 to 1 : 1, 9, more preferably in the range of 1: 1, 7 to 1: 1.8.
  • step (a) can take place in various ways. It is conceivable to introduce the hydrolyzable silicon compound in the reactor and to add the aqueous acid solution. It is conceivable to present the hydrolyzable silicon compound in a suitable solvent (for example ethanol in the case of TEOS).
  • a further preferred embodiment relates to a process for producing a silica sol material in which both the acid and the hydrolyzable silicon compound are added in a controlled manner to a solvent in parallel.
  • the hydrolyzable silicon compound is pre-mixed with a portion of the solvent, preferably 35 to 38% of the solvent. Overall, the amount of solvent thus preferably does not change.
  • the acid and the hydrolyzable silicon compound can be metered in independently of each other (for example via different reaction vessel openings and pump systems) over different periods of time.
  • the same period of time for metering is selected in proportion to the volume flow.
  • the added hydrolyzable silicon compound quantity or the added amount of acid is preferably constant per unit time.
  • This embodiment of the invention is preferably carried out under quasi-isothermal conditions. - - leads.
  • the hydrolyzable silicon compound or acid is metered in over a period of at least 15 minutes, preferably at least 30 minutes and more preferably at least 1 hour.
  • Another object of the present invention is directed to a process for the preparation of a silica sol material in which a hydrolyzable silicon compound is added to an acid present in a solvent.
  • This controlled combination also referred to below as "inverse dosing"
  • inverse dosing surprisingly leads to a novel sol which is reproducible and can be prepared in a controlled manner but whose physical properties differ from those described in the prior art Sol can be spun into a fiber and is also biodegradable and / or resorbable.
  • This sol has a lower viscosity at the same loss factor as compared to those described in the prior art.
  • the loss factor is the quotient of the viscous to elastic portion of the dynamic viscosity. Too low a loss factor means too much elasticity of the material, e.g. prevents the formation of a stable thread during spinning (gelling, tearing of the thread). If the loss factor is too high, the material is so fluid that stable thread formation is not possible (drop formation).
  • the loss factor is an important parameter for determining the quality of the silica sol material for its further use (see below for more details). If the viscosity at the same loss factor is lower than in the case of the silica sol material resulting from the inverse addition, such a material is easier to process and is accordingly advantageous.
  • the hydrolyzable silicon compound is preferably not previously or only in a small part of a solvent, preferably 0 to 5%, dissolved. Overall, the amount of solvent thus preferably does not change. However, at the beginning of the reaction, there is no or proportionately less solvent in the reaction vessel to which the silicon compound or the mixture of a part of the solvent and the hydrolyzable silicon compound is metered in in a controlled manner.
  • the inverse dosage is preferably carried out under quasi-isothermal conditions.
  • the amount of hydrolyzable silicon compound added per unit time is preferably constant or approximately constant.
  • the hydrolyzable silicon compound is metered in over a period of at least 15 minutes, preferably at least 30 minutes and more preferably at least 1 hour.
  • Another object of the invention is directed to a silica sol material prepared by a controlled metered addition of a hydrolyzable silicon compound to an in-solvent acid, followed by evaporation to a single-phase solution having a viscosity in the range 0.5 to 1.5 Pa ⁇ s at a shear rate of 10 s -1 at 4 ° C, and ripening of this single-phase solution to a silica sol material having a viscosity of 30 Pa ⁇ s at a shear rate of 10 s -1 at 4 ° C, a loss factor of third
  • reaction mixture is preferably stirred for some time until a dynamic equilibrium has been established.
  • the duration of the reaction depends on the selected temperature and the period of the controlled metered addition. For example, the reaction, at a temperature of 55 ° C and a controlled metered addition of the acid to the hydrolyzable silicon compound present in the solvent over a period of one hour, takes a total of about 5 hours on a laboratory scale. At a temperature of 37 ° C and otherwise the same conditions, the reaction lasts 18 hours.
  • the hydrolysis condensation is preferably carried out without pressure (i.e., without overpressure at about 101325 Pa), preferably at a temperature of 0 ° C to 78 ° C. By appropriate pressure regulation, it is also possible to carry out the reaction at temperatures above the boiling point of ethanol (i.e., 78 ° C).
  • Reactive evaporation in step (b) to give a single-phase solution is carried out as described in the prior art up to a dynamic viscosity ( ⁇ ) of the mixture at 0.5 to 30 Pa ⁇ s at a shear rate of 10 s -1 at 4 ° C , preferably 0.5 to 2 Pa ⁇ s at a shear rate of 10 s -1 at 4 ° C., more preferably 1 Pa ⁇ s at a shear rate of 10 s -1 at 4 ° C.
  • step (b) is carried out in a closed apparatus in which mixing is possible and at the same time the solvent (ie, water, ethanol) can be evaporated.
  • the bottom temperature is maintained by pressure regulation (temporally variable adjustment between preferably 500 to 120 mbar) constant (ie ⁇ 5 ° C, preferably of ⁇ 2 ° C), so that continuously solvent under , , light boiling from the batch to the above viscosity is removed.
  • the reaction temperature may be selected as described in the prior art, ie preferably between 30 ° C to 78 ° C, and more preferably between 60 ° C and 75 ° C.
  • step (b) is carried out with careful mixing of the reaction system.
  • the single-phase solution resulting from step (b) is subjected to ripening in step (c).
  • the single-phase solution is preferably stirred in this maturation process. Mixing the system with agitation causes the ripening to be slightly accelerated. In addition, the mixing of the single-phase solution leads to a degradation of temperature gradients, which in turn causes a better temperature control and thus an easier scalability of the process.
  • the speed of the stirrer is chosen so that no bubbles can arise in the single-phase solution. Speeds of 4 to 50 rpm, especially of less than 25 rpm, in particular those of less than 10 rpm, have proven to be expedient.
  • active substances are defined as substances which produce a specific action, a reaction, in a small dose in an organism
  • Temperature-sensitive active substances or pharmaceutical substances are those whose degradation is markedly accelerated at temperatures below 8 ° C., preferably below 2 ° C.
  • step (c) An important factor influencing maturation (step (c)) is the temperature.
  • the ripening can be carried out at temperatures of up to -80 ° C to 78 ° C and with regulation of the pressure also above it.
  • a sol known in the art may be prepared.
  • the production time at these temperatures is significantly shortened (from 2 to 3 weeks when ripening is carried out at 4 ° C compared to 2 days when the reaction is carried out at 31 ° C).
  • the maturation should ideally not exceed a temperature of 45 ° C, otherwise the ripening of the maturation - can not be guaranteed at the below target values for viscosity and loss factor, the reaction continues to run and a material is obtained, which is not desirable, that is no longer biodegradable or exceeds the gel point and is no longer spinnable.
  • the silica sol material obtained in step (c) preferably has a viscosity between 30 and 100 Pa ⁇ s (shear rate 10 s -1 at 4 ° C.), preferably from 35 to 70 Pa ⁇ s (shear rate 10 s -1 at 4 ° C) with a loss factor (at 4 ° C, shear rate 10 s -1 , 1% deformation) of 2 to 5, preferably from 2.5 to 3.5, and more preferably from 2.8 to 3.2
  • a loss factor at 4 ° C, shear rate 10 s -1 , 1% deformation
  • the silica sol material produced by the process according to the invention can be further processed into a fiber, a fleece, a powder, monolith and / or a coating. Further processing is known to the person skilled in the art.
  • all preparation steps (a) to (c) are carried out in one and the same reaction vessel.
  • all preparation steps (a) to (c) are carried out with moderate stirring.
  • the reaction vessel is preferably a stirred tank, which comprises the following features: 1) It is closable and pressure-resistant to at least 10 bar and at least from -20 ° C to 80 ° C tempered. The pressure and temperature are recorded, displayed and can be regulated. 2) It has an access to the metering of the respective liquid components, a bottom outlet valve for taking out the product and a gas access for pressure application or to remove part of the gaseous alcohol and the aqueous acid by distillation from the reaction mixture.
  • reaction vessel It is conceivable to equip the reaction vessel with probes for measuring the viscosity of the reaction mixture.
  • Other probes such as IR or Raman probes, can be used to monitor the concentrations of reaction components.
  • the method according to the invention overcomes the disadvantages of the prior art. Controlled merging of the starting materials makes the production process overall easier to control. The reproducibility is increased and the manufacturing process becomes scalable. Further improvements result from the additional measure of stirring the single-phase solution in the ripening step (c), preferably at a temperature of 25 ° C to 35 ° C. In particular, carrying out the ripening at the described preferred temperatures also causes a considerable acceleration of the entire production process without having to accept the required product properties of the silica sol material. By the influencing variables described in the invention, the total synthesis time could be reduced by almost 90%. A prediction method now also makes it possible, among other things due to the improved manufacturing process, to predict the end of the silica sol material production process at the beginning of production within a range of ⁇ 2 hours.
  • Figure 1 shows the schematic structure of a synthesis boiler and its immediate periphery for the production of spinnable and biodegradable silica sol material.
  • EXAMPLE 1 As starting materials for the hydrolysis condensation, 5.4 mol of TEOS (tetraethoxysiloxane) in ethanol were initially charged with 6.8 mol in a closed reaction vessel. 9.6 mol of water in the form of a 0.006 N HN0 3 solution were mixed in advance and then metered into the ethanol / TEOS mixture over a period of 1 hour at a constant temperature (isothermal procedure) of 37 ° C. The reaction solution is stirred for 17 hours until reaching an ethanol concentration of about 68% by weight. Thereafter, the single-phase solution was successively evaporated at a constant bottom temperature of 62 ° C.
  • TEOS tetraethoxysiloxane
  • Ethanol (2.6 mol, 100%) was placed in a closed reaction vessel.
  • the remaining ethanol (4.2 mol, 100%) was metered in together with 5.4 mol of TEOS via an access to the ethanol in the reaction vessel over a period of one hour in a controlled manner.
  • 9.6 mol of water in the form of a 0.006 N HN0 3 solution over a period of one hour were added via another access to the reaction vessel.
  • the reaction was carried out so that the bottom temperature in the reaction vessel during the entire reaction is 37 ° C (isothermal mode).
  • the further process steps were carried out as described in the first embodiment, with the exception of the ripening temperature.
  • the ripening temperature was 4 ° C.
  • EMBODIMENT Ethanol (6.8 mol, 100%) was charged together with 9.6 mol of water in the form of a 0.006 N HNO 3 solution in a closed reaction vessel.
  • TEOS tetraethoxysiloxane
  • the reaction was carried out so that the bottom temperature in the reaction vessel during the entire reaction was 37 ° C (isothermal mode).
  • the further procedural steps were carried out as described in the first exemplary embodiment. The maturation of the - - -
  • Silica sol material was stirred at a temperature of 7 ° C to a viscosity of 30 Pa ⁇ s at a shear rate of 10 s -1 at 4 ° C and a loss factor of 3.1.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Silicon Compounds (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

L'invention concerne un procédé amélioré pour produire une substance biodégradable et/ou biorésorbable à base de sol de silice, ce procédé étant avantageux en particulier en ce qui concerne la reproductibilité de la substance, la rapidité de la synthèse et la possibilité de produire la substance à base de sol de silice à grande échelle. L'invention concerne également une substance biodégradable et/ou biorésorbable à base de sol de silice qui peut être produite au moyen du procédé de synthèse selon l'invention.
EP11725672.7A 2010-06-10 2011-06-06 Procédé de production d'une substance à base de sol de silice Withdrawn EP2580173A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010023336A DE102010023336A1 (de) 2010-06-10 2010-06-10 Verfahren zur Herstellung eines Kieselsol-Materials
PCT/EP2011/059302 WO2011154361A2 (fr) 2010-06-10 2011-06-06 Procédé de production d'une substance à base de sol de silice

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EP2580173A2 true EP2580173A2 (fr) 2013-04-17

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EP11725672.7A Withdrawn EP2580173A2 (fr) 2010-06-10 2011-06-06 Procédé de production d'une substance à base de sol de silice

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US (1) US9221690B2 (fr)
EP (1) EP2580173A2 (fr)
JP (1) JP2013528154A (fr)
AU (1) AU2011263823A1 (fr)
BR (1) BR112012031454A2 (fr)
CA (1) CA2801970C (fr)
DE (1) DE102010023336A1 (fr)
MX (1) MX2012014213A (fr)
WO (1) WO2011154361A2 (fr)

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Publication number Priority date Publication date Assignee Title
EP2734482A1 (fr) 2011-07-21 2014-05-28 Bayer Innovation GmbH Procédé de production d'un matériau à base de sol de silice filable
DE102012213843B3 (de) 2012-08-03 2013-09-19 Automotive Lighting Reutlingen Gmbh Primäroptikeinheit für ein Lichtmodul
WO2014172556A1 (fr) 2013-04-17 2014-10-23 Silbond Corporation Solution colloïdale et son procédé de fabrication
US10442899B2 (en) 2014-11-17 2019-10-15 Silbond Corporation Stable ethylsilicate polymers and method of making the same
CN105819455B (zh) * 2016-03-31 2017-08-25 上海理工大学 一种介孔硅胶纳米颗粒的制备方法及其应用
DE102017217539B4 (de) * 2017-10-02 2021-04-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Biodegradierbare Fasern, Verfahren zu deren Herstellung und deren Verwendung, sowie diese enthaltende Fasergeflechte oder -filter

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DE19609551C1 (de) 1996-03-12 1997-07-17 Fraunhofer Ges Forschung Biologisch degradierbare und/oder biologisch resorbierbare (Endlos)Fasern, Verfahren zu deren Herstellung und deren Verwendung als Verstärkungsfasern
DE102004063599B4 (de) 2004-12-30 2007-07-12 Bayer Innovation Gmbh Verkürzte Wundheilungsprozesse mittels neuartiger Faservliese
DE102007061873A1 (de) * 2007-01-15 2008-07-17 Bayer Innovation Gmbh Kieselsol-Material zur Herstellung von biologisch degradierbaren und/oder resorbierbaren Kieselgel-Materialien dessen Herstellung und Verwendung
DE102007026043B4 (de) * 2007-06-04 2018-08-16 Jiangsu Synecoun Medical Technology Co., Ltd. Nicht-toxisches Polyethoxysiloxan-Material zur Herstellung von biologisch resorbierbares und/oder bioaktives Polyethoxysiloxan-Material enthaltenden Artikeln, dessen Herstellung und Verwendung
DE102007061874A1 (de) 2007-12-19 2009-06-25 Bayer Innovation Gmbh Nicht-toxisches Polysiloxan-Material zur Herstellung von biologisch resorbierbaren und/oder bioaktiven Polysiloxan-Material enthaltenden Artikeln, dessen Herstellung und Verwendung
DE102008033327A1 (de) * 2008-07-16 2010-01-21 Bayer Innovation Gmbh Kieselsol-Material mit mindestens einem therapeutisch aktiven Wirkstoff zur Herstellung von biologisch degradierbaren und/oder resorbierbaren Kieselgel-Materialien für die Humanmedizin und/oder Medizintechnik

Non-Patent Citations (1)

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Title
See references of WO2011154361A2 *

Also Published As

Publication number Publication date
CA2801970A1 (fr) 2011-12-15
JP2013528154A (ja) 2013-07-08
US20130145964A1 (en) 2013-06-13
BR112012031454A2 (pt) 2016-11-08
WO2011154361A2 (fr) 2011-12-15
US9221690B2 (en) 2015-12-29
WO2011154361A3 (fr) 2012-04-12
MX2012014213A (es) 2013-02-07
CA2801970C (fr) 2017-10-24
RU2012157528A (ru) 2014-07-20
AU2011263823A1 (en) 2013-01-24
DE102010023336A1 (de) 2011-12-15

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