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US20040147029A1 - Silicon dioxide dispersion - Google Patents

Silicon dioxide dispersion Download PDF

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Publication number
US20040147029A1
US20040147029A1 US10/469,254 US46925404A US2004147029A1 US 20040147029 A1 US20040147029 A1 US 20040147029A1 US 46925404 A US46925404 A US 46925404A US 2004147029 A1 US2004147029 A1 US 2004147029A1
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Prior art keywords
dispersion
phase
parts
weight
silicon dioxide
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Johannes Adam
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Evonik Operations GmbH
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Publication of US20040147029A1 publication Critical patent/US20040147029A1/en
Priority to US12/191,294 priority Critical patent/US20080306203A1/en
Assigned to EVONIK HANSE GMBH reassignment EVONIK HANSE GMBH CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: HANSE CHEMIE AG
Priority to US14/512,017 priority patent/US9376544B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/10—Composition for standardization, calibration, simulation, stabilization, preparation or preservation; processes of use in preparation for chemical testing

Definitions

  • the invention relates to a silicon dioxide dispersion comprising:
  • SiO 2 silicon dioxide
  • Natural (mineral) SiO 2 can, for example, be brought to desired particle size by grinding and mixed with the polymer or a polymer precursor.
  • Ground SiO 2 generally has a very broad particle size distribution and an irregular particle structure. Particle sizes of less than 1 ⁇ m are difficult to obtain or unobtainable by mechanical comminution of the SiO 2 .
  • pyrogenic silica by flame hydrolysis of silicon halogen compounds. This produces particles of very complex morphology and extremely broad particle size distribution, since the primary particles produced in the flame hydrolysis undergo partial agglomeration and form other associated superstructures. Pyrogenic silica, moreover, is expensive to prepare.
  • the present invention is based on the object of providing a silicon dioxide dispersion of the type specified at the outset which is easy to process even at relatively high filler concentrations, which produces an effective improvement in mechanical and/or electrical properties of the polymer end product, and which can be prepared from a process, likewise in accordance with the invention from inexpensively obtainable starting materials.
  • the silicon dioxide dispersion accordingly comprises
  • the average particle size d max of the silicon dioxide as measured by means of small-angle neutron scattering (SANS) is between 3 and 50 nm at a maximum half-width of the distribution curve of 1.5 d max .
  • the so-called external phase of the silicon dioxide dispersion of the invention is fluid. This means that at customary processing temperatures (e.g., 18 to 300° C., preferably 18 to 100° C.) it is either liquid or else sufficiently fluid or viscous to be subjected to the desired further processing, in particular mixing with further constituents of the polymeric material to be produced or shaping as part of processing.
  • customary processing temperatures e.g., 18 to 300° C., preferably 18 to 100° C.
  • This external phase comprises, in accordance with one aspect of the invention, polymerizable monomers, oligomers and/or prepolymers. Prepolymers are relatively small polymer units which are able to crosslink and/or polymerize to form larger polymers. “Polymerizable” means that in this external phase there are still polymerizable and/or crosslinkable groups which are able to enter into a polymerization reaction and/or crosslinking reaction in the course of further processing of the dispersion.
  • the external phase comprises polymerizable constituents which are convertible to polymers by non radical reactions. This means that the polymerization to polymers does not proceed by way of a free-radical mechanism.
  • Polymerizable acrylates or methacrylates are all monomeric, oligomeric or prepolymeric acrylates or methacrylates which in the course of the production of a material from the dispersion are deliberately subjected to a further polymerization.
  • One example of the polyadditions is the synthesis of polyurethanes from diols and isocyanates, one example of polycondensations is the reaction of dicarboxylic acids with diols to form polyesters.
  • the external fluid phase may comprise a polymer or two or more polymers.
  • Polymers in this sense are macromolecules which are no longer reactive and which therefore do not react to form larger polymer units.
  • the material in question may in particular be a melted and/or dissolved material which can be converted to said material again physically by cooling and/or removal of the solvent.
  • the dispersion of the invention does not cure chemically to form a polymer; instead, use is made as the external phase of a ready-produced polymer which for the purpose of preparation of the dispersion is brought by merely physical means (thermally and/or by solvent addition) into a liquid or viscous aggregate state, in order to allow the mixing in of the disperse phase.
  • a material comprising the disperse phase, and whose polymer composition is substantially unchanged in comparison with the polymeric material originally employed as external phase can be produced by cooling and/or by removal of the solvent.
  • substantially unchanged means that, in the course of the conversion of the original material into the external phase (thermally or by solvent addition) and of the resolidification which takes place after the disperse phase has been mixed in, to form a material of the invention (by cooling or stripping of the solvent), there is no deliberate further polymerization; instead, at the most, polymer reactions occur to a slight extent as secondary reactions.
  • Example 21 in the experimental section is an example of this version of the invention.
  • the disperse phase comprises amorphous silicon dioxide.
  • amorphous silicon dioxide Preferably it consists essentially of amorphous silicon dioxides.
  • the method employed for measuring the amorphous silicon dioxide particles is that of small-angle neutron scattering (SANS). This measurement method is familiar to the skilled worker and requires no more detailed elucidation here.
  • SANS small-angle neutron scattering
  • a particle size distribution curve is contained in which the volume fraction of particles of corresponding size (diameter) is parted against the particle diameter.
  • the average particle size for the purposes of the invention is the peak of such a SANS distribution curve, i.e., the greatest volume fraction with particles of corresponding diameter.
  • the half-width of the distribution curve is the width (in nm) of the distribution curve at half its height, i.e., at the half of the particle volume fraction at the distribution curve peak d max , or, expressed alternatively, the width of the distribution curve at half the height of the Y axis (relative to the height of the curve at d max ).
  • the average particle size is preferably been 6 and 40 nm, more preferably between 8 and 30 nm, with particular preference between 10 and 25 nm.
  • Silicon dioxide dispersions according to the invention have good processing properties and, even where the concentration of the disperse phase is relatively high, exhibit a rheology which approximates to the ideal Newtonian flow behavior. At the given particle concentration they generally have a lower viscosity than corresponding prior art dispersions.
  • the half-width of the distribution curve is, in accordance with the invention, preferably not more than 1-2 d max , more preferably not more than d max , with particular preference not more than 0.75 d max .
  • the fraction of the external phase as a proportion of the dispersion can in the context of the invention be between 20 and 90% by weight, preferably from 30 to 80% by weight, more preferably from 40 to 70% by weight. Accordingly the fraction of the disperse phase can be between 10 and 80% by weight, preferably from 20 to 70% by weight, more preferably from 30 to 60% by weight.
  • the silicon dioxide particles of the dispersion of the invention are preferably substantially spherical.
  • the dispersion may further comprise auxiliaries selected from the group consisting of solvents, plasticizers, crosslinkers, catalysts, stabilizers, dispersants, curing agents, reaction mediators and agents for influencing the fluidity of the dispersion.
  • the dispersion of the invention is water-free, i.e., it contains only small traces of water which remain even after conventional methods of removing water, described in more detail below, have been performed.
  • the external phase may be one of two or more reaction constituents for the preparation of a polymer.
  • the polymers can be thermoplastics or thermosets.
  • thermoplastics or thermosets By way of example mention may be made of polyurethanes, polyureas, expoxy resins, polyester resins, polysiloxanes (silicones), and, in general, reactive resins for the production of thermosets. It can, for example, comprise a substance selected from the group consisting of polyols, polyamines, linear or branched polyglycol ethers, polyesters and polylactones.
  • polyols used with preference for the external phase of the dispersion of the invention are linear or branched aliphatic glycols, the external phase of the SiO 2 dispersion featuring with particular preference ethylene glycol, 1,2- or 1,3-propanediol, 1,2- or 1,4-butanediol, 1,6-hexanediol, 2,2,4-trimethylpentane-1,3-diol and/or neopentylglycol.
  • Use is further made, as aliphatic polyols, of, preferably, glycerol, trimethylolpropane, and also sugar alcohols, especially erythritol, xylitol, mannitol and/or sorbitol.
  • the external phase may further comprise, as preferred polyols, one or more alicyqlic polyols, especially 1,4-cyclohexane-dimethanol, and/or sucrose.
  • Suitable polymeric polyols for the external phase include preferably those having an average molecular weight of from 200 to 20,000, the polymeric polyol preferably being one based on akylene glycol (polymeth)acrylates.
  • the external phase of the dispersion of the invention may further comprise preferably polymeric polyols which are obtained by hydrolysis or partial hydrolysis of vinyl-ester-containing polymers.
  • Suitable polyethers for the external phase include in particular the linear or branched polyglycol ethers obtainable by ring-opening polymerization of cyclic ethers in the presence of polyols, e.g., the aforementioned polyols; of these polyglycol ethers, preference is given, on account of their relatively easy availability, to polyethylene glycol, polypropylene glycol and/or polytetramethylene glycol or the copolymers thereof.
  • Suitable polyesters for the external phase of the dispersion of the invention include those based on polyols and aliphatic, cycloaliphatic and aromatic polyfunctional carboxylic acids (for example, dicarboxylic acids), and specifically all corresponding saturated polyesters which are liquid at temperatures of 18 to 300° C., preferably 18 to 150° C.: preferably succinic esters, glutaric esters, adipic esters, citric esters, phthalic esters, isophthalic esters, terephthalic esters and/or the esters of the corresponding hydrogenation products, with the alcohol component being composed of monomeric or polymeric polyols, for example, of those of the above-mentioned kind.
  • polycarbonates of bisphenol A having an average molecular weight of from 500 to 100,000.
  • polystyrene resin instead of the aforementioned polyols, polyethers and saturated polyesters, it is also possible for the purpose of the invention to use mixtures of the aforementioned classes of substance for the external phase of the dispersion of the invention.
  • the use of such mixtures may be an advantage, for example, in respect of a reduction in the glass transition temperature and/or melting temperature of the resultant products.
  • the aforementioned polyethers and polyesters may carry functional groups, such as hydroxyl, carboxyl, amino or isocyanato groups, for example.
  • the polyols, polyethers and saturated polyesters and/or mixtures thereof provided in accordance with the invention for the external phase may where appropriate be admixed with further suitable auxiliaries, particularly solvents, plasticizers, diluents and the like.
  • the external phase may comprise at least one reactive resin.
  • reactive resins are precursors or prepolymers which before and during the processing and/or shaping operation are liquid or plastic and give rise after the processing operation, which is normally a shaping operation, to thermosets as a result of polymerization (polycondensation, polyaddition).
  • the polymerization produces a three-dimensionally crosslinked, hard, nonmeltable resin, the thermoset, which thus differs fundamentally from thermoplastics, which, as is known, can always be liquefied again or plastified by renewed heating.
  • the crosslinked reactive resins exhibit a range of valuable properties, which are the reason why together with the thermoplastics they are among the most used of polymers. These valuable properties include, in particular, hardness, strength, chemical resistance and temperature stability. On the basis of these properties these reactive resins are employed in a very wide variety of fields: for example for the production of fibre reinforced plastics, for insulating materials in electrical engineering, for the production of construction adhesives, laminates, baking varnishes and the like.
  • Suitable reactive resins in accordance with the invention are all polymeric or oligomeric organic compounds which are provided with suitable reactive groups in sufficient number for a curing reaction.
  • suitable starting products for the preparation of the inventively modified reactive resins include, in general, all reactive resins which can be processed to thermosets, irrespective of the particular crosslinking mechanism which proceeds in the course of the curing of the particular reactive resin.
  • reactive resins having free-radically polymerizable double bonds which on account of their particular reactivity are less suitable for the process of the invention. They may be present, if at all, as an optionally additional constituent in the external phase.
  • the reactive resins which can be used in accordance with the invention as starting products can be divided fundamentally into two groups in accordance with the nature of their crosslinking by addition or condensation.
  • Epoxy resins and urethane resins are generally crosslinked by the addition of stoichiometric amounts of a curing agent containing hydroxyl, amino, carboxyl or carboxylic anhydride groups, the curing reaction taking place by addition reaction of the oxirane and/or isocyanate groups of the resin with the corresponding groups of the curing agent.
  • epoxy resins a further possibility is that of the so-called catalytic curing by polyaddition of the oxirane groups themselves.
  • Air-drying alkyd resins crosslink by autooxidation with atmospheric oxygen.
  • Examples of the second group of reactive resins, crosslinked by polycondensation are condensation products of aldehydes, e.g., formaldehyde, with aliphatic or aromatic compounds containing amine groups, e.g., urea or melamine, or with aromatic compounds such as phenol, resorcinol, cresol, xylene, etc., and also furan resins, saturated polyester resins and silicone resins. Curing in this case generally takes place by an increase in temperature accompanied by elimination of water, low molecular mass alcohols or other low molecular mass compounds.
  • aldehydes e.g., formaldehyde
  • aliphatic or aromatic compounds containing amine groups e.g., urea or melamine
  • aromatic compounds such as phenol, resorcinol, cresol, xylene, etc.
  • furan resins saturated polyester resins and silicone resins.
  • phenolic resins specifically both resoles and novolaks
  • cresol resins specifically both resoles and novolaks
  • urea-formaldehyde precondensates and melamine-formaldehyde preconden-sates furan resins
  • saturated polyester resins and/or silicone resins specifically both resoles and novolaks
  • thermosets having considerably improved fracture toughness and impact strength, which other essential properties characteristic of the thermosets, such as strength, heat distortion resistance and chemical resistance, remain substantially unaffected.
  • the reactive resins or reactive resin mixtures used in accordance with the invention are liquid at temperatures in the range from 18 to 100° C.
  • the reactive resins or reactive resin mixtures used have an average molecular weight in the range from 200 to 500,000, preferably from 300 to 20,000.
  • monomers and oligomers include in particular those monomeric or oligomeric compounds which can be reacted to form polymers by polyaddition or polycondensation.
  • the invention possesses considerable advantages in particular when employed in the context of reactive resins.
  • Prior art reactive resins are brittle owing to their highly crosslinked state and have a low impact strength, particularly at relatively low temperatures.
  • thermoset polymer can be considerably improved in accordance with the invention without adversely affecting hardness, strength and softening temperature.
  • thermosets in which on the one hand the liquid reactive resin is still easy to process despite a high fraction of filler and on the other hand, by virtue of the filling addition of monomodal particles of low diameter, a considerable improvement occurs in the mechanical properties (especially tensile strength, elongation at break or fracture toughness) of the cured thermoset polymer.
  • the polymerizable monomers, oligomers and/or prepolymers contain carbon, oxygen, nitrogen and/or sulfur atoms in the main chain.
  • the polymers in question are therefore organic hydrocarbon polymers (with or without heteroatoms); polysiloxanes do not come under this preferred embodiment.
  • the external fluid phase may with preference comprise polymerizable monomers without radically polymerizable double bonds and also reactive resins.
  • the external fluid phase may further comprise silanes.
  • the silanes may have hydrolyzable and nonhydrolyzable, optionally functional groups.
  • hydrolyzable groups are halogen, alkoxy, alkenoxy, acyloxy, oximino and aminoxy groups.
  • functional, nonhydrolyzable groups are vinyl, aminopropyl, chloropropyl, aminoethylamino propyl, glycidyloxypropyl, mercaptopropyl or methacryloyloxypropyl groups.
  • nonhydrolyzable nonfunctional groups are monovalent C 1 to C 8 hydrocarbon radicals.
  • silanes which can be used in accordance with the invention are: ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, ⁇ -aminopropyldimethylmethoxysilane, glycidyloxypropyltrimethoxysilane, glycidyloxypropyldimethylmethoxysilane, methacryloyloxypropyltrimethoxysilane, chloropropyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltrispropenoxysilane, vinyldimethylbutanone oxime silane, vinyltrisbutanone oxime silane, trimethylchlorosilane, vinyldimethylchlorosilane, dimethylchlorosilane, vinylmethylchlorosilane.
  • the silanes are used preferably in a concentration of from 40 to 200 mol % and with particular preference from 60 to 150 mol % based on the molar amount of silanol groups on the surface.
  • an aqueous silicate solution is introduced. It can be an alkali metal silicate solution, in particular a sodium silicate and or potassium silicate solution.
  • concentration of this aqueous silicate solution is preferably in the range between 20 and 50% by weight.
  • the preferred ratio of SiO 2 to Na 2 O is between 2 and 3.
  • the silicate is polycondensed to a particle size of from 3 to 50 nm. This can take place, for example, by treating the alkali metal silicate solution with acidic ion exchangers which replace the alkali metal ions with H + ions and so initiate the desired polycondensation.
  • the silica sol obtained is adjusted to an alkaline pH (pH>8, preferably >9, more preferably >10, with particular preference between 10 and 12) and in this way is stabilized against further polycondensation or agglomeration of existing particles.
  • the sol can be concentrated, for example, by distillation, preferably to an SiO 2 concentration of from 30 to 40% by weight.
  • the sol is mixed with constituents of the external fluid phase of the dispersion.
  • the constituents of the external fluid phase can be added or mixed in either simultaneously or in two or more substeps in succession.
  • water and/or other solvent constituents are removed from the dispersion, since the intention is to use the dispersions of the invention to prepare, with particular preference water-free plastics (referred to as water-free nanocomposites).
  • water-free plastics referred to as water-free nanocomposites.
  • Use may be made of all of the customary separation techniques familiar to the skilled worker, such as, for example, distillation, preferably in vacuo, membrane separation, sedimentation where appropriate, solvent extraction, use of a molecular sieve, etc.
  • distillation it is possible where appropriate to add solvents which form an azeotrope with water and so act as an azeotropic entrainer.
  • solvent constituents require removal, this can also be carried out simultaneously or by means of two or more sequential substeps.
  • substeps of the process steps e) and f) of claim 16 are mixed with one another, so to speak. It is possible, therefore, following the addition of one or more constituents in step e), first to remove one or more solvent constituents in step f) and then to carry out further substeps (addition of material) in step e), again remove other solvent constituents in step f), and so on. Consequently, substeps of the process steps e) and f) of claim 16 can be mixed with one another and swapped with one another.
  • the silicon dioxide component of a dispersion of the invention is prepared exclusively and hence in its entirety by the stated process.
  • the silanes in question can be mono-, di-, tri- or tetraalkoxy silanes; there must be a sufficient fraction present of silanes having three or four hydrolyzable groups.
  • non hydrolyzable radicals is an aliphatic (preferably having 1 to 18 carbon atoms) or aromatic hydrocarbon radical which may additionally contain a functional group, for example, a vinyl, allyl, (meth)acryloyl, glycidyl, halogen, hydroxyl or mercapto group.
  • Any further non hydrolyzable radicals present are preferably methyl or ethyl.
  • disperse phase is prepared in the manner stated by silane hydrolysis, it is possible where appropriate for additional solvents to be added which may serve as solubilizers between silane and external phase of the dispersion.
  • additional solvents include water-miscible alcohols of low molecular mass (preferably C 1 to C 4 alcohols), ketones, amines, amides or heterocyclic compounds such as THF or pyridine, for example.
  • the invention further provides for the use of a dispersion defined above for producing a polymeric material.
  • the polymeric material can be a thermoplastic or thermoset polymer.
  • the polymeric material can on the one hand be a thermoplastic or on the other hand a chemically crosslinked, thermoset or elastomeric polymer.
  • thermoset and/or elastomeric polymers mention may be made of: polyurethanes, polyureas, epoxy resins, polyester resins, polyimide resins, polysiloxanes, alkyd resins, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polybutadiene rubber.
  • thermoplastic polymers which can be used in accordance with the invention in the external phase mention may be made of the following: polyolefins, polystyrene, styrene-acrylonitrile copolymers, polyamides, polyvinyl chloride and its copolymers, polyvinyl alcohols, and polyvinyl acetates and polyvinyl ethers and also copolymers of these substances, polycarbonate, polymethyl acrylates and polymethyl methacrylates, including their copolymers, polyurethanes, polysulfones, polyether ketones, polyesters.
  • the polymeric materials for the purposes of this invention are not only compact materials; instead, the dispersions of the invention can also be used with advantage as part of the binder in paints, inks and coatings.
  • the dispersions of the invention can also be used with advantage as part of the binder in paints, inks and coatings.
  • it is particularly advantageous that, through the amount of silicon dioxide on the one hand the abrasion resistance, the scratch resistance and also the barrier effect to the penetration of the coating by gases and moisture are increased, but on the other hand, through the narrow particle size distribution, the viscosity is increased to much less of an extent than in the case of silicon dioxide fillers in accordance with the conventional state of the art. This is a considerable advantage particularly in the case of surface coatings.
  • the polymeric materials modified in accordance with the invention may also be closed-cell or open-cell foams, based for example on polyurethanes, polysiloxanes, polyolefins or polystyrene.
  • the particular advantage of the dispersion of the invention arises in this case from the fact that, owing to the low particle size and the narrow particle distribution, the particles can be present in the thin lamellae of the foam without disrupting the foam structure per se. As a result it becomes possible, for example, to raise the hardness and compressive strength of the foam with its density unchanged or to maintain said properties despite a decrease in density.
  • a further embodiment of the polymeric materials modified in accordance with the invention are liquid, curable casting and impregnating compounds for the production, for example, of electrical insulating resins or fiber composites.
  • electrical insulating resins e.g., in the casting of coils or transformers
  • the critical factor is the ability of the impregnating resin to flow as far as possible easily and without defect through the spacings of the coil windings, which are often just a few ⁇ m, a task virtually impossible for resins filled with prior art fillers owing to their particle size and irregular distribution.
  • a further advantageous quality of the polymeric materials modified with the dispersions of the invention is their optical clarity, which is again a result of the extremely low particle size and narrow diameter distribution for silicon dioxide.
  • the prior art does not provide any possibility for adding more than just a very small fraction of inorganic fillers to the polymer without detriment to its optical properties. Consequently, in the case of polymer applications where optical clarity is important, it is virtually impossible to improve properties such as hardness or modulus of elasticity, scratch resistance, fracture strength, thermal conductivity, expansion coefficient, diffusion barrier effect, and so on, which in the case of non transparent systems would normally be effected by adding inorganic fillers.
  • this relates to a very large number of polymeric materials and their applications, e.g., polymethyl methacrylate, polycarbonate, polyalkylene terephthalates, a variety of clearcoat systems, for example, for top coats of vehicles, furniture, flooring, printed matter, etc.
  • the dispersion of the invention can comprise polyols or polyamines of the type described in more detail above from which polyurethanes and/or polyureas can be produced.
  • the dispersion is then mixed conventionally with polyisocyanates and reacted in order to prepare the desired polymeric materials whose properties have been modified accordingly by the disperse SiO 2 phase.
  • the polymerization reaction can be implemented in one or more stages, where appropriate at elevated temperature.
  • the dispersion of the invention includes a reactive resin
  • it can be subjected in a known manner to further processing, by the known single-stage or multistage processes of reactive resin engineering, to give a polymer, preferably a thermoset polymer.
  • a three-dimensional polymeric network is developed.
  • Further additives and adjuvants can be added to the reactive resin prior to crosslinking, examples being organic or inorganic fillers, fibres, pigments, flow assistants, reaction accelerants or retardants, plasticizers or the like.
  • a commercial aqueous alkali silicate solution having a water content of 47% and a ratio of SiO 2 to Na 2 O of 2.4 was diluted with demineralized water to a water content of 97%. 100 parts of this diluted solution were passed at a rate of 20 parts per hour through a column packed with a commercially acidic ion exchanger and subsequently was supplied to a distillation receiver in which the incoming deionized silicate solution was held at boiling temperature and the water distilling off was removed from the solution. After the end of the introduction the silica sol formed was concentrated by further heating to 10 parts. The pH was adjusted to 10.5 to 11.
  • Example 2 polypropylenediol (PPG), molar mass (MM) 1000
  • Example 3 PPG end capped with 15% polyethylene glycol (PEG) MM 4000
  • Example 4 Polypropylenetriol, MM 6000
  • the three samples obtained were water-clear.
  • the particle size distribution was measured by means of SANS and for all three samples gave a diameter distribution which matched within the bounds of measurement accuracy and was 47 ⁇ 11 nm.
  • Example 1 was repeated with the difference that the water content of the diluted alkali metal silicate solution was adjusted to 98% and the rate of introduction to the distillation receiver was 15 parts per hour. Following concentration, 9 parts of silica sol were obtained. The pH was adjusted to 10.5 to 11.
  • Example 7 PPG with 10% ethylene oxide randomly copolymerized, MM 3000
  • Example 8 Polypropylenetriol, MM 550
  • Example 9 Polypropylenetriol end capped with 20% PEG, MM 2000
  • Example 10 Polytetramethylene glycol, MM 650
  • the five samples obtained were water-clear.
  • the particle size distribution was measured by means of SANS and for all samples gave a diameter distribution which matched within the bounds of measurement accuracy and was 30 ⁇ 7 nm.
  • Example 1 was repeated with the difference that the rate of introduction to the distillation receiver was 30 parts per hour. Following concentration, 15 parts of silica sol were obtained. The pH was adjusted to 10.5 to 11.
  • Example 1 was repeated with the difference that the rate of introduction to the distillation receiver was 43 parts per hour. Following concentration, 8 parts of silica sol were obtained. The pH is adjusted to 10.5 to 11.
  • Example a Branched polyester polyol (“Desmophen 1100”, Bayer AG)
  • Example b Polycarbonate-polyester polyol (“Desmophen C 200”, Bayer AG)
  • Example c Polycaprolactonpolyol (“TONE 2241”, Dow Chemical)
  • the example demonstrates the considerably improved mechanical and thermal characteristics of the Plexiglas, without marked detriment to its optical properties from the addition of the silicon dioxide.
  • AEROSIL® R8200 is a pyrogenic silica prepared by flame hydrolysis from silicon tetrachloride, obtainable from Degussa.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Silicon Compounds (AREA)
  • Graft Or Block Polymers (AREA)
US10/469,254 2001-02-28 2002-02-28 Silicon dioxide dispersion Abandoned US20040147029A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US12/191,294 US20080306203A1 (en) 2001-02-28 2008-08-13 Silicon Dioxide Dispersion
US14/512,017 US9376544B2 (en) 2001-02-28 2014-10-10 Silicon dioxide dispersion

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP01104919.4 2001-02-28
EP01104919A EP1236765A1 (fr) 2001-02-28 2001-02-28 Dispersion de silice
PCT/EP2002/002198 WO2002083776A1 (fr) 2001-02-28 2002-02-28 Dispersion d'oxyde de silicium

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/002198 A-371-Of-International WO2002083776A1 (fr) 2001-02-28 2002-02-28 Dispersion d'oxyde de silicium

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CA2442369A1 (fr) 2002-10-24
WO2002083776A1 (fr) 2002-10-24
US9376544B2 (en) 2016-06-28
EP1366112A1 (fr) 2003-12-03
ES2225792T3 (es) 2005-03-16
EP1366112B1 (fr) 2004-07-21
DE50200666D1 (de) 2004-08-26
US20080306203A1 (en) 2008-12-11
US20150094386A1 (en) 2015-04-02
ATE271580T1 (de) 2004-08-15
EP1236765A1 (fr) 2002-09-04

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