WO2020120169A1 - Aqueous dispersions and dispersion powder of microsilica - Google Patents
Aqueous dispersions and dispersion powder of microsilica Download PDFInfo
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- 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
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- 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
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
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- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
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- C04B40/0042—Powdery mixtures
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0066—Film forming polymers
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
- C04B2103/0082—Segregation-preventing agents; Sedimentation-preventing agents
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00637—Uses not provided for elsewhere in C04B2111/00 as glue or binder for uniting building or structural materials
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1037—Cement free compositions, e.g. hydraulically hardening mixtures based on waste materials, not containing cement as such
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/72—Repairing or restoring existing buildings or building materials
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- Aqueous dispersions and dispersible polymer powders from microsilica are Aqueous dispersions and dispersible polymer powders from microsilica
- the invention relates to aqueous dispersions and dispersion powder of microsilica, processes for their preparation and their use.
- Microsilica (silica fume, silica dust) is an extremely fine-grained, mineral substance that is created, for example, as filter dust in the manufacture of silicon.
- the starting material for this is quartz, which together with coal is reduced to metallic silicon in electric arc furnaces.
- the resulting silicon monoxide reacts with the oxygen contained in the furnace air and S1O 2 is again formed as a by-product, which is present in the finest pearls (silica fume) and is called microsilica.
- Microsilica is an artificial pozzolana and is used as an additive in the construction industry. It reacts with calcium hydroxide, the hydration product of cement and water, to form calcium silicate hydrate and leads to an improvement in the mechanical properties, for example the concrete pressure resistance, of the hardened cementitious masses. In addition, an improvement in the tightness and chemical resistance, for example against the penetration of chlorides, of building materials can be achieved.
- Microsilica is available in powder form or in aqueous dispersion. For large-scale commercial use in the construction industry, it is necessary to offer microsilica in a safe, easy-to-use form that can be transported using pumps, for example. These requirements are best met by providing microsilica in the form of an aqueous dispersion. To the shipping and storage costs to minimize, it is desirable to use microsilica dispersions with a high solids concentration, that is to say with a proportion of at least 30% by weight of microsilica particles.
- microsilica dispersions with such high solids concentrations tend to sediment and gel. Since the use in the construction industry often results in transport and storage times of up to several weeks, the prevention of sedimentation and gelation is of particular importance.
- microsilica dispersions with a combination of complexing agent, for example EDTA, and anionic dispersing agent, for example naphthalene sulfonate-formaldehyde condensation polymer, and setting a pH of 5.0 to 8.5 to improve.
- complexing agent for example EDTA
- anionic dispersing agent for example naphthalene sulfonate-formaldehyde condensation polymer
- setting a pH of 5.0 to 8.5 to improve.
- EDTA is added for stabilization and a pH of 3 to 6 is set.
- US 4,888,058 tripolyphosphate and / or citric acid and their salts are used to stabilize the microsilica dispersions.
- US 2005/0167105 A1 microsilica particles are used as granules, which are bound with biodegradable polymers, for example cellulose.
- WO 2018/052307 A1 describes aqueous microsilica dispersions which are stabilized by adjusting the pH to a range from 4 to 7 and adding polylactic acid. The problem with all of these processes is that the additives used delay the hydraulic bonding in cementitious materials or pollute the environment.
- the invention relates to aqueous dispersions and dispersion powders of microsilica particles, characterized in that they are stabilized with vinyl alcohol copolymer.
- Microsilica is a fine-grained silicon dioxide that fulfills the requirements and conformation criteria according to DIN EN 13263-1.
- the microsilica particles preferably have an average primary particle particle size d-PP of 45 mth, determined by means of statistical laser diffraction analysis.
- the microsilica products mentioned are commercially available, for example from Elkem ASA.
- Vinyl alcohol copolymers with are suitable for stabilization
- Most preferred as monomers c) are vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and their salts.
- Suitable monomers d) are vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate and vinyl esters of o-branched monocarboxylic acids with 5 to 13 carbon atoms, for example vinyl pivalate, VeoVa9 R , VeoVal0 R or Ve- oVall R (trade name of Hexion).
- the vinyl esters of a-branched monocarboxylic acids with 9 to 10 carbon atoms (VeoVa9 R and VeoVal0 R ) are preferred.
- the vinyl alcohol polymers can be prepared in a known manner by means of free-radical polymerization of vinyl acetate, if appropriate using the comonomers mentioned under c) and d) and then hydrolysing the polymers obtained in this way.
- Suitable polyvinyl alcohols and sulfonated polyvinyl alcohols are also commercially available.
- the aqueous dispersions of microsilica particles contain 20 to 60% by weight, preferably 30 to 50% by weight, of microsilica, in each case based on the sum of the parts by weight of microsilica and water.
- the amount of vinyl alcohol copolymer in the aqueous microsilica dispersion or in the microsilica dispersion powder is 1 to 20 wt .-%, preferably 3 to 10 wt .-% vinyl alcohol copolymer, each based on the proportion by weight of microsilica ver in the dispersion or in the dispersion powder.
- the procedure is preferably such that the vinyl alcohol copolymer is initially dissolved in water and the powdery microsilica particles are added to this solution and dispersed.
- the microsilica particles can be packaged, for example in sacks, or stored in bulk, for example in silos or large containers.
- the microsilica particles can be added via sack dumpers, dosing loos with and without weighing or by direct conveyance from storage silos or large containers using suitable conveyor systems such as compressed air diaphragm pumps.
- suitable conveyor systems such as compressed air diaphragm pumps.
- the microsilica particles are incorporated by shaking, for example using a tumble mixer or a high-speed mixer, or by stirring, for example using a bar stirrer or dissolver.
- the microsilica particles can be dispersed subsequently or in parallel with the addition of the microsilica particles.
- Parallel dispersion means that when the microsilica particles begin to be metered into the aqueous phase, the dispersion process begins.
- High-speed stirrers, high-speed dissolvers, for example with circulation speeds of 1 to 50 m / s, high-speed rotor-stator systems, sonolators, shear gaps, nozzles or ball mills are preferably suitable for this.
- the use of ultrasound in the range from 5 Hz to 500 kHz is suitable for dispersing the microsilica particles.
- the dispersion can be carried out by combining various methods, e.g. Predispersion using a dissolver or inductor followed by fine dispersion using ultrasound treatment.
- the production can be carried out in batch and continuous processes. Continuous processes are preferred.
- the aqueous microsilica dispersions are adjusted to a pH of 6 to 8.
- the aqueous dispersion of the microsilica particles can be dried, for example, by means of fluidized-bed drying, freeze-drying or spray drying.
- the microsilica dispersions are preferably spray-dried.
- aqueous dispersions or water-dispersible dispersion powders of microsilica particles are suitable for use in cementitious or non-cemented building materials, in pasty form or as dry mortar. Examples of building materials are plasters, mortar, screeds and concrete.
- the aqueous dispersions or dispersion powders of microsilica particles are also suitable for use in adhesives, sealants, fillers and paints.
- a monomer mixture 1 with 999 g VeoVa R 10 and 18661 g vinyl acetate was metered in with a metering time of 180 minutes.
- a monomer solution 2 from 1319 g of a 25% aqueous solution of vinyl sulfonate was metered in with a metering time of 195 minutes.
- the reactor was locked, the pressure in the reactor was increased to 0.2 bar and post-polymerized at 100 ° C. for one hour.
- the polymer solution was then cooled to 30 ° C. and diluted with methanol to a 31% by weight solution.
- the polymer solution was overlaid without stirring with 38440 g of methanol and then a mixture of 775 g of methanol and 657 g of 46% sodium hydroxide solution was added and stirred. After two hours the solution was neutralized with 342 g acetic acid (99.8%). Then methanol and the by-products were removed by steam stripping. After stripping, the vinyl alcohol copolymer was taken up in water and diluted to a 20% by weight solution.
- Polyvinyl alcohol 2 (PVOH 2): A 20% aqueous solution of a vinyl alcohol copolymer with 88 mol% vinyl alcohol and 12 mol% vinyl acetate monomer units was used as PVOH 2.
- microsilica dispersions produced were stored closed at room temperature. After 24 hours, it was examined whether a phase separation (sedimentation) had taken place.
- microsilica dispersions were dried at room temperature. After drying, the microsilica dispersion powder obtained was ground and sieved (mesh size of 1 mm).
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Abstract
The invention relates to aqueous dispersions and dispersion powder of microsilica particles, characterized in that these are stabilized with vinylalcohol copolymerizate.
Description
Wässrige Dispersionen und Dispersionspulver von Mikrosilika Aqueous dispersions and dispersible polymer powders from microsilica
Die Erfindung betrifft wässrige Dispersionen und Dispersions pulver von Mikrosilika, Verfahren zu deren Herstellung sowie deren Verwendung . The invention relates to aqueous dispersions and dispersion powder of microsilica, processes for their preparation and their use.
Mikrosilika (Silikastaub , engl, silica fume, silica dust) ist ein extrem feinkörniger, mineralischer Stoff der beispielsweise als Filterstaub bei der Herstellung von Silicium entsteht. Aus gangsstoff hierfür ist Quarz, der zusammen mit Kohle in elek trischen Lichtbogenöfen zu metallischen Silicium reduziert wird. Das dabei entstehende Siliciummonoxid reagiert mit dem in der Ofenluft enthaltenen Sauerstoff und als Nebenprodukt wird wieder S1O2 gebildet, welches in feinsten Perlen (Silikastaub) vorliegt und als Mikrosilika bezeichnet wird. Microsilica (silica fume, silica dust) is an extremely fine-grained, mineral substance that is created, for example, as filter dust in the manufacture of silicon. The starting material for this is quartz, which together with coal is reduced to metallic silicon in electric arc furnaces. The resulting silicon monoxide reacts with the oxygen contained in the furnace air and S1O 2 is again formed as a by-product, which is present in the finest pearls (silica fume) and is called microsilica.
Mikrosilika zählt zu den künstlichen Puzzolanen und wird in der Bauindustrie als Additiv eingesetzt. Es reagiert mit Calcium hydroxid, dem Hydratationsprodukt von Zement und Wasser, unter Bildung von Calciumsilikathydrat und führt zur Verbesserung der mechanischen Eigenschaften, beispielsweise der Betondruckfes tigkeit, der ausgehärteten zementären Massen. Darüberhinaus kann eine Verbesserung der Dichtigkeit und der Chemikalienre sistenz, beispielsweise gegen Eindringen von Chloriden, von Baustoffen erzielt werden. Microsilica is an artificial pozzolana and is used as an additive in the construction industry. It reacts with calcium hydroxide, the hydration product of cement and water, to form calcium silicate hydrate and leads to an improvement in the mechanical properties, for example the concrete pressure resistance, of the hardened cementitious masses. In addition, an improvement in the tightness and chemical resistance, for example against the penetration of chlorides, of building materials can be achieved.
Mikrosilika werden pulverförmig oder in wässriger Dispersion angeboten. Für die großtechnische kommerzielle Nutzung in der Bauindustrie ist es notwendig, Mikrosilika in einer sicheren, leicht zu handhabenden Form anzubieten, die beispielsweise mit tels Pumpen transportierbar ist. Diese Anforderungen werden am ehesten durch die Bereitstellung von Mikrosilika in Form einer wässrigen Dispersion erfüllt. Um die Versand- und Lagerkosten
zu minimieren, ist es wünschenswert, Mikrosilika-Dispersionen mit einer hohen Feststoffkonzentration zu verwenden, das heißt mit einem Anteil von mindestens 30 Gew.-% an Mikrosilika-Parti- keln . Microsilica is available in powder form or in aqueous dispersion. For large-scale commercial use in the construction industry, it is necessary to offer microsilica in a safe, easy-to-use form that can be transported using pumps, for example. These requirements are best met by providing microsilica in the form of an aqueous dispersion. To the shipping and storage costs to minimize, it is desirable to use microsilica dispersions with a high solids concentration, that is to say with a proportion of at least 30% by weight of microsilica particles.
Problematisch ist dabei, dass Mikrosilika-Dispersion mit so ho hen Feststoffkonzentrationen zur Sedimentation und Gelierung neigen. Da die Verwendung in der Bauindustrie vielfach Trans port- und Lager-Zeiten von bis zu mehreren Wochen mit sich bringt, ist die Verhinderung von Sedimentation und Gelierung von besonderer Bedeutung. The problem here is that microsilica dispersions with such high solids concentrations tend to sediment and gel. Since the use in the construction industry often results in transport and storage times of up to several weeks, the prevention of sedimentation and gelation is of particular importance.
Aus der EP 0 246 181 Al ist bekannt, die Lagerstabilität vom Mikrosilika-Dispersionen mit einer Kombination aus Komplexbil- ner, beispielsweise EDTA, und anionischem Dispergiermittel, beispielsweise Naphthalinsulfonat-Formaldehyd-Kondensationspo lymer, und Einstellung eines pH-Werts von 5,0 bis 8,5 zu ver bessern. Bei dem Verfahren der US 4,321,243 wird zur Stabili sierung EDTA zugegeben und ein pH-Wert von 3 bis 6 eingestellt. In der US 4,888,058 werden zur Stabilisierung vom Mikrosilika- Dispersionen Tripolyphosphat und/oder Zitronensäure sowie deren Salze eingesetzt. In der US 2005/0167105 Al werden Mikrosilika- Partikel als Granulate eingesetzt, welche mit biologisch abbau baren Polymeren, beispielsweise Cellulose, gebunden sind. Die WO 2018/052307 Al beschreibt wässrige Mikrosilika-Dispersionen, welche mittels pH-Einstellung auf einen Bereich von 4 bis 7 und Zugabe von Polymilchsäure stabilisiert werden. Problematisch bei allen diesen Verfahren ist, dass die dabei eingesetzten Zu satzstoffe die hydraulische Bindung in zementären Massen verzö gern oder die Umwelt belasten. It is known from EP 0 246 181 Al that the storage stability of microsilica dispersions with a combination of complexing agent, for example EDTA, and anionic dispersing agent, for example naphthalene sulfonate-formaldehyde condensation polymer, and setting a pH of 5.0 to 8.5 to improve. In the process of US 4,321,243, EDTA is added for stabilization and a pH of 3 to 6 is set. In US 4,888,058 tripolyphosphate and / or citric acid and their salts are used to stabilize the microsilica dispersions. In US 2005/0167105 A1 microsilica particles are used as granules, which are bound with biodegradable polymers, for example cellulose. WO 2018/052307 A1 describes aqueous microsilica dispersions which are stabilized by adjusting the pH to a range from 4 to 7 and adding polylactic acid. The problem with all of these processes is that the additives used delay the hydraulic bonding in cementitious materials or pollute the environment.
Daher war es erwünscht, wässrige Mikrosilika-Dispersionen her zustellen, die zumindest für die typischen Versand- und
Lagerzeiten stabil bleiben und die eben genannten Nachteile nicht aufweisen. It was therefore desirable to produce aqueous microsilica dispersions which are at least suitable for the typical shipping and Storage times remain stable and do not have the disadvantages just mentioned.
Gegenstand der Erfindung sind wässrige Dispersionen und Disper sionspulver von Mikrosilika-Partikeln, dadurch gekennzeichnet dass diese mit Vinylalkohol -Copolymerisat stabilisiert sind. The invention relates to aqueous dispersions and dispersion powders of microsilica particles, characterized in that they are stabilized with vinyl alcohol copolymer.
Unter Mikrosilika ist ein feinkörniges Siliziumdioxid zu ver stehen, welches die Anforderungen und Konformationskriterien gemäß DIN EN 13263-1 erfüllt. Die Mikrosilika-Partikel haben vorzugsweise eine mittlere Primärteilchen-Partikelgröße d-PP von 45 mth, bestimmt mittels statistischer Laserbeugungsana lyse. Die genannten Mikrosilika-Produkte sind im Handel erhält lich, beispielsweise von der Firma Elkem ASA. Microsilica is a fine-grained silicon dioxide that fulfills the requirements and conformation criteria according to DIN EN 13263-1. The microsilica particles preferably have an average primary particle particle size d-PP of 45 mth, determined by means of statistical laser diffraction analysis. The microsilica products mentioned are commercially available, for example from Elkem ASA.
Zur Stabilisierung geeignet sind Vinylalkohol -Copolymerisate mit Vinyl alcohol copolymers with are suitable for stabilization
a) 80 bis 99,5 Mol-%, vorzugsweise 85 bis 97 Mol-% Vinylalko hol -Monomereinheiten, a) 80 to 99.5 mol%, preferably 85 to 97 mol% of vinyl alcohol monomer units,
b) 0,5 bis 15 Mol-%, vorzugsweise 1 bis 5 Mol-% Vinylacetat-Mo nomereinheiten, b) 0.5 to 15 mol%, preferably 1 to 5 mol% of vinyl acetate monomer units,
c) 0 bis 10 Mol-%, vorzugsweise 1 bis 10 Mol-% Monomereinhei ten, welche sich von ethylenisch ungesättigten Monomeren mit einem oder mehreren Sulfonsäure-Resten sowie deren Salze, ab leiten, c) 0 to 10 mol%, preferably 1 to 10 mol%, of monomer units derived from ethylenically unsaturated monomers with one or more sulfonic acid residues and their salts,
d) 0 bis 10 Mol-%, vorzugsweise 1 bis 10 Mol-% Monomereinhei ten, welche sich von Vinylestern von unverzweigten oder ver zweigten Alkylcarbonsäuren mit 3 bis 18 C-Atomen ableiten, wobei sich die Angaben in Mol-% jeweils auf 100 Mol-% aufaddie ren . d) 0 to 10 mol%, preferably 1 to 10 mol%, of monomer units which are derived from vinyl esters of unbranched or branched alkylcarboxylic acids having 3 to 18 carbon atoms, the details in mol% each being based on 100 mol - Add%.
Als Monomere c) geeignete Monomere mit Sulfonsäure-Gruppe sind Vinylsulfonsäure, Styrolsulfonsäure, Allylsulfonsäure,
Methallylsulfonsäure, p-Methallyloxyphenylsulfonsäure , und Sul fonsäuren der allgemeinen Formel CH2=CR1-C0-X-CR2R3-R4-S03H, wo bei X = 0 oder NH, und R1, R2, R3 gleich oder verschieden sind und die Bedeutung H und Ci- bis C3-Alkyl haben, und R4 Ci- bis C4-Alkylen ist, sowie die Salze der genannten Säuren. Be vorzugt werden Vinylsulfonsäure, Sulfopropyl (meth) acrylat ,Monomers having a sulfonic acid group which are suitable as monomers c) are vinylsulfonic acid, styrene sulfonic acid, allylsulfonic acid, Methallylsulfonic acid, p-methallyloxyphenylsulfonic acid, and sulfonic acids of the general formula CH2 = CR 1 -C0-X-CR 2 R 3 -R 4 -S03H, where at X = 0 or NH, and R 1 , R 2 , R 3 are the same or are different and have the meaning H and Ci to C3 alkyl, and R 4 is Ci to C4 alkylene, and the salts of the acids mentioned. Be preferred vinyl sulfonic acid, sulfopropyl (meth) acrylate,
2 -Acrylamido-2 -Methylpropansulfonsäure und Methallylsulfon säure, l-Allyloxy-2 -Hydroxy-Sulfonsäure , Acrylsäure- (3-sulfop- ropyl) -Ester , Methacrylsäure- (3 -sulfopropyl) -Ester, Itacon- säure-bis- (3 -sulfopropyl) -Ester, sowie die Salze der genannten Säuren. Am meisten bevorzugt werden als Monomere c) Vinylsul fonsäure, 2 -Acrylamido-2 -methylpropansulfonsäure , und deren Salze . 2-acrylamido-2-methylpropanesulfonic acid and methallylsulfonic acid, l-allyloxy-2-hydroxy sulfonic acid, acrylic acid (3-sulfopropyl) ester, methacrylic acid (3-sulfopropyl) ester, itaconic acid bis- ( 3 -sulfopropyl) esters, and the salts of the acids mentioned. Most preferred as monomers c) are vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and their salts.
Als Monomere d) geeignet sind Vinylpropionat, Vinylbutyrat , Vi nyl-2 -ethylhexanoat , Vinyllaurat, 1-Methylvinylacetat und Vi nylester von oc-verzweigten Monocarbonsäuren mit 5 bis 13 C-Ato men, beispielsweise Vinylpivalat , VeoVa9R, VeoVal0R oder Ve- oVallR (Handelsnamen der Firma Hexion) . Bevorzugt sind die Vi nylester von a-verzweigten Monocarbonsäuren mit 9 bis 10 C-Ato- men (VeoVa9R und VeoVal0R) . Suitable monomers d) are vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate and vinyl esters of o-branched monocarboxylic acids with 5 to 13 carbon atoms, for example vinyl pivalate, VeoVa9 R , VeoVal0 R or Ve- oVall R (trade name of Hexion). The vinyl esters of a-branched monocarboxylic acids with 9 to 10 carbon atoms (VeoVa9 R and VeoVal0 R ) are preferred.
Die Vinylalkohol-Colymerisate können in bekannter Weise mittels radikalischer Polymerisation von Vinylacetat, gegebenenfalls mit den unter c) und d) genannten Comonomeren und anschließen der Hydrolyse der dabei erhaltenen Polymerisate hergestellt werden. Geeignete Polyvinylalkohole und sulfonierte Polyvinyl alkohole sind auch im Handel erhältlich. The vinyl alcohol polymers can be prepared in a known manner by means of free-radical polymerization of vinyl acetate, if appropriate using the comonomers mentioned under c) and d) and then hydrolysing the polymers obtained in this way. Suitable polyvinyl alcohols and sulfonated polyvinyl alcohols are also commercially available.
Die wässrigen Dispersionen von Mikrosilika-Partikeln enthalten 20 bis 60 Gew.-%, vorzugsweise 30 bis 50 Gew.-% Mikrosilika, jeweils bezogen auf die Summe der Gewichtsanteile von Mikrosi lika und Wasser. Die Menge an Vinylalkohol-Copolymerisat in der
wässrigen Mikrosilika-Dispersion oder im Mikrosilika-Dispersi- onspulver beträgt 1 bis 20 Gew.-%, vorzugsweise 3 bis 10 Gew.-% Vinylalkohol -Copolymerisat, jeweils bezogen auf den Gewichtsan teil von Mikrosilika in der Dispersion oder im Dispersionspul ver . The aqueous dispersions of microsilica particles contain 20 to 60% by weight, preferably 30 to 50% by weight, of microsilica, in each case based on the sum of the parts by weight of microsilica and water. The amount of vinyl alcohol copolymer in the aqueous microsilica dispersion or in the microsilica dispersion powder is 1 to 20 wt .-%, preferably 3 to 10 wt .-% vinyl alcohol copolymer, each based on the proportion by weight of microsilica ver in the dispersion or in the dispersion powder.
Zur Herstellung der wässrigen Dispersionen von Mikrosilika-Par- tikeln wird vorzugsweise so vorgegangen, dass das Vinylalkohol- Copoly erisat in Wasser gelöst vorgelegt wird und die pulver förmigen Mikrosilika-Partikel zu dieser Lösung zugegeben und dispergiert werden. To prepare the aqueous dispersions of microsilica particles, the procedure is preferably such that the vinyl alcohol copolymer is initially dissolved in water and the powdery microsilica particles are added to this solution and dispersed.
Die Mikrosilika-Partikel können vor der Einarbeitung verpackt, beispielsweise in Säcken, vorliegen oder in loser Form gelagert sein, beispielsweise in Silos oder Großgebinden. Die Zudosie rung der Mikrosilika-Partikel kann über Sackschütten, Dosiersi los mit und ohne Verwägung oder durch direkte Förderung aus La gersilos oder Großgebinden durch geeignete Förderanlagen wie Druckluftmembranpumpen erfolgen. Zum Dispergieren werden die Mikrosilika-Partikel mittels Schütteln, beispielsweise mit ei nem Taumelmischer oder einem High Speed Mixer, oder mittels Rühren, beispielsweise mit einem Balkenrührer oder Dissolver, eingearbeitet . Before being incorporated, the microsilica particles can be packaged, for example in sacks, or stored in bulk, for example in silos or large containers. The microsilica particles can be added via sack dumpers, dosing loos with and without weighing or by direct conveyance from storage silos or large containers using suitable conveyor systems such as compressed air diaphragm pumps. For dispersing, the microsilica particles are incorporated by shaking, for example using a tumble mixer or a high-speed mixer, or by stirring, for example using a bar stirrer or dissolver.
Das Dispergieren der Mikrosilika-Partikel kann anschließend oder parallel zur Zugabe der Mikrosilika-Partikel erfolgen. Be vorzugt ist paralleles Dispergieren. Paralleles Dispergieren bedeutet dabei, dass mit Beginn des Zudosierens der Mikrosi lika-Partikel in die wässrige Phase der Dispergierprozess be ginnt. Hierfür sind vorzugsweise schnellaufende Rührer, schnel laufende Dissolver, beispielsweise mit Umlaufgeschwindigkeiten von 1 bis 50 m/s, schnellaufende Rotor-Stator Systeme, Sonola- toren, Scherspalte, Düsen oder Kugelmühlen geeignet . Besonders
geeignet ist zur Dispergierung der Mikrosilika-Partikel der Einsatz von Ultraschall im Bereich von 5 Hz bis 500 kHz. The microsilica particles can be dispersed subsequently or in parallel with the addition of the microsilica particles. Parallel dispersion is preferred. Parallel dispersion means that when the microsilica particles begin to be metered into the aqueous phase, the dispersion process begins. High-speed stirrers, high-speed dissolvers, for example with circulation speeds of 1 to 50 m / s, high-speed rotor-stator systems, sonolators, shear gaps, nozzles or ball mills are preferably suitable for this. Especially The use of ultrasound in the range from 5 Hz to 500 kHz is suitable for dispersing the microsilica particles.
Gegebenenfalls kann die Dispergierung durch Kombination ver schiedener Methoden erfolgen, z.B. Vordispergierung mittels Dissolver oder Induktor mit anschließender Feindispergierung durch Ultraschallbehandlung. Die Herstellung kann in diskonti nuierlichen und in kontinuierlichen Verfahren erfolgen. Bevor zugt sind kontinuierliche Verfahren. If necessary, the dispersion can be carried out by combining various methods, e.g. Predispersion using a dissolver or inductor followed by fine dispersion using ultrasound treatment. The production can be carried out in batch and continuous processes. Continuous processes are preferred.
In einer bevorzugten Ausführungsform werden die wässrigen Mik- rosilika-Dispersionen auf einen pH-Wert von 6 bis 8 einge stellt . In a preferred embodiment, the aqueous microsilica dispersions are adjusted to a pH of 6 to 8.
Die Trocknung der wässrigen Dispersion der Mikrosilika-Partikel kann beispielsweise mittels Wirbelschichttrocknung, Gefrier trocknung oder Sprühtrocknung erfolgen. Vorzugsweise werden die Mikrosilikadispersionen sprühgetrocknet . The aqueous dispersion of the microsilica particles can be dried, for example, by means of fluidized-bed drying, freeze-drying or spray drying. The microsilica dispersions are preferably spray-dried.
Die wässrigen Dispersionen oder in Wasser dispergierbaren Dis persionspulver von Mikrosilika-Partikeln eignen sich zur Ver wendung in zementhaltigen oder zementfreien Baustoffmassen, in pastöser Form oder als Trockenmörtel. Beispiele für Baustoff- massen sind Putze, Mörtel, Estriche und Beton. Die wässrigen Dispersionen oder Dispersionspulver von Mikrosilika-Partikeln eignen sich auch zur Verwendung in Klebe-, Dichtungs-, Spach tel- und Anstrichmassen. The aqueous dispersions or water-dispersible dispersion powders of microsilica particles are suitable for use in cementitious or non-cemented building materials, in pasty form or as dry mortar. Examples of building materials are plasters, mortar, screeds and concrete. The aqueous dispersions or dispersion powders of microsilica particles are also suitable for use in adhesives, sealants, fillers and paints.
Die nachfolgenden Beispiele dienen der weiteren Erläuterung der Erfindung : The following examples serve to explain the invention further:
Herstellung von Polyvinylalkohol 1 (PVOH 1) : Production of polyvinyl alcohol 1 (PVOH 1):
In einem 70 -Liter-Reaktor mit Rührer und Kühler wurden folgende Stoffe vorgelegt:
12660 g Methanol, 31 g t-Butyl-Peroxypivalat (PPV, 75 %-ige wässrige Lösung) , 177 g Vinylester der VersaticsäureR10 (Veo- VaR10) , 3290 g Vinylacetat, 233 g Vinylsulfonat (25 %-ige wäss rige Lösung) . The following substances were placed in a 70 liter reactor with stirrer and cooler: 12,660 g of methanol, 31 g of t-butyl peroxypivalate (PPV, 75% aqueous solution), 177 g of vinyl ester of versatic acid R 10 (Veo-Va R 10), 3,290 g of vinyl acetate, 233 g of vinyl sulfonate (25% aqueous solution) solution).
Unter Rühren unter Stickstoffatmosphäre wurde die Mischung auf 60 °C aufgeheizt und 30 Minuten polymerisiert. Danach wurden folgende Stoffe zudosiert: With stirring under a nitrogen atmosphere, the mixture was heated to 60 ° C. and polymerized for 30 minutes. The following substances were then added:
Eine Initiatorlösung mit 125 g PPV in 1880 g Methanol wurde in nerhalb 240 Minuten zudosiert. An initiator solution with 125 g PPV in 1880 g methanol was metered in within 240 minutes.
Eine Monomermischung 1 mit 999 g VeoVaR10 und 18661 g Vi nylacetat wurde mit einer Dosierzeit von 180 Minuten zudosiert. Eine Monomerlösung 2 aus 1319 g einer 25 %-igen, wässrigen Lö sung von Vinylsulfonat wurde mit einer Dosierzeit von 195 Minu ten zudosiert. A monomer mixture 1 with 999 g VeoVa R 10 and 18661 g vinyl acetate was metered in with a metering time of 180 minutes. A monomer solution 2 from 1319 g of a 25% aqueous solution of vinyl sulfonate was metered in with a metering time of 195 minutes.
Nach Dosierende wurde der Reaktor verriegelt, der Druck im Re aktor auf 0,2 bar erhöht und bei 100°C eine Stunde nachpolyme risiert. Danach wurde die Polymerlösung auf 30°C abgekühlt und mit Methanol auf eine 31 Gew. -%-ige Lösung verdünnt. Die Poly merlösung wurde ohne Rühren mit 38440 g Methanol überschichtet und danach eine Mischung aus 775 g Methanol und 657 g 46 %-iger Natronlauge zugegeben und gerührt. Nach zwei Stunden wurde die Lösung mit 342 g Essigsäure (99,8 %-ig) neutralisiert. An schließend wurden Methanol und die Nebenprodukte mittels Dampf - strippen entfernt. Nach dem Strippen wurde das Vinylalkohol -Co- polymerisat in Wasser aufgenommen und auf eine 20 Gew. %-ige Lö sung verdünnt . After the end of the metering, the reactor was locked, the pressure in the reactor was increased to 0.2 bar and post-polymerized at 100 ° C. for one hour. The polymer solution was then cooled to 30 ° C. and diluted with methanol to a 31% by weight solution. The polymer solution was overlaid without stirring with 38440 g of methanol and then a mixture of 775 g of methanol and 657 g of 46% sodium hydroxide solution was added and stirred. After two hours the solution was neutralized with 342 g acetic acid (99.8%). Then methanol and the by-products were removed by steam stripping. After stripping, the vinyl alcohol copolymer was taken up in water and diluted to a 20% by weight solution.
Es wurde ein sulfonierter Polyvinylalkohol mit 2 Mol-% Vi nylacetat-, 94,5 Mol-% Vinylalkohol-, 1,1 Mol-% Vinylsulfonat- und 2,3 Mol-% VeoVaR10 -Monomereinheiten mit einer Viskosität der 20 Gew. -%-igen wässrigen Lösung von 1.355 mPa . s erhalten. It was a sulfonated polyvinyl alcohol with 2 mol% of vinyl acetate, 94.5 mol% of vinyl alcohol, 1.1 mol% of vinyl sulfonate and 2.3 mol% of VeoVa R 10 monomer units with a viscosity of 20 wt. -% - aqueous solution of 1.355 mPa. s received.
Polyvinylalkohol 2 (PVOH 2) :
Als PVOH 2 wurde eine 20 %-ige wässrige Lösung eines Vinylalko- hol-Copolymerisats mit 88 Mol-% Vinylalkohol- und 12 Mol-% Vi nylacetat-Monomereinheiten verwendet . Polyvinyl alcohol 2 (PVOH 2): A 20% aqueous solution of a vinyl alcohol copolymer with 88 mol% vinyl alcohol and 12 mol% vinyl acetate monomer units was used as PVOH 2.
Mikrosilika : Microsilica:
Es wurde ein Mikrosilika der Wacker Chemie AG mit einer mittle ren Partikelgröße von 45 pm und mit einem SiCL-Anteil von über 96 Gew.-% verwendet. A microsilica from Wacker Chemie AG with an average particle size of 45 pm and with a SiCL content of over 96% by weight was used.
Herstellung der Mikrosilika-Dispersionen : Production of microsilica dispersions:
Die 20 Gew.-%-igen wässrigen Lösungen von PVOH 1 oder PVOH 2 wurden jeweils mit der in Tabelle 1 angegebenen Menge Wasser in einem Becher vorgelegt. Anschließend wurde das Mikrosilika un ter Rühren zugegeben und 5 Minuten weitergerührt. Es wurden ho mogene Dispersionen erhalten. The 20% by weight aqueous solutions of PVOH 1 or PVOH 2 were each placed in a beaker with the amount of water given in Table 1. The microsilica was then added with stirring and stirring continued for 5 minutes. Homogeneous dispersions were obtained.
Testung der Stabilität der Mikrosilika-Dispersionen: Testing the stability of the microsilica dispersions:
Die hergestellten Mikrosilika-Dispersionen wurden verschlossen bei Raumtemperatur gelagert. Nach 24 Stunden wurde untersucht, ob eine Phasentrennung (Sedimentation) stattgefunden hatte. The microsilica dispersions produced were stored closed at room temperature. After 24 hours, it was examined whether a phase separation (sedimentation) had taken place.
Testung der Redispergierbarkeit : Redispersibility testing:
Für die Bestimmung der Redispergierbarkeit wurden die Mikrosi lika-Dispersionen bei Raumtemperatur getrocknet. Nach der Trocknung wurden die damit erhaltenen Mikrosilika-Dispersions- pulver gemahlen und gesiebt (Maschenweite von 1 mm) . To determine the redispersibility, the microsilica dispersions were dried at room temperature. After drying, the microsilica dispersion powder obtained was ground and sieved (mesh size of 1 mm).
Für den Redispergierbarkeitstest wurde 100 g Wasser in einem Becher vorgelegt und 50 g Mikrosilika-Dispersionspulver unter Rühren (Magnetrührer) zugegeben. Nach 5 Minuten Rühren wurde die damit erhaltene Dispersion filtriert (Maschenweite von 1 mm) und der Siebrückstand bestimmt.
Die Ergebnisse in Tabelle 1 zeigen, dass mit den erfindungsge mäß stabilisierten wässrigen Dispersionen oder in Wasser dis pergierbaren Dispersionspulvern von Mikrosilika-Partikeln keine Sedimentation auftritt und sehr gute Redispergierbarkeit in Wasser erhalten wird. For the redispersibility test, 100 g of water were placed in a beaker and 50 g of microsilica dispersion powder were added with stirring (magnetic stirrer). After stirring for 5 minutes, the dispersion thus obtained was filtered (mesh size of 1 mm) and the sieve residue was determined. The results in Table 1 show that with the aqueous dispersions stabilized according to the invention or water-dispersible dispersion powders of microsilica particles, no sedimentation occurs and very good redispersibility in water is obtained.
Tabelle 1: Table 1:
Claims
1. Wässrige Dispersionen und Dispersionspulver von Mikrosi- lika-Partikeln, dadurch gekennzeichnet dass diese mit Vi- nylalkohol-Copolymerisat stabilisiert sind. 1. Aqueous dispersions and dispersion powders of microsilica particles, characterized in that they are stabilized with vinyl alcohol copolymer.
2. Wässrige Dispersionen und Dispersionspulver von Mikrosi- lika-Partikeln nach Anspruch 1, dadurch gekennzeichnet, dass diese mit Vinylalkohol-Copolymerisaten stabilisiert sind, mit 2. Aqueous dispersions and dispersion powders of microsilica particles according to claim 1, characterized in that they are stabilized with vinyl alcohol copolymers, with
a) 80 bis 99,5 Mol-% Vinylalkohol-Monomereinheiten, b) 0,5 bis 15 Mol-% Vinylacetat-Monomereinheiten, a) 80 to 99.5 mol% of vinyl alcohol monomer units, b) 0.5 to 15 mol% of vinyl acetate monomer units,
c) 0 bis 10 Mol-% Monomereinheiten, welche sich von ethyl- enisch ungesättigten Monomeren mit einer oder mehreren Sulfonsäure-Resten sowie deren Salze, ableiten, c) 0 to 10 mol% of monomer units which are derived from ethylenically unsaturated monomers with one or more sulfonic acid residues and their salts,
d) 0 bis 10 Mol-% Monomereinheiten, welche sich von Vi nylestern von unverzweigten oder verzweigten Alkylcarbon säuren mit 3 bis 18 C-Atomen ableiten, d) 0 to 10 mol% of monomer units which are derived from vinyl esters of unbranched or branched alkylcarbon acids having 3 to 18 carbon atoms,
wobei sich die Angaben in Mol-% jeweils auf 100 Mol-% auf addieren . where the data in mol% add up to 100 mol%.
3. Wässrige Dispersionen und Dispersionspulver von Mikrosi- lika-Partikeln nach Anspruch 2, dadurch gekennzeichnet, dass diese mit Vinylalkohol-Copolymerisaten stabilisiert sind, mit c) 1 bis 10 Mol-% Monomereinheiten, welche sich von ethylenisch ungesättigten Monomeren mit einem oder mehreren Sulfonsäure-Resten sowie deren Salze, ableiten, 3. Aqueous dispersions and dispersion powder of microsilica particles according to claim 2, characterized in that they are stabilized with vinyl alcohol copolymers, with c) 1 to 10 mol% of monomer units, which are composed of ethylenically unsaturated monomers with one or more sulfonic acid Residues and their salts,
4. Wässrige Dispersionen und Dispersionspulver von Mikrosi- lika-Partikeln nach Anspruch 2 oder 3, dadurch gekenn zeichnet, dass diese mit Vinylalkohol-Copolymerisaten sta bilisiert sind, mit d) 1 bis 10 Mol-% Monomereinheiten,
welche sich von Vinylestern von unverzweigten oder ver zweigten Alkylcarbonsäuren mit 3 bis 18 C-Atomen ableiten. 4. Aqueous dispersions and dispersion powders of microsilica particles according to claim 2 or 3, characterized in that they are sta bilized with vinyl alcohol copolymers, with d) 1 to 10 mol% of monomer units, which are derived from vinyl esters of unbranched or branched alkyl carboxylic acids having 3 to 18 carbon atoms.
5. Wässrige Dispersionen von Mikrosilika-Partikeln nach An spruch 1 bis 4, dadurch gekennzeichnet, dass die wässrigen Dispersionen von Mikrosilika-Partikeln 20 bis 60 Gew.-%, Mikrosilika enthalten, bezogen auf die Summe der Gewichts anteile von Mikrosilika und Wasser. 5. Aqueous dispersions of microsilica particles according to claim 1 to 4, characterized in that the aqueous dispersions of microsilica particles contain 20 to 60 wt .-%, microsilica, based on the sum of the parts by weight of microsilica and water.
6. Wässrige Dispersionen und Dispersionspulver von Mikrosi lika-Partikeln nach Anspruch 1 bis 4, dadurch gekennzeich net, dass die Menge an Vinylalkohol-Copoly erisat in der wässrigen Mikrosilika-Dispersion oder im Mikrosilika-Dis- persionspulver 1 bis 20 Gew.-% beträgt, bezogen auf den Gewichtsanteil von Mikrosilika in der Dispersion oder im Dispersionspulver . 6. Aqueous dispersions and dispersion powders of microsilica particles according to claims 1 to 4, characterized in that the amount of vinyl alcohol copolymer in the aqueous microsilica dispersion or in the microsilica dispersion powder is 1 to 20% by weight , based on the weight fraction of microsilica in the dispersion or in the dispersion powder.
7. Verfahren zur Herstellung der wässrigen Dispersionen von Mikrosilika-Partikeln nach Anspruch 1 bis 6, dadurch ge kennzeichnet, dass das Vinylalkohol -Copolymerisat in Was ser gelöst vorgelegt wird und die pulverförmigen Mikrosi- lika-Partikel zu dieser Lösung zugegeben und dispergiert werden . 7. The method for producing the aqueous dispersions of microsilica particles according to claims 1 to 6, characterized in that the vinyl alcohol copolymer is initially dissolved in water and the powdery microsilica particles are added to this solution and dispersed.
8. Verfahren zur Herstellung der Dispersionspulver von Mikro silika-Partikeln nach Anspruch 1 bis 4 und 6, dadurch ge kennzeichnet, dass die nach Anspruch 7 erhaltene wässrige Dispersion von Mikrosilika-Partikeln getrocknet wird. 8. A method for producing the dispersion powder of microsilica particles according to claims 1 to 4 and 6, characterized in that the aqueous dispersion of microsilica particles obtained according to claim 7 is dried.
9. Verwendung der wässrigen Dispersionen und Dispersionspul ver von Mikrosilika-Partikeln nach Anspruch 1 bis 6 in zementhaltigen oder zementfreien Baustoffmassen, jeweils in pastöser Form oder als Trockenmörtel.
9. Use of the aqueous dispersions and Dispersionspul ver of microsilica particles according to claim 1 to 6 in cement-containing or cement-free building materials, each in pasty form or as dry mortar.
10. Verwendung der wässrigen Dispersionen und Dispersionspul ver von Mikrosilika-Partikeln nach Anspruch 1 bis 6 in Klebe-, Dichtungs-, Spachtel- und Anstrichmassen.
10. Use of the aqueous dispersions and Dispersionspul ver of microsilica particles according to claim 1 to 6 in adhesives, sealants, fillers and paints.
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US4888058A (en) | 1986-09-29 | 1989-12-19 | W. R. Grace & Co.-Conn. | Silica fume slurry |
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US20040097645A1 (en) * | 2002-11-14 | 2004-05-20 | Wacker Polymer Systems Gmbh & Co. Kg | Protective-colloid-stabilized polymers in the form of their aqueous dispersions or of their water-redispersible powders |
US20050167105A1 (en) | 2004-01-30 | 2005-08-04 | Roddy Craig W. | Contained micro-particles for use in well bore operations |
US20070213430A1 (en) * | 2003-10-09 | 2007-09-13 | Werner Bauer | Polymeric compositions containing modified polyvinyl alcohols |
US20140243457A1 (en) * | 2011-10-05 | 2014-08-28 | Wacker Chemie Ag | Dry building material formulations containing polymer powders |
WO2018052307A1 (en) | 2016-09-13 | 2018-03-22 | Elkem As | Microsilica slurry and method for producing such slurry |
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2018
- 2018-12-11 DE DE102018221446.8A patent/DE102018221446A1/en not_active Withdrawn
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2019
- 2019-11-29 WO PCT/EP2019/083036 patent/WO2020120169A1/en active Application Filing
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US4321243A (en) | 1980-08-05 | 1982-03-23 | Cornwell Charles E | Method of producing stabilized aqueous dispersions of silica fume |
EP0246181A1 (en) | 1986-05-13 | 1987-11-19 | W.R. Grace & Co. | Microsilica slurries and method of preparation |
US4888058A (en) | 1986-09-29 | 1989-12-19 | W. R. Grace & Co.-Conn. | Silica fume slurry |
US6653372B1 (en) * | 1996-06-12 | 2003-11-25 | Basf Aktiengesellschaft | Preparation of addition-polymer powder |
US20040097645A1 (en) * | 2002-11-14 | 2004-05-20 | Wacker Polymer Systems Gmbh & Co. Kg | Protective-colloid-stabilized polymers in the form of their aqueous dispersions or of their water-redispersible powders |
US20070213430A1 (en) * | 2003-10-09 | 2007-09-13 | Werner Bauer | Polymeric compositions containing modified polyvinyl alcohols |
US20050167105A1 (en) | 2004-01-30 | 2005-08-04 | Roddy Craig W. | Contained micro-particles for use in well bore operations |
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