EP3538565A1 - Kontinuierliches und modulares verfahren zur herstellung von in wasser redispergierbaren polymerpulverzusammensetzungen - Google Patents
Kontinuierliches und modulares verfahren zur herstellung von in wasser redispergierbaren polymerpulverzusammensetzungenInfo
- Publication number
- EP3538565A1 EP3538565A1 EP16823276.7A EP16823276A EP3538565A1 EP 3538565 A1 EP3538565 A1 EP 3538565A1 EP 16823276 A EP16823276 A EP 16823276A EP 3538565 A1 EP3538565 A1 EP 3538565A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymerization
- drying
- water
- modules
- redispersible
- 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- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/10—Making granules by moulding the material, i.e. treating it in the molten state
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/122—Pulverisation by spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/16—Auxiliary treatment of granules
- B29B2009/163—Coating, i.e. applying a layer of liquid or solid material on the granule
Definitions
- the invention relates to a continuous and modular process for the preparation of water-redispersible polymer powder compositions and to a modular apparatus for carrying out this process.
- Water-redispersible polymer powder compositions are generally prepared by drying the corresponding aqueous dispersions of a base polymer.
- the preparation of the aqueous dispersion of the base polymer is preferably carried out by means of free-radical initi ⁇ FOURTH emulsion polymerization of one or more ethyle- cally unsaturated monomers.
- Dispersion of the base polymer vorzugswei ⁇ se is then, in the presence of a drying aid (generally a protective colloid), for example by spray drying, getrock ⁇ net.
- a drying aid generally a protective colloid
- antiblocking agents or other additives may be added during or after the drying.
- ⁇ on the basis of the protective colloid fraction ⁇ process on the one hand prevented during drying that the polymer ver ⁇ adhere irreversibly, as the polymer particles are surrounded by the protective colloid particles.
- this protective colloid matrix which dissolves again when the polymer powder composition is dispersed in water, causes the polymer particles to again be present with the particle size of the starting dispersion in the aqueous (re) dispersion (TIZ ausberichte, 1985, Vol. 109 (9) , 698).
- Such dispersion powders are used in many applications, inter alia, in coating compositions and in adhesives for a wide variety of substrates.
- the advantage of the water-redispersible polymer powder lies in the ability to use them in prefabricated, storable dry mixes, optionally together with mineral binders such as cement, and to make it only immediacy ⁇ cash ready prior to use by adding water.
- Such dry blends can be more easily transported with respect to pasty sen systems (without the water component) and offer advantages in storage, such as insensitivity to frost, resistance to micro ⁇ benbefall.
- EP 0056622 Bl redispersible poly ⁇ merpulverzusammen stuen are described in water which are prepared by spray drying an aqueous polymer dispersion with addition of hydrophobic silica.
- EP 1 174 445 A1 describes a process for the preparation of protective colloid-stabilized polymers by means of continuous polymerization. The polymer dispersions obtained therewith can be dried to give dispersion powders.
- EP 2 341 084 A1 describes the preparation of water-redispersible polymer powder compositions in which a polymer dispersion is dried in the presence of chelating agents. From EP 2 739
- No. 673 B1 discloses a process for the preparation of dispersion powders in which an aqueous polymer dispersion is dried in a rotary atomizing dryer.
- WO 2005/080478 describes a process for the preparation of polymer powders which are readily redispersible in water by means of spray drying in the presence of a special spray drying aid.
- WO 2013/017463 A1 describes a process for the preparation of dispersion powders by means of spray drying of aqueous polymer dispersions with addition of antiblocking agent.
- an aqueous polymer dispersion was prepared batchwise or continuously in a first step.
- the polymer dispersion was stored in egg nem tank and batch spray drying delivered ⁇ leads.
- additives such as drying aids were added to the polymer dispersion.
- this preparation was fed as a feed to the dryer and the water removed by spray drying.
- the object was to make available a method and to provide a device for carrying out this method with which, with the lowest possible specific investment costs (investment costs based on the product quantity), dispersible polymer powders are available in variable quantities and without quality fluctuations.
- the invention relates to a process for preparing water-redispersible polymer powder compositions based on polymers of one or more ethylenically unsaturated monomers, wherein in a first step an aqueous polymer dispersion is prepared by free-radically initiated polymerization of one or more ethylenically unsaturated monomers in an aqueous medium, which is converted by means of drying into the water-redispersible polymer powder composition, characterized in that the polymerization and the drying are each carried out continuously, and the polymerization and the drying are carried out in separate, interconnected modules.
- Continuously means within the scope of the invention that in the process with at least two process steps in series, in the first process step, preferably the polymerization, continuously educt is fed and an aqueous product stream is continuously transported in a subsequent step, preferably drying, and finally steadily the powdered product is taken ⁇ product.
- Modular in the context of the invention means that the individual
- Steps of the method according to the invention are carried out in separate, interconnected modules, wherein the modules can be preconfigured and closed.
- modules within the meaning of the invention are a polymerization module and a drying module.
- the interconnected modules of the process are in each case preference ⁇ transportable units or composed of trans ⁇ portable subunits, which can be a desired production location, in a correspondingly equipped kitchens ⁇ preparing production plant is to be installed, transported.
- the modules Preferably, have a housing to allow easy transport of the module.
- the modules can be connected, preferably via standardized couplings, to a local, permanently installed supply network / disposal network with which the modules can be supplied with substances (for example educts) and / or energy and / or into the substances (for example products , Waste) can be discharged, so that by means of the connected modules continuous production can be performed.
- one or more can be connected to a local supply network.
- closable storage container for liquid, solid and / or gas ⁇ shaped substances be provided within the housing of a module.
- the modules may have ⁇ example, devices for filling, emptying, heating, cooling, mixing, separating, ventilating and / or venting that enable the polymerization or drying to be performed.
- Each module may have control and / or regulating device, via which the respective module can be controlled and / or regulated for carrying out a specific process step of production.
- the method according to the invention uses a device which is equipped with a polymerization module and a downstream drying module.
- Additional modules may include Steue ⁇ rung- and infrastructure elements insofar as they are not installed locally fixed or are included in the above-mentioned modules.
- the Polymerisationsmodul is preferably equipped with lines for ⁇ To guide of starting materials, and preferably with food holding Lagerbe ⁇ (tanks) equipped for the intermediate storage of the starting materials. Also advantageous are facilities with which you can premix various starting materials and then perform this as a mixture of the polymerization.
- the polymerization module can be equipped, for example, as a polymerization reactor with a stirred tank or several, series stirred tanks, or equipped with one or more serially arranged tubular reactors, which are each equipped with heating and cooling devices and are each equipped with a device for mixing the polymerization.
- the starting materials or mixtures thereof are fed to the polymerization reactor via feed supplied.
- the polymerization product, the aqueous poly ⁇ merisatdispersion is supplied after completion of the polymerization, preferably with a supply line, batchwise or continuously, the drying module.
- the drying module is preferably equipped with a spray dryer for drying the aqueous polymer dispersion.
- this is a cylindrical container with nozzles or with a spray disk for the delivery of the polymer dispersion.
- the drying module is equipped with a storage container, which is arranged in front of the spray dryer and can buffer asynchronisms during operation of the polymerization module and the drying module.
- the drying module also contains facilities for supplying and heating the drying air, and La ⁇ ger organizations and / or leads for the supply of additives for drying, for example, drying aid, anti-blocking agent or defoamers.
- Further devices in the drying module are preferably filters and collecting devices for obtaining the dry polymer powder.
- the drying module also includes means for packaging the polymer powder such as bagging in small containers or big bags.
- Suitable ethylenically unsaturated monomers for the preparation of the polymers are those from the group comprising vinyl esters of carboxylic acids having 1 to 15 carbon atoms, methacrylic acid esters, acrylic esters of carboxylic acids with unbranched or branched alcohols having 1 to 15 carbon atoms, olefins, Dienes, vinylaromatics and vinyl halides.
- Preferred vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of alpha-branched monocarboxylic acids having 5 to 13 C atoms, for example VeoVa9 R or VeoValO R (cf. Trade name of company Momentive). Especially before ⁇ is Trains t vinyl acetate.
- Preferred methacrylic esters or acrylic esters are esters of unbranched or branched alcohols having 1 to 15 C atoms, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate.
- Be ⁇ are particularly preferred methyl acrylate, methyl methacrylate, tylacrylat n-butyl and 2-ethylhexyl acrylate.
- Preferred olefins or dienes are ethylene, propylene and 1,3-butadiene.
- Preferred vinyl aromatics are styrene and vinyl toluene.
- a preferred vinyl halide is vinyl chloride.
- auxiliary ⁇ monomers are ethylenically unsaturated mono- and dicarboxylic acids, ethylenically unsaturated carboxamides, ethylenically unsaturated sulfonic acids or salts thereof, precrosslinking Comono ⁇ mers such as multiply ethylenically unsaturated comonomers, nachver ⁇ wetting comonomers, such as N-methylolacrylamide, epoxidfunktionel- le comonomers , silicon-functional comonomers.
- vinyl acetate and mixtures of vinyl acetate are polymerized with from 1 to 40% by weight of ethylene;
- Vinylestern having 1 to 12 carbon atoms in the carboxylic acid moiety such as vinyl acetate, vinyl propionate, Vi ⁇ laurate, Vinylester of alpha-branched carboxylic acids having 5 to 13 carbon atoms, such as VeoVa9 R, VeoVal0 R, VeoVall R, 1 to 40 % By weight of ethylene and 1 to 60% by weight of vinyl chloride;
- auxiliary monomers can be copolymerized in the stated amounts, and the information in wt .-% add up to each 100 wt .-%. It is preferred to polymerize mixtures of Methylmethac ⁇ triacrylate with n-butyl acrylate and / or 2-ethylhexyl acrylate and, where appropriate, ⁇ ethylene;
- styrene with one or more monomers selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; Mixtures of styrene with 1,3-butadiene;
- mixtures can each still contain the said auxiliary monomers in the stated amounts, and the information in wt .-% add up to 100 wt .-%.
- the monomers or the choice of the weight fractions of the comonomers is preferably such that a glass transition temperature ⁇ resulting Tg of the polymers from -20 ° C to + 40 ° C, vorzugswei ⁇ se -20 ° C to + 20 ° C.
- the glass transition temperature Tg of the polymers can be determined in a known manner by means of differential scanning calorimetry (DSC) according to DIN 53520.
- Tgn the glass transition temperature in Kelvin of the homopolymer of the monomer n.
- Tg values for homopolymers are listed in Po ⁇ lymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975).
- the polymer dispersions are preferably prepared by the emulsion polymerization process.
- the polymerization temperature is preferably from 40 ° C to 120 ° C, more preferably from 60 ° C to 90 ° C.
- gaseous comonomers such as ethylene, 1,3-butadiene or vinyl chloride
- the initiation of the polymerization preferably takes place with the water-soluble initiators customary for emulsion polymerization, preferably with redox initiator combinations.
- the polymerization takes place in the presence of a protective colloid, ge ⁇ optionally in combination with emulsifiers.
- Suitable protective colloids for the polymerization are polyvinyl alcohols; Polyvinyl acetals; Polyvinyl pyrrolidones; Polysaccharides in wasserlös ⁇ Licher form such as starches (amylose and amylopectin), celluloses and their carboxymethyl, methyl, hydroxyethyl, hydroxypropyl pyl derivatives, dextrins and cyclodextrins; Proteins such as casein or caseinate, soy protein, gelatin; Lignosulfonates; synthe ⁇ diagram polymers such as poly (meth) acrylic acid, copolymers of (meth) acrylates with carboxyl-functional comonomer units, poly (meth) acrylamide, polyvinylsulfonic acids and their wasserlös ⁇ union copolymers; Melamine formaldehyde sulfonates, naphthalene formaldehyde sulfonates, styrene male
- Partially hydrolyzed or fully hydrolyzed polyvinyl preferably ⁇ alcohols with a degree of hydrolysis of 80 to 100 mol%, insbeson ⁇ particular partially saponified polyvinyl alcohols having a degree of hydrolysis of 80 to 95 mol% and a Höppler viscosity, in 4% strength aqueous solution of 1 to 30 mPas (Method according to Höppler at 20 ° C, DIN 53015) used.
- the protective colloids are mean in general ⁇ in an amount of 0.5 to 30 wt .-%, based on the total weight of the monomers added during the polymerization.
- emulsifiers are anionic, cationic and nonionic emulsifiers, for example anionic surfactants, such as alkyl sulfates having a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl ether sulfates having 8 to 18 carbon atoms in the hydrophobic radical and up to 40 ethylene or propylene oxide units, men alkyl- or alkylarylsulfonates having 8 to 18 C-Ato, esters and Halbester of sulfosuccinic acid with einwerti ⁇ gen alcohols or alkylphenols, or nonionic surfactants such as alkyl polyglycol ethers or alkylaryl polyglycol ethers having 8 to 40 ethylene oxide units.
- anionic surfactants such as alkyl sulfates having a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl ether sulfates having 8 to 18 carbon atoms in the hydropho
- postpolymerization can be postpolymerized to reduce the residual monomer content using known methods, generally by postpolymerization initiated with the redox catalyst.
- Volatile residual monomers can also be removed by means of distillation, preferably under reduced pressure, and optionally by passing or passing inert inert gases, such as air, nitrogen or steam.
- inert inert gases such as air, nitrogen or steam.
- the aqueous polymer dispersions obtainable therewith have a solids content of from 30 to 75% by weight, preferably from 40 to 60% by weight, particularly preferably from 45 to 55% by weight.
- the polymer dispersions have a viscosity suitable for the subsequent drying of 10 to 3000 mPas, preferably from 100 to 500 mPas (Brookfield viscosity Bf20 by means of Brookfield viscometer at 23 ° C and 20 rpm).
- the aqueous polymer dispersions thus obtainable already contain, after completion of the polymerization, the protective colloid necessary as a drying aid. No protective colloids are therefore preferably added before drying the aqueous Polymerisatdis ⁇ persion.
- the aqueous polymer dispersions optionally after further addition of protective colloid as a drying aid to the polymer dispersion, dried by spray drying.
- Suitable drying aids are those previously listed as protective colloids: polyvinyl alcohols; Polyvinyl acetals; Polyvinyl pyrrolidones; Poly ⁇ saccharide dextrins in water-soluble form such as starches (amylose and amylopectin), celluloses and their carboxymethyl, methyl, hydroxyethyl and hydroxypropyl derivatives, dextrins and cyclo; Proteins such as casein or caseinate, soy protein, ge ⁇ latins; Lignosulfonates; synthetic polymers such as poly (meth) acrylic acid, copolymers of (meth) acrylates with carboxyl-functional comonomer units, poly (meth) acrylamide, polyvinylsulfonic acids and their water-soluble copolymers;
- Partially saponified polyvinyl alcohols are preferred or fully hydrolyzed with a degree of hydrolysis of 80 to 100 mol%, in particular teilver ⁇ soaped polyvinyl alcohols having a degree of hydrolysis of 80 to 95 mol% and a Höppler viscosity in each case, in 4% strength solution (7)ssri- ger 1-30 mPas (method according to Höppler at 20 ° C, DIN 53015) used.
- the aqueous polymerizate dispersions contain the drying aid before they are dried
- the dispersion powder can be added to the poly merisatdispersion additional additives to the powder optionally kidney for certain applications to kon Stammio ⁇ .
- additional additives are defoamers, hydro ⁇ repellent agent and rheological additives.
- the spray drying takes place by means of atomization in the spray dryer, in which the energy for the evaporation of the aqueous phase is transferred by heat conduction from the drying gas to the polymer dispersion (feed) to be dried.
- the food is generally supplied to the nozzles by means of pumps.
- the drying takes place by intimately mixing the atomized polymer dispersion (food) with the drying gas.
- the drying gas used is generally air.
- the drying gas is preheated, preferably to an inlet temperature of 130 ° C to 210 ° C (hot air), more preferably to 150 ° C to 190 ° C.
- the spray drying is preferably carried out according to the DC principle.
- the polymer dispersion (feed) and the drying gas are fed to the top of the spray dryer, generally a cylindrical container.
- the dryer outlet at the lower end of the spray dryer can be designed differently, for example, the dried polymer powder with the
- Drying gas discharged and isolated by means of a filter and / or cyclone separator The outlet temperature of the drying gas is preferably 45 ° C to 120 ° C, depending on the system, Tg of the polymer and the desired degree of drying.
- the dispersion powders may still contain antiblocking agents.
- Suitable antiblocking agent are known in the art, such as aluminum silicates, such as kaolin, bentonite, fumed silica or precipitated silica which gegebe ⁇ can applicable, be rendered hydrophobic, talc, clays, light spar, carbonates such as calcium carbonate, magnesium carbonate and Ca / Mg carbonate, barium sulfate , It is also possible to use mixtures of antiblocking agents.
- the antiblocking agents are on the total weight of the polymeric components to be in general ⁇ my in an amount of 0.1 to 30 wt .-%, preferably 2 to 30 wt .-%, particularly preferably 7 to 30 wt .-%, each based zer ⁇ dusting polymer dispersion used.
- pyro- gener silica or precipitated silica are vorzugswei ⁇ se 0.1 to 2 wt .-%, based on the polymeric components of the polymer dispersion to be sprayed, are used.
- the proportion of the polymeric constituents of the to be atomized Polymerisatdis ⁇ persion is composed of the base polymer of the poly- merisatdispersion and optionally the protective colloid component.
- the addition of the anti-blocking agent is preferably carried out continu ously ⁇ and at the same time, but separately from the polymer dispersion to be atomized (feed).
- the anti-block agent is conveyed in a conveyor line by means of a conveying gas, generally air (conveying air), for drying, preferably at the upper end in the dryer tower.
- the anti-blocking agent may also be wholly or partly be added to the finished ge ⁇ dried polymer powder before or after the deposition from the drying gas.
- the apparatus comprises a module 1, the poly ⁇ merisationsmodul, and a module 2, the drying module.
- Module 1 is equipped with a storage container 1, which vinyl acetate
- a mixture of water, polyvinyl alcohol, initiators and buffer is kept in stock in the quantities required for the polymerization.
- the contents of the containers 1 and 2 are guided via pumps 6 in a mixer 3, and passed the mixture produced in the polymerization reactor 4.
- the polymerization container is filled with the original, the batch is heated to a polymerization temperature of 70 ° C, which is maintained by means of cooling during the polymerization. Thereafter, the polymer dispersion formed in the polymerization reactor 4 is continuously transferred into the degassing tank 5.
- the amounts of reactant which correspond to the quantities which are fed into the degassing vessel 5 are continuously fed to the reactor 4 via the mixer 3.
- the polymer dispersion is transferred with a pump 6 in the module 2, the drying module and heated with the heat exchanger 7 to a temperature of 90 ° C.
- the polymer dispersion is introduced into the dryer 8 via an atomizer disk 9.
- further protective colloid for example polyvinyl alcohol, may be added as drying aid during the drying process via line 13 and pump 14.
- the air for atomization of the polymer dispersion is fed via line 10 and nozzle 11 of the atomizer disk 9 and heated with the heat exchanger 12.
- the dry polymer powder is removed from the separator 15 and packaged in the packaging device 17 in bags 18.
- the moist drying air escapes via line 16.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2016/082191 WO2018113955A1 (de) | 2016-12-21 | 2016-12-21 | Kontinuierliches und modulares verfahren zur herstellung von in wasser redispergierbaren polymerpulverzusammensetzungen |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3538565A1 true EP3538565A1 (de) | 2019-09-18 |
Family
ID=57758607
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16823276.7A Withdrawn EP3538565A1 (de) | 2016-12-21 | 2016-12-21 | Kontinuierliches und modulares verfahren zur herstellung von in wasser redispergierbaren polymerpulverzusammensetzungen |
Country Status (4)
Country | Link |
---|---|
US (1) | US12060444B2 (de) |
EP (1) | EP3538565A1 (de) |
CN (1) | CN110191900A (de) |
WO (1) | WO2018113955A1 (de) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2020025312A1 (de) * | 2018-08-03 | 2020-02-06 | Dressler Group GmbH & Co. KG | Verfahren und vorrichtung zum zerkleinern eines kunststoffs und zur herstellung von pulverförmigen stoffen aus diesem kunststoff |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3101413C2 (de) | 1981-01-17 | 1983-10-20 | Hoechst Ag, 6230 Frankfurt | Pulverförmige Polymerisatmasse, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE4440236A1 (de) | 1994-11-10 | 1996-05-15 | Wacker Chemie Gmbh | Redispergierbare Polymerpulver-Zusammensetzung enthaltend Cyclodextrine oder Cyclodextrin-Derivate |
DE19644309A1 (de) * | 1996-10-24 | 1998-04-30 | Basf Ag | Pulverförmiger Klebstoff |
DE10035587A1 (de) | 2000-07-21 | 2002-02-07 | Wacker Polymer Systems Gmbh | Verfahren zur Herstellung von Schutzkolloid-stabilisierten Polymerisaten mittels kontinuierlicher Emulsionspolymerisation |
DE102004009739A1 (de) | 2004-02-25 | 2005-09-15 | Basf Ag | Verfahren zur Herstellung von gut in Wasser redispergierbaren Polymerisatpulvern |
DE102006050336A1 (de) | 2006-10-25 | 2008-05-08 | Wacker Polymer Systems Gmbh & Co. Kg | Geminitensid enthaltende Dispersionspulverzusammensetzungen |
EP1923405A1 (de) | 2006-11-17 | 2008-05-21 | Elotex AG | Verfahren zur Herstellung von Dispersionen und deren Verwendung |
DE102007038332A1 (de) | 2007-08-14 | 2009-02-19 | Wacker Chemie Ag | Kontinuierliches Polymerisationsverfahren |
EP2341084B1 (de) | 2009-12-30 | 2015-02-25 | Dow Global Technologies LLC | Mit schützenden Kolloidzusammensetzungen stabilisierte, erneut dispergierbare Polymerpulver |
DE102011080235A1 (de) | 2011-08-01 | 2013-02-07 | Wacker Chemie Ag | Verfahren zur Herstellung von Dispersionspulvern |
DE102011080233A1 (de) | 2011-08-01 | 2013-02-07 | Wacker Chemie Ag | Verfahren zur Herstellung von Dispersionspulvern |
-
2016
- 2016-12-21 EP EP16823276.7A patent/EP3538565A1/de not_active Withdrawn
- 2016-12-21 US US16/471,554 patent/US12060444B2/en active Active
- 2016-12-21 WO PCT/EP2016/082191 patent/WO2018113955A1/de active Search and Examination
- 2016-12-21 CN CN201680091745.0A patent/CN110191900A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
WO2018113955A8 (de) | 2019-05-09 |
US12060444B2 (en) | 2024-08-13 |
US20200270374A1 (en) | 2020-08-27 |
WO2018113955A1 (de) | 2018-06-28 |
CN110191900A (zh) | 2019-08-30 |
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