Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/10—Coating or impregnating
  • C04B20/1018—Coating or impregnating with organic materials
  • C04B20/1029—Macromolecular compounds
  • C04B20/1033—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/24—Macromolecular compounds
  • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
  • C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers containing polyether side chains
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
  • C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
• • 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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
• • 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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
  • C04B2103/40—Surface-active agents, dispersants
  • C04B2103/408—Dispersants

Definitions

• the present invention relates to powdery polymer compositions based on polyether carboxylates, processes for their preparation and their use.
• Water-soluble polymers consisting of polyoxyalkylene-containing structural units, carboxylic acid and / or carboxylic anhydride monomers and optionally further monomers - hereinafter referred to as polyether carboxylates - have recently found access to a number of applications.
• polyether carboxylates are preferably used in building materials, such as concrete, mortar, bitumen, leveling compounds, adhesives, pigment-containing paint and coating preparations, in ceramic materials, in the refractory industry and petroleum processing in order to specifically influence the rheological and / or the wetting properties of these building materials.
• polyether carboxylates Through adsorptive interactions, which polyether carboxylates can enter into with the hydraulic binder particles of these building materials (cement, lime, calcium sulfate, etc.), the mineral particles are stabilized combined with a reduced internal friction and thus an improved flow and processing ability.
• these polymers only consist of two essential structural units, namely a polyoxyalkylene-containing building block and a carboxylic acid (anhydride) monomer, the type of linkage be very diverse.
• the structural range of variation of such polyether carboxylates ranges from statistical, alternating, built up in blocks to comb polymers with carboxyl groups in the main and polyether units in the side chain.
• graft copolymers which are formed by functionalizing polyethers with monomers containing carboxylic acid groups.
• polyesters formed by reacting polyethers such as polyethylene glycol with polybasic carboxylic acids or carboxylic acid anhydrides can also be assigned to the group of polyether carboxylates, it being irrelevant whether these polymers are present as free acid or in their salt form.
• aqueous preparations can be completely ruled out in other fields of application where the polymers are required as an additive in dry mixtures prepared in the factory.
• Powders also have a number of technical advantages over aqueous preparations.
• the stabilization before infestation with microorganisms by adding biocides is eliminated, as is the u. U. elaborate measures for tank hygiene. Since polyether carboxylates can introduce undesirably high amounts of air into the building material due to their surface-active properties, defoamers are generally added to the aqueous preparations after they have been prepared.
• polyether units in the polyether carboxylates in the main chain or as a side chain constituent on the main chain are linked via ester groups, undesired hydrolysis can occur even during storage of the aqueous preparations, destroying the polymer structure.
• polymer powders based on polyether carboxylate are obtained by spraying the aqueous preparations in a hot air stream (spray drying), it being advantageous to add antioxidants and spray auxiliaries in order to a) to prevent the self-heating or self-ignition of such polymers during and after the drying process
• the present invention was therefore based on the object of providing powdered polymer compositions based on polyether carboxylates which avoid the disadvantages of the prior art, i.e. deliver products that are stable in storage at high temperatures and, on the other hand, frost-resistant products that do not require any preservative additives, are stable against self-ignition and thermo-oxidative decay, supply powder that is resistant to sticking and caking, and are accessible with low energy consumption and a rational process.
• the incorporation of the polyether carboxylates (component a) into the mineral component b) can be designed so effectively that up to 90% by weight of active compound, ie. H. Polyether carbonate content in the polymer composition can be achieved.
• the water-soluble polymers used to prepare the polymer composition according to the invention are products which contain polyox ⁇ alkylene groups, preferably polyethylene or polypropylene glycol groups, in the main chain or in the side chain and, moreover, from carboxylic acid and / or carboxylic anhydride monomers such as preferably acrylic acid, methacrylic acid, maleic acid, Maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride are built up.
• polyether carboxylates such as styrene, ⁇ -methylstyrene, isobutene, diisobutene, cyclopentadiene, ethylene, propylene, isoprene, butadiene, acrylonitrile, chloroprene, vinyl acetate, N-vinylpyrrolidone, methyl acrylate, Methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, acrylamide, methacrylamide, acrylamido methyl propane sulfonic acid, styrene sulfonic acid, vinyl chloride, methyl vinyl ether, ethyl vinyl ether, allyl alcohol, allylsulfonic acid, allyl chloride and others.
• the polymers can be linear, short-chain branched, long-chain branched or cross-linked and can be in comb form, star form, dumbbell form and other morphologically conceivable structures.
• Examples are block copolymers of polymethacrylic acid and polyethylene glycol, comb-like polymers composed of a polymethacrylic acid main chain and individual polyethylene oxide side chains bonded via ester groupings, maleic anhydride / styrene copolymers partially esterified with methyl polyethylene glycol, allypolyethylene glycol / maleic acid copolymers, vinyl malefic copolymers, maleic acid copolymers, from a polyethylene or polypropylene glycol backbone and maleic anhydride or acrylic acid side chains, which in turn can be esterified or partially esterified.
• Ionic groups and therefore water-soluble polyesters, polyamides and polyurethanes based on alkylene oxides such as ethylene oxide, propylene oxide or butylene oxide are also possible.
• polyether carboxylates can be in the form of their free acids or in neutralized form and can be prepared by the process of solution, substance, inverse emulsion or suspension polymerization.
• polyether carboxylates produced in bulk are used.
• the use according to the invention is particularly high since, according to the prior art, they are first diluted with water, neutralized and then converted into a powder by spray drying, eliminating the water previously supplied.
• the finely divided mineral carrier materials used have a specific surface area of 0.5 to 500 m 2 / g (determined according to BET in accordance with DIN 66 1 31).
• the proportions by weight of carrier materials in the powdery polymer compositions depend on the type, the composition and the form of incorporation of the polymer as well as on the specific surface and the adsorption capacity of the mineral carrier material. They can therefore vary in a very wide range from 5 to 95% by weight.
• These support materials is not particularly limited. It is essential that the material is well compatible with the polyether carboxylate, does not adversely affect the effect of the polymer, and results in polymer compositions which are resistant to sticking and caking, even in small amounts.
• Chalk, silica, calcite, dolomite, quartz powder, bentonite, pumice powder, titanium dioxide, fly ash, cement (Portland cement, blast furnace cement, etc.) can preferably be used.
• the mineral carrier material already comprises one or more mineral components of a building material.
• the finely divided carrier materials have a preferred particle size of 0.1 to 1000 ⁇ m.
• the mineral carrier materials can be used in combination with organic (non-mineral) additives such as cellulose powders or fibers and powders or fibers of organic polymers (polyacrylonitrile, polystyrene, etc.).
• organic (non-mineral) additives such as cellulose powders or fibers and powders or fibers of organic polymers (polyacrylonitrile, polystyrene, etc.).
• the invention also relates to a method for producing the powdery polymer compositions, which is characterized in that the polyether carboxylate is incorporated into the respective mineral carrier material immediately after the polymerization production process.
• the polymer is preferably introduced into the optionally preheated mineral carrier material in as finely divided a form as possible, the polyether carboxylate being a bulk polymer or being in the form of an aqueous solution, an inverse emulsion or suspension.
• a polyether carboxylate produced by bulk polymerization at 110 to 140 ° C. in the temperature range from 70 to 120 ° C. is sprayed onto a preheated mineral carrier material (for example of the silica type) in a mixer.
• a particularly effective incorporation which is associated with a very low consumption of mineral carrier material, can be achieved by atomizing the polyether carboxylate onto the preheated carrier material. The effectiveness drops if the polymer is sprayed, dripped or poured onto the carrier material because the surface of the substance to be incorporated becomes smaller in the order given.
• Carrier materials with a pronounced porous structure such as. B. silicas have a particularly high adsorption capacity.
• Mixers on the mixing tools of which high shear forces act, can destroy the porous structure, as a result of which the polyether carboxylates held in the cavities are pressed out again. It is therefore advisable to use mixing devices with low shear forces, such as drum mixers, V mixers, tumble mixers or other representatives from the group of free-fall mixers, for this type of carrier.
• conical mixers, ploughshare mixers or spiral mixers with vertical or horizontal mixing tools are suitable for porous carriers.
• mineral carriers the structure of which cannot be disturbed by the mixing process, all other types of apparatus can also be used, such as dissolvers, screw mixers, twin-screw mixers, air mix mixers and others.
• Another object of the invention is the use of at least one powdered polymer composition according to the present invention in building materials, wherein as building materials bitumen products such as asphalt, bituminous adhesives, sealants, fillers and paints or coatings (parking deck), or on hydraulic setting binders such as cement or latent hydraulic binders such as fly ash and trass-based products such as mortar (grout), screeds, concrete, plasters, adhesives, sealants and fillers as well as paints.
• bitumen products such as asphalt, bituminous adhesives, sealants, fillers and paints or coatings (parking deck)
• hydraulic setting binders such as cement or latent hydraulic binders such as fly ash and trass-based products such as mortar (grout), screeds, concrete, plasters, adhesives, sealants and fillers as well as paints.
• gypsum-based building materials mortar, plaster, screed
• the anhydrite-based building materials the other calcium sulfate-based building
• the polymer compositions according to the invention can also be used in dispersion-based building materials such as dispersion tile adhesives, elastic sealing slurries, primers, mortar additives and powdery interior and exterior wall paints.
• the powdered polymer compositions according to the invention can also be used in combination of the above-mentioned building material groups, e.g. B. in bituminous cementitious screeds, grouts, etc.
• the incorporation of the powdered polyether carboxylates into the building material is usually carried out together with other fillers and building material additives such as dispersion powders, water retention agents, thickeners, retarders, accelerators, wetting agents and the like. a.
• the proportion of polyether carboxylate is usually 0.1 to 5% by weight, based on the weight of the building material.
• the powdered polymer compositions according to the invention have a number of advantages over powdered polyether carboxylates obtained in a conventional manner. This will be explained in more detail using the following examples.
• a powdery polymer composition consisting of 75 g of a precipitated silica preheated to 80 ° C. with a specific surface area of 1 90 m 2 / g and 425 g of one is mixed by mixing over a period of 75 min melted polyether carboxylate (A) at 80 ° C.
• the polyether carboxylate (A) was prepared by a solvent-free polymerization as follows:
• Comparative Example 1 According to the prior art, the bulk polymer synthesized in Example 1 was cooled to 80 ° C. and stirred into 425 g of water. After the aqueous solution obtained had cooled, a pH of 8.5 was set by slowly adding dilute sodium hydroxide solution. 0.5% by weight, based on the polymer content of an antioxidant, was stirred in, and the polymer solution, further diluted with water to 30% by weight for water reasons, was converted into a powder in a laboratory spray dryer from NIRO. A slightly brown-colored powder with an average particle diameter of 54 mm was obtained, which had a strong tendency to calk.
• Solids content 45%, sodium salt, pH 6.5
• polyether carboxylates B to G listed in Examples 10 to 15 were diluted, neutralized, provided with antioxidants and converted into powder by spray drying using the procedure given in Comparative Example 1.
• test results obtained from inventive examples 1 to 15 and comparative examples 1 to 7 are summarized in the following application examples.
• the polymer content was determined by gel permeation chromatography (conditions: Waters (Milford, MA); Shodex OH Pak KB-804 and KB-802.5; standard: polyethylene glycol; eluent: NH 4 COO / CH 3 CN 80: 20 v / v). It has been shown that the direct conversion of the polymers according to Examples 1 to 15 into powder is not associated with a reduction in the effective polymer content. In contrast, in the case of polymers which contain ester bonds and are converted into powder according to the state of the art, the polymer content after spray drying is significantly reduced. This is due to the fact that part of the polyether constituents bound via ester groups of the polyether carboxylates present as comb or graft copolymers are split off in the dilution, neutralization and spray-drying process.
• the flowability was determined according to K. Klein: soaps, oils, fats, waxes 94 (1968), page 12 for different polymer composites. Settlements determined. For this purpose, siliconized glass outlet vessels with different outlet diameters were filled to the brim with the test substance. The evaluation was carried out with the marks 1, ie the powder flows without stopping from the pouring vessel with the smallest outlet opening (0 2.5 mm) up to grade 6, ie the powder no longer flows out of the measuring vessel with the largest opening (0 18 mm). The measurements for each powder were started with the measuring vessel with the largest outlet opening.
• Powdery products tend to cake when stacked in bags or in a silo.
• the powder to be tested was filled into a steel cylinder with an internal diameter of 50 mm and a height of approx. 20 mm and loaded with a pressure stamp of 1.2 kg and a support weight of 2 kg.
• the pressure in this test arrangement is 0.17 kg / cm 2 , which corresponds to the pressure of 10 to 12 sacks with a filling weight of 50 kg. After 24 hours of exposure, the support weight is removed and the "powder tablet" is pressed out of the sleeve.
• the hardness of the powder tablet is regarded as a criterion for the resistance to caking according to the following evaluation scheme.
• the powders according to the invention and the powders obtained from the comparative examples were tested for their application properties in a mortar formulation.
• the powdery polymer compositions were dry-mixed with the proportions of sand and Portland cement (CEM I 42.5 R Kiefersfelden) prescribed in accordance with DIN 1164 Part 7. Then water was added and the components were mixed in accordance with the standards. The spread of the fresh mortar for each powder type was determined immediately and after 15, 30, 45 and 60 minutes. Table 7
• mortar mixtures which contain polymer powders produced according to the prior art lose processability much more quickly than mixtures with powdered polymer compositions according to the invention. This is due to the reduced steric stabilization of the cement particles.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Ceramic Engineering (AREA)
• Materials Engineering (AREA)
• Structural Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Paints Or Removers (AREA)

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• 1999
  • 1999-02-10 DE DE19905488A patent/DE19905488A1/de not_active Withdrawn
• 2000
  • 2000-02-08 US US09/913,148 patent/US6620879B1/en not_active Expired - Lifetime
  • 2000-02-08 WO PCT/EP2000/000999 patent/WO2000047533A1/de not_active Ceased
  • 2000-02-08 JP JP2000598457A patent/JP4921640B2/ja not_active Expired - Lifetime
  • 2000-02-08 AT AT00910652T patent/ATE221863T1/de active
  • 2000-02-08 AU AU32790/00A patent/AU3279000A/en not_active Abandoned
  • 2000-02-08 DE DE50000360T patent/DE50000360D1/de not_active Expired - Lifetime
  • 2000-02-08 CA CA002362378A patent/CA2362378C/en not_active Expired - Fee Related
  • 2000-02-08 ES ES00910652T patent/ES2177511T3/es not_active Expired - Lifetime
  • 2000-02-08 DK DK00910652T patent/DK1154967T3/da active
  • 2000-02-08 EP EP00910652A patent/EP1154967B1/de not_active Expired - Lifetime
  • 2000-02-08 PT PT00910652T patent/PT1154967E/pt unknown

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