EP3497069A1 - Dispersant composition for inorganic solid suspensions - Google Patents
Dispersant composition for inorganic solid suspensionsInfo
- Publication number
- EP3497069A1 EP3497069A1 EP17751071.6A EP17751071A EP3497069A1 EP 3497069 A1 EP3497069 A1 EP 3497069A1 EP 17751071 A EP17751071 A EP 17751071A EP 3497069 A1 EP3497069 A1 EP 3497069A1
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- European Patent Office
- Prior art keywords
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- water
- represented
- group
- composition according
- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- 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
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- 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
- 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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- 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
- 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
- C04B28/04—Portland cements
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- 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
- 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
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- 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
- 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
- C04B40/0039—Premixtures of ingredients
- C04B40/0042—Powdery mixtures
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- 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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1458—Monomers containing nitrogen
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- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- 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
- C08G6/00—Condensation polymers of aldehydes or ketones only
- C08G6/02—Condensation polymers of aldehydes or ketones only of aldehydes with ketones
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- 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
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/34—Flow improvers
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- 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
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- 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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- 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
Definitions
- Dispersant composition for inorganic solid suspensions Dispersant composition for inorganic solid suspensions
- the invention relates to a composition in the form of a solid, which is suitable as a dispersant for inorganic solid suspensions. Further disclosed is a process for preparing the composition and its use in an inorganic binder composition.
- Such inorganic solids in the construction industry mostly comprise inorganic binders such as e.g. Cement based on Portland cement (EN 197), cement with special properties (DIN 1 164), white cement, calcium aluminate cement or
- the inorganic solid suspensions usually contain fillers, in particular aggregate consisting of z.
- additives additives
- organic binders such. B. latex powder may be included.
- substantially more mixing water is generally required than would be necessary for the subsequent hydration or hardening process.
- the void fraction in the structure formed by the excess, later evaporating water leads to a significantly deteriorated mechanical strength, durability and durability.
- additives generally referred to in construction chemicals as water reducers or superplasticizers are used.
- water reducers or superplasticizers especially polycondensation products based on naphthalene or alkylnaphthalenesulfonic acids or sulfonic acid groups containing melamine formaldehyde resins are known.
- DE 3530258 describes the use of water-soluble sodium naphthalenesulfonic acid-formaldehyde condensates as additives for inorganic binders and Building materials. These additives are used to improve the flowability of the binder such. As cement, anhydrite or gypsum and the building materials produced therewith.
- DE 2948698 describes hydraulic mortars for screeds which contain superplasticizers based on melamine-formaldehyde condensation products and / or sulfonated formaldehyde naphthalene condensates and / or lignin sulfonate and, as binders, Portland cement, clay-containing limestone marl, clay and weak clinker brick.
- the newer group of flow agents are weakly anionic comb polymers which usually carry anionic charges on the main chain and contain nonionic polyalkylene oxide side chains.
- WO 01/96007 describes these weakly anionic flow and grinding auxiliaries for aqueous mineral suspensions which are prepared by free-radical polymerization of vinyl group-containing monomers and which contain polyalkylene oxide groups as a main component.
- DE 19513126 and DE 19834173 describe copolymers based on unsaturated dicarboxylic acid derivatives and oxyalkylene glycol alkenyl ethers and their use as additives for hydraulic binders, in particular cement.
- the aim of adding flow agents in the construction industry is either to increase the plasticity of the binder system or to reduce the amount of water required under the same processing conditions.
- polycarboxylate esters wherein the ester function is hydrolyzed after incorporation into a cementitious, aqueous mixture to form a polycarboxylate ether.
- Polycarboxylate esters have the advantage that they develop their effect only after some time in the cementitious mixture and thus the dispersing effect can be maintained over a longer period.
- Dispersants based on polycarboxylate ethers and derivatives thereof are available either as a solid in powder form or as an aqueous solution.
- Powdered polycarboxylate ethers may, for example, be added to a dry mortar during its production. When mixing the dry mortar with water, the polycarboxylate ethers dissolve and can subsequently exert their effect.
- DE 199 05 488 discloses powdered polymer compositions based on polyether carboxylates, these comprising from 5 to 95% by weight of the water-soluble polymer and from 5 to 95% by weight of a finely divided mineral carrier material. The products are made by contacting the mineral support material with a melt or an aqueous solution of the polymer. The advantages of this product compared to spray-dried products, a significantly increased adhesion and caking resistance called.
- WO 2013/020862 discloses a process for preparing a solid dispersant for a hydraulically setting composition, wherein a comb polymer comprising carboxyl groups and at least one second polymer selected from a condensate of an aromatic compound and formaldehyde or lignosulfonate are spray-dried together in the form of an aqueous composition ,
- the dispersants thus obtained have the disadvantage that they lead to a delay in the setting process in the hydraulically setting compositions.
- Spray drying also called atomization drying, is a process for drying solutions, suspensions or pasty masses.
- the material to be dried is introduced into a hot air stream, which dries it to a fine powder in a very short time.
- the hot air flows in the direction of the spray jet, ie according to the direct current principle or against the spray jet, ie according to the countercurrent principle.
- the spraying device is preferably located at the upper part of a spray tower. The resulting dry material is separated in this case in particular by a cyclone separator from the air flow and can be removed there. It is also known to operate spray drier continuously or discontinuously.
- composition according to the invention has excellent application properties both in hydraulic binder compositions comprising, for example, Portland cement and in non-hydraulic binder compositions comprising, for example, gypsum.
- the water-soluble polymers A) according to the invention comprising polyether groups, preferably contain at least two monomer building blocks. However, it may also be advantageous to use copolymers with three or more monomer units.
- the water-soluble polymer A) according to the invention particularly preferably comprises at least one group from the series carboxyester, carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy, sulfoalkyloxy, sulfinoalkyloxy and phosphonooxy groups. Most preferably, the polymer of the invention comprises an acid group.
- the term "acid group” is understood as meaning both the free acid and its salts, and the acid may preferably be at least one of the series carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy
- the water-soluble polymer A) according to the invention comprises at least one carboxyester group, in particular a hydroxyalkyl ester
- the hydroxyalkyl ester preferably comprises 1 to 6, preferably 2 to 4, C atoms.
- Water-soluble polymers in the context of the present application are polymers which in water at 20 ° C.
- the polyether groups of the at least one water-soluble polymer A) are polyether groups of the structural unit (I),
- U is a chemical bond or an alkylene group with 1 to 8 carbon atoms
- X represents oxygen, sulfur or a group NR 1 ,
- k 0 or 1
- n is an integer whose average value, based on the polymer, is in the range from 3 to 300,
- Alk is C 2 -C 4 -alkylene, where Alk within the group (Alk-0) n may be identical or different,
- W is a hydrogen, a C 1 -C 6 -alkyl or an aryl radical or
- Y is a linear or branched alkylene group having 2 to 8 C atoms
- F stands for a nitrogen-bonded 5- to 10-membered nitrogen heterocycle, which as ring members, next to the nitrogen atom and next
- R 1 is hydrogen, C 1 -C 4 -alkyl or benzyl
- R 2 is hydrogen, Ci-C 4 alkyl or benzyl.
- n has a value of from 5 to 135, in particular from 10 to 70 and particularly preferably from 15 to 50.
- the water-soluble polymer A) comprising polyether groups is a polycondensation product containing
- A is the same or different and is represented by a substituted or unsubstituted aromatic or heteroaromatic compound having 5 to 10 C atoms in the aromatic system, the other radicals having the meaning given for structural unit (I);
- D is identical or different and represented by a substituted or unsubstituted aromatic or heteroaromatic compound having 5 to 10 C atoms in the aromatic system.
- R 3 and R 4 are each independently the same or different and represented by a branched or unbranched C 1 to C 10 alkyl radical, C 5 to C 8 cycloalkyl radical, aryl radical, heteroaryl radical or H, preferably by H, methyl, ethyl or phenyl, more preferably by H or methyl, and more preferably by H.
- the polycondensation product preferably contains a further structural unit (IV), which is represented by the following formula
- Y are independently the same or different and represented by (II), (III) or the other constituents of the polycondensation product.
- R 5 and R 6 are the same or different and represented by H, CH 3, COOH or a substituted or unsubstituted aromatic or heteroaromatic compound having 5 to 10 C atoms.
- R 5 and R 6 in structural unit (IV) independently of one another are preferably represented by H, COOH and / or methyl.
- R 5 and R 6 are represented by H.
- the molar ratio of the structural units (II), (III) and (IV) of the phosphated polycondensation product according to the invention can be varied within wide limits. It has proved to be advantageous that the molar ratio of the structural units [(II) + (III)]: (IV) 1: 0.8 to 3, preferably 1: 0.9 to 2 and particularly preferably 1: 0.95 to 1, 2 is.
- the molar ratio of the structural units (II): (III) is normally from 1:10 to 10: 1, preferably from 1: 7 to 5: 1 and more preferably from 1: 5 to 3: 1.
- the groups A and D in the structural units (II) and (III) of the polycondensation product are usually replaced by phenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, naphthyl, 2-hydroxynaphthyl, 4-hydroxynaphthyl, 2-methoxynaphthyl, 4-methoxynaphthyl preferably represents phenyl, where A and D can be selected independently of one another and can also each consist of a mixture of the compounds mentioned.
- the groups X and E are independently represented by O, preferably.
- N in structural unit (I) is preferably represented by an integer from 5 to 280, in particular 10 to 160 and particularly preferably 12 to 120 and b in structural unit (III) by an integer from 0 to 10, preferably 1 to 7 and especially preferably 1 to 5.
- the respective radicals, the length of which is defined by n or b, can in this case consist of uniform assemblies, but it may also be expedient that they are a mixture of different assemblies.
- the radicals of the structural units (II) and (III) may each independently have the same chain length, n or b being each represented by a number.
- the present invention further provides that it is a sodium, potassium, ammonium and / or calcium salt, and preferably a sodium and / or potassium salt, of the phosphated polycondensation product.
- the phosphated polycondensation product according to the invention has a weight average molecular weight of 5000 g / mol to 150,000 g / mol, preferably 10,000 to 100,000 g / mol and particularly preferably 20,000 to 75,000 g / mol.
- the water-soluble polymer A) is at least one copolymer which is obtainable by polymerization of a mixture of monomers comprising
- Carboxylic imide includes
- Polyether group wherein the polyether group preferably by
- the structural unit (I) is represented.
- the copolymers according to the present invention contain at least two monomer building blocks. However, it may also be advantageous to use copolymers with three or more monomer units.
- the ethylenically unsaturated monomer (V) is represented by at least one of the following general formulas from the group (Va), (Vb) and (Vc):
- R 7 and R 8 are independently hydrogen or aliphatic Hydrocarbon radical having 1 to 20 carbon atoms, preferably a methyl group.
- B is H, -COOM a , -CO-O (C q H 2q O) r -R 9 , -CO-NH- (C q H 2q O) r R 9 .
- Substituted ammonium groups which are derived from primary, secondary or tertiary C 1-20 -alkylamines, C 1-20 -alkanolamines, C 3-5 -cycloalkylamines and C 6-14 -arylamines are preferably used as organic amine radicals.
- Examples of the corresponding amines are methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, cyclohexylamine, dicyclohexylamine, phenylamine, diphenylamine in the protonated (ammonium) form.
- the aliphatic hydrocarbons here may be linear or branched and saturated or unsaturated.
- Preferred cycloalkyl radicals are cyclopentyl or cyclohexyl radicals, and the preferred aryl radicals are phenyl or naphthyl radicals, which may in particular be substituted by hydroxyl, carboxyl or sulfonic acid groups.
- Z is O or NR 16 , where R 16 is independently the same or different and is represented by a branched or unbranched C 1 to C 10 alkyl radical, C 8 to C 8 cycloalkyl radical, aryl radical, heteroaryl radical or H.
- R 16 is independently the same or different and is represented by a branched or unbranched C 1 to C 10 alkyl radical, C 8 to C 8 cycloalkyl radical, aryl radical, heteroaryl radical or H.
- the following formula represents the monomer (Vc):
- R 10 and R 11 independently of one another are hydrogen or an aliphatic hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, an optionally substituted aryl radical having 6 to 14 C atoms ,
- R 13 is H, -COOM a , -CO-O (C q H 2q O) r -R 9 , -CO-NH- (C q H 2q O) r R 9 , where M a , R 9 , q and r have the meanings mentioned above.
- R 14 is hydrogen, an aliphatic hydrocarbon radical having 1 to 10 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, an optionally substituted aryl radical having 6 to 14 C atoms.
- Q is identical or different and is represented by NH, NR 15 or O, where R 15 is an aliphatic hydrocarbon radical having 1 to 10 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms or an optionally substituted aryl radical 6 to 14 carbon atoms.
- the ethylenically unsaturated monomer (VI) is represented by the following general formulas (VI)
- the copolymer has an average molecular weight (Mw) between 5000 and 150,000 g / mol, more preferably 10,000 to 80,000 g / mol, and most preferably 15,000 to 60,000 g / mol, which is determined by gel permeation chromatography.
- the polymers are analyzed by size exclusion chromatography for average molecular weight and conversion (column combinations: Shodex OH-Pak SB 804 HQ and OH-Pak SB 802.5 HQ from Showa Denko, Japan; Eluant: 80% by volume aqueous solution of HCO 2 NH 4 (0 , 05 mol / l) and 20 vol .-% MeOH, injection volume 100 ⁇ , flow rate 0.5 ml / min)).
- the copolymer according to the invention preferably meets the requirements of the industrial standard EN 934-2 (February 2002). Furthermore, the composition according to the invention comprises at least one water-soluble condensation product B) based on monomers, which contains at least one acid group and / or salt thereof
- the acid groups of the condensation product B) are particularly preferably at least one from the series carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy, sulfoalkyloxy, sulfinoalkyloxy and phosphonooxy group and / or their salts, which also is designated as structural unit ⁇ ).
- the condensation product B) has a monomer ratio of the monomers a) to ⁇ ) of 1 to 2 to 3. Particularly preferably, the condensation product B) has a ratio of the monomers a) to ß) to structural unit ⁇ ) of 1 to 2 to 3 to 0.33 to 1.
- the monomer having a ketone residue a) of the condensation product B) is preferably at least one ketone from the series methyl ethyl ketone, acetone, diacetone alcohol, ethyl acetoacetate, levulinic acid, methyl vinyl ketone, mesityl oxide, 2,6-dimethyl-2,5 Heptadien-4-one, acetophenone, 4-methoxy-acetophenone, 4-acetylbenzenesulfonic acid, diacetyl, acetylacetone, benzoylacetone and cyclohexanone. Especially preferred are cyclohexanone and acetone.
- the composition according to the invention comprises 5 to 95% by weight, preferably 25 to 60% by weight and particularly preferably 30 to 50% by weight of A) of the at least one water-soluble polymer comprising polyether groups and 5 to 95 Wt .-%, preferably 40 to 75 wt .-% and particularly preferably 50 to 70 wt .-% B) of the at least one acid group and / or salts thereof containing water-soluble condensation product.
- the condensation product B) according to the invention comprises as monomer a) in particular cyclohexanone or acetone or a mixture thereof.
- monomer ⁇ in particular formaldehyde is to be regarded as particularly preferred.
- acid groups of the condensation product B these can preferably be introduced by sulfite.
- the condensation product B) according to the invention is particularly preferably prepared from cyclohexanone, formaldehyde and sulfite. It should also be mentioned that the condensation product B) according to the invention does not comprise any polyether groups.
- the condensation product B) has an average molecular weight (Mw) between 10,000 and 40,000 g / mol, in particular between 15,000 and 25,000 g / mol, which is determined by size exclusion chromatography, the measurement according to Section 2.3 of the publication “ Cement and Concrete Research ", Volume 42, Issue 1, January 2012, page 1 18 to 123 (" Synthesis, working mechanism and effectiveness of a novel cycloaliphatic superplasticizer for concrete ", L. Lei, J. Plank).
- Mw average molecular weight
- condensation product B to be used in accordance with the present invention and its preparation, reference is made to patent applications DE 2341923, in particular page 3, last paragraph to page 5, third paragraph and page 7, example 1 A), the content of which is hereby incorporated into the application is recorded.
- condensation product B preferably to be used according to the present invention and its preparation
- a further subject of the present invention is a process for producing a composition according to the invention, the process comprising the following steps:
- Suitable spray nozzles are single-fluid nozzles and multichannel nozzles such as two-component nozzles, three-channel nozzles or four-channel nozzles. Such nozzles may also be designed as so-called “ultrasonic nozzles.” Such nozzles are commercially available.
- a sputtering gas can be supplied.
- a sputtering gas air or an inert gas such as nitrogen or argon can be used.
- the gas pressure of the atomizing gas may preferably be up to 1 MPa absolute, preferably 0.12 to 0.5 MPa absolute.
- the preparation of the aqueous mixture comprising the at least one water-soluble polymer comprising polyether groups and the water-soluble condensation product B) is carried out before the spray-drying step d).
- the aqueous mixture used according to the invention is preferably prepared by mixing an aqueous solution of the polymer A) with an aqueous solution of the condensation product B).
- special nozzles are also suitable in which different liquid phases within the nozzle body are mixed and then atomized.
- an aqueous solution or an aqueous suspension comprising the at least one water-soluble polymer comprising polyether groups, hereinafter also referred to as component A), and an aqueous solution or an aqueous suspension comprising the water-soluble condensation product B), hereinafter also as a component B) the nozzle are first fed separately and then mixed together within the nozzle head.
- An embodiment of the invention relates to ultrasonic nozzles.
- Ultrasonic nozzles can be operated with or without atomizing gas. In ultrasonic nozzles, the atomization takes place by causing the phase to be atomized to vibrate. Depending on the nozzle size and design, the ultrasonic nozzles can be operated with a frequency of 16 to 120 kHz.
- the throughput of liquid phase to be sprayed per nozzle depends on the nozzle size.
- the throughput can be 500 g / h to 1000 kg / h solution or suspension. In the production of commercial quantities, the throughput is preferably in the range of 10 to 1000 kg / h. If no atomizing gas is used, the liquid pressure may be 0.2 to 40 MPa absolute. If an atomizing gas is used, the liquid can be fed without pressure.
- the spray drying apparatus is supplied with a drying gas such as air or one of the inert gases mentioned.
- the drying gas can be supplied in cocurrent or countercurrent to the sprayed liquid, preferably in cocurrent.
- the inlet temperature of the drying gas may be 120 to 300 ° C, preferably 150 to 230 ° C, the outlet temperature 60 to 135 ° C.
- the magnitudes of the spray parameters to be used depend decisively on the size of the devices.
- the devices are commercially available and usually the manufacturer recommends corresponding orders of magnitude.
- the spraying process is preferably operated such that the average droplet size of the sprayed phases is 5 to 2,000 ⁇ m, preferably 5 to 500 ⁇ m, particularly preferably 5 to 200 ⁇ m.
- the mean droplet size can be determined by laser diffraction or high-speed cameras coupled with an image analysis.
- a particular embodiment is a method in which the spray nozzle is a multi-channel nozzle.
- the spraying of the components takes place through a multi-channel nozzle, wherein the components are brought into contact with one another at the outlet of the spray nozzle.
- the multi-channel nozzle may be a three-channel nozzle or a two-channel nozzle.
- one of the three channels preferably uses a sputtering gas, more preferably air or nitrogen, the other two channels are for component A) or component B).
- the required atomization of the two components A) and B) is achieved either by the use of ultrasound or by the use of a centrifugal force nozzle.
- the use of a three-channel nozzle with a channel for the atomizing gas and two channels for the components A) and B) is preferred.
- the channels for the components A) and B) are separated both in the case of a two-channel nozzle, as well as a three-channel nozzle to avoid premature mixing of the components.
- the components A) and B) are brought into contact only at the outlet of the two channels for the components A) and B) of the spray nozzle.
- the nebulizer gas causes the formation of fine droplets, in particular in the form of a mist, from the components A) and B) which have been brought into contact with one another.
- the multichannel nozzle has two channels, the component A) and the component B) first being premixed with one another and then fed to the two-channel nozzle, the drying gas being introduced via the second channel.
- the aqueous mixture prior to spray-drying, comprises 1 to 55% by weight, preferably 5 to 40% by weight and more preferably 15 to 25% by weight of the water-soluble polymer comprising polyether groups and 1 to 55 wt .-%, preferably 5 to 40 wt .-% and particularly preferably 25 to 35 wt .-% of the water-soluble condensation product B) and 20 to 80 wt .-%, preferably 35 to 75 wt .-% water ,
- the aqueous mixture in process step c) is prepared and preheated before it enters the spray dryer.
- components A) and B) may also be preheated independently prior to entering the spray dryer.
- the inlet temperature of component A) and independently thereof component B) or the inlet temperature of the mixture in the spray dryer may be between 50 and 200 ° C, preferably between 70 and 130 ° C.
- the resulting powdery solid may then be sieved to remove agglomerates.
- the solid obtained by the process according to the invention is obtained in the form of a dry powder having good flowability. However, the powder can also be converted, for example, by pressure into another solid form.
- the process of the invention also includes solid compositions in the form of pellets or granules.
- the process according to the invention thus preferably provides that the solid obtained after spray-drying is present as powder or granules.
- the aqueous mixture used in the process according to the invention may also contain further additives.
- components A) and B) may independently contain further additives. These may in particular be stabilizers or by-products from the manufacturing process. Furthermore, in particular antioxidants can be added as additives.
- the solid obtained by the process according to the invention, after incorporation into water (50% by weight mixture), preferably has a pH of between 2 and 9, preferably between 3.5 and 6.5. In a specific embodiment, it is also possible to adjust the pH of the aqueous mixtures used according to the invention before the spray-drying by adding an acid or a base.
- the present invention provides for the use of the dispersant obtained by the process of the invention in an inorganic binder composition.
- the inorganic binder is preferably at least one of the series based on Portland cement, white cement, calcium aluminate cement, calcium sulfoaluminate cement, calcium sulfate n-hydrate and latently hydraulic or pozzolanic binder.
- the binder composition is preferably a dry mortar.
- the constant pursuit of extensive rationalization and improved product quality has meant that in the construction sector mortar for a variety of applications today is virtually no longer mixed together on the construction site itself from the starting materials.
- Today, this task is largely taken over by the building materials industry at the factory and the ready-mixed mixtures are provided as so-called dry mortar.
- finished mixtures which are made on the construction site exclusively by the addition of water and skillsmi- seen processable, according to DIN 18557 referred to as work mortar, especially as dry mortar.
- work mortar especially as dry mortar.
- Such mortar systems can fulfill a wide variety of building physics tasks.
- the binder which may contain, for example, cement and / or lime and / or calcium sulfate, further additives or additives are added to adjust the dry mortar to the specific application.
- the dry mortar according to the invention may, in particular, be masonry mortar, plaster, mortar for thermal insulation composite systems, rendering plasters, joint mortar, tile adhesives, thin-bed mortar, screed mortar, grout, grout, leveling compounds, sealing slurries or lining mortar (eg for drinking water pipes).
- factory mortars which can be provided with other components, in particular liquid and / or powdery additives and / or with aggregate in the production on the site except with water (two-component systems).
- the binder composition according to the invention which comprises at least one inorganic binder
- the binder may in particular also be a binder mixture.
- these are understood as meaning mixtures of at least two binders from the series cement, pozzolanic and / or latent hydraulic binder, white cement, special cement, calcium aluminate cement, calcium sulfoaluminate cement and the various hydrous and anhydrous calcium sulfates. These may possibly contain further additives.
- the following examples are intended to explain the invention in more detail.
- acetone resin was prepared in accordance with polymer 6 of W015039890 (see Table 1 on page 13 i.V.m. page 15, specification C))
- the cyclohexanone resin was prepared according to Polymer 14 of W015039890 (see Table 1 on page 13, i.V., page 15, Specification B))
- Polymer A is a copolymer of ethoxylated vinyloxybutanol with a chain length of 23 ethylene oxide units and acrylic acid.
- the copolymer was prepared as follows: A glass reactor equipped with several feeds, stirrer and dropping funnel was charged with 500 ml of water and 359 g of macromonomer 1 (prepared by ethoxylation of vinyloxybutanol with 23 mol of EO) and heated to 13 ° C. To this was added 0.01 g of ferrous sulfate heptahydrate and 5.5 g of Brxgolit FF6.
- Polymer B is a copolymer of hydroxyethyl acrylate and ethoxylated isoprenol with 23 ethylene oxide units (EO).
- the copolymer was prepared as follows: A glass reactor was equipped with a stirrer, pH meter and metering units and filled with 267 g of water. 330 g of the molten ethoxylated isoprenol were mixed with the water. The temperature was adjusted to 13 ° C, the pH by adding 25% sulfuric acid to about 7. To this was added 4 mg of iron (II) sulfate heptahydrate, 8.25 g of mercaptoethanol and 3.2 g of hydrogen peroxide.
- II iron
- Polymer C is a copolymer of methacrylic acid and methyl polyethylene glycol methacrylate ester with 23 ethylene oxide units (EO).
- the auxiliary polymer was prepared analogously to page 18, Synthesis Example 1 of WO 03/097721.
- the lignosulfonate used was a commercially available lignosulfonate Bretax from Burgos.
- the sulfonated melamine-formaldehyde condensation product used was Melment F10 from BASF Construction Solutions GmbH.
- the molecular weight was determined by means of gel permeation chromatography (GPC) using the following method: Column combination: Shodex OH-Pak SB 804 HQ and OH-Pak SB 802.5 HQ from Showa Denko, Japan; Eluent: 80% by volume aqueous solution of HCO 2 NH 4 (0.05 mol / L) and 20% by volume MeOH; Injection volume 100 ⁇ ; Flow rate 0.5 ml / min). The calibration of the molecular weight was carried out with standards from PSS Polymer Standard Service, Germany. Poly (styrene sulfonate) standards were used for the UV detector, and poly (ethylene oxide) standards were used for the RI detector. To determine the molecular weight, the results of the R1 detector were used.
- GPC gel permeation chromatography
- a spray drier from GEA Niro of the Mobile Minor type MM-I was used. It was dried with the help of a two-fluid nozzle in the head of the tower. The drying was done with nitrogen, which was co-current with the
- Drying material was blown from top to bottom was dried.
- the temperature of the drying gas was 220 ° C at the tower entrance.
- the feed rate of the material to be dried was adjusted so that the starting temperature of the drying gas at the tower outlet was 100 ° C.
- the discharged from the drying tower, with the drying gas, powder was separated by means of a cyclone from the drying gas.
- Spray dryness was evaluated as follows:
- the particle size was determined with a "Mastersizer 2000" from Malvern Instruments which is the Volumetric Grain Diameter
- the thermal-mechanical properties of the powder were tested as follows: All required metal parts were heated to 80 ° C. before use in a drying oven Tube with a length of 70 mm and an inner diameter of 50 mm with a wall thickness of 2.5 mm was placed on a brass base plate with a 7 mm high tube attachment at 55 mm inner diameter., In the tube 2 g of powder were added, a A brass cylinder weighing 1558 g was then inserted into the tube, this cylinder was rotated 360 times without pressure, then the cylinder and tube were removed and the sample was ranked according to the following factors: Table 2
- PulPolyFst. Mass Carrier [% Fst. Mass BeurteBeurteiver mer (Grams) of Ge (Gramm) lung B total weight]
- Fst. Solids content of the aqueous mixture
- the dispersing properties were determined by a mortar test.
- the cement mortar was composed of 40.0% by weight of Portland cement (CEM I 52.5 N, Milke) and 60.0% by weight of standard sand (DIN EN 196-1).
- the water cement value (weight ratio of water to cement) was 0.35.
- a polymer powder according to Table 3 was added to liquefy the cement mortar. The content of the polymer powder is shown in Table 4 and is based on the amount of cement.
- the cement mortar was produced in accordance with DIN EN 196-1: 2005 in a mortar mixer with a capacity of approx. 5 liters.
- water, polymer powder, 0.45 g of the powdery defoamer Vinapor DF 9010 F (available from BASF Construction Solutions GmbH) and cement were added to the mixing vessel.
- the low-speed mixing of the vortex 140 revolutions per minute (rpm)
- the standard sand was added evenly over 30 seconds to the mixture.
- the mixer was switched to a higher speed (285 rpm) and mixing continued for a further 30 seconds.
- the mixer was stopped for 90 seconds.
- the cement mortar stuck to the wall and bottom of the bowl was removed with a rubber raspper and placed in the center of the bowl. After Pause the cement mortar was mixed for a further 60 seconds at the higher mixing speed.
- the total mixing time was 4 minutes.
- the diameter was determined with a measuring slide on two axes at right angles to each other and the mean value calculated.
- the test of the flow rate was repeated after 10, 20, 30, 45, 60, 90 and 120 minutes. Before each test, the cement mortar was mixed for 10 seconds in a mortar mixer at a speed of 140 revolutions per minute (rpm).
- Powder V8 was prepared analogously to the disclosure of WO 2013/020862 and can be compared directly with the powder 6 according to the invention. This shows that the powder 6 according to the invention causes a significantly lower delay in the setting of the inorganic binder compared to powder V8 and furthermore has a significantly better dosing efficiency.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
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EP16183684 | 2016-08-11 | ||
PCT/EP2017/069767 WO2018029095A1 (en) | 2016-08-11 | 2017-08-04 | Dispersant composition for inorganic solid suspensions |
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US (1) | US20200317905A1 (en) |
EP (1) | EP3497069A1 (en) |
CN (1) | CN109562996A (en) |
RU (1) | RU2741290C2 (en) |
WO (1) | WO2018029095A1 (en) |
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WO2020007664A1 (en) * | 2018-07-06 | 2020-01-09 | Basf Se | Composition for flowable fire-resistant materials |
CN117157361A (en) | 2021-04-09 | 2023-12-01 | 巴斯夫欧洲公司 | Use of polyethers in pigment dispersions |
Family Cites Families (25)
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DE2341923C3 (en) | 1973-08-18 | 1980-01-31 | Bayer Ag, 5090 Leverkusen | Inorganic binding agent mortar, method of making and using the same |
DE2948698A1 (en) | 1979-12-04 | 1981-06-11 | Cempro Ag, Vaduz | Hydraulic mortar for sound and heat insulating tile prodn. - comprising e.g. melamine formaldehyde! resin fluidiser, Portland cement and clay binder, accelerator and sand |
US4557763A (en) | 1984-05-30 | 1985-12-10 | Halliburton Company | Dispersant and fluid loss additives for oil field cements |
DE3530258A1 (en) | 1985-08-23 | 1987-02-26 | Lentia Gmbh | USE OF SALTS OF WATER-SOLUBLE NAPHTALINE SULPHONIC ACID FORMALDEHYDE CONDENSATES AS ADDITIVES FOR INORGANIC BINDERS AND BUILDING MATERIAL |
DE19513126A1 (en) | 1995-04-07 | 1996-10-10 | Sueddeutsche Kalkstickstoff | Copolymers based on oxyalkylene glycol alkenyl ethers and unsaturated dicarboxylic acid derivatives |
FR2740462B1 (en) * | 1995-10-25 | 1997-12-19 | Rhone Poulenc Chimie | WATER REDISPERSABLE POWDER COMPOSITION OF FILM-FORMING POLYMERS PREPARED FROM ETHYLENICALLY UNSATURATED MONOMERS |
DE19834173A1 (en) | 1997-08-01 | 1999-02-04 | Sueddeutsche Kalkstickstoff | Copolymer based on unsaturated di:carboxylic acid derivatives and oxyalkylene glycol-alkenyl ether(s) |
DE19905488A1 (en) | 1999-02-10 | 2000-08-17 | Sueddeutsche Kalkstickstoff | Powdery polymer compositions based on polyether carboxylates |
FR2810261B1 (en) | 2000-06-15 | 2002-08-30 | Coatex Sa | USE OF LOW ANIONIC COPOLYMERS AS A DISPERSING AGENT AND / OR AID FOR GRINDING AQUEOUS SUSPENSION OF MINERALS, AQUEOUS SUSPENSIONS OBTAINED AND USES THEREOF |
ATE380840T1 (en) | 2002-05-22 | 2007-12-15 | Basf Constr Polymers Gmbh | USE OF WATER-SOLUBLE POLYMERS AS DRYING AIDS FOR THE PRODUCTION OF POLYMERIC DISPERSANTS |
DE102004050395A1 (en) | 2004-10-15 | 2006-04-27 | Construction Research & Technology Gmbh | Polycondensation product based on aromatic or heteroaromatic compounds, process for its preparation and its use |
JPWO2006059723A1 (en) * | 2004-12-02 | 2008-06-05 | 日本シーカ株式会社 | Powdered polycarboxylic acid cement dispersant and dispersant composition containing the dispersant |
DE102006047091A1 (en) * | 2006-10-05 | 2008-04-10 | Basf Construction Polymers Gmbh | New composition based on polyvinyl alcohol |
EP2006258B1 (en) * | 2007-06-11 | 2012-08-15 | Sika Technology AG | Dispersant for gypsum compositions |
US8519029B2 (en) | 2008-06-16 | 2013-08-27 | Construction Research & Technology Gmbh | Copolymer admixture system for workability retention of cementitious compositions |
WO2010040611A1 (en) * | 2008-10-06 | 2010-04-15 | Construction Research & Technology Gmbh | Method for producing phosphated polycondensation products and the use thereof |
CN102239127B (en) | 2008-10-06 | 2014-08-06 | 建筑研究和技术有限公司 | Phosphated polycondensation product, method for production and use thereof |
WO2011089085A1 (en) * | 2010-01-21 | 2011-07-28 | Basf Construction Polymers Gmbh | Dispersing agent |
EP2561003B1 (en) * | 2010-04-23 | 2018-09-05 | Lubrizol Advanced Materials, Inc. | Dispersant composition |
US9309152B2 (en) | 2011-08-10 | 2016-04-12 | Sika Technology Ag | Process for drying concrete dispersants |
EP2574636B1 (en) * | 2011-09-30 | 2014-04-16 | BASF Construction Solutions GmbH | Quickly suspending power-form compound |
EP2848597A1 (en) | 2013-09-17 | 2015-03-18 | Basf Se | Light-weight gypsum board with improved strength and method for making same |
EP2899171A1 (en) * | 2014-01-22 | 2015-07-29 | Construction Research & Technology GmbH | Additive for hydraulic setting masses |
US20150344369A1 (en) * | 2015-08-13 | 2015-12-03 | Construction Research & Technology, Gmbh | Concrete admixture and production method |
CN105399943A (en) * | 2015-12-31 | 2016-03-16 | 江苏苏博特新材料股份有限公司 | Preparation method and application of anti-soil polymer |
-
2017
- 2017-08-04 CN CN201780049363.6A patent/CN109562996A/en active Pending
- 2017-08-04 US US16/324,201 patent/US20200317905A1/en not_active Abandoned
- 2017-08-04 WO PCT/EP2017/069767 patent/WO2018029095A1/en unknown
- 2017-08-04 EP EP17751071.6A patent/EP3497069A1/en active Pending
- 2017-08-04 RU RU2019106269A patent/RU2741290C2/en active
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WO2018029095A1 (en) | 2018-02-15 |
CN109562996A (en) | 2019-04-02 |
RU2019106269A (en) | 2020-09-11 |
RU2741290C2 (en) | 2021-01-25 |
RU2019106269A3 (en) | 2020-11-26 |
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