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
  • 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
• • 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
• • 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
• • 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
  • C04B7/00—Hydraulic cements
  • C04B7/36—Manufacture of hydraulic cements in general
  • C04B7/48—Clinker treatment
  • C04B7/52—Grinding ; After-treatment of ground cement
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • 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
  • C04B2103/20—Retarders
  • C04B2103/24—Hardening retarders
• • 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
  • C04B2103/52—Grinding aids; Additives added during grinding
• • 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
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
  • C04B2111/1006—Absence of well-defined organic compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P40/00—Technologies relating to the processing of minerals
  • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

• the additive according to the invention is distinguished by an excellent retarding action in the case of hydraulically setting
• compositions containing ground clinker with the inventive additive from.
• a key step in cement production is the milling of cement clinker. Since cement clinker are very hard, the crushing is very energy consuming. It is important for the properties of the cement to be present as a fine powder. Therefore, the fineness of the cement is an important quality feature. In order to facilitate comminution in powder form so-called Zementmahloskar be used. This greatly reduces meals and energy costs.
• Organic amines with a molecular weight M w of less than 500 g / mol, or their ammonium salts, are very common grinding aids.
• organic amines are alkanolamines such as
• TIPA triisopropanolamine
• TAA triethanolamine
• retardants also called retarders in the following, are added in order to delay the start of stiffening, or to increase the time difference between the end of solidification and the start of solidification.
• the Adding these retarders to the hydraulic binders is typically done with the addition of the make-up water or shortly thereafter.
• inventive additive composition Z the disadvantages of the known grinding aids canceled, or greatly reduced, can be, without losing the beneficial effects of the usual Zementmahlosstoff lost.
• additive composition Z has no negative influence on the
• Compressive strength of the hardened mineral binder has.
• the retarder does not lose its retarding effect during the milling process. Further, due to the finer in the course of the milling process achieved Distribution of the retarder, compared to the addition of the mixing water, much less retarder can be used.
• the present invention relates to an additive composition
• Z comprising at least one grinding assistant selected from the group consisting of glycols, monocarboxylic acids having 1 to 4 carbon atoms and comb polymers, and at least one retarder, wherein the
• Additive composition Z is substantially free of organic amines having a molecular weight M w of less than 500 g / mol, or their ammonium salts.
• the weight proportion of grinding aid is preferably 0.2-99.8% by weight, based on the weight of the additive composition Z.
• the comb polymer is a
• Comb polymer KP with side chains attached via ester or ether groups to the main chain As a comb polymer KP are on the one hand comb polymers with over
• Side chains can be introduced by polymerization of vinyl ethers or allyl ethers.
• the vinyl ethers or allyl ethers have in particular the formula (II).
• R ' is H or an aliphatic hydrocarbon radical having 1 to 20 C atoms or a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms or an optionally substituted, aryl radical having 6 to 14 C atoms.
• Substructure elements can be alternating, block-like or random
• such comb polymers are copolymers of vinyl ether or allyl ether with maleic anhydride, maleic acid, and / or (meth) acrylic acid.
• comb polymers having side chains bonded via ester groups to the linear polymer backbone are suitable as the comb polymer KP.
• This type of comb polymer KP is preferred over the comb polymers with side chains attached via ether groups to the linear polymer backbone.
• Particularly preferred comb polymers KP are copolymers of
• M independently of one another represent H + , alkali metal ion, alkaline earth metals, divalent or trivalent metal ion, ammonium ion, or organic ammonium group.
• the term "independently of one another" in the present document in each case means that a substituent can have different meanings available in the same molecule:
• the copolymer of the formula (I) can simultaneously have carboxylic acid groups and sodium carboxylate groups, ie for M in this Trap H + and Na + are independent of each other.
• substituents R independently of one another represent hydrogen or a methyl group.
• the substituents R 1 independently of one another are - [AO] q -R 4 .
• the substituents R 2 independently of one another are a C 1 - to C 20 -alkyl group, -cycloalkyl group, -alkylaryl group or - [AO] q -R 4 .
• the substituent A in both cases independently of one another is a C 2 - to C 4 -alkylene group and R 4 is a C 1 - to C 20 -alkyl group, -cyclohexyl group or -alkylaryl group, while q is from 2 to 250, in particular from 8 to 200, more preferably from 1 to 150.
• R 3 independently of one another are -NH 2 , -NR 5 R 6 , -OR 7 NR 8 R 9 .
• R 5 and R 6 independently of one another are a C 1 - to C 20 -alkyl group, -cycloalkyl group or -alkylaryl group or -aryl group or for a hydroxyalkyl group or for an acetoxyethyl- (CH 3 -CO-O-CH 2 -CH 2 -) or a hydroxyl group isopropyl (HO-CH (CH 3 ) -CH 2 -) or an acetoxyisopropyl group (CH 3 -CO-O-CH (CH 3 ) -CH 2 -); or R 5 and R 6 together form a ring of which the nitrogen is a part to form a morpholine or imidazoline ring.
• the substituent R 7 is a C 2 -C 4 -alkylene group.
• substituents R 8 and R 9 each independently represent a C 1 - to C 20 -alkyl group, -cycloalkyl group, -alkylaryl group, -aryl group or a hydroxyalkyl group.
• the sequence of the substructure elements designated as s1, s2, s3 and s4 in formula (I) can here be arranged alternately, blockwise or randomly.
• indices a, b, c and d represent molar ratios of the structural units s1, s2, s3 and s4. These structural elements are in a ratio of
• the sum c + d is preferably greater than 0.
• the preparation of the comb polymer KP of the formula (I) can on the one hand by free radical polymerization of the corresponding monomers of the formula (III a ), (III b ), (III c ) or (IIId), which then leads to the structural elements of structural units s1 and s4
• the polycarboxylic acid of the formula (IV) is esterified or amidated with the corresponding alcohols, amines and then at most neutralized or partially neutralized (depending on the nature of the radical M, for example with metal hydroxides or ammonia). Details of the polymer-analogous reaction are disclosed, for example, in US 2002/0002218 A1 on page 5 in section [0077] to and with [0083], as well as in its examples or in US Pat. No. 6,387,176 B1 on page 5, line 18 to line 58 and in US Pat its the examples.
• Embodiment of the comb polymers KP of the formula (I) are those in which c + d> 0, in particular d> 0, are.
• the radical R 3 in particular -NH-CH 2 -CH 2 -OH has proved to be particularly advantageous.
• Comb polymers KP as sold commercially by Sika Nurse AG under the trade name series ViscoCrete®, have proved to be particularly advantageous.
• the proportion by weight is typically 0.2-40% by weight, preferably 5-35, particularly preferably 15-35% by weight, based on the weight of the additive composition Z.
• Suitable glycols are glycols which are selected from the list consisting of ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, reaction products of ethylene oxide and propylene oxide,
• Reaction products of polypropylene glycol with compounds with active basic hydrogen (polyalcohols, polycarboxylic acids, polyamines, or Polyphenols), neopentyl glycol, pentanediol, butanediol and unsaturated diols, and mixtures thereof and derivatives thereof.
• glycols are mono-, di- and polyglycols of ethylene and propylene, and mixtures thereof, because they are inexpensive and readily soluble in water.
• diglycols especially diethylene glycol.
• the weight fraction is typically 0.2-99.8% by weight, preferably 5-50% by weight, particularly preferably 15-30% by weight, based on the weight of the additive composition Z.
• the proportion by weight is typically 0.2 to 15% by weight, preferably 1 to 5% by weight, particularly preferably 2 to 4% by weight, based on the weight of the additive composition Z.
• organic amines having a molecular weight M w less than 500 g / mol, such as alkanolamines, especially
• Trialkanolamine such as triisopropanolamine (TIPA) or triethanolamine (TEA) or ammonium salts of organic amines. These have the disadvantage that they accelerate the stiffening beginning after a certain amount, or the time difference between solidification end and
• the additive composition Z is substantially free of mentioned organic amines having a molecular weight M w of less than 500 g / mol, respectively their ammonium salts.
• the term "essentially free" in the present document means that the proportion of organic amines having a molecular weight M w of less than 500 g / mol, or their ammonium salts, 0-2% by weight, preferably 0-1.0% by weight, %, based on the weight of the additive composition Z.
• the proportion of said organic amines is so low that no accelerating effect and / or brown discoloration of the set hydraulic binders are detectable, particularly preferably the additive composition Z is free from mentioned organic amines.
• the additive composition Z comprises at least one retarder.
• the term "retarder” is understood to mean additives which, in the case of aqueous mineral binders containing this additive, postpone the start of solidification or increase the time difference between solidification start and solidification start, compared to aqueous mineral binders without addition of this admixture.
• Suitable retarders are, for example, cellulose ethers, casein and
• Dextrin or inorganic compounds such as zinc and lead and especially complexing agents for calcium and those which form sparingly soluble compounds with calcium, for example phosphates, phosphonates, silicone fluorides, and boric acid, tartaric acid, gluconic acid, heptonic acid, citric acid, gallic acid, malic acid and the salts of mentioned acids, sucrose, glucose, and fructose.
• complexing agents for calcium for example phosphates, phosphonates, silicone fluorides, and boric acid, tartaric acid, gluconic acid, heptonic acid, citric acid, gallic acid, malic acid and the salts of mentioned acids, sucrose, glucose, and fructose.
• the at least one retarder is selected from the group consisting of cellulose ether, casein, dextrin, zinc, lead,
• Phosphates, phosphonates, silicone fluorides boric acid, oxalic acid, lactic acid, succinic acid, adipic acid, tartaric acid, gluconic acid, heptonic acid,
• Citric acid gallic acid, malic acid, sucrose, glucose and fructose, respectively, the salts of the acids mentioned.
• Particularly preferred is the at least one retarder selected from the group consisting of boric acid, gluconic acid,
• Sucrose, glucose and fructose respectively the salts of said acids.
• the proportion by weight is preferably 0.2-10% by weight, in the case of sucrose, glucose, fructose or gluconate preferably 5-30% by weight, based on the weight of the additive composition Z.
• the mineral binders are hydraulic binders and / or latently hydraulic binders and / or pozzolanic binders.
• the term hydraulic binders are used in the
• binders that bind or harden under water, such as hydraulic lime or cement.
• latent hydraulic binders is understood to mean binders which only set or harden by the action of additives (exciters), such as, for example, granulated blastfurnace slag.
• pozzolanic binders in the present document means binders which do not self-set but after moisture storage by binding calcium hydroxide provide strength-forming reaction products such as fly ash, silica fume, and natural pozzolans, such as. B. Trass.
• the hydraulic binder is to
• the additive composition Z can be used as free-flowing
• Composition for example as a powder, or as a liquid composition, for example as an aqueous composition.
• the additive composition Z may contain other ingredients.
• solvents or additives as are familiar in concrete technology, in particular surface-active substances, Stabilizers against heat and light, dyes, defoamers,
• a possible preferred additive composition Z comprises:
• Alkylene glycol in particular diethylene glycol, 15-30 wt.
• Acetic acid 1-5% by weight, based on the additive composition Z;
• the additive composition Z further comprises;
• Preservative 0.1-0.4% by weight, based on additive composition Z;
• the present invention relates to
• the proportion of additive composition Z is 0.005-0.5% by weight, preferably 0.01-0.2% by weight, particularly preferably between 0.025-0.1% by weight, based on the material to be milled
• Additive composition Z in particular the at least one
• Mahlosmittel or at least one retarder, separated in time be added before and / or during the grinding of cement clinker.
• cement clinker is understood to mean the bodies, which are typically approximately nut-sized, which on heating the lime-clay mixtures arise at 1250-1500 ° C. and yield cement during grinding.
• the milling process usually takes place in a cement mill. However, in principle, other mills, such as are known in the cement industry, can be used. Depending on the grinding time, the cement has different fineness.
• the fineness of cement is typically given by Blaine in cm 2 / g. On the other hand, the fineness is also the
• particle size distribution of practical relevance are usually determined by laser granulometry or air jet sieves.
• the cement ground in this way finds like every other ground
• admixture composition Z is added to the cement before and / or during the milling of the cement clinker, after its
• additive composition Z has no negative influence on the efficiency of the milling process.
• additive composition Z did not impair the effect of grinding aids in the milling process.
• the present invention relates to
• an additive composition Z for retarding the setting of an aqueous mineral binder, wherein the aqueous mineral binder comprising admixture composition Z comprises ground cement clinker, upon cementing to cement, the admixture composition Z was present.
• the mineral binders are mineral binders, as previously described.
• the additives were added briefly from the grinding according to the amounts in Table 2, and Table 6, the cement clinker to be ground.
• Table 1 amount in wt .-% refers to the
• the cement clinker used was 60% C3S, 20% C2S, 10% C3A and 10% C4AF.
• Milling time 0 oo The time was determined until the mixture after milling in the ball mill had a Blaine fineness according to DIN EN 196-6 of 4000 cm 2 / g.
• Fineness The fineness was determined according to Blaine by Blaine Automat of Wasag Chemie.
• Table 2 * Amount in wt .-% refers to the weight of the clinker to be ground.
• the cement used was the cement obtained in the grinding trials above. He had a fineness Blaine (EN 196-6) of about 4000 cm 2 / g
• the mortar was produced according to EN 196-1 and introduced into the molds and compacted. Of the mortar mixtures obtained, the Compressive strength measured (see Table 3). The test for determining the compressive strength (in N / mm 2 ) on prisms (40 x 40 x 160 mm) after 1 day and 2 days was carried out according to EN 196-1.
• Table 3 Compressive strengths in N / mm after 1 day and 2 days (d).
• the slump size according to EN 196-3 was measured after 5 minutes, 30 minutes and 60 minutes.
• Comparative Example C4 which comprises TlPA and TEA, organic amines having a molecular weight M w of less than 500 g / mol, as a grinding aid, despite this
• V2, V3 and Z4 were in a cement plant with a
• Ball mill with classifier used for the grinding of clinker made from the obtained cements concrete mixtures and of which
• Slump size according to EN 12350-5 measured after 3 minutes, 8 minutes, 15 minutes, 30 minutes, 45 minutes and 60 minutes.
• Table 5 Slump in mm after 3 min, 8 min, 15 min, 30 min, 45 l 60 min.
• inventive additive composition the delay of the stiffening longer than when using organic amines as grinding aids (V2) or organic amines as grinding aids in
• a mortar mixture was prepared according to the table below:
• the cement was made in a drum mill of the company Siebtechnik, according to the previously described method, with the addition of the additives given in Table 6, from cement clinker (60% C3S, 20% C2S, 10% C3A, 10% C4AF) to a Blaine fineness (EN 196-6) of about 4000 cm 2 / g milled.
• the mortar was produced according to EN 196-1, provided with a foaming agent, so that a polybag filled PE ziplock bag and formed into approximately 0.5 cm thick plates. This was sealed and stored for 7 days at 20 ° C / 65% relative humidity.
• the addition of a foaming agent causes a readily processable mortar, which despite a high w / c value does not tend to give off water.
• Foaming agent ensures that in the mortar a comparable porosity is present.
• the polybag PE zipper bag was provided at 2 places with a 10 mm long incision.
• the existing water in the mortar can evaporate through these incisions and lead there to an efflorescence.
• the color of the efflorescence varies from "white” to "yellow” to a strong "brown”.
• the specimens were stored for 28 days at 20 ° C / 65% relative humidity. Thereafter, the efflorescence was quantitatively assessed on the sample bodies by means of a color measurement. The results are shown in Table 6.
• the sample body have a significantly lower brown discoloration than when using grinding aids, which have organic amines having a molecular weight M w less than 500 g / mol.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
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• Polymers & Plastics (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)
• Inorganic Chemistry (AREA)
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• 2009
  • 2009-12-08 EP EP09178250A patent/EP2336100A1/de not_active Withdrawn
• 2010
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