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    • 专利摘要:
    POLYCONDENSATION PRODUCT, PROCESS AND USE OF THE SAME. A polycondensation product is proposed, comprising as monomer components, at least one polyoxyalkylene aryl ether, at least one vicinally disubstituted aromatic compound, at least one aldehyde and also optionally additional aromatic compounds; processes for the same preparation, and also, respective use as a dispersant for aqueous suspensions of inorganic binders and as a grinding assistant for inorganic binders.
    公开号:BR112014021187B1
    申请号:R112014021187-6
    申请日:2013-04-03
    公开日:2020-12-08
    发明作者:Frank Dierschke；Torben Gädt；Uwe Gehrig；Michael Melchart；Mario Vierle；Peter Schwesig；Klaus Hartl；Madalina Andreea Stefan；Tatiana Mitkina；Maxim Pulkin
    申请人:Construction Research & Technology Gmbh；
    IPC主号:
    专利说明:

    [0001] Polycondensation product based on aromatic compounds, process for the respective preparation and use.
    [0002] The present invention relates to a polycondensation product comprising as monomer components at least one polyoxyalkylene aryl ether, at least one aromatically distributed compound, at least one aldehyde and optionally also additional aromatic compounds; for processes for their preparation and also for their use as dispersants for aqueous suspensions of inorganic binders and as grinding assistants for inorganic binders.
    [0003] Portland cement had the first reference made in British Patent BP 5022, since whose time has undergone additional continuous development. Nowadays it is considered one of the most widespread inorganic binders. Portland cement hardens hydraulically due to its high CaO content.
    [0004] Certain wastes from metallurgical processes can be used in the form of latent hydraulic binders as mixtures with Portland cement. Activation with strong alkalis, such as alkali metal hydroxides or liquid glasses, for example, is also possible.
    [0005] Inorganic binder systems based on reactive compounds, insoluble in water based on SiO2 20 together with Al2O3, which cure in aqueous-alkaline medium, likewise, are common knowledge. Cured binder systems of this type are also called "geopolymers" and are described, for example, in U.S.4.349.386, WO 85/03699 and U.S.4.472.199.
    [0006] Reactive oxide mixtures used in this context include metakaolin, microsilica, residues, fly ash, activated clay, pozzolans or their mixtures. The alkaline medium for activating the binders typically consists of aqueous solutions of alkali metal carbonates, alkali metal fluorides, alkali metal hydroxides, alkali metal aluminates and / or alkali metal silicates, such as soluble liquid glass. Compared to Portland cement, geopolymers can be more profitable and more stable and can have a more favorable balance of CO2 emissions.
    [0007] Aqueous cement suspensions are often mixed with mixtures in the form of dispersants in order to improve their processing properties, such as, malleability, fluidity, sprayability, spreadability or pumping capacity. These additives are able to interrupt agglomerates, by adsorption to the surface of the particles and to disperse the formed particles. Especially in the case of highly concentrated dispersions, this results in a significant improvement in the processing of properties.
    [0008] In the production of cement mixtures of construction material such as concrete, this effect can be used for a particularly advantageous effect, provided that otherwise, in order to achieve a processable consistency, substantially more water would be needed than would be necessary for the subsequent hydration process. As a result of this excess water, which evaporates gradually after hardening, cavities remain, which significantly decrease the mechanical strength and robustness of the constructions. Said plasticizers or dispersants are used to reduce the water fraction, which is excessive in the sense of hydration and / or to optimize the processing properties for a given water / cement ratio.
    [0009] Examples of cement dispersants or plasticizers used mainly today are salts of naphthalenesulfonic acid / formaldehyde condensates (cf. EP 214412 A1; hereinafter identified as naphthalenesulfonates), condensate salts of formaldehyde / melamine sulphonic acid (cf. DE 1671017 A; identified below as melaminesulfonates) and also salts of polycarboxylic acids (cf. US 5,707,445 BI, EP 1110981A2, EP 1142847 A2; identified below as polycarboxylates). Such polycarboxylates are prepared primarily by radical copolymerization of ethylenically unsaturated carboxylic acids (such as acrylic acid, methacrylic acid or maleic acid and / or their salts) and poly (alkylene oxides) having a group of polymerizable ends (such as methacrylates, allyl ethers or vinyl ethers). This method of preparation leads to polymers having a comb-like structure.
    [0010] The activity of the molecules used derives from two different effects. Firstly, the acid groups negatively charged from the adsorption of the plasticizers on the cement granulation surface, which is positively charged through calcium ions. The double electrostatic layer formed in this way results in electrostatic repulsion between the particles, which is relatively weak, however. In the case of the comb-shaped polymers referred to above, this electrostatic repulsion is further reinforced by the stenosis volume of the non-adsorbent poly (alkylene oxide) chains. This steric repulsion is much stronger than electrostatic repulsion, and thus it is easy to explain why the plasticizing effect of polycarboxylates is much greater than that of naphthalene - or sulphonates-melamine; in other words, in order to obtain comparable plasticization, polycarboxylate can be added at a significantly lower rate.
    [0011] WO 2006/042709 A1 describes a polycondensation product, consisting of A) an aromatic or heteroaromatic compound with 5 to 10 atoms and / or heteroatoms, this compound, having an average of 1 to 300 oxyethylene and / or oxypropylene groups per molecule, which are linked via an O or N atom to the aromatic or heteroaromatic compound; and also optionally B) an aromatic compound selected from the group of phenols, phenol ethers, naphthols, naphthol ethers, anilines, furfuryl alcohols and / or an old amino resin selected from the group of melamine (derivatives), urea (derivatives) and carboxamides; and C) an aldehyde selected from the group of formaldehyde, glyoxylic acid and benzaldehyde or their mixtures, making it possible for benzaldehyde to additionally contain acid groups in the form of COOMa, SO3Ma and PO3Ma and for M to be H, alkali metal or metal alkaline earth, ammonium or organic amine radicals and also because it is%, 1 or 2. This polycondensation product has been found to produce very good plasticization in hydraulic binders, such as cement. Compared to naphthalenesulfonates or melaminesulfonates, substantially better plasticization of the construction material results in a lower addition rate and fluidity can be maintained over a long period of time. In WO 2006/042709 A1, however, in contrast to the present invention, there is no description as component B) of any bisubstituted aromatic compound.
    [0012] An additional example of a polycondensation product is described in EP 0780348 A1, as a dispersant for cement. In that patent, components including alkoxylated phenol and hydroxybenzoic acids are subject to polycondensation in the presence of formaldehyde.
    [0013] The aforementioned geopolymers present distinct differences in relation to cement systems, these differences, making it more difficult or impossible to use the declared plasticizers. In order to obtain acceptable hardening times, reactive oxide components require strong alkaline activation. This higher level of alkalinity imposes particular rules on dispersants, these requirements, in the case of many concrete commercial plasticizers, are not sufficiently guaranteed. In addition, these low-calcium systems generally do not have any positively charged granulation surfaces. Instead, the surfaces are silicatic or SiO2 surfaces. In addition, the high level of alkalinity that is required for activation also constitutes a high salt load, which can cancel out a dispersion effect that is possible at lower pH levels (compared to cement).
    [0014] The problem addressed by the inventors was that of substantially avoiding at least some of the disadvantages of the prior art discussed above. The intention was more particularly to find dispersants that are capable of absorbing low-calcium binders at relatively high pH levels and, consequently, also of plasticizing geopolymer systems. These dispersants must exhibit a high affinity for silica surfaces, preferably even at very high pH levels. They should ideally also be suitable for the dispersion of mixed systems, comprising not only Portland cement, but also geopolymer raw materials, such as microsilica, residues, fly ash, clays, pozzolans or mixtures thereof (known as "supplementary cementitious materials" or "SCM '); in other words, they must also be suitable for composite cements in the CEM II-V and also CEM X categories (currently non-standard composite cements with a high level of SCM additions).
    [0015] The problems identified above are solved with the characteristics of the independent claims. The dependent claims refer to preferential modalities.
    [0016] It has been found that the polycondensation products of the invention, which comprise in the polymer chain at least one component of a vicinally disubstituted aromatic monomer, such as pyrocatechol, salicylic acid or dihydroxybenzoic acid, are capable, even at relatively high pH levels. , to disperse inorganic low-calcium binders, more particularly, geopolymers. The polyoxyalkylene groups connected by ether bonds, moreover, are substantially more stable to hydrolysis than the polyoxyalkylene groups, joined through ester bonds, of the known state of the art of polycarboxylate ethers. The polycondensation products of the invention are also suitable as demoating aids for inorganic binders.
    [0017] The present invention accordingly provides a polycondensation product comprising as monomer components: A) at least one polyoxyalkylene aryl ether of formula (I)
    where Ar is an aryl group, R1 and R2 each, independently of each other, are selected from H, methyl and ethyl, preferably at least one of the groups R1 and R2 being H, m is an integer from 1 to 300 eR3 is selected from the group consisting of H, alkyl, aryl, aralkyl, alkaryl, phosphate, and also their mixtures; B) at least one aromatic compound of the formula (II),
    where R4 and R5 each independently of each other are selected from H, R8, OH, OR8, C (O) R8, COOH, COOR8, SO3H, SO3R8 and NO2 and also alkali metal salts, alkaline earth metal salts and salts of these or together are an additional fused ring, where R8 each independently is selected from the group consisting of alkyl, aryl, aralkyl, alkaryl and R6 and R7 each independently of each other are selected from OH, OR9, C (O) R9, COOH and COOR9 and also alkali metal salts and alkaline earth metal salts and respective deamonium salts, where Ra each independent is selected from the group consisting of alkyl, aryl, aralkyl, alkaryl; C) at least one aldehyde; and also, optionally, D) at least one additional aromatic compound, selected from the group consisting of phenol, 2-phenoxyethanol, 2-phenoxyethyl phosphonate and phosphonate, 2-phenoxyacetic acid, 2- (2-phenoxyethoxy) ethanol, phosphate and phosphonate 2- [4- (2-hydroxyethoxy) phenoxy] ethyl de2- (2-phenoxyethoxy) ethyl, phosphate and 2- [4- (2-phosphonatooxyethoxy) phenoxy] ethyl, methoxyphenol, acid-phenenesulfonic acid, furfuryl alcohol and also their mixtures.
    [0018] Where at least one of the substituents in the general formula (II) is a COOH group, it is preferred for each of the groups R6 and R7 to be OH groups.
    The "Ar" aryl group is a homo- or heteroaryl group, preferably a homoaryl group, having 6 to 10 carbon atoms in the ring system, more particularly a phenyl group or a naphthyl group. The Ar group, in addition, can be replaced by one or more additional groups, which are selected from C1-10 alkyl, C1-10 alkoxy, C6-10 aryl, C7-11 aralkyl, C7-11 alkaryl, preferably methoxy.
    [0020] The number "m" is preferably an integer from 3 to 280, more preferably from 10 to 160 and more particularly from 12 to 120.
    [0021] "R3" is preferably selected from the group consisting of H C1-10 alkyl, C6-10 aryl, C7-11 aralkyl, C7.11 alkaryl and phosphate, with R3 being, more particularly, H.
    [0022] The polyoxyalkylene aryl ether oxyalkylene groups of formula (I) are preferably selected from ethylene oxide and / or propylene oxide groups which are arranged randomly, alternately, gradually and / or by blocks along the chain. polyoxyalkylene.
    [0023] With particular preference the polyoxyalkylene aryl ether of formula (I) is a monophenyl polyethylene glycol ether of formula (III),
    where m is the specified definition.
    [0024] This monophenyl polyethylene glycol ether of the formula (Ill) may also include a mixture having different values for m within the definition specified above.
    [0025] The above-mentioned groups "R8" and "R9" are preferably each independently selected from C1-10 alkyl, C6-10 aryl, C7-11 aralkyl and C7-11 alkaryl and more particularly are H.
    [0026] According to particularly preferred embodiments, the aromatic compounds of formula (II) are selected from the group consisting of benzene 1,2-dial, benzene-1, 2,3-triol, 2-hydroxy-benzoic acid, 2,3- and 3,4-dihydrobenzoic acid, 3,4,5-trihydroxybenzoic acid, phthalic acid, 3-hydroxyphthalic acid, 2,3- and 3,4-dihydroxybenzenesulfonic acid, 1,2- and 2,3-dihydroxy - naphthalene, 5- or 6-sulfonic acid of 1,2- and 2,3-dihydroxinaphthalene and also their mixtures.
    [0027] More particularly preferred in this context are benzene-1,2-diol, benzene-1, 2,3-triol, 2,3- and 3,4-dihodroxyphthalic acid, 2,3- and 3,4- acid dihydroxybenzenesulfonic, 1,2- and 2,3-dihydroxy naphthalene, 5- or 6-sulfonic acid of 1,2- and 2,3-dihydroxinaphthalene and also mixtures thereof, while, for example, 2-hydroxybenzoic acid is less preferred.
    [0028] Here too, as has already been said in general in relation to component B, alkali metal salts, alkaline earth metal salts 40 and ammonium salts of the corresponding acids are possible. For the purposes of the present invention, "ammonium salts" is intended to refer to both NH4 * salts and salts of amines or nitrogen-containing polymers, such as, for example, polyethyleneimine salts. In addition, as far as the completed polycondensation product is concerned, it is irrelevant whether said aromatic compounds are used directly as salts or whether these salts are only obtained following an acidic neutralization by neutralization. At very high pH levels, of the type found in the geopolymer sector, amines and / or polymers containing nitrogen can also be present in free form.
    [0029] The aldehyde component C) is preferably selected from the group consisting of formaldehyde, 10 paraformaldehyde, glyoxylic acid, benzaldehyde, benzaldehyde sulfonic acid, benzaldehydodisulfonic acid, vanillin and Isovaniline and also their mixtures. Formaldehyde as such or in the form of paraformaldehyde is particularly preferred in this context.
    [0030] Monomer components A, B, C and D (minus the water formed in the polycondensation reaction are present in particular molar proportions of the polycondensation product of the invention. Thus, the molar ratio of component C: (A + B) preferably it is 1: 3 to 3: 1, more preferably 1: 2 to 2: 1 and more particularly 1: 0.9 to 1: 1.
    [0031] The molar ratio of components A: B is preferably 1:10 to 10: 1, more preferably 1; 7 to 5: 1 and more particularly 1: 5 to 3: 1. Thus, the molar ratio of components D: (A + B) is preferably O to 3: 1, more preferably, O to 2: 1 and more particularly O to 1: 1, with component D representing an optional component.
    [0032] The polycondensation product of the invention is preferably in the form of a comb-shaped polymer with novolak structure, in other words, in the case of formaldehyde as the aldehyde component, the aromatic monomer components are joined together another by means of -CH2- groups, since then, as noted later, below, the polycondensation reaction is advantageously carried out in the acid range. This produces molecular weights for the polycondensation products which are preferably in the range of 1000 to 100,000, more preferably, in the range of 2000 to 75,000 and more particularly in the range of 4000 to 50,000 g / mol.
    [0033] The present invention additionally provides a process for preparing the polycondensation product of the invention, said process being characterized in that components A), B), C) and, optionally, D) are subjected to polycondensation in aqueous solution at a temperature from 20 to 140 ° C under a pressure of 1 to 10 bar.
    [0034] If an acid that is not strong enough is used as a monomer component, B, C or D, it is advisable to use an acid catalyst. As an acid catalyst, it is possible to use an acid selected from the group consisting of sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, phosphoric and oxalic acid and also mixtures thereof;
    [0035] Following the reaction, according to the invention, the reaction mixture can be subjected to a post-treatment at a pH of 8.0 to 13.0, a temperature of 60 to 120 ° C and, preferably , a pressure from 0.01 to 0.9 bar, more particularly in order to reduce the amount of unreacted free aldehyde component.
    [0036] Said pH can be adjusted by adding an aqueous alkali, such as NaOH, or a polyethyleneimine, and the salts formed during neutralization are advantageously removed.
    [0037] The present invention further provides for the use of the polycondensation products of the invention as dispersants for aqueous suspensions of inorganic binders selected from the group comprising hydraulic binders, latent hydraulic binders, pozzolanic binders, alkaline activated aluminum silicate binders and also their mixtures.
    [0038] In this context, said ligands are advantageously selected from the following groups:
    [0039] hydraulic cement binders, more particularly from Portland cement and aluminate cement and also mixtures thereof,
    [0040] latent hydraulic binders for industrial and / or synthetic waste, more particularly from blast furnace waste, sand residue, ground residual sand, waste from electrothermal matches, stainless acid waste and mixtures thereof, and the binders amorphous silica pozzolanics, preferably precipitated silica, pyrogenic silica and microsilica, finely ground glass, fly ash, preferably lignite fly ash and coal ash, metakaolin, natural pozzolans such as tuff, trass and volcanic ash, natural zeolites and synthetics and also their mixtures.
    [0041] Portland Cement contains about 70% by weight of CaO + MgO, about 20% by weight of SiO2 and about 10% by weight of Al2O3 + Fe2O3. Aluminate cement ("high alumina cement") contains about 25% to 40% by weight of CaO, up to about 5% by weight of SiO2, about 40% to 80% by weight of Al2O3 and up to about 20 % by weight of Fe2O3. These cements are well known in the art.
    [0042] The residues can be both industrial residues, that is, residues from industrial processes and residues reproduced synthetically. The latter is advantageous, since industrial residues are not always available in consistent quality and quantity.
    [0043] For the purposes of the present invention, a hydraulic latent binder is preferably a binder in which the molar ratio of (CaO + MgO): SlO2 is between 0.8 and 2.5 and, more preferably, between 1.0 and 2.0.
    [0044] Blast furnace wastes, a typical hydraulic latent binder generally contains 30% to 45% by weight of CaO, about 4% to 17% by weight of MgO, about 30% to 45% by weight of SiO2 and about from 5% to 15% by weight, Al2O3, usually about 40% by weight of CaO, about 10% by weight of MgO, about 35% by weight of SiO2 and about 12% by weight of Al2O3. Cured products generally have the properties of hydraulically cured systems.
    [0045] Blast furnace wastes are waste products from the blast furnace process. Residual sand is granulated blast furnace waste and ground residual sand (“blast and granulated blast furnace waste”) is finely pulverized residual sand. Residual ground sand varies according to the origin and form of processing, in its particle size and granular size distribution, with particle size affecting reactivity. As a variable characteristic for the particle size, the figure known as the Blaine value is employed, which is typically in the order of magnitude from 200 to 1000, preferably between 300 and 500 m2 kg-1. The more refined the grind, the greater the reactivity.
    [0046] Electrothermal phosphorous waste is waste from the production of phosphorus by electrothermal means. It is less reactive than blast furnace waste and contains about 45% to 50% by weight of CaO, about 0.5% to 3% by weight of MgO, about 38% to 43% by weight of SiO2, about 2% to 5% by weight of Al2O3 about 0.2% to 3% by weight of Fe2O3 and also fluoride and phosphate. Stainless steel wastes are wastes from various steelmaking processes, with a highly varied composition (see Caijun Shi, Pavel V. Krivenko, Della Roy, Activated and Concrete Alkaline Cements, Taylor & Francis, London & New York, 2006, pp. 42-51).
    [0047] Amorphous silica is preferably an x-ray amorphous silica, that is, a silica which does not exhibit crystallinity in a powder diffraction procedure. The amorphous silica of the invention advantageously has a SiO2 content of at least 80% by weight, preferably at least 30% by weight. Precipitated silica is obtained industrially through precipitation processes from liquid glass. Depending on the manufacturing method, precipitated silica is also called silica gel. Pyrogenic silica is generated by reaction chlorosilanes, such as silicon tetrachloride, in an oxhydrogen flame. Pyrogenic silica is an amorphous SiO2 powder with a particle diameter of 5 to 50 nm and a specific surface area of 50 to 600 m2 g-1.
    [0048] Microsilica, also called silica powder, is a by-product of the manufacture of silicon or ferro-silicon and, in the same way, consists largely of amorphous SiO2 powder. The particles have diameters in the order of magnitude of 0.1 pm. The specific surface area is in the order of magnitude from 15 to 30 m2 g-1. In contrast, commercial silica sand is crystalline and has relatively large particles and a relatively low specific surface area. According to the invention, this can be used as an inert aggregate.
    [0049] Fly ash is formed in operations, including the combustion of coal in power plants. Class C fly ash (lignite fly ash) contains, according to WO 08/012438 about 10% by weight of CaO, whereas Class F fly ash (coal ash) contains less than 8% by weight , preferably less than 4% by weight and typically about 2% by weight CaO.
    [0050] Metacaolin is formed in the dehydrogenation of kaolin. Considering that kaolin releases physically bound water from 100 to 200 ° C, dehydroxylation occurs from 500 to 800 ° C, with the collapse of the lattice structure and formation of metakaolin (AI2Si2O7). Pure metakaolin therefore contains about 54% by weight of SiO2 and about 46% by weight of AI2O3.
    [0051] An overview of suitable additional pozzolanic binders, according to the invention, is found for example in Caijun Shi, Pavel V. Krivenko, Della Roy, alkaline and concrete activated cements, Taylor & Francis, London & New York, 2006 , pp. 51-63. Tests for the pozzolana activity can take place according to DIN EN 196 part 5.
    [0052] According to one embodiment, therefore, the polycondensation product of the invention is suitable as a dispersant for alkaline-activated fraluminosilicate binders (geopolymers). According to another modality, it is suitable for mixed dispersing systems which comprise not only Portland cement but also geopolymer raw materials, such as microsilica, residues, fly ash, clays, pozzolans or their mixtures (known as SCMs), that is , for cements composed of CEM categories it-V and also CEM X. (Use as a dispersant for pure Portland cement or aluminate cement (CEM category I) is also possible, although not particularly interesting from an economic point of view.)
    [0053] For the purposes of the present invention, "alkali-activated alumosilicate binders" are binder systems which comprise latent hydraulic and / or pozzolanic binders as defined above and also. Alkaline activators, such as aqueous solutions of alkali metal carbonates, alkali metal fluorides, alkali metal hydroxides, alkali metal aluminates, alkali metal silicates (such as soluble liquid glass) and / or mixtures thereof. Conversely, "alkali-activated alumo-silicate binders" means binder systems of the same type, which, although activable by alkali, have not yet been activated. In both cases, the amount of Portland cement and / or total aluminate cement should be kept below 20% by weight, preferably below 10% by weight, in order to discard hydraulic curing of the cement component. In addition, for the purposes of the present invention, the dry alkaline activator or the solid contents of the aqueous alkaline activator is to be considered part of the inorganic binder. In addition, mixtures of dry alkaline activators and aqueous alkaline activators can also be used to advantage.
    [0054] Said alkali metal silicate is advantageously selected from compounds having the empirical formula m SiO2 • n M2O, where M represents Li, Na, K and NH4 and also their mixtures, preferably for Na and K. The molar ratio m : n is advantageously 0.5 to 4.0, preferably 0.6 to 3.0 and more particularly 0.7 to 2.5. The alkali metal silicate is preferably liquid glass, more preferably liquid liquid glass and, more particularly, liquid sodium or potassium glass. However, lithium or liquid ammonium glasses can also be used, as well as mixtures of the indicated liquid glasses.
    [0055] The ratio specified above m: n (also called "module") should preferably not be exceeded, as otherwise it is no longer likely that there will be any complete reaction of the components. It is also possible to employ lower modules, such as about 0.2. Liquid glasses having larger modules must, before use, be adjusted for modules in the range according to the invention, using an appropriate aqueous alkali metal hydroxide.
    [0056] Liquid potassium glasses in the advantageous module range are mainly marketed as aqueous solutions, being highly hygroscopic; liquid sodium glasses in the advantageous module range are also commercially available as solids. The solids content of liquid glass solutions are generally 20% by weight to 60% by weight, preferably 30% to 50% by weight.
    [0057] Liquid glasses can be prepared industrially by melting silica sand with the corresponding alkali metal carbonates. Alternatively, they can also be obtained without difficulty from mixtures of reactive silicas with the corresponding aqueous alkali metal hydroxides. According to the invention, therefore, it is possible to replace at least part of the alkali metal silicate with a mixture of a reactive silica and the corresponding alkali metal hydroxide.
    [0058] The inventive polycondensation product can be used as a constituent of building material formulations and / or building material products such as on-site concrete, precast concrete parts, manufactured concrete, cast concrete stones and also in situ concrete, air-poured concrete, ready mix concrete, construction adhesives and adhesives for composite thermal insulation systems, concrete repair systems, one-component and two-component sealing, pastes, mortars, fillers and fillers leveling, tile adhesives, plasters, adhesives and sealants, coating systems, especially for tunnels, wastewater channels, splash protection and condensate lines, dry, dry mortars, joint grouts, drainage mortars and / or Repair.
    [0059] In the case of cements in CEM-V and also CEM X categories, dispersants should advantageously be added in the range of 0.01% to 2.0%, preferably from 0.05% to 2.0% in weight, based on the sum of inorganic binders. (Not included in this account are, for example, fillers and aggregates, such as sand and gravel and, also, water and other possible additions).
    [0060] Where the polycondensation product of the invention is used as a dispersant for alkaline activated aluminosilicate binders (geopolymers), however, the levels of addition should be higher due to the sometimes low measurement efficiency. The level of dispersant addition here advantageously should be in the range of 0.01% to 10.0%, preferably from 0.02% to 5.0% and more particularly from 0.05% to 3.0% , by weight, based on the sum of inorganic binders.
    [0061] The present invention further provides for the use of the polycondensation products of the invention as grinding assistants for inorganic binders selected from the group comprising hydraulic binders, latent hydraulic binders, pozzolanic binders, as defined above, and / or aluminosilicate binders alkaline and also their mixtures.
    [0062] These grinding assistants facilitate the grinding of cement, such as Portland cement and aluminate cement, that is, of CEM category cements I, but also of cements composed of CEM categories 11-V and X of CEM, from latent hydraulic binders and pozzolanic binders and also alkaline-activating aluminosilicate binders, as defined above, comprise dry alkaline activators.
    [0063] The level at which the grinding assistants are added here should be in the range of 0.005% to 0.30%, preferably from 0.01 ° / 0 to 0.05% by weight, based on the sum of the binders inorganic.
    [0064] The milling assistants and dispersants of the invention can be used together additionally, with additions or auxiliaries, selected from the group comprising glycols, polyalcohols, amine alcohols, organic acids, amino acids, sugars, molasses, organic and inorganic salts , polycarboxylate ether, naphthalenesulfonate, melamine-formaldehyde polycondensation products, lignosulfonate and mixtures thereof. Additional additives contemplated include defoamers, retention agents, pigments, fibers, dispersion powders, wetting agents, retarders, accelerators, such as calcium silicate hydrate, complexing agents, aqueous dispersions and rheology modifiers.
    [0065] Particularly noteworthy in this context is that when the dispersants of the invention are used in combination with commercial polycarboxylate ethers, the hydration of the composite cement is significantly faster in the case of approximately the same measurement efficiency.
    [0066] The present invention is now elucidated with greater precision through the examples below and the drawings added. In the figures: Fig.1 shows a graphical representation of the particle size distributions of milled residual sand as a function of the milling assistant used during cold milling; Fig. 2 shows a graphical representation of the particle size distributions of milled residual sand as a function of the milling assistant used during heat milling; EXAMPLES EXAMPLE 1
    [0067] A heatable reactor, equipped with agitator and metering pump is charged under nitrogen at 90 ° C with 320 parts of poly (ethylene oxide) monophenyl ether (average molecular weight 2000 g / mol), 49 parts of acid 3 , 4-dihydroxybenzoic and 16 parts of paraformaldehyde. The reaction mixture is heated by stirring at 110 ° C until all dissolved solids and then 44 parts of methanesulfonic acid (70% strength - here and in all subsequent syntheses, in the form of an aqueous solution) are added over 20 minutes at such a rate that the reaction temperature does not exceed 115 ° C. After the measurement is complete, the reaction mixture is stirred at 110 ° C for an additional 3 hours. It is then left to cool, mixed with 350 parts of water, heated to 100 ° C for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution. Example 2
    [0068] A heatable reactor, equipped with agitator and metering pump is charged under nitrogen at 90 ° C with 320 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 2000 g / mol), 46 parts of vanillin ( > 99%, 4-hydroxy-3-methoxybenzaldehyde) and 14.9 pieces of paraformaldehyde. The reaction mixture is heated by stirring it at 110 ° C and then 51.4 parts of methanesulfonic acid (70%) are added over 20 minutes at a rate such that the reaction temperature does not exceed 115 ° C. After the end of the measurement, the reaction mixture is stirred at 110 ° C for an additional 2.5 hours. It is then left to cool, mixed with 350 parts of water, heated to 100 ° C for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution. Example 3
    [0069] A heatable reactor, equipped with agitator and metering pump is charged under nitrogen at 90 ° C with 400 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 5000 g / mol), 24.6 parts of 3,4-dihydroxybenzoic acid and 8 parts of paraformaldehyde. The reaction mixture is heated with stirring to 115 ° C, and then 38.4 parts of methanesulfonic acid (70%) are added over 10 minutes at a rate such that the reaction temperature does not exceed 115 ° C. After the end of the measurement, the reaction mixture is stirred at 110 ° C for an additional 3 hours. It is then left to cool, mixed with 400 parts of water, heated to 100 ° C for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution. Example 4
    [0070] A heatable reactor, equipped with agitator and metering pump is charged under nitrogen at 80 ° C with 260 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 2000 g / mol), 43 parts of pyrocatechol ( 1,2-dihydroxybenzene), 80 parts of water and 15.6 parts of paraformaldehyde. The reaction mixture is mixed in sequence with stirring 12.5 parts of methanesulfonic acid (50%) over 20 minutes at a rate such that the reaction temperature does not exceed 80 ° C. After the end of the measurement, the reaction mixture is stirred at 80 ° C for an additional 2 hours. It is then left to cool, mixed with 350 parts of water and neutralized to a pH of about TO using 50% strength aqueous sodium hydroxide solution. Example 5
    [0071] A heatable reactor, equipped with agitator and metering pump is charged under nitrogen at 90 ° C with 300 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 2000 g / mol), 46.2 parts of 3,4-benzoic acid, 33 parts of 2-phenoxyethyl phosphate and 19.9 parts of paraformaldehyde. The reaction mixture is heated by stirring at 110 ° C, and then 41 parts of methanesulfonic acid (70%) are added over 25 minutes, at a rate such that the reaction temperature does not exceed 115 ° C. After the end of the measurement, the reaction mixture is stirred at 110 ° C for an additional 2.5 hours. Then it is allowed to cool, mixed with 350 parts of water, heated to 100 ° C for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.
    [0072] Said 2-phenoxyethyl phosphate is synthesized in general by charging a heatable reactor, equipped with agitator and metering pump, under nitrogen at 20 ° C with 621.8 parts of 2-phenoxyethanol. Subsequently, with refrigeration, 449.7 parts of polyphosphoric acid are added for more than 100 minutes at such a rate that the temperature does not rise above 35 ° C. After the end of the measurement, the reaction mixture is stirred at about 70 ° C for an additional 15 minutes and is discharged before solidification. Example 6
    [0073] A heatable reactor, equipped with agitator and metering pump is charged under nitrogen at 90 ° C with 300 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 2000 glml), 45.7 parts of vanillin ( > 99%, 4-hydroxy-3-methoxybenzaldehyde), 32.7 parts of 2-phenoxyethyl phosphate and 19.9 parts of paraformaldehyde. The reaction mixture is heated with stirring to 110 ° C, and then 41.4 parts of methanesulfonic acid (70%) are added over 20 minutes at a rate such that the reaction temperature does not exceed 115 ° C. After the end of the measurement, the reaction mixture is stirred at 110 ° C for an additional 2.5 hours. Then, it is allowed to cool, mixed with 350 parts of water, heated to 100 ° C for 30 minutes and neutralized to a pH of about TO using 50% strength aqueous sodium hydroxide solution. Example 7
    [0074] A heatable reactor, equipped with a stirrer and metering pump is charged under nitrogen at 90 ° C with 300 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 2000 glml), 45.6 parts of isovaniline ( 3-hydroxy-4-methoxybenzaldehyde), 33 parts of 2-phenoxyethyl phosphate and 19.9 parts of paraformaldehyde. The reaction mixture is heated with stirring to 110 ° C, and then 41.4 parts of methanesulfonic acid (70%) are added over 20 minutes at a rate such that the reaction temperature does not exceed 115 ° C. After the end of the measurement, the reaction mixture is stirred at 110 ° C for an additional 2 hours. It is then left to cool, mixed with 350 parts of water, heated to 100 ° C for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution. Example 8
    [0075] A heated reactor, equipped with agitator and metering pump is charged under nitrogen at 80 ° C with 300 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 2000 g / mol), 72.1 parts of 2, 3-dihydroxybenzoic acid and 18.0 parts of paraformaldehyde. The reaction mixture is mixed in sequence with stirring 12.5 parts of methanesulfonic acid (50%) over 30 minutes at a rate such that the reaction temperature does not exceed 80 ° C. After the end of the measurement, the reaction mixture is stirred at 80 ° C for an additional 75 minutes. It is then left to cool, mixed with 350 parts of water and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution. Example 9
    [0076] A heatable reactor, equipped with agitator and metering pump is loaded with 320 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 750 g / mol) and 41.5 parts of 2-phenoxyethanol. Subsequently, with refrigeration, 66.0 parts of polyphosphoric acid are added over 30 minutes and the mixture is stirred at 90-95 ° C for 60 minutes. 92.5 parts of 3,4-dihydroxybenzoic acid and 39.8 parts of paraformaldehyde are added to this reaction mixture at 90 ° C, under a stream of nitrogen. The reaction mixture is heated to about 100 ° C with stirring, and then 51.6 parts of methanesulfonic acid (70%) are added over 25 minutes at a rate such that the reaction temperature does not exceed 105 ° C . After the end of the measurement, the reaction mixture is stirred at 100 ° C for an additional 15 minutes. It is then left to cool, mixed with 350 parts of water and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution. Example 10
    [0077] A heatable reactor, equipped with agitator and metering pump is loaded with 225 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 750 g / mol) and 82.9 parts of 2-phenoxyethanol. Subsequently, with refrigeration, 99.0 parts of polyphosphoric acid are added for 20 minutes and the mixture is stirred at 90-95 ° C for 40 minutes. Added to this reaction mixture at 90 ° C under a stream of nitrogen are 46.2 parts of 3,4-dihydroxybenzoic acid and 39.8 parts of paraformaldehyde. The reaction mixture is heated to about 100 ° C, with stirring and then 57.6 parts of methanesulfonic acid (70%) are added over 25 minutes at a rate such that the reaction temperature does not exceed 105 ° C . After the end of the measurement, the reaction mixture is stirred at 100 ° C for an additional 15 minutes. Then left to cool, mixed with 350 parts of water and neutralized to a pH of about 7.0 using polyethylaneimine (LupasolK 35 G100, BASF SE). Example 11 Aluminosilicate mortars were produced according to the following formula: Microsilica 150 g Fly ash, type F 150 g Silica sand700 g KOH (0.2%) 250 g
    [0078] The raw materials were mixed in the laboratory with a mortar mixer, according to DIN EN 196-1. The mixing operation was carried out as described in DIN EN 196-1, with the difference that the silica sand was added at the beginning and not only later, for the mixture. The alkaline activator used was a force of 0.2% by weight of aqueous KOH solution. All polymeric dispersants had foam removed using anti-foam DF93 from BASF SE or triisobutyl phosphate.
    [0079] The dispersant was used as an aqueous solution, as obtained in the examples above. The level of addition in each case was 3 g (calculated as a solid). For comparison, the determinations were made of the drop without additive and in each case with 3 g of polycarboxylate ethers Melflux ® 2453 (comparative example 1), Glenium 51 (comparative example 2) and Melflux PCE 26L. (comparative example 3), all available from BASF SE.
    [0080] Compositions of ground residual sand and type F of fly ash as follows [% by weight]:

    [0081] The drop was determined in each case, typing 15 times on a drop table with a Hagermann cone (DIN EN 1015-3). The results are shown in table 1.Table 1
    Example 12
    [0082] Example 11 it was repeated with the modification that 5.0% strength by weight of the aqueous KOH solution was used as an activator. The results are shown in table 2. Formula: Microsilica 150g Fly ash, type F 150g Silica sand700g
    KOH (5.0%) 262.63g Table 2 Example 13
    [0083] Example 11 it was repeated with the modification that the residual ground sand was used in formulation 5, the results are shown in table 3. Formula: Residual ground sand300g Silica sand700g KOH (0.2%) 250gTable 3

    Example 14
    [0084] Example 13 was repeated with the modification that 5.0% strength by weight of the aqueous KOH solution was used as an activator. The results are shown in Table 4. Formula: Residual ground sand 300g Silica sand 700g KOH (5.0%) 189.09gTable 4
    Example 15
    [0085] Example 14 it was repeated with the modification that 3.3% strength by weight of the aqueous Na2CO3 solution was used as an activator. The drop [in cm] was determined after 6 minutes and 30 minutes. The results are shown in Table 5. Formula: Residual ground sand300g Silica sand700g Na2CO3 (3.3%) 181g Table 5
    Example 16
    [0086] Example 15 it was repeated with the modification that 3.3% of a strength by weight of the aqueous Na2SiO3 solution was used as an activator. The drop [in cm] was determined after 5 minutes and 20 30 minutes. The results are shown in table 6. Formula: Residual ground sand300g Silica sand700g Na2SiO3 (3.3%) 181g Table 6

    [0087] As it becomes evident from these performance tests, the polymers of the invention enable a distinct improvement in the consistency of the aluminosilicate mortars, in comparison with the sample without dispersants. In some cases, the flow of mortar mixtures, as a result of the addition of polymers of the invention, exceeds the dimensions of 30cm by hitting the plate. Plasticizing performance can be achieved here in different bonding compositions and with different activators such as KOH, Na2CO3 or liquid glass. In addition, it can be seen that, in contrast to polycarboxylate ethers, the plasticization of activated alkaline aluminosilicate binders is possible with the polymers of the invention. Example 17
    [0088] A heatable reactor, equipped with agitator and metering pump is charged under nitrogen at 90 ° C with 320 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 2000 g / mol), 44.2 parts of salicylic acid and 15.9 parts of paraformaldehyde. The reaction mixture is heated with stirring at 110 ° C until all solids are dissolved and then 66 parts of methanesulfonic acid (70%) are added over 15 minutes at a rate such that the reaction temperature does not exceed 110 ° C. After the end of the measurement, the reaction mixture is stirred at 110 ° C for an additional 4 hours. It is then left to cool, mixed with 350 parts of water, heated to 100 ° C for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution. Example 18
    [0089] A heatable reactor, equipped with agitator and metering pump is charged under nitrogen at 90 ° C with 320 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 2000 g / mol), 44.2 parts of salicylic acid, 35 parts of 2-phenoxyethyl phosphate and 21.2 parts of paraformaldehyde. The reaction mixture is heated with stirring to 110 ° C and then 44 parts of methanesulfonic acid (70%) are added over 15 minutes at a rate such that the reaction temperature does not exceed 115 ° C. After the end of the measurement, the reaction mixture is stirred at 110 ° C for an additional 2.75 hours. It is then left to cool, mixed with 350 parts of water, heated to 100 ° C for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution. Example 19
    [0090] The heated reactor equipped with agitator and metering pump is charged under nitrogen at 90 ° C with 225 parts of poly (ethylene oxide) monophenyl ether (average molecular weight 750 g / mol), 82.9 parts of acid salicylic, 65.4 parts of 2-phenoxyethyl phosphate, 25 parts of water and 39.8 parts of paraformaldehyde. The reaction mixture is heated by stirring it at 110 ° C and then 115.2 parts of methanesulfonic acid (50%) are added over 40 minutes at a rate such that the reaction temperature does not exceed 105 ° C. After the end of the measurement, the reaction mixture is stirred at 105 ° C for an additional 4 hours. It is then left to cool, mixed with 400 parts of water and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution. Example 20
    [0091] A heatable reactor, equipped with agitator and metering pump is charged under nitrogen at 90 ° C with 225 parts of poly (ethylene oxide) monophenyl ether (average molecular weight 750g / mol) 165.7 parts of salicylic acid and 48.4 parts of paraformaldehyde. The reaction mixture is heated with stirring to 95 ° C, and then 57.6 parts of methanesulfonic acid (50%) are added over 25 minutes at a rate such that the reaction temperature does not exceed 115 ° C. After the end of the measurement, the reaction mixture is stirred at 105 ° C for an additional 90 minutes. Then left to cool, mixed with 300 parts of water and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution. Example 21
    [0092] A heatable reactor, equipped with agitator and metering pump is charged under nitrogen at 90 ° C with 225 parts of poly (ethylene oxide) monophenyl ether (average molecular weight 750g / mol) 82.9 parts of salicylic acid , 65.4 parts of 2-phenoxyethyl phosphate and 127.6 parts of formalin (30% strength in 1-120). The reaction mixture is heated with stirring to 100 ° C, and then 85.2 parts of sulfuric acid (70%) are added over 20 minutes at a rate such that the reaction temperature does not exceed 105 ° C. After the end of the measurement, the reaction mixture is stirred at 105 ° C for an additional 3 hours. It is then left to cool, mixed with 300 parts of water, heated to 100 ° C for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution. Example 22
    [0093] A heatable reactor, equipped with agitator and metering pump is charged under nitrogen at 90 ° C with 320 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 2000 g / mol), 44.2 parts of salicylic acid, 22.1 parts of 2-phenoxyethanol phosphate and 21.2 parts of paraformaldehyde. 43.9 parts of methanesulfonic acid (70%) are then added to the reaction mixture over 15 minutes at a rate such that the reaction temperature does not exceed 105 ° C. After the end of the measurement, the reaction mixture is stirred at 110 ° C for an additional 1 hour. It is then left to cool, mixed with 350 parts of water, heated to 100 ° C for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution. Example 23
    [0094] A heatable reactor, equipped with agitator and metering pump is charged under nitrogen at 95 ° C with 225 parts of poly (ethylene oxide) monophenyl ether (average molecular weight 750 g / mol), 82.9 parts of acid salicylic, 65.4 parts of 2-phenoxyethyl phosphate and 82.3 parts of methanesulfonic acid (70%). The reaction mixture is heated with stirring to about 105 ° C and then 128.2 parts of formalin acid (30% strength) are added over 70 minutes at a rate such that the reaction temperature does not exceed 110 ° Ç. After the end of the measurement, the reaction mixture is stirred at 100 ° C for an additional 4.75 hours. It is then left to cool, mixed with 300 parts of water and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution. Example 24
    [0095] A heatable reactor, equipped with agitator and metering pump is loaded with 263 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 750 g / mol) and conditioned at 30 ° C. Then, over 20 minutes, 42 parts of polyphosphoric acid are added, followed by the subsequent reaction for 15 minutes. This reaction mixture is mixed with 96.7 parts of salicylic acid, 76.4 parts of 2-phenoxyethyl phosphate, 50 parts of water and 46.5 parts of paraformaldehyde under nitrogen at 95 ° C. The reaction mixture is heated to about 105 ° C with stirring, and in this step 66.2 parts of methanesulfonic acid (70%) are added over 30 minutes at a rate such that the reaction temperature does not exceed 110 ° C After the end of the measurement, the reaction mixture is stirred at 105 ° C for an additional 3.25 hours. It is then left to cool, mixed with 300 parts of water and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution. Example 25
    [0096] Example 12 was repeated with the polymers containing salicylic acid from examples 19 to 24. The 20 results are shown in table 7. Formulation: Microsilica 150g Fly ash, type F 150g Silica sand700g KOH (5.0%) 262.63g Table 7
    Example 26
    [0097] Example 25 it was repeated with the modification that 0.2% strength by weight of the aqueous KOH solution was used as an activator. The results are shown in table 8. Formulation: Microsilica 150g Fly ash, type F 150g Silica sand700g KOH (0.2%) 250g Table 8
    Example 27
    [0098] Example 13 was repeated with the polymers containing salicylic acids from examples 17 to 24. The results are shown in table 9. Formulation: Residual ground sand300g Silica sand700g KOH (0.2%) 180g Table 9
    Example 28
    [0099] Example 27 it was repeated with the modification that 5.0% strength by weight of the aqueous KOH solution was used as an activator. The results are shown in table 10. Formulation: Residual ground sand 300g Silica sand 700g KOH (5.0%) 189.09g Table 10
    Example 29
    [00100] Example 28 it was repeated with the modification that 15.0% strength by weight of the aqueous KOH solution was used as an activator. The results are shown in table 11. Formulation: Residual ground sand300g Silica sand700g KOH (15%) 211.34g Table 11

    [00101] As these examples show, the polymers of the invention allow a significant improvement in the consistency of aluminosilicate mortars. Here, the polymers of the invention allow for an improvement in the consistency of geopolymer systems with different binder compositions, such as fly ash, micro or silica residual sand and with different activator solutions. In addition, it can be seen from tests that standard plasticizers such as polycarboxylic ethers have virtually no effect, considering that the polymers of the invention allow excellent plasticization and, therefore, water reduction. Example 30
    [00102] A heatable reactor, equipped with agitator and metering pump, is charged with 262.5 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 750 g / mol) and 48.4 parts of 2-phenoxyethanol. Subsequently, with refrigeration, 77.0 parts of polyphosphoric acid are added over 15 minutes and the mixture is stirred at about 95 ° C for 45 minutes. Added to this reaction mixture at approximately 90 ° C under a stream of nitrogen are 96.7 parts of salicylic acid, 50 parts of water and 46.5 parts of paraformaldehyde. The reaction mixture is heated to about 90 ° C, with stirring and then 67.3 parts of methanesulfonic acid (70%) are added over 30 minutes at a rate such that the reaction temperature does not exceed 110 ° C . After the end of the measurement, the reaction mixture is stirred at about 100 ° C for an additional 120 minutes. Then left to cool, mixed with 350 parts of water and neutralized to a pH of about 7.0 using aqueous sodium hydroxide solution (50%). The neutralized dispersant is in the form of a strength of approximately 35.0% by weight of aqueous solution. Example 31
    [00103] A heatable reactor, equipped with agitator and metering pump is loaded with 225 parts of polyethylene oxide) monophenyl ether (average molecular weight of 750 g / mol) and 82.9 parts of 2-phenoxyethanol. Thereafter, with refrigeration, 99.0 parts of polyphosphoric acid are added for 35 minutes and the mixture is stirred at about 90-95 ° C for 60 minutes. Added to this reaction mixture under a stream of nitrogen are 41.4 parts of salicylic acid, 40 parts of water and 39.8 parts of paraformaldehyde. The reaction mixture is heated to about 85 ° C with stirring and then 57.7 parts of methanesulfonic acid (70%) are added over 15 minutes at a rate such that the reaction temperature does not exceed 105 ° C. After the end of the measurement, the reaction mixture is stirred at 100 ° C for an additional 140 minutes. Then left to cool, mixed with 350 parts of water and neutralized to a pH of about 7.0 using polyethylaneimine (Lupasol® G100 from BASF SE). The neutralized dispersant is in the form of a strength of approximately 30.4% by weight of aqueous solution. Example 32 Aluminosilicate mortars were produced according to the following formula: Microsilica 150g Ashes Flywheel, type F150g Silica sand700g Na2AI20415g Anti-foam 0.12g Water, total 250g
    [00104] The raw materials were mixed in the laboratory with a mortar mixer, according to DIN EN 196-1. The mixing operation was carried out as described in DIN EN 196-1, with the difference that the silica sand was added right at the beginning and not only later, to the mixture. The alkaline activator used was sodium aluminate dissolved in replacement water. As the defoamer, the defoamer product DF40 from BASF SE was used. The dispersant was used as an aqueous solution as obtained in examples 1 and 2 (indicated as content of polymer solids).
    [00105] F type fly ash and microsilica compositions were as follows [% by weight]:

    [00106] The drop was determined after 6 minutes in each case, typing 15 times on a drop table with a Hagermann cone (DIN EN 1015-3). The results are shown in table 12. Table 12

    [00107] This table shows that the dispersants of the invention also allow a significant improvement in the drops of aluminosilicate mortar mixtures when in combination with sodium aluminate as an alkaline activator. Here, an improvement in consistency is obtained by Na salts and polyethyleneimine salts of the polymers of the invention. Example 33
    [00108] Example 3 was repeated. A water-soluble and brown polymer was obtained which had a molecular weight of 20 (max. Peak) Mp = 24.3 kEa (column combinations: OH- Pak SB- G, OH-Pak SB 804 HQ and OH-Pak SB 802.5 HQ from Shodex, Japan; Eluent: 80% by volume of aqueous ammonium formate solution (0.05 mol / l) and 20% by volume of acetonitrile ; injection volume 100p; flow rate: 0.5 mL / min Example 34
    [00109] A heatable reactor, equipped with agitator, reflux condenser and metering pump is charged with 150 parts of polyethylene oxide) monophenyl ether (average molecular weight 750 g / mol), 101 parts of hydroquinone bis ether (2- hydroxyethyl) and 28 parts of salicylic acid and heated to 90 ° C under nitrogen. Then 132 pieces of polyphosphoric acid are added over 33 minutes, followed by a subsequent reaction for 10 minutes. The reaction mixture is mixed with 48 parts of methanesulfonic acid (70%) and 2 parts of water at 98 ° C. The mixed reaction is cooled to about 90 ° C, with stirring and 95 parts of formalin solution (30%) are added over 50 minutes at a rate such that the reaction temperature does not exceed 110 ° C. After the end of the measurement, the reaction mixture is stirred at 100 ° C for an additional 20 minutes. It is then left to cool, mixed with 760 parts of water and neutralized to a pH of about 7.3 using 50% strength aqueous sodium hydroxide solution. Example 35
    [00110] A heatable reactor, equipped with a stirrer, reflux condenser and metering pump is loaded with 188 parts of poly (ethylene oxide) monophenyl ether (average molecular weight 750 g / mol) and 35 parts of phenoxyethanol and heated to 25 ° C under nitrogen. Then, 55 parts of polyphosphoric acid are added over 8 minutes, after which the reaction mixture is heated to 92 ° C and then reacted at this temperature for 100 minutes. The reaction mixture is mixed with 104 parts of salicylic acid and 69 parts of methanesulfonic acid (70%) and, after 10 minutes, 131 parts of formalin solution (30%) are added over 60 minutes at such a rate that the reaction temperature does not exceed 110 ° C. After the end of the measurement, the reaction mixture is stirred at 100 ° C for an additional 3.5 hours. It is then left to cool, mixed with 500 parts of water and neutralized to a pH of about 7.3 using 50% strength aqueous sodium hydroxide solution. Example 36
    [00111] A heatable reactor, equipped with agitator, reflux condenser and metering pump is loaded with 188 parts of poly (ethylene oxide) monophenyl ether (average molecular weight 750 g / mol) and an additional 28 parts of polyphosphoric acid are added under nitrogen over 8 minutes. After 10 minutes from the end of the measurement, the reaction mixture is heated to 90 ° C with stirring and then reacted at around 95 ° C for 4 hours. Then 35 parts of phenoxyethanol and, 30 minutes later, 104 parts of salicylic acid and 69 parts of methanesulfonic acid (70%) are added. The reaction mixture is heated to 100 ° C with stirring and when that temperature is reached, 132 parts of formalin solution (30%) are added over 50 minutes at a rate such that the reaction temperature does not exceed 110 ° Ç. After the end of the measurement, the reaction mixture is stirred at 95 ° C for an additional 3.7 hours. It is then left to cool, mixed with 450 parts of water and neutralized to a pH of about 7.3 using 50% strength aqueous sodium hydroxide solution. Example 37
    [00112] A heated reactor, equipped with agitator, reflux condenser and metering pump is loaded with 135 parts of poly (ethylene oxide) monophenyl ether (average molecular weight 750 g / mol) and additionally 20 parts of polyphosphoric acid are added under nitrogen over 6 minutes. After 10 minutes from the end of the measurement, the reaction mixture is heated to 90 ° C with stirring and then reacted at around 95 ° C for 4 hours. Then 50 parts of phenoxyethanol and, 15 minutes later, 149 parts of salicylic acid and 99 parts of methanesulfonic acid (70%) are added. The reaction mixture is heated to approximately 90 ° C with stirring and when that temperature is reached, 170 parts of formalin solution (30%) are added over 60 minutes at a rate such that the reaction temperature does not exceed 110 ° C. After the end of the measurement, the reaction mixture is stirred at 95 ° C for an additional 2.75 hours. Then left to cool, mixed with 500 parts of water and neutralized to a pH of about 7.3 using a 50% strength aqueous sodium hydroxide solution. Example 38
    [00113] Aluminosilicate mortars were produced according to the following formula: Residual ground sand 300g Silica sand 700g KOH 12g Na2CO312g Defoamer 0.12g Water, total 175g
    [00114] The raw materials were mixed in the laboratory with a mortar mixer, according to DIN EN 196-1. The mixing operation was carried out as described in DIN EN 196-1, with the difference that the silica sand was added right at the beginning and not only later, to the mixture. The alkaline activator used was potassium hydroxide and sodium carbonate dissolved in the replacement water. As the defoamer, the defoamer product DF40 from BASF SE was used. The dispersant was used as an aqueous solution as obtained in examples 1 and 2 (content of polymer solids in the mortar: 3g).
    [00115] The crushed residual sand compositions were as follows [% by weight]:

    [00116] The drop was determined after 6 minutes and after 30 minutes in each case, typing 15 times in a drop table with a Hagermann cone (DIN EN 1015-3). The results are shown in table 13.Table 13
    Example 39
    [00117] In a metal container 100.0 g of a CEM III / A 32.5 N type compound waste sand cement was weighed in. The amount of dispersant indicated below, calculated as solids content, was mixed, taking into account in the calculation of the water present in the dispersant, with the amount of water corresponding to a water / cement ratio of 0.3. In this context, the expression "bwoc" is intended to denote "%, by weight, based on the amount of cement".
    [00118] After adding the water / dispersant mixture to the cement, the mixture was stirred intensely with a paddle stirrer for 1 minute. The cement paste obtained in this way was introduced into a metal cone (internal diameter upper / lower 2.0 / 4.0 cm, height 6.0 cm) which was placed on a glass plate arranged horizontally. The metal cone was lifted, and the cement paste was subjected to a falling flow. The fall flow ("SF" or "scattered", diameter of the cement paste tablet) was subsequently determined at 3 points, and the mean was taken. Average values are shown in table 14. (Glenium® SKY 115 is a commercial high-performance dispersant from BASF Construction Polymers GmbH, based on polycarboxylate ether).

    [00119] It was found that when the amount of high-performance dispersant added was halved (Comparative 2), as expected, it was not possible to achieve the reference drop flow of Comparative 1 cement paste. Just by adding the polycondensation product of the invention (example 33) it was possible to bring the drop flow back almost to the reference level.
    [00120] The defined amount of cement paste thus obtained was transferred to a calorimeter, and the development of the hydration heat was recorded calorimetrically. For this purpose, the calorimeter was previously balanced at 20.0 ° C (reference isothermium calorimeter for TA Instruments, model TAM-AIR). After 48 hours, the measurement was stopped and the data was evaluated. For this purpose, the differential of heat generation dH / dt (mW / g, standardized for 1g of cement paste) and also the integral heat generation H (J / g; after 6, 12, 24 and 48 hours) were employees. The results are shown in table 15.Table 15

    [00121] It has been revealed that significantly faster hydration is achievable when using the polycondensation product of example 33. Despite the addition of polymer at a higher general level, a significantly faster heat release was observed, which suggests a rapid hydration of cement. The maximum in heat generation of cement paste formulated using the polycondensation product of the invention was reached after just 18 hours and 54 minutes, considering that cement paste formulated using commercial high performance concrete plasticizer does not reach its generation maximum heat up to 5 hours later. This is also reflected in the generation of integral heat; After 6, 12, 24 and 48 hours, the observable levels of heat generation have always been higher. Example 40
    [00122] 100.0 g of a CEM VIA 32.5 N waste compound / residual sand cement was weighed in a metal container, the amount of dispersant indicated below, calculated as solids content, was mixed, taking into account account the calculation of the water present in the dispersant, with the amount of water corresponding to a water / cement ratio of 0.33. After adding the water / dispersant mixture to the cement, the mixture was stirred intensely with a paddle stirrer for 1 minute. The cement paste obtained in this way was introduced into a metal cone (upper / lower internal diameter 2.0 / 4.0 cm, height 6.0 cm) that was placed on a horizontally arranged glass plate. The metal cone was lifted, and the cement paste was subjected to a falling flow. The drop flow was subsequently determined at 3 points, and the mean was taken. The average values are shown in table 16. Table 16

    [00123] It was found that when the amount of high-performance dispersant was halved and the polycondensation product of the invention was added, the reference drop flow of Comparative 3 cement paste could be raised to close to the level of reference. Example 41
    [00124] Example 3 was repeated with 450 parts of poly (ethylene oxide) monophenyl ether (average molecular weight 5000 g / mol), 27.3 parts of 3,4-dihydrobenzoic acid, 9.3 parts of paraformaldehyde and 49.4 parts of methanesulfonic acid (70%). The pH after neutralization with 50% strength aqueous sodium hydroxide solution was about 7.3. The polymer obtained was completely soluble in water and dark brown, in the form of a strength of 32.4% by weight of aqueous solution. The molecular weight was approximately 12-23 kDa (Mp = 11.6 and 22.5 and 22.5 kDa; GPC conditions as in example 33). Example 42
    [00125] Example 20 was repeated with 262.5 parts of poly (ethylene oxide) monophenyl ether (average molecular weight of 750 g / mol, 145.0 parts of salicylic acid, 50 parts of water, 46.5 parts of paraformaldehyde and 67.2 parts of methanesulfonic acid (70%) .The pH after neutralization with 50% strength aqueous sodium hydroxide solution was about 7.3 The obtained polymer was totally soluble in water and yellowish, under the in the form of a force of 28.0% by weight of aqueous solution.The average molecular weight of was approximately 5.4 kDa (GPC conditions as in example 33). Example 43
    [00126] Example 20 was repeated with 300 parts of poly (ethylene oxide) monophenyl ether (average molecular weight 2000 g / mol), 82.9 parts of salicylic acid, 26.1 parts of paraformaldehyde and 72.1 parts methanesulfonic acid (50%). The reaction took place at 105-108 ° C. The molecular weight was about 16 kDa. Example 44
    [00127] 12.3 kg of ground residual sand ("GBFS") from Salzgitter, mixed with a strength of 32.4% aqueous solution of the polymer of example 41 (identified as "E41" in Fig. 1 and tables 17 and 18) or with a strength of 28.0% aqueous solution of the polymer of example 42 (identified as "E42" in Fig. 1 and tables 17 and 18) (in each case 0.03% by weight of polymer, based on in sand weight) were ground for 125 minutes with stainless steel balls in a laboratory ball mill (LAB BAS LM0504-S7DA GmbH) without additional external heating. The resulting powder was sieved through a 5 mm sieve. For comparison, a GBFS sample without adding additives (identified as "blank" in Fig. 1) was ground and sieved. The particle size distribution of the resulting powders was determined using a Mastersizer 2000 from Malvern Instruments and Blaine values were determined using a SEGER Tonindustrie analyzer. The particle size distributions are shown in Fig. 1. Of each of the resulting residual sand samples, 700 g were separated into "coarse" and "fine" fractions using a 100 MZR (flat) cyclone from Hosokawa Alpine with a defined limit particle size of 15 pm, an air speed of 49 m / s (constant) and a rotation speed of 6000 rpm. For each of the separate samples, the particle size distribution of the coarse and fine fractions was measured. Example 45
    [00128] Example 44 was repeated. 0.08% by weight of each of the following additives, based on the weight of residual ground sand, was used: "TEA" (triethanolamine), "RheoPlus 18" (strength of 44.2% aqueous solution, containing 5% defoamer Plurafac LF305), polymer of example 41 (identified as "E41", in the form of an aqueous solution of 32.4% strength, containing 5% of defoamer Plurafac LF305), the polymer of example 42 (identified as " E42 ", in the form of an aqueous solution of 28.0% strength, containing 5% of the defoamer Plurafac LF305) and the polymer of example 43 (identified as" E43 "in Fig. 2, in the form of an aqueous strength solution 31.7%, containing 5% of the defoamer Plurafac LF305). Grinding was carried out at 120 ° C. Here again, for comparison, a GBFS of the sample with no additives added (identified as "blank" in Fig. 2) was ground and sieved. Fig. 2 shows the corresponding departmental size distribution. Discussion:
    [00129] Fig. 1 shows that the main difference in the particle size distribution is found in the region of coarse particles (15-300 pm), that is, that the addition of the corresponding milling assistant leads to a reduction in the amount of coarse particles, with a significant drop in d (0.5) and values of d (0.9), with the grinding assistants and a significant increase in Blaine values (see table 17). The time for complete separation of the fractions is shortened when using the milling assistants of the invention, with beneficial consequences for energy costs, and the average particle size of the coarse fraction is significantly reduced (see table 18). With this it can be inferred that the polycondensation products of the invention enhance the grinding capacity of the residues.
    Table 18

    [00130] Fig. 2 and table 19 show distributions of department size and Blaine values of heat-milled residual sands with the various additives identified in example 40. Average particle sizes d (0.5) of the milled residual sands with polymers "E42" and "E43" are significantly smaller, and the corresponding Blaine values higher than that of the sample without additives ("blank") and the sample ground with "TEA" or RheoPlus 18 (high performance cement plasticizer) BASF SE) .Table 19
    权利要求:
    Claims (24)
    [0001]
    1.POLICONDENSATION PRODUCT, characterized by comprising as components of the monomer: A) at least one polyoxyalkylene aryl ether of the formula (I)
    [0002]
    2. POLYCONDENSATION PRODUCT, according to claim 1, characterized in that the Ar group is an aryl group having 6 to 10 carbon atoms in the ring system, more particularly a phenyl group or a naphthyl group.
    [0003]
    POLYCONDENSATION PRODUCT, according to any one of claims 1 to 2, characterized in that m is an integer from 3 to 280, preferably from 10 to 160 and more particularly from 12 to 120.
    [0004]
    4. POLYCONDENSATION PRODUCT, according to any one of claims 1 to 3, characterized in that R3 is selected from the group consisting of H, C1-10 alkyl, C6-10 aryl, C7-11 aralkyl, C7-11 alcaryl and phosphate.
    [0005]
    5. POLYCONDENSATION PRODUCT, according to claim 3, characterized in that the polyoxyalkylene aryl ether oxyalkylene groups of formula (I) are preferably selected from ethylene oxide groups and / or propylene oxide groups, the which are arranged randomly, alternately, gradually and / or by blocks along the chain.
    [0006]
    6. POLYCONDENSATION PRODUCT, according to claim 3, characterized in that the polyoxyalkylene aryl ether of the formula (I) is a monophenyl polyethylene glycol ether of the formula (Ill)
    [0007]
    7. POLYCONDENSATION PRODUCT, according to claim 6, characterized in that the monophenyl polyethylene glycol ether of the formula (Ill) is a mixture with different values for m within the specified definition.
    [0008]
    8. POLYCONDENSATION PRODUCT, according to any one of claims 1 to 7, characterized in that R8 and R9 each, independently, are selected from H, C1-10 alkyl, C6-10 aryl, C7-11 aralkyl and C7- 11 caraway.
    [0009]
    9. POLYCONDENSATION PRODUCT, according to any one of claims 1 to 8, characterized in that the aromatic compound of the formula (II) is selected from the group consisting of benzene-1,2-diol, benzene-1,2,3- triol, 2-hydroxybenzoic acid and 2,3- and 3,4-dihydrobenzoic acid, 3,4,5-trihydroxybenzoic acid, phthalic acid, 3-hydroxyphthalic acid, 2,3- and 3,4-dihydroxybenzenesulfonic acid, 1 , 2- and 2,3-dihydroxinaphthalene, 1,2- and 2,3-dihydroxinaphthalene, 5- or 6-sulfonic acid of 1,2- and 2,3-dihydroxinaphthalene and also their mixtures.
    [0010]
    10. POLYCONDENSATION PRODUCT, according to any one of claims 1 to 9, characterized in that the aldehyde component C) is selected from the group consisting of formaldehyde, paraformaldehyde, glyoxylic acid, benzaldehyde, benzaldehyde sulfonic acid, benzaldehydodisulfonic acid, vanillin and isovaniline and also their mixtures.
    [0011]
    11. POLYCONDENSATION PRODUCT, according to any one of claims 1 to 10, characterized in that the molar ratio of components C: (A + B) is 1: 3 to 3: 1, preferably 1: 2 to 2: 1 and more particularly 1: 0.9 to 1: 1.1.
    [0012]
    12. POLYCONDENSATION PRODUCT according to any one of claims 1 to 11, characterized in that the molar ratio of components A: B is 1:10 to 10: 1, preferably 1: 7 to 5: 1 and more preferably , 1: 5 to 3: 1.
    [0013]
    13. POLYCONDENSATION PRODUCT, according to any one of claims 1 to 12, characterized in that it is in the form of a comb-shaped polymer with a novolak structure.
    [0014]
    14. POLYCONDENSATION PRODUCT, according to any one of claims 1 to 13, characterized in that it has a molecular weight in the range of 1,000 to 100,000, preferably 2,000 to 75,000 and more particularly 4,000 to 50,000 g / mol.
    [0015]
    15. PROCESS FOR PREPARING THE POLYCONDENSATION PRODUCT, as defined in any one of claims 1 to 14, characterized by components A), B), C) and D) being subjected to polycondensation in aqueous solution at a temperature of 20 to 140 ° C under a pressure of 1 to 10 bar.
    [0016]
    16. PROCESS, according to claim 15, characterized in that the polycondensation takes place in the presence of an acid catalyst, preferably selected from the group consisting of sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, oxalic acid, phosphoric acid and also their mixtures.
    [0017]
    17. PROCESS according to any one of claims 15 to 16, characterized in that, after completion of the polycondensation, the reaction mixture is subjected to a post-treatment at a pH of 8.0 to 13.0, at a temperature 60 to 120 ° C and, preferably, under a pressure of 0.01 to 0.9 bar.
    [0018]
    PROCESS, according to claim 17, characterized in that the pH is adjusted by the addition of an aqueous alkali, such as NaOH and the salts formed during neutralization are removed.
    [0019]
    19. USE OF THE POLYCONDENSATION PRODUCT, as defined in any one of claims 1 to 14, characterized by being as a dispersant for aqueous suspensions of inorganic binders, selected from the group comprising latent hydraulic binders, pozzolanic binders, activated aluminosilicate binders and / or activable by alkali, and also their mixtures.
    [0020]
    20. USE, according to claim 19, characterized by: the latent hydraulic binders are selected from industrial and / or synthetic waste, blast furnace waste, residual sand, ground residual sand, electrothermal phosphorous waste, stainless steel waste and also their mixtures, and the pozzolanic binders being selected from amorphous silica, precipitated silica, pyrogenic silica and microsilica, finely ground glass, fly ash, lignite fly ash, coal ash fly, metakaolin, natural pozzolans, tuff, tuff volcanic, volcanic ash, natural and synthetic zeolites and their mixtures.
    [0021]
    21. USE according to any one of claims 19 to 20, characterized in that the alkali-bonded aluminosilicate binders comprise latent hydraulic binders and / or pozzolanic binders and also alkaline activators, such as aqueous solutions of alkali metal carbonates, metal fluorides alkali, alkali metal hydroxides, alkali metal aluminates, alkali metal silicates, such as liquid glass and also mixtures thereof.
    [0022]
    22. USE, according to any one of claims 19 to 21, characterized as being a constituent of construction material formulations and / or construction material products such as on-site concrete, precast concrete parts, concrete, cast concrete stones and also concrete in situ, air-poured concrete, ready mix concrete, construction adhesive, adhesives for thermal insulation composite systems, concrete repair systems, one component and two component sealing pastes, mortars, filling and leveling compounds, tile adhesives, plasters, adhesives and sealants, coating systems, more particularly for tunnels, wastewater channels, splash protection and condensed lines, dry mortars, grout joints, drainage mortars and / or repair mortars.
    [0023]
    23. USE OF THE POLYCONDENSATION PRODUCT, as defined in any of claims 1 to 14, characterized as being a grinding assistant for inorganic binders, selected from the group comprising hydraulic binders, latent hydraulic binders and pozzolan binders, as defined above and / or alkali-activable aluminosilicate binders, and also mixtures thereof.
    [0024]
    24. USE according to any one of claims 19 to 23, characterized in that together with additional auxiliaries selected from the group, which comprises glycols, polyalcohols, amine alcohols, organic acids, amino acids, sugars, molasses, organic salts and inorganic, polycarboxylate ethers, naphthalenesulfonate, melamine / formaldehyde polycondensation products, lignosulfonate and mixtures thereof.
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    同族专利:
    公开号 | 公开日
    AU2013245612B2|2016-04-21|
    CN104220472A|2014-12-17|
    MX2014012273A|2014-12-05|
    CN104220472B|2017-03-01|
    EP3339341A1|2018-06-27|
    JP6290176B2|2018-03-07|
    JP2015518506A|2015-07-02|
    US10392306B2|2019-08-27|
    CA2871720C|2020-07-21|
    RU2638380C2|2017-12-15|
    US20150080500A1|2015-03-19|
    EP2836529B1|2018-03-28|
    TR201808481T4|2018-07-23|
    WO2013152963A1|2013-10-17|
    AU2013245612A1|2014-10-30|
    CA2871720A1|2013-10-17|
    US20170044064A1|2017-02-16|
    MX361631B|2018-12-13|
    RU2014145103A|2016-06-10|
    EP2836529A1|2015-02-18|
    ES2672251T3|2018-06-13|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-11-05| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-09-15| B09A| Decision: intention to grant|
    2020-12-08| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12163706|2012-04-11|
    EP12163706.0|2012-04-11|
    PCT/EP2013/056761|WO2013152963A1|2012-04-11|2013-04-03|Polycondensation product based on aromatic compounds, method for the preparation and use therof|
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