• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a phosphate-based inorganic binder obtained by reaction between at least one basic component and an acid phosphate salt, in the presence of a retarding agent which is an X + A- salt whose solubility in aqueous medium measured at 25 ° C is greater than that of the acidic phosphate salt, and wherein X + is a cation selected from alkali metals, alkaline earth metals, aluminum and ammonium ion, and A- is an acetate, citrate, formate anion , benzoate, tartrate, oleate, bromide or iodide.
    公开号:FR3030498A1
    申请号:FR1463243
    申请日:2014-12-23
    公开日:2016-06-24
    发明作者:Munoz Raul Leiva；Sanz Joel Nunez；Zahia Toutou-Melinge
    申请人:Saint Gobain Weber SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a mineral binder based on phosphates. This type of binder used in construction products results from an acid-base reaction between a metal oxide and a salt or a phosphoric acid derivative. Most basic oxides which react with phosphoric acid or one of its acid derivatives form, when mixed with water, a homogeneous mass which hardens with time at room temperature. Among the best-known phosphatic cements, mention may be made of phosphomagnesium cements which have been developed to compete with synthetic resins since they make it possible to obtain quick-setting concretes with an almost immediate appearance of the desired resistances. They find their particular application in the biomedical field and in dentistry, in the rapid repair of roads, tracks or bridges, or in the encapsulation of hazardous waste. A cement of this type called Ceramicrete developed in the United States is obtained by mixing magnesium oxide or magnesia, with potassium monophosphate KH2PO4. In the presence of water, magnesia reacts with phosphate groups under acidic conditions to form an insoluble phosphate phase which hardens and has the properties of a ceramic. This phase is k-struvite of formula MgKPO4,6H20. The formation reaction of this phase is very fast and requires the use of a retarding agent. Boric acid is very often used to increase the workability time of this type of cement. However, according to European regulations and in particular the REACH Directive, boric acid is classified as a toxic substance for reproduction. Other solutions for controlling setting time are therefore contemplated. Articles describe the possibility of lengthening the setting time and therefore the workability by using a particular magnesium oxide, namely calcined magnesia at high temperature and by varying the particle size of the basic metal oxide used. However, this does not allow to achieve setting times or working time comparable to those obtained for systems based on Portland cements. Another disadvantage of this type of system is related to the strong exothermicity of the reaction which takes place between magnesia and phosphate. Boric acid used as retarder does not control the thermodynamics of the reaction. The end user must therefore take into account this high exothermicity which causes a significant evaporation of the water present in the system during the preparation of the construction material.
    [0002] On the other hand, another drawback related to the high reactivity and setting of these systems is the appearance of blanched areas at the surface of the cured material, which reflects a rise in the surface of unreacted salts. It is about efflorescence which gives a defect of esthetic aspect important which is not acceptable for the sought applications.
    [0003] It is necessary to develop phosphate binder systems which can be used in mortar compositions which have longer workability times, compatible with the desired applications, and which do not have the drawbacks described above. This is the context of the present invention.
    [0004] The present invention relates to a phosphate-based inorganic binder obtained by reaction between at least one basic component and an acid phosphate salt, in the presence of a retarding agent which is a salt X ± A- whose solubility in aqueous medium measured at 25 ° C is greater than that of the acidic phosphate salt, and wherein X + is a cation selected from alkali metals, alkaline earth metals, aluminum and ammonium ion, and A- is an acetate, citrate anion, formate, benzoate, tartrate, oleate, bromide or iodide. The presence of the retarding agent as described above advantageously makes it possible to control the kinetics and exothermicity of the acid-base reaction which takes place between the basic constituent (s) present and the acidic phosphate salt. The use of such a retarding agent makes it possible to avoid the use of boric acid or its derivatives. The basic constituent, acting as a base in the acid-base reaction for obtaining the binder according to the invention is chosen from metal oxides, metal hydroxides or sulphates. The metal oxides may be calcium oxide, magnesium oxide, zinc oxide, aluminum oxide, and / or iron oxide. The metal oxide may also be introduced in the form of a more complex inorganic compound which comprises one or more metal oxides. Mention may be made in this category of silicates, metallurgical slags (for example steelworks slags or blast furnace slags), lime, fly ash, dolomite, mica, kaolin and / or metakaolin. Metal hydroxides such as magnesium or calcium hydroxide can also be used as the basic component for forming the binder according to the present invention. Sulphates such as calcium sulphate can also be used as the basic component for forming the binder according to the present invention. Sources of calcium sulphates include plaster, gypsum, hemihydrate and / or anhydrite. It is possible to use a mixture of these different sources of metal oxides or hydroxides and sulfates to prepare the binder according to the present invention. Preferably, the binder according to the present invention is obtained from a mixture of at least two basic constituents, at least one of them being chosen from magnesium oxide, calcium hydroxide or magnesium, wollastonite, alumina, metallurgical slags and calcium sulphate. The additional basic constituent can then be chosen from kaolin, metakaolin, fly ash, lime, dolomite, calcined clays, mica and / or talc, for example.
    [0005] The acidic phosphate salt participating in the acid-base reaction for the formation of the binder according to the present invention is chosen from: potassium, calcium, magnesium, aluminum, sodium or ammonium hydrogenphosphates, dihydrogenphosphates potassium, calcium, magnesium, aluminum, sodium or ammonium, potassium, calcium, magnesium, aluminum, sodium or ammonium pyrophosphates, and / or polyphosphates of potassium, calcium, magnesium, aluminum, sodium or ammonium. These acid phosphate salts may be used alone or in admixture. Hydrogen phosphates are salts comprising the HPO42- anion. Dihydrogen phosphates are salts comprising the H2PO4 anion. The acidic pyrophosphates are salts derived from pyrophosphoric acid and correspond to the formulas MH3P207, M21-12P207 and M3HP207. The acid polyphosphates are salts derived from polyphosphoric acid and correspond to the general formula Hn + 2PnO3n ± 1 in which n is an integer strictly greater than 2. The acidic phosphate salt therefore comprises at least one proton capable of being released. during the aqueous dissolution of the binder, resulting in an acid attack to dissolve the metal oxide present in solution. Preferably, the acidic phosphate salt is chosen from potassium dihydrogen phosphate KH2PO4 (MKP), ammonium dihydrogen phosphate (NH4) H2PO4 (MAP), diammonium hydrogenphosphate (NH4) 2HPO4 (DAP), dihydrogenphosphate of calcium Ca (H2PO4) 2, sodium dihydrogenphosphate NaH2PO4, alumina hydrophosphate Al H3 (PO4) 2, xH2O, calcium metaphosphate Ca (HPO3) 2, magnesium dihydrogen phosphate Mg (H2PO4) 2 or aluminum trihydrogenphosphate Al (H2PO4) 3. The preferred acidic phosphate salts are those not releasing ammonia during the reaction and therefore are selected from potassium dihydrogen phosphate KH2PO4 (MKP), calcium dihydrogen phosphate Ca (H2PO4) 2, calcium metaphosphate Ca (HPO3) 2, sodium dihydrogen phosphate NaH2PO4, and aluminum hydrophosphate AIH3 (PO4) 2, xH2O, magnesium dihydrogen phosphate Mg (H2PO4) 2 or aluminum trihydrogenophosphate Al (H2P003.
    [0006] The retarding agent used to control the reactivity of the binder according to the present invention is an ionic salt of formula X ± A- in which the X + cation is chosen from alkali metals, alkaline earth metals, aluminum and ammonium ion, and the anion A- is chosen from acetate, citrate, formate, benzoate, tartrate, oleate, bromide or iodide anions. These salts are soluble in water and must, in order to play their role of retarder, be more soluble in aqueous medium than the acidic phosphate salt. Table 1 below gives as an indication the solubility in grams in 100 ml of water at 25 ° C. of salts which can be used as retarding agents. 30 K Na Mg Ca NH4 + Acetate 253 50 55 35 1480 ° Trate 167 92 20 <1 1000 Formant 348 98 15 17 143 Tartrate 24 <1 <1 63 Benzoate 65 63 - 3 21 Bromide 67 95 103 143 76 Iodide 147 180 150 66 172 Table 1 Table 2 gives the solubility in grams in 100 mL of water at 25 ° C. ° C. acid phosphate salts which can be used in the binder formation reaction according to the present invention. solubility Sodium hydrogen phosphate NaH2PO4 12 Potassium hydrogen phosphate KH2PO4 23 Ammonium hydrogen phosphate NH4H2PO4 Dipotassium hydrogen phosphate K2HPO4 149 Diammonium hydrogen phosphate (N1-14) 21-1PO4 Disodium hydrogen phosphate Na2HPO4 12 D Magnesium hydrogenphosphate 2 Mg (H2PO4) Al aluminum hydrogen phosphate (H2PO4) 3 2 D calcium hydrogen phosphate Ca (H2PO4) 2 2 Table 2 The retarding agent is selected depending on the acid phosphate salt used in the binder formation reaction. It is essential that its solubility be greater than that of the acid phosphate salt. In a preferred manner, a salt whose cation is identical to the cation of the acid phosphate salt involved in the binder formation reaction will be chosen as a retarding agent. The retarders whose anions are acetates or formates are preferred. These anions make it possible to obtain a longer workability time and a better control of the exothermicity of the reaction. The amount of retarding agent is between 1 and 10% by weight of the total amount of binder components. In a preferred manner, the amount of retarding agent is between 2 and 7% by weight. The binder according to the present invention may comprise, in addition to the acidic phosphate salt, another phosphate compound chosen from the salts of orthophosphates, polyphosphates or pyrophosphates in which the cation is chosen from sodium, potassium, calcium or the ammonium ion. The orthophosphate salts are salts derived from orthophosphoric acid comprising the P043- anion. Pyrophosphates are salts derived from pyrophosphoric acid comprising the P2074- anion. Mention may in particular be made of tri sodium polyphosphate Na5P3010 (Na-TPP) or calcium pyrophosphate Ca207P2. This other phosphate compound participates in particular in the retarding effect. For example, the solubility of sodium tripolyphosphate is about 14.5 g in 100 ml water at 25 ° C. That of sodium pyrophosphate Na4P207 is about 7 under the same conditions. As this additional phosphate compound is a base, it is important that the amounts introduced into the binder composition remain however low, in order to maintain the acidic character of the phosphorus-based constituent involved in the acid-base reaction. The present invention also relates to a mortar or concrete composition comprising at least one binder as described above. The composition contains aggregates, aggregates and! or sands, and it is commonly referred to as mortar or concrete depending on the size of aggregates. Lightened aggregates such as expanded clays, perlite, aerogels, vermiculite, expanded glass or expanded polystyrene may also be used in the mortar or concrete composition of the present invention. These compounds play in particular on the rheology, the hardness or the final appearance of the product. They are generally formed of siliceous, calcareous and / or silico-calcareous sands. The composition may also comprise components called fillers, limestone or siliceous and other possible additives and adjuvants conferring particular properties. For example, rheological agents, water-retaining agents, air-entraining agents, thickening agents, agents for protecting against the growth of algae and fungi such as biocides, fungicides, algicides and bactericides. , dispersing agents, pigments, accelerators and / or setting retarders, as well as other agents to improve setting, hardening, stability of the products after application and in particular to adjust the color, the workability, the implementation or impermeability.
    [0007] The present invention also relates to structural products, such as grouting mortars, tile joints, tile adhesives, screeds, floor coatings, technical mortars, insulating mortars or facings obtained from from the concrete or mortar composition defined above. These products are obtained by mixing the composition with water, the pasty composition thus formed then being cured. Technical mortars include special mortars formulated for special applications, such as sealing mortars, repair mortars, mortars or mortars. Pre-fabricated elements can also be obtained from compositions comprising the binder according to the present invention. The building products according to the invention can be prepared on site or prefabricated. The products thus obtained have workability times compatible with the desired applications, since the product remains usable after mixing for a longer time than when the composition does not include the retarding agent. On the other hand, the products obtained from the mortar or concrete compositions according to the present invention do not include aesthetic defects due to efflorescence phenomena. The examples below illustrate the invention without limiting its scope.
    [0008] In the following examples, the practical duration of use is measured for different binder compositions. This practical duration of use corresponds to the maximum duration after the preparation of the binder, that is to say after the mixing of the different powdery constituents with the mixing water, during which the wet paste thus obtained can be used. The determination of the practical duration of use is made by measuring the time that elapses between the moment when the product is prepared with the desired consistency of dough and the moment when the viscosity of the dough has increased so that the product does not be more fluid enough to apply. The practical duration of use is correlated with the initial setting time due to hardening of the dough, the setting time being measured according to the Vicat test according to the NF EN 196-3 standard.
    [0009] The workability time is defined as the time during which a fresh dough retains a sufficiently low viscosity to be easily applied with good workability. For all the examples below, the powdery products are mixed together before adding the mixing water to prepare the fresh dough. The amount of water that is added and given in% by weight of water may vary depending on the application and desired workability so as to obtain the consistency of the desired pulp. The determination of the consistency of the fresh dough is performed at the shaking table according to standard NF EN 1015-3. The powder mixture is mixed with the water so as to obtain a homogeneous paste. The fresh dough is poured into a given mold on the tray of a defined shaking table. After removal of the mold, the fresh dough is subjected to a given number of vertical shaking. The diameter of the circle of fresh dough is measured. Identical diameters make it possible to ensure that the consistencies of the pastas are comparable.
    [0010] Different binder compositions according to the present invention are prepared. Practical duration measurements are carried out on identical compositions with or without retarding agents. The binder compositions are prepared by mixing the basic component (s) with the acidic phosphate salt in the presence of the salt used as a retarding agent. The content of each of the constituents is given as a percentage by weight, the total sum of the quantities of pulverulent products equaling 100%. The mixing water which is added is indicated for each example and corresponds to the quantity of water necessary to obtain the same consistency of dough. The water content indicated in each example corresponds to the amount which is added to a mixture which comprises 100% of pulverulent products.
    [0011] Example 1 A mixture consisting of 50% by weight lightly calcined magnesium oxide (ISAAF) and 50% by weight potassium dihydrogen phosphate KH2PO4 (Prayon) is prepared. The water is added to the powder mixture thus obtained in an amount representing 20% by weight relative to the total amount of powder constituents. The measured practical use time of the dough is 0.5 min. The same composition is prepared by adding 3% by weight of potassium acetate as a retarding agent. The amount of water added is also 20% by weight.
    [0012] The measured practical duration of use of the paste comprising the retarding agent is then 7 min. Example 2 A mixture consisting of 50% by weight of Ca 903 wollastonite (Nordkalk) and 50% by weight of calcium dihydrogen phosphate monohydrate Ca (H2PO4) 2.H2O (Budenheim) is prepared. The water is added to the pulverulent mixture thus obtained in an amount representing 50% by weight relative to the total amount of powder constituents. The measured practical duration of use of this paste is 0.2 min. The same composition is prepared by adding 3% by weight of calcium acetate as a retarding agent. The amount of water added is also 50% by weight. The practical duration of measured use of the paste comprising the retarding agent is then 3 min.
    [0013] Example 3 Three different mixtures of magnesium oxide highly calcined at high temperature (1500 ° C) and sintered (Grecian Magnesite) and potassium dihydrogen phosphate KH2PO4 (Prayon) are prepared by varying the weight ratio MgO: MKP.
    [0014] Composition 3-1 corresponds to 25% by weight of MgO and 75% by weight of MKP. The amount of water added is 20% by weight relative to the total sum of the pulverulent compounds.
    [0015] Composition 3-2 corresponds to 50% by weight of MgO and 50% by weight of MKP. The amount of water added is 21% by weight relative to the total sum of the pulverulent compounds. The composition 3-3 corresponds to 75% by weight of MgO and 25% by weight of MKP. The amount of water added is 22% by weight based on the sum total of the pulverulent compounds. The practical times of application of these 3 pastes are measured and are respectively 17 min for the paste obtained from the composition 3-1, 5 min for the paste obtained from the composition 3-2 and 4 min for the paste obtained from the composition 3-3. 3% by weight of potassium acetate is added to each of compositions 3-1, 3-2 and 3-3. The mixing water is added in the same proportions. The practical durations of use of the pastes obtained from the compositions 3-1, 3-2 and 3-3 to which the retarding agent has been added have been measured and are worth respectively 80 min for the paste obtained from the composition 3-1, 50 min for the paste obtained from composition 3-2 and 18 min for the paste obtained from composition 3-3. Example 4 A mixture (composition 4-1) consisting of: - 15.8% by weight of highly calcined magnesia at high temperature (1500 ° C) and sintered (Grecian Magnesite) - 3% by weight of CaSO 3 wollastonite ( Nordkalk) - 1% by weight of calcined alumina A1203 (RBH) 25 - 79.2% by weight of potassium dihydrogenphosphate KH2PO4 (Prayon) - 1% by weight of a mineral pigment (Oximed 12A Europigments) which makes it possible to color sample and visually reveal the presence of efflorescence. The amount of water added is 17% by weight relative to the total sum of the pulverulent compounds. The practical duration of application of this paste is 13 minutes. The same dough composition is prepared by adding 3% by weight of potassium acetate (composition 4-2). The practical duration of application of this paste is increased and is 40 min.
    [0016] Figures 1 and 2 show the cured products obtained from these compositions 4-1 and 4-2: we note the presence of white areas in Figure 1, reflecting the phenomena of efflorescence. In the presence of potassium acetate, this phenomenon of efflorescence is controlled, the color of the sample being more uniform. EXAMPLE 5 A mortar composition is prepared by mixing the following different constituents: 40% by weight of highly calcined magnesia at high temperature (1500 ° C.) and sintered (Grecian Magnesite) 40% by weight of potassium dihydrogen phosphate KH 2 PO 4 ( Prayon) - 20% by weight of silica sand.
    [0017] The amount of water added is 20% by weight, based on the total sum of the pulverulent compounds. The practical duration of application of this paste is 4.5 min. The same dough composition is prepared by adding 3% by weight of potassium acetate. The practical duration of application of this paste is increased and is 32 min.
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. A phosphate-based inorganic binder obtained by reaction between at least one basic component and an acid phosphate salt, in the presence of a retarding agent which is a X ± A salt whose solubility in aqueous medium measured at 25 ° C is greater than that of the acidic phosphate salt, and wherein X + is a cation selected from alkali metals, alkaline earth metals, aluminum and ammonium ion, and A is an acetate, citrate, formate, benzoate, tartrate, oleate anion, bromide or iodide.
    [0002]
    2. Binder according to claim 1 characterized in that the basic constituent is selected from metal oxides, metal hydroxides or sulfates.
    [0003]
    3. Binder according to claim 1 characterized in that the basic constituent is selected from iron oxide, aluminum oxide, zinc oxide, magnesium oxide or calcium oxide, silicates calcium sulphate sources such as plaster, gypsum, hemihydrate and / or anhydrite, and metallurgical slags.
    [0004]
    Binder according to one of the preceding claims, characterized in that it is obtained from a mixture of at least two basic constituents, at least one of them being chosen from magnesium oxide. , calcium or magnesium hydroxide, wollastonite, alumina, metallurgical slags and calcium sulphate.
    [0005]
    5. Binder according to claim 4 characterized in that said mixture comprises an additional basic constituent selected from kaolin, metakaolin, calcined clays, fly ash, lime, dolomite, mica and / or talc.
    [0006]
    6. Binder according to one of the preceding claims characterized in that the acidic phosphate salt participating in the acid-base reaction of binder formation is selected from: - hydrogen phosphates of potassium, calcium, magnesium, aluminum, Sodium or ammonium, potassium, calcium, magnesium, aluminum, sodium or ammonium dihydrogen phosphates, potassium, calcium, magnesium, aluminum, sodium, potassium pyrophosphates or ammonium, and / or polyphosphates acid potassium, calcium, magnesium, aluminum, sodium or ammonium, alone or in mixture.
    [0007]
    7. Binder according to one of the preceding claims characterized in that the cation X + of the retarding agent is selected from potassium, calcium, magnesium, sodium, aluminum or ammonium ion.
    [0008]
    8. Binder according to one of claims 6 or 7 characterized in that the X + cation of the retarding agent is identical to the cation of the acidic phosphate salt involved in the binder formation reaction.
    [0009]
    Binder according to one of the preceding claims, characterized in that the anion A is an acetate ion or a formate ion.
    [0010]
    Binder according to one of the preceding claims, characterized in that the content of retarding agent represents between 1 and 10% by weight, preferably between 2 and 7% by weight, of the total amount of constituents of the binder.
    [0011]
    11. Binder according to one of the preceding claims characterized in that it comprises another phosphate compound selected from the salts of orthophosphates, polyphosphates or pyrophosphates wherein the cation is selected from sodium, potassium, calcium or the ammonium ion.
    [0012]
    12. A mortar or concrete composition characterized in that it comprises at least one binder according to one of the preceding claims.
    [0013]
    13. Construction products, prepared on site or prefabricated, such as grouting mortars, tile joints, tile adhesives, screeds, floor coatings or technical mortars, insulating mortars or facings obtained from the concrete or mortar composition according to claim 12.
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    法律状态:
    2015-12-15| PLFP| Fee payment|Year of fee payment: 2 |
    2016-06-24| PLSC| Publication of the preliminary search report|Effective date: 20160624 |
    2016-12-16| PLFP| Fee payment|Year of fee payment: 3 |
    2017-12-21| PLFP| Fee payment|Year of fee payment: 4 |
    2019-12-13| PLFP| Fee payment|Year of fee payment: 6 |
    2021-09-10| ST| Notification of lapse|Effective date: 20210806 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1463243A|FR3030498B1|2014-12-23|2014-12-23|ACIDO-BASIC BINDER COMPRISING PHOSPHATE CEMENTS|
    FR1463243|2014-12-23|FR1463243A| FR3030498B1|2014-12-23|2014-12-23|ACIDO-BASIC BINDER COMPRISING PHOSPHATE CEMENTS|
    CN201580076765.6A| CN107428615A|2014-12-23|2015-12-21|Acid/base binding agent comprising the cement based on phosphate compounds|
    EP15832810.4A| EP3237354A2|2014-12-23|2015-12-21|Acid-based binder comprising phosphate-based cements|
    MX2017008297A| MX2017008297A|2014-12-23|2015-12-21|Acid-based binder comprising phosphate-based cements.|
    BR112017012561-7A| BR112017012561A2|2014-12-23|2015-12-21|acid-base binder comprising phosphate-based cements|
    US15/538,734| US10322972B2|2014-12-23|2015-12-21|Acid/base binder comprising phosphate-based cements|
    PCT/FR2015/053692| WO2016102868A2|2014-12-23|2015-12-21|Acid-based binder comprising phosphate-based cements|
    CA2970705A| CA2970705A1|2014-12-23|2015-12-21|Acid-based binder comprising phosphate-based cements|
    RU2017126181A| RU2707316C2|2014-12-23|2015-12-21|Acid-base binding material containing phosphate-based cements|
    ARP150104212A| AR103189A1|2014-12-23|2015-12-21|LIGHT ACID-BASIC THAT INCLUDES PHOSPHATE BASED CEMENTS|
    CL2017001667A| CL2017001667A1|2014-12-23|2017-06-22|Acid-basic binder comprising phosphate-based cements|
    SA517381813A| SA517381813B1|2014-12-23|2017-06-22|Acid/base binder comprising phosphate-based cements|
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