Hydraulic binder composition comprising blast furnace slag

Abstract

The invention relates to a hydraulic binder composition comprising: - a hydraulic binder comprising at least one aluminosilicate compound, such as blast furnace slag, and an alkaline or sulphate activator and up to 10% by weight of clinker, preferably from 0% to 10% by weight of clinker; - a guanidinium salt and / or a zinc salt; - a polymer (P) comprising units of formula (I) and formula (II).

Description

Technical Field

[0001] The present invention relates to a hydraulic adhesive composition comprising at least one aluminosilicate compound and an alkaline or sulfate activator, and a reduced amount of clinker, and relates to maintaining the processability of the obtained hydraulic composition, particularly by adding water to the hydraulic adhesive composition to maintain the processability of the obtained hydraulic composition. Background Technology

[0002] Common cement compositions contain a variable, and sometimes high, proportion of clinker. For example, cement compositions according to the 2012 standard NFEN 197-1 contain 5% to 95% clinker by weight.

[0003] However, clinker production requires the use of powerful kilns, resulting in significant carbon dioxide emissions. The extraction of raw materials is also a source of carbon dioxide emissions.

[0004] Therefore, there is a need to reduce the clinker content of cement compositions to minimize their carbon impact while maintaining their mechanical and rheological properties.

[0005] To address this, new hydraulic adhesive compositions have been developed in which the amount of clinker is reduced.

[0006] Cement compositions in which the hydraulic binder is blast furnace slag have been previously disclosed, and these compositions are typically activated. However, the workability of these compositions decreases sharply, meaning they change from fluid to almost solid in less than 30 minutes. From a rheological perspective, a threshold stress of 1 Pa to 10 Pa is typically observed 5 minutes after mixing, and this value increases to 50 Pa to 100 Pa within 30 to 60 minutes after mixing.

[0007] Therefore, it is of interest to provide a solution that can enhance the flowability of a composition comprising at least one aluminosilicate compound (e.g., blast furnace slag) and an alkaline or sulfate activator. Summary of the Invention

[0008] One object of the present invention is to provide a composition comprising at least one aluminosilicate compound, such as blast furnace slag, and an alkaline or sulfate activator, such that a hydraulic composition exhibiting enhanced fluidity retention can be obtained.

[0009] Another object of the present invention is to provide a composition that allows the fluidity to be maintained for 1 hour or 1 hour and 30 minutes.

[0010] Other additional objectives will also become apparent upon reading the following description of the invention.

[0011] All these objectives are achieved in this application, which relates to a hydraulic binder composition (HBC) comprising:

[0012] - A hydraulic binder comprising at least one aluminosilicate compound, such as blast furnace slag, and an alkaline or sulfate activator and up to 10% by weight of clinker, preferably 0% to 10% by weight of clinker;

[0013] -Guidin salts and / or zinc salts;

[0014] -A polymer (P) comprising units having the following formulas (I) and (II):

[0015]

[0016] in:

[0017] -R 1 and R 2 Independently representing hydrogen or methyl;

[0018] -R 3 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0019] -R 4 It indicates that it has the formula -(CH2). p -(OAlk) q -R5 groups, wherein:

[0020] -p indicates 1 or 2;

[0021] -q represents an integer from 3 to 300;

[0022] -group-(OAlk) q - Each OAlk unit's Alk independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms;

[0023] -R 5 It represents -OH or a straight-chain or branched alkoxy group containing 1 to 4 carbon atoms;

[0024] -R 11 and R 12 Independently representing hydrogen or methyl;

[0025] -R 13 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0026] -M indicates an H or m-valent cation;

[0027] - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M;

[0028] -a is a value between 0.05 and 0.25, such that (100×a) represents the molar percentage of units of formula (I) within the polymer; and

[0029] -b is a value of 0.75 to 0.95, such that (100×b) represents the molar percentage of units of formula (II) in the polymer.

[0030] The inventors have demonstrated in an advantageous manner that, compared with compositions containing no guanidine salt, zinc salt, and polymer (P) according to the invention, the addition of guanidine salt and / or zinc salt and polymer (P) provides an enhanced way of maintaining the fluidity (also known as maintaining processability) of hydraulic compositions prepared from hydraulic binder compositions (HBC) over time, particularly by adding at least water.

[0031] In the context of this invention, for example, by measuring the gradual change in the threshold stress of the hydraulic composition obtained from composition HBC, particularly by adding water, the enhancement in processability retention over time is preferably long-term; that is, when the composition is used at 20°C, the processability retention of the composition is enhanced over a period of time greater than or equal to 45 minutes, particularly greater than 60 minutes, or even greater than 90 minutes. Therefore, when the composition is used at 20°C, a threshold stress of approximately 1 Pa to 10 Pa is required over the same time interval, i.e., a period of time greater than or equal to 45 minutes, particularly greater than 60 minutes, or practically even greater than 90 minutes.

[0032] Specifically, the threshold stress can be measured using a rheometer by taking multiple measurements of the applied stress to obtain each corresponding strain rate value. The applied stress value at which the strain rate becomes very low or zero can be considered the threshold stress.

[0033] Hydraulic binder compositions (HBCs) may be clinker-free.

[0034] Parts 3.7 and 3.6 of the NF EN 15167-1 standard provide a specific definition for blast furnace slag. Blast furnace slag is primarily a glassy material and is a byproduct of the cast iron production process. The blast furnace slag used in hydraulic binder compositions is finely ground, preferably to a maximum diameter of 100 μm to 150 μm, which is measured by any suitable method known to those skilled in the art, such as laser particle size analysis. Blast furnace slag typically requires calcium or calcium thiosulfate activation or activation using a strong alkali.

[0035] Therefore, the hydraulic binder composition (HBC) of the present invention comprises an alkaline or sulfate activator for aluminosilicate compounds (especially blast furnace slag); preferably a calcium or sulfate activator, preferably a calcium thio-activator; or an alkaline salt, preferably sodium carbonate or potassium carbonate, sodium hydroxide or potassium hydroxide, or sodium silicate or potassium silicate, or a mixture thereof; or a calcium sulfate activator. The activator is preferably used in a proportion of 0.1% to 20% of the total weight of the hydraulic binder, more preferably in a proportion of 0.1% to 20% of the total weight of the hydraulic binder.

[0036] The activator may also exist in an amount equal to 0% to 10% of dry weight relative to the weight of the hydraulic adhesive.

[0037] Hydraulic binder compositions containing blast furnace slag and calcium sulfate (particularly in proportions of 5% to 20% by weight) are also known as supersulfate cement (SSC), and are specifically defined as in standard NF EN 15743+A1.

[0038] Preferably, the hydraulic binder composition (HBC) according to the invention comprises: a hydraulic binder comprising at least one aluminosilicate compound, such as blast furnace slag; an activator, preferably a calcium or sulfate activator, preferably a calcium thioate activator, or an alkaline salt; and up to 10% by weight of clinker, preferably 0% to 10% by weight of clinker.

[0039] In the context of this invention, the term "aluminosilicate compound" is used to refer to fly ash (as defined in section 5.2.4 of standard cement NF EN197-1 (2012); metakaolin, such as type A metakaolin or calcined clay conforming to standard NF P 18-513 (August 2012); aluminosilicates, particularly inorganic geopolymer-type aluminosilicates.

[0040] The compositions of the present invention may comprise a mixture of aluminosilicate compounds.

[0041] Preferably, the hydraulic binder consists of an aluminosilicate compound and an alkaline or sulfate activator. More preferably, the hydraulic binder consists of blast furnace slag and an alkaline or sulfate activator.

[0042] The hydraulic binder may also contain mineral additives, the amount of which is preferably 0% to 10% by weight relative to the total weight of the hydraulic binder.

[0043] The term "mineral additive" is used to refer to volcanic ash materials (as defined in paragraph 5.2.3 of standard cement NF EN 197-1 (2012)), calcined shale (as defined in paragraph 5.2.5 of standard cement NF EN 197-1 (2012)), limestone (as defined in paragraph 5.2.6 of standard cement NF EN 197-1 (2012)), or even silica fume (as defined in paragraph 5.2.7 of standard cement NF EN 197-1 (2012)) or mixtures thereof. Other additives not currently recognized in standard cement NF EN 197-1 (2012) may also be used. These include silica additives, such as silica additives with quartz (Qz) mineralogical conformation to standard NF P 18-509 (September 2012). The proportions and properties of the additives may also conform to standard prEN 197-5, which defines that Portland composite cement CEMII / CM contains 50%–64% clinker and 36%–50% blast furnace slag, and composite cement CEM VI contains 35%–49% clinker, 31%–59% blast furnace slag, and 6%–20% of the mineral additives defined above.

[0044] Preferably, the aluminosilicate compound is blast furnace slag, and the hydraulic binder may also contain mineral additives. The term "mineral additives" is used to refer to pozzolanic materials (as defined in section 5.2.3 of standard cement NF EN 197-1 (2012)), fly ash (as defined in section 5.2.4 of standard cement NF EN 197-1 (2012)), calcined shale (as defined in section 5.2.5 of standard cement NF EN 197-1 (2012)), limestone (as defined in section 5.2.6 of standard cement NF EN 197-1 (2012)), or even silica fume (as defined in section 5.2.7 of standard cement NF EN 197-1 (2012)), or mixtures thereof. Other additives not currently recognized in standard cement NF EN 197-1 (2012) may also be used. These include metakaolin, such as type A metakaolin or calcined clay conforming to standard NF P 18-513 (August 2012); silica additives, such as silica additives with quartz (Qz) mineralogical conforming to standard NF P 18-509 (September 2012); and aluminosilicates, particularly inorganic geopolymer-type aluminosilicates. The proportions and properties of the additives may also conform to standard prEN 197-5, which defines Portland composite cement CEMII / CM as containing 50%–64% clinker and 36%–50% blast furnace slag, and composite cement CEM VI as containing 35%–49% clinker, 31%–59% blast furnace slag, and 6%–20% of the aforementioned defined mineral additives.

[0045] Therefore, in the context of this invention, the hydraulic binder comprises: blast furnace slag, optionally a slag activator as defined above, optionally clinker, and optionally mineral additives as described above.

[0046] Preferably, the hydraulic adhesive composition contains 75% to 99% by weight of an aluminosilicate compound, more preferably 80% to 95% by weight, for example 80% to 90% by weight, relative to the total weight of the hydraulic adhesive.

[0047] Advantageously, the guanidine salt and / or zinc salt mixtures of the present invention form a water-soluble solution rather than a suspension with the polymer. Advantageously, this allows for easy use in hydraulic adhesive compositions.

[0048] In one embodiment, the HBC composition comprises a guanidine salt.

[0049] In another embodiment, the HBC composition comprises a zinc salt.

[0050] In the last embodiment, the HBC composition comprises a guanidine salt and a zinc salt.

[0051] The amount of guanidine salt and / or zinc salt in the hydraulic binder composition (HBC) is 0.1% to 5% dry weight, preferably 1.0% to 2.5% dry weight, relative to the total weight of the hydraulic binder.

[0052] Guanidine salts can be selected from guanidine thiocyanate, guanidine acetate, and guanidine nitrate.

[0053] Zinc salts can be selected from zinc chloride and zinc nitrate.

[0054] When guanidine salts and thiocyanates are used simultaneously, the mixture of guanidine salts and thiocyanates contains 30% to 50% dry weight of guanidine salts and 50% to 70% dry weight of zinc salts.

[0055] Preferably, the HBC composition comprises 0.1% to 3.0% of polymer (P) relative to the total weight of the hydraulic binder, more preferably 0.3% to 1.0% of polymer (P).

[0056] In the context of this invention, the term "total weight of hydraulic binder" refers to the weight of the aluminosilicate compound (preferably blast furnace slag), activator, clinker (if present), and mineral additives (if present).

[0057] The following embodiments of the polymer (P) units of formulas (I) and (II) can be considered independently or in combination:

[0058] -R 1 H represents;

[0059] -R 3 H represents;

[0060] -R 1 and R 3 H represents;

[0061] -R 2 Indicates methyl;

[0062] -p means 1;

[0063] -Alk represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-,

[0064] -CH2-CHMe-, -CHMe-CH2-;

[0065] -group-(OAlk) q - At least 80% of Alk represents -CH2-CH 2- or even groups

[0066] -(OAlk) q -All Alk representations are -CH2-CH2-;

[0067] -q represents an integer from 5 to 200, especially an integer from 10 to 100, and preferably an integer from 25 to 75;

[0068] -R 5 Represents -OH or -OMe, preferably R 5 It represents -OH;

[0069] - The sum of a and b is 1;

[0070] -R 11 H represents;

[0071] -R 13 H represents;

[0072] -R 11 and R 13 H represents;

[0073] -R 12 Indicates H; and / or

[0074] -M represents H or a monovalent or divalent cation, where m represents 1 or 2, and the monovalent cation is preferably selected from the ammonium salt NH4. + Primary ammonium cations, secondary ammonium cations, tertiary ammonium cations or quaternary ammonium cations and alkali metal cations, such as sodium ions, lithium ions or potassium ions, and the divalent cations are preferably alkaline earth metal cations, such as magnesium ions or calcium ions;

[0075] -a is a value of 0.05 to 0.20, preferably a represents a value of 0.10 to 0.20;

[0076] -b is a value between 0.80 and 0.95, preferably b represents a value between 0.80 and 0.90.

[0077] Preferably, the polymer (P) having a unit of formula (I) has the following formula (I'):

[0078]

[0079] in:

[0080] -R 2 Independently representing hydrogen or methyl, preferably methyl;

[0081] -R' 4 This indicates the expression -CH2-(O-CH2-CH2). q -R5 groups, wherein:

[0082] -q represents an integer from 3 to 500;

[0083] -R 5 It can be represented as -OH or -OMe, preferably -OH;

[0084] -a is a value of 0.05 to 0.25, such that (100×a) represents the molar percentage of units of formula (I') in the polymer (P);

[0085] Preferably, the polymer (P) having units of formula (II) has the following formula (II'):

[0086]

[0087] in:

[0088] -R 12 Indicates hydrogen or methyl, preferably hydrogen;

[0089] -M indicates an H or m-valent cation;

[0090] - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M;

[0091] -b is a value of 0.75 to 0.95, such that (100×b) represents the molar percentage of units of formula (II') in the polymer.

[0092] Preferably, the polymer (P) comprises units having formula (I') and formula (II').

[0093] The following embodiments of polymers (P) of formulas (I') and (II') can be considered independently or in combination:

[0094] -q represents an integer from 5 to 200, especially an integer from 10 to 100, and preferably an integer from 25 to 75;

[0095] -R 5 Represents -OH or -OMe, preferably R 5 It represents -OH;

[0096] -a is a value of 0.05 to 0.20, preferably a represents a value of 0.10 to 0.20;

[0097] -b is a value between 0.80 and 0.95, preferably b represents a value between 0.80 and 0.90;

[0098] -a and b sum to 1 (meaning the polymer is composed of units having formulas (I) and (II)); and / or

[0099] -M represents H or a monovalent or divalent cation, and m represents 1 or 2. The monovalent cation is preferably selected from the ammonium salt NH4. + Primary ammonium cations, secondary ammonium cations, tertiary ammonium cations or quaternary ammonium cations and alkali metal cations, such as sodium ions, lithium ions or potassium ions, and the divalent cations are preferably alkaline earth metal cations, such as magnesium ions or calcium ions.

[0100] In addition to the units having formulas (I) and (II), polymer (P) may also contain one or more additional units. Preferably, polymer (P) does not contain units having the following formula (III):

[0101]

[0102] Wherein, M represents H or a cation, such as sodium. In a particularly preferred embodiment, the polymer (P) does not contain sulfonic acid or sulfonate groups.

[0103] Preferably, the polymer (P) is composed of units having formulas (I) and (II). It does not contain any other units besides those having formulas (I) and (II). Therefore, the sum of a and b is 1.

[0104] The weight-average molar mass of the polymer is typically 10,000 g / mol to 200,000 g / mol, especially 10,000 g / mol to 100,000 g / mol.

[0105] Typically, polymers (P) are obtained through free radical polymerization.

[0106] Therefore, polymer (P) is a comb-type polymer, in which side chain groups are connected to the main carbon chain via ether groups.

[0107] The hydraulic binder composition (HBC) may also contain a polyalkoxylated polyphosphonate-based polymer, preferably in a dry weight ratio of 0.1% to 3.0% relative to the total weight of the hydraulic binder; optionally, it contains mineral additives, preferably in a dry weight ratio of 0.3% to 1.0% relative to the total weight of the hydraulic binder, particularly as described in patent EP0663892 (e.g. FluidOptima 100).

[0108] In the context of this invention, polyalkoxylated phosphonates are preferably one of polyalkoxylated phosphonate polymers having formula (V) or salts thereof, alone or as a mixture:

[0109]

[0110] in:

[0111] R5 is a hydrogen atom or a monovalent hydrocarbon group containing 1 to 18 carbon atoms and optionally one or more heteroatoms;

[0112] Ri may be similar to or different from each other, representing an alkylene group, such as ethylene, propylene, butene, pentene, octene, or cyclohexene; or an aryl group, such as styrene or methylstyrene; Ri may optionally contain one or more heteroatoms;

[0113] Q is a hydrocarbon group containing 2 to 18 carbon atoms and optionally one or more heteroatoms;

[0114] A is an alkylene group containing 1 to 5 carbon atoms; R j They may be similar to or different from each other, and can be selected from:

[0115] - Group A-PO3H2, where A has the aforementioned definition;

[0116] -alkyl group, containing 1 to 18 carbon atoms, and may include a [R] group. 5 -O(R i -O) m R5 and Ri have the aforementioned definitions;

[0117] “m” is a value greater than or equal to 0;

[0118] “r” is a group carried by all Rj [R 5 -O(R i -O) m The quantity of ];

[0119] “q” is a group [R] carried by Q. 5 -O(R i -O)m The quantity of ];

[0120] The sum of “r+q” is 1 to 10;

[0121] “y” is an integer from 1 to 3;

[0122] Q, N, and R j They can form one or more rings together, and the aforementioned one or more rings may also contain one or more other heteroatoms.

[0123] In a particularly preferred embodiment, the polyalkoxylated phosphonate comprises a water-soluble or water-dispersible organic compound containing at least one amino di(alkylphosphonic acid) group and at least one polyalkoxylated chain or at least one salt thereof.

[0124] Preferably, the polyalkoxylated phosphonate is a compound having formula (V), wherein:

[0125] R 5 It is a hydrogen atom, or a monovalent hydrocarbon group containing 1 to 8 carbon atoms, or optionally one or more heteroatoms, whether saturated or unsaturated;

[0126] Ri represents ethylene, or propylene, or a mixture of ethylene or propylene, preferably 60% to 100% of Ri is ethylene;

[0127] Q is a hydrocarbon group containing 2 to 8 carbon atoms and optionally one or more heteroatoms;

[0128] A is methylene;

[0129] Each Rj represents the group CH2-PO3H2;

[0130] m is an integer from 10 to 250;

[0131] q is an integer equal to 1 or 2;

[0132] y is an integer equal to 1 or 2.

[0133] Specifically, the polyalkoxylated phosphonate can be a polyalkoxylated phosphonate having formula (V), wherein R5 is a methyl group, R i It consists of ethylene and propylene groups, m is 30-50, r+q equals 1, Q is the ethylene group, A is the methylene group, y equals 1, and R j It corresponds to the group CH2-PO3H2.

[0134] Preferably, relative to the total weight of the hydraulic adhesive, the hydraulic adhesive composition (HBC) according to the invention comprises 0.1% to 5.0% dry weight, preferably 0.5% to 2.0% dry weight, of guanidine salt and / or zinc salt, and 0.1% to 3.0% dry weight, preferably 0.3% to 1% dry weight, of polymer (P).

[0135] When guanidine salts and thiocyanates are used simultaneously, the mixture of guanidine salts and thiocyanates contains 30% to 50% dry weight of guanidine salts and 50% to 70% dry weight of zinc salts.

[0136] This application also relates to hydraulic adhesive compositions (HBC) comprising:

[0137] - A hydraulic binder comprising blast furnace slag and up to 10% by weight of clinker, preferably 0% to 10% by weight of clinker;

[0138] -Guidin salts and / or zinc salts;

[0139] -A polymer (P) comprising units having the following formulas (I) and (II):

[0140]

[0141] in:

[0142] -R 1 and R 2 Independently representing hydrogen or methyl;

[0143] -R 3 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0144] -R 4 It indicates that it has the formula -(CH2). p -(OAlk) q -R5 groups, wherein;

[0145] -p indicates 1 or 2;

[0146] -q represents an integer from 3 to 300;

[0147] -group-(OAlk) q - Each OAlk unit's Alk independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms;

[0148] -R 5 It represents -OH or a straight-chain or branched alkoxy group containing 1 to 4 carbon atoms;

[0149] -R 11 and R 12Independently representing hydrogen or methyl;

[0150] -R 13 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0151] -M indicates an H or m-valent cation;

[0152] - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M;

[0153] -a is a value between 0.05 and 0.25, such that (100×a) represents the molar percentage of units of formula (I) within the polymer; and

[0154] -b is a value of 0.75 to 0.95, such that (100×b) represents the molar percentage of units of formula (II) in the polymer.

[0155] The above-mentioned elements regarding hydraulic adhesives, guanidine salts, zinc salts, and polymers (P) also apply.

[0156] The present invention also relates to an admixture composition (AC) comprising:

[0157] -Guidin salts and / or zinc salts;

[0158] - Polymers containing units having the following formulas (I) and (II):

[0159]

[0160] in:

[0161] -R 1 and R 2 Independently representing hydrogen or methyl;

[0162] -R 3 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0163] -R 4 It indicates that it has the formula -(CH2). p -(OAlk) q -R5 groups, wherein;

[0164] -p indicates 1 or 2;

[0165] -q represents an integer from 3 to 300;

[0166] -group-(OAlk) q - Each OAlk unit's Alk independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms;

[0167] -R 5 It represents -OH or a straight-chain or branched alkoxy group containing 1 to 4 carbon atoms;

[0168] -R 11 and R 12 Independently representing hydrogen or methyl;

[0169] -R 13 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0170] -M indicates an H or m-valent cation;

[0171] - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M;

[0172] -a is a value between 0.05 and 0.25, such that (100×a) represents the molar percentage of units of formula (I) within the polymer; and

[0173] -b is a value of 0.75 to 0.95, such that (100×b) represents the molar percentage of units of formula (II) in the polymer.

[0174] Preferably, the admixture composition of the present invention comprises: 1 part of polymer on a dry weight basis; 0 to 4 parts, preferably 1 to 4 parts, preferably 1.5 to 2.5 parts of guanidine salt; and 0 to 5 parts, preferably 1 to 5 parts, preferably 2.5 to 3.5 parts of zinc salt.

[0175] Preferably, the admixture composition of the present invention comprises: 1 part of polymer on a dry weight basis; 1 to 4 parts, preferably 1.5 to 2.5 parts, of guanidine salt; and 1 to 5 parts, preferably 2.5 to 3.5 parts, of zinc salt.

[0176] In one embodiment, the admixture composition comprises a guanidine salt.

[0177] In another embodiment, the admixture composition comprises a zinc salt.

[0178] In the last embodiment, the admixture composition comprises guanidine salt and zinc salt.

[0179] Zinc salts and thiocyanates, as well as polymers (P), are as described above.

[0180] This application also relates to the use of the admixture composition in preparing a hydraulic binder composition as defined above, or in preparing a hydraulic composition as defined below, by adding the admixture composition to a hydraulic binder composition comprising a hydraulic binder as defined above, or to a composition comprising a hydraulic binder as defined above, water, and optionally at least one aggregate.

[0181] Compared to the same hydraulic composition without admixtures, using the admixture composition according to the invention makes it possible to enhance the fluidity retention of the hydraulic composition.

[0182] Guanidine salts can be selected from guanidine thiocyanate, guanidine acetate, and guanidine nitrate.

[0183] Zinc salts can be selected from zinc chloride and zinc nitrate.

[0184] When guanidine salts and thiocyanates are used simultaneously, the mixture of guanidine salts and thiocyanates contains 30% to 50% dry weight of guanidine salts and 50% to 70% dry weight of zinc salts.

[0185] The amount of admixture composition according to the invention used relative to the total weight of the hydraulic binder is such that the amount of guanidine salt and / or zinc salt added is 0.1% to 5% dry weight, preferably 1.0% to 2.5% dry weight.

[0186] The amount of the admixture composition according to the invention used relative to the total weight of the hydraulic adhesive is such that the amount of polymer (P) is 0.1% to 3.0% of dry weight, preferably 0.3% to 1.0% of dry weight.

[0187] The amount of the admixture composition according to the invention used is such that: the amount of guanidine salt and / or zinc salt added is 0.1% to 5% dry weight, preferably 1.0% to 2.5% dry weight, relative to the total weight of the hydraulic binder; and the amount of polymer (P) added is 0.1% to 3.0% dry weight, preferably 0.3% to 1.0% dry weight, relative to the total weight of the hydraulic binder.

[0188] The present invention also relates to the use of the hydraulic binder composition (HBC) as defined above for the preparation of hydraulic compositions (HC).

[0189] The present invention also relates to a hydraulic composition (HC) comprising (or even consisting of): a hydraulic binder composition (HBC) as defined above, water, and optionally at least one aggregate.

[0190] This invention relates to a hydraulic composition (HC) comprising:

[0191] - A hydraulic binder comprising at least one aluminosilicate compound, preferably blast furnace slag, and an alkaline or sulfate activator and up to 10% by weight of clinker, preferably 0% to 10% by weight of clinker, and optionally mineral additives as defined above.

[0192] -water;

[0193] -Optionally, at least one type of aggregate;

[0194] -Guidine salts and / or zinc salts; and

[0195] - Polymers (P) comprising units having the following formulas (I) and (II):

[0196]

[0197] in:

[0198] -R 1 and R 2 Independently representing hydrogen or methyl;

[0199] -R 3 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0200] -R 4 It indicates that it has the formula -(CH2). p -(OAlk) q -R5 groups, wherein;

[0201] -p indicates 1 or 2;

[0202] -q represents an integer from 3 to 300;

[0203] -group-(OAlk) q - Each OAlk unit's Alk independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms;

[0204] -R 5 It represents -OH or a straight-chain or branched alkoxy group containing 1 to 4 carbon atoms;

[0205] -R 11 and R 12 Independently representing hydrogen or methyl;

[0206] -R 13 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0207] -M indicates an H or m-valent cation;

[0208] - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M;

[0209] -a is a value between 0.05 and 0.25, such that (100×a) represents the molar percentage of units of formula (I) within the polymer; and

[0210] -b is a value of 0.75 to 0.95, such that (100×b) represents the molar percentage of units of formula (II) in the polymer.

[0211] Hydraulic binders, activators, guanidine and zinc salts, mineral additives, and polymers (P) are as defined above.

[0212] This invention relates to a hydraulic composition (HC) comprising:

[0213] - A hydraulic binder comprising blast furnace slag and up to 10% by weight of clinker, preferably 0% to 10% by weight of clinker, 0% to 10% by dry weight of the activator as described above, and optionally the mineral additives as described above.

[0214] -water;

[0215] -Optionally, at least one type of aggregate;

[0216] -Guidine salts and / or zinc salts; and

[0217] - Polymers (P) comprising units having the following formulas (I) and (II):

[0218]

[0219] in:

[0220] -R 1 and R 2 Independently representing hydrogen or methyl;

[0221] -R 3 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0222] -R 4 It indicates that it has the formula -(CH2). p -(OAlk) q -R5 groups, wherein;

[0223] -p indicates 1 or 2;

[0224] -q represents an integer from 3 to 300;

[0225] -group-(OAlk) q- Each OAlk unit's Alk independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms;

[0226] -R 5 It represents -OH or a straight-chain or branched alkoxy group containing 1 to 4 carbon atoms;

[0227] -R 11 and R 12 Independently representing hydrogen or methyl;

[0228] -R 13 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0229] -M indicates an H or m-valent cation;

[0230] - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M;

[0231] -a is a value between 0.05 and 0.25, such that (100×a) represents the molar percentage of units of formula (I) within the polymer; and

[0232] -b is a value of 0.75 to 0.95, such that (100×b) represents the molar percentage of units of formula (II) in the polymer.

[0233] Hydraulic binders, guanidine salts and zinc salts, activators, mineral additives, and polymers (P) are as defined above.

[0234] The hydraulic composition may also contain a polyalkoxylated polyphosphonate-based polymer, preferably in a proportion of 0.1% to 3.0% dry weight, more preferably 0.3% to 1.0% dry weight, relative to the total weight of the hydraulic binder. This polymer is as described above.

[0235] In one embodiment, the hydraulic composition comprises a guanidine salt.

[0236] In another embodiment, the hydraulic composition comprises a zinc salt.

[0237] In the last embodiment, the hydraulic composition comprises guanidine salt and zinc salt.

[0238] The amount of guanidine salt and / or zinc salt in the hydraulic composition is 0.1% to 5% dry weight, preferably 1.0% to 2.5% dry weight, relative to the total weight of the hydraulic binder.

[0239] Guanidine salts can be selected from guanidine thiocyanate, guanidine acetate, and guanidine nitrate.

[0240] Zinc salts can be selected from zinc chloride and zinc nitrate.

[0241] When guanidine salts and thiocyanates are used simultaneously, the mixture of guanidine salts and thiocyanates contains 30% to 50% dry weight of guanidine salts and 50% to 70% dry weight of zinc salts.

[0242] Preferably, the hydraulic composition comprises 0.1% to 3.0% of polymer (P) relative to the total weight of the hydraulic binder, more preferably 0.3% to 1.0% of polymer (P).

[0243] Preferably, the hydraulic composition comprises 0.1% to 5% dry weight, more preferably 1.0% to 2.5% dry weight of polymer (P) relative to the total weight of the hydraulic adhesive; and the hydraulic composition comprises 0.1% to 3.0% dry weight, more preferably 0.3% to 1.0% dry weight of polymer (P) relative to the total weight of the hydraulic adhesive.

[0244] The hydraulic composition is preferably a concrete, mortar, or screed composition.

[0245] The term "aggregates" refers to a group of mineral particles with an average diameter of 0 mm to 125 mm. Based on their diameter, aggregates are classified into one of the following six categories: filler, gravel, sand, gravel, crushed stone, and ballast (standard XPP18-545). The most commonly used aggregates are:

[0246] - Filler material with a diameter less than 2 mm, and at least 85% of the aggregate with a diameter less than 1.25 mm, and at least 70% of the aggregate with a diameter less than 0.063 mm;

[0247] - Sand, with a diameter of 0mm to 4mm (in standard 13-242, the diameter can reach 6mm);

[0248] - Gravel, with a diameter greater than 6.3 mm;

[0249] - Crushed stone, with a diameter of 2mm to 63mm.

[0250] Therefore, sand is included in the definition of aggregate according to the present invention.

[0251] In terms of source, the filler can be derived in particular from limestone or dolomite.

[0252] Other additives may also be added to the hydraulic composition (CH) according to the invention, such as anti-air entrainment additive, defoamer, coagulation accelerator or retarder, rheology modifier or other fluidizing agent (“plasticizer” or “superplasticizer”).

[0253] The inventors have demonstrated in an advantageous manner that the addition of guanidine salts and / or zinc salts and polymers (P) according to the invention provides a way to enhance the retention of the fluidity of the hydraulic composition over time (also known as the retention of processability) compared to the same composition which does not contain any of the guanidine salts, zinc salts and polymers (P) according to the invention.

[0254] In the context of this invention, the enhancement of processability retention (e.g., measured by a gradual change in the threshold stress of the hydraulic composition) is preferably long-term, that is, when the composition is used at 20°C, the enhancement of processability retention over a period of 45 minutes or more, particularly 60 minutes, or practically even 90 minutes. Therefore, when the composition is used at 20°C, a threshold stress of about 1 Pa to 10 Pa is desired over the same time interval, i.e., a period of 45 minutes or more, particularly 60 minutes, or practically even 90 minutes.

[0255] This application also relates to a composition preparation method for preparing a hydraulic composition according to the invention, wherein guanidine salts and / or zinc salts, as well as polymers (P) and optionally polyalkoxylated polyphosphonate-based polymers, are added to a hydraulic binder.

[0256] This application also relates to a composition preparation method for preparing a hydraulic composition according to the invention, wherein a guanidine salt and / or a zinc salt are added to a hydraulic binder, and a polymer (P) and optionally a polyalkoxylated polyphosphonate polymer are added together with water, for example, to a mixed water.

[0257] The hydraulic composition is prepared by mixing the aforementioned components in a conventional manner. The polymer (P) according to the invention, and suitable polyalkoxylated polyphosphonate-based polymers, can be added to the components of the hydraulic composition in dry form (usually in powder form) or in solution, preferably in aqueous solution. The water in the aqueous solution can be mixed water or pre-wetting water (a portion of the total water used to wet the aggregate before mixing, thereby simulating the hygroscopic state of the aggregate, which is often wet in concrete plants or construction sites).

[0258] The present invention also relates to guanidine salts and / or zinc salts, and the use of polymers comprising units having the following formulas (I) and (II) for the preparation of hydraulic compositions:

[0259]

[0260] in:

[0261] -R 1 and R 2 Independently representing hydrogen or methyl;

[0262] -R 3 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0263] -R 4 It indicates that it has the formula -(CH2). p -(OAlk) q -R5 groups, wherein;

[0264] -p indicates 1 or 2;

[0265] -q represents an integer from 3 to 300;

[0266] -group-(OAlk) q - Each OAlk unit's Alk independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms;

[0267] -R 5 It represents -OH or a straight-chain or branched alkoxy group containing 1 to 4 carbon atoms;

[0268] -R 11 and R 12 Independently representing hydrogen or methyl;

[0269] -R 13 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0270] -M indicates an H or m-valent cation;

[0271] - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M;

[0272] -a is a value between 0.05 and 0.25, such that (100×a) represents the molar percentage of units of formula (I) within the polymer; and

[0273] -b is a value of 0.75 to 0.95, such that (100×b) represents the molar percentage of units of formula (II) in the polymer;

[0274] The hydraulic composition comprises a hydraulic binder comprising blast furnace slag and up to 10% by weight of clinker, preferably 0% to 10.0% by weight of clinker, 0% to 10.0% by weight of the activator as described above, and optionally the mineral additives as described above, water, and optionally at least one aggregate.

[0275] Hydraulic binders, guanidine salts and zinc salts, activators, mineral additives, and polymers (P) are as defined above.

[0276] The present invention also relates to the use of guanidine salts and / or zinc salts, and polymers comprising units having formulas (I) and (II) for enhancing the flowability of hydraulic compositions, particularly for maintaining the processability of hydraulic compositions:

[0277]

[0278] in:

[0279] -R 1 and R 2 Independently representing hydrogen or methyl;

[0280] -R 3 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0281] -R 4 It indicates that it has the formula -(CH2). p -(OAlk) q -R5 groups, wherein;

[0282] -p indicates 1 or 2;

[0283] -q represents an integer from 3 to 300;

[0284] -group-(OAlk) q - Each OAlk unit's Alk independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms;

[0285] -R 5 It represents -OH or a straight-chain or branched alkoxy group containing 1 to 4 carbon atoms;

[0286] -R 11 and R 12 Independently representing hydrogen or methyl;

[0287] -R 13 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0288] -M indicates an H or m-valent cation;

[0289] - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M;

[0290] -a is a value between 0.05 and 0.25, such that (100×a) represents the molar percentage of units of formula (I) within the polymer; and

[0291] -b is a value of 0.75 to 0.95, such that (100×b) represents the molar percentage of units of formula (II) in the polymer;

[0292] The hydraulic composition comprises a hydraulic binder comprising blast furnace slag and up to 10% by weight of clinker, preferably 0% to 10.0% by weight of clinker, 0% to 10% by weight of the activator as described above, and optionally the mineral additives as described above, water, and optionally at least one aggregate.

[0293] Hydraulic binders, guanidine salts and zinc salts, activators, mineral additives, and polymers (P) are as defined above.

[0294] In one implementation, only guanidine salts are used.

[0295] In another implementation, only zinc salts are used.

[0296] In the last embodiment, guanidine salts and zinc salts are used.

[0297] The amount of guanidine salt and / or zinc salt added to the hydraulic composition relative to the total weight of the hydraulic binder is 0.1% to 5% dry weight, preferably 1.0% to 2.5% dry weight.

[0298] Guanidine salts can be selected from guanidine thiocyanate, guanidine acetate, and guanidine nitrate.

[0299] Zinc salts can be selected from zinc chloride and zinc nitrate.

[0300] When guanidine salts and thiocyanates are used simultaneously, the mixture of guanidine salts and thiocyanates contains 30% to 50% dry weight of guanidine salts and 50% to 70% dry weight of zinc salts.

[0301] Preferably, the amount of polymer (P) added to the hydraulic composition is 0.1% to 3.0% of dry weight, more preferably 0.3% to 1.0% of dry weight, relative to the total weight of the hydraulic binder.

[0302] Preferably, the following substances are added to the hydraulic composition (HC): 0.1% to 5% dry weight, preferably 1.0% to 2.5% dry weight, of guanidine salt and / or zinc salt relative to the total weight of the hydraulic binder; and 1% to 3.0% dry weight, preferably 0.3% to 1.0% dry weight, of polymer (P) relative to the total weight of the hydraulic binder.

[0303] Advantageously, the use of the invention provides a way to enhance the retention of the fluidity (also known as the retention of processability) of the hydraulic composition over time compared to the same hydraulic composition without the guanidine salt or zinc salt of the invention and the polymer. The enhancement of fluidity retention is as described above.

[0304] In an advantageous manner, polyalkoxylated polyphosphonate polymers as described above may also be added, particularly in the proportions described above.

[0305] The present invention also relates to guanidine salts and / or zinc salts, and the use of polymers comprising units having the following formulas (I) and (II) for the preparation of hydraulic compositions:

[0306]

[0307] in:

[0308] -R 1 and R 2 Independently representing hydrogen or methyl;

[0309] -R 3 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0310] -R 4 It indicates that it has the formula -(CH2). p -(OAlk) q -R5 groups, wherein;

[0311] -p indicates 1 or 2;

[0312] -q represents an integer from 3 to 300;

[0313] -group-(OAlk) q - Each OAlk unit's Alk independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms;

[0314] -R 5 It represents -OH or a straight-chain or branched alkoxy group containing 1 to 4 carbon atoms;

[0315] -R 11 and R 12 Independently representing hydrogen or methyl;

[0316] -R 13 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0317] -M indicates an H or m-valent cation;

[0318] - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M;

[0319] -a is a value between 0.05 and 0.25, such that (100×a) represents the molar percentage of units of formula (I) within the polymer; and

[0320] -b is a value of 0.75 to 0.95, such that (100×b) represents the molar percentage of units of formula (II) in the polymer;

[0321] The hydraulic composition comprises a hydraulic binder comprising blast furnace slag and up to 10% by weight of clinker, preferably 0% to 10.0% by weight of clinker, 0% to 10.0% by weight of the activator as described above, and optionally mineral additives as described above, water, and optionally at least one aggregate.

[0322] Hydraulic binders, guanidine salts and zinc salts, activators, mineral additives, and polymers (P) are as defined above.

[0323] The present invention also relates to guanidine salts and / or zinc salts, and the use of polymers comprising units having formulas (I) and (II) for enhancing the flowability of hydraulic compositions, particularly for maintaining the processability of hydraulic compositions:

[0324]

[0325] in:

[0326] -R 1 and R 2 Independently representing hydrogen or methyl;

[0327] -R 3 Represents hydrogen or has the formula -COO(M) 1 / m Groups;

[0328] -R 4 It indicates that it has the formula -(CH2). p -(OAlk) q -R5 groups, wherein;

[0329] -p indicates 1 or 2;

[0330] -q represents an integer from 3 to 300;

[0331] -group-(OAlk) q - Each OAlk unit's Alk independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms;

[0332] -R 5 It represents -OH or a straight-chain or branched alkoxy group containing 1 to 4 carbon atoms;

[0333] -R 11 and R 12 Independently representing hydrogen or methyl;

[0334] -R 13 Represents hydrogen or has the formula -COO(M)1 / m Groups;

[0335] -M indicates an H or m-valent cation;

[0336] - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M;

[0337] -a is a value between 0.05 and 0.25, such that (100×a) represents the molar percentage of units of formula (I) within the polymer; and

[0338] -b is a value of 0.75 to 0.95, such that (100×b) represents the molar percentage of units of formula (II) in the polymer;

[0339] The hydraulic composition comprises a hydraulic binder comprising blast furnace slag and up to 10% by weight of clinker, preferably 0% to 10.0% by weight of clinker, 0% to 10% by weight of the activator as described above, and optionally mineral additives as described above, water, and optionally at least one aggregate.

[0340] Hydraulic binders, guanidine salts and zinc salts, activators, mineral additives, and polymers (P) are as defined above.

[0341] In an advantageous manner, polyalkoxylated polyphosphonate polymers as described above may also be added, particularly in the proportions described above.

[0342] The present invention also relates to a method for enhancing the retention of fluidity (also known as the retention of processability) over time in a hydraulic composition comprising a hydraulic binder comprising at least one aluminosilicate compound, preferably blast furnace slag, an alkaline or sulfate activator, and up to 10% by weight of clinker, preferably 0% to 10% by weight of clinker, optionally mineral additives as described above, water, and optionally at least one aggregate; wherein the method comprises adding guanidine salts and / or zinc salts, and a polymer comprising units having formulas (I) and (II) as defined above.

[0343] As mentioned above, liquidity has been enhanced.

[0344] The present invention also relates to a method for enhancing the retention of fluidity (also known as the retention of processability) over time in a hydraulic composition comprising a hydraulic binder comprising blast furnace slag and up to 10% by weight of clinker, preferably 0% to 10% by weight of clinker, 0% to 10% by weight of an activator as described above and optionally mineral additives as described above, water and optionally at least one aggregate; wherein the method comprises adding guanidine salts and / or zinc salts, and a polymer comprising units having formulas (I) and (II) as defined above.

[0345] Hydraulic adhesives are as defined above.

[0346] In the first implementation, only guanidine salts are used.

[0347] In the second embodiment, only thiocyanate is used.

[0348] In the third embodiment, guanidine salts and thiocyanates are used.

[0349] Preferably, relative to the total weight of the hydraulic binder, the method according to the invention includes adding 0.1% to 5% dry weight, preferably 1.0% to 2.5% dry weight, of zinc salt and / or guanidine salt.

[0350] Preferably, relative to the total weight of the hydraulic adhesive, the method according to the invention comprises adding 0.1% to 3.0% of the polymer (P), preferably 0.3% to 1.0% of the polymer (P).

[0351] When guanidine salts and thiocyanates are used simultaneously, the mixture of guanidine salts and thiocyanates contains 30% to 50% dry weight of guanidine salts and 50% to 70% dry weight of zinc salts.

[0352] Preferably, relative to the total weight of the hydraulic binder, the method according to the invention includes adding 0.1% to 5% dry weight, preferably 1.0% to 2.5% dry weight of zinc salt and / or guanidine salt; and adding 0.1% to 3.0% dry weight of polymer (P), preferably 0.3% to 1.0% dry weight of polymer (P), relative to the total weight of the hydraulic binder.

[0353] Zinc salts and guanidine salts, as well as polymers (P), are described above.

[0354] Activators and mineral additives are as described above.

[0355] The method of the present invention may further include adding a polyalkoxylated polyphosphonate-based polymer, preferably in a proportion of 0.1% to 3.0% by weight, more preferably 0.3% to 1.0% by weight, relative to the total weight of the hydraulic adhesive. These polymers are as described above.

[0356] Guanidine salts and zinc salts can be added to the hydraulic binder, and the polymer and optionally a polyalkoxylated polyphosphonate-based polymer can be added to water, referred to as mixed water. The polymer (P) according to the invention, along with suitable polyalkoxylated polyphosphonate-based polymers, can be added to the components of the hydraulic composition in dry form (typically in powder form) or in solution, preferably in aqueous solution. The water in the aqueous solution can be mixed water or pre-wetting water (a portion of the total water used to wet the aggregate before mixing, thereby simulating the hygroscopic state of the aggregate, which is often wet in the concrete plant or construction site).

[0357] Guanidine salts and zinc salts, as well as polymers (P) and optional polyalkoxylated polyphosphonate-based polymers, can be added to hydraulic adhesives. Detailed Implementation

[0358] The present invention will now be described using the following embodiments.

[0359] Example 1: Characterization of the admixture composition and guanidine salt according to the present invention

[0360] Mortar compositions were prepared to evaluate the properties of the polymer admixture and guanidine salt composition.

[0361] The mortar components are as follows.

[0362] [Table 1]

[0363] Hydraulic binder (blast furnace slag + activator (7% sodium silicate by weight)) 210 Palvadeau sand 0 / 0.315 mm 190 tap water 84

[0364] Prepare the following using a KENWOOD KM01 1CHEF TITANIUM mixer with a stainless steel bowl (4.6L capacity) and metal agitator / stirring blades shaped like sage leaves (13cm high, 13.6cm wide):

[0365] 1. Weigh the water and admixture into the mixing bowl, then start the mixer at 43 revolutions per minute (rpm).

[0366] 2. Start the timer and introduce the hydraulic composition of blast furnace slag and sand into the bowl within 30 seconds.

[0367] 3. Increase the speed to 96 rpm and mix for 1 minute.

[0368] 4. Stop the mixer for 30 seconds, and use a trowel to scrape any mortar composition that has splashed onto the walls back to the center.

[0369] 5. Mix the obtained mortar composition at 96 rpm for one minute.

[0370] At the end of mixing, the resulting paste-like mortar composition is poured into the cylindrical measuring unit of a Kinexus Pro rheometer (Netzsch), which has a fin-type measuring geometry.

[0371] After mixing for 5 minutes, add the mortar composition at 200 seconds. -1 The mortar composition was pre-sheared at a strain rate of 1 minute. Subsequently, it was subjected to a series of decreasing strain rate increments with logarithmic steps of 200 s. -1 ~0.01s -1 The rheometer records the stress applied at each point. This then allows the generation of flow curves associated with the applied stress to obtain each strain rate value. These flow curves show the minimum stress that is interpreted as the threshold stress, that is, the minimum stress required to induce flow. This value varies inversely with the flowability, which is why it is desirable to reduce it as much as possible.

[0372] Then, the flow profile was measured every 30 minutes until 120 minutes after mixing began to monitor changes in flowability over time.

[0373] Polymer 2 (the polymer according to the invention, a = 0.2, q = 114, R1 = R3 = R11 = R13 = H, R2 = R12 = CH3, M = Na) is introduced into the mortar composition at a dosage of 0.5% dry weight, relative to the total weight of the hydraulic binder. The dry weight percentage of salt is given relative to the total weight of the hydraulic binder.

[0374] The results obtained are as follows:

[0375] [Table 2]

[0376]

[0377] [Table 3]

[0378]

[0379] These results clearly demonstrate the synergistic effect between the polymer and guanidine salt of the present invention, such as enhancing the retention of fluidity in hydraulic adhesive compositions.

[0380] Example 2: Characterization of the admixture composition according to the present invention with zinc salt

[0381] The same mortar composition was used, and the properties were evaluated in the same manner as in Example 1.

[0382] Polymer 2 (the polymer according to the invention, a = 0.2, q = 114, R1 = R3 = R11 = R13 = H, R2 = R12 = CH3, M = Na) is introduced into the mortar composition at a dosage of 0.5% dry weight, relative to the total weight of the hydraulic binder. The dry weight percentage of salt is given relative to the total weight of the hydraulic binder.

[0383] The results are shown below:

[0384] [Table 4]

[0385]

[0386] These results clearly demonstrate the synergistic effect between the polymer and zinc salt of the present invention, such as enhancing the retention of fluidity in hydraulic adhesive compositions.

[0387] Example 3: Characterization of the admixture composition according to the present invention with zinc salt and guanidine salt

[0388] The same mortar composition was used, and the properties were evaluated in the same manner as in Example 1.

[0389] Polymer 2 (the polymer according to the invention, a = 0.2, q = 114, R1 = R3 = R11 = R13 = H, R2 = R12 = CH3, M = Na) is introduced into the mortar composition at a dosage of 0.5% dry weight, relative to the total weight of the hydraulic binder. The dry weight percentage of salt is given relative to the total weight of the hydraulic binder.

[0390] The results are shown below:

[0391] [Table 5]

[0392]

[0393] These results clearly demonstrate the synergistic effect between the polymers of the present invention and the combination of zinc and guanidine salts, such as enhancing the flowability retention of hydraulic adhesive compositions.

Claims

1. A hydraulic adhesive composition comprising: - A hydraulic binder comprising at least one aluminosilicate compound and an alkaline or sulfate activator and up to 10% by weight of clinker; - Guanidine salts and / or zinc salts; - Polymers comprising units having the following formulas (I) and (II): in: - R 1 and R 2 Independently representing hydrogen or methyl; - R 3 Represents hydrogen or has the formula -COO(M) 1 / m group; - R 4 It indicates that it has the formula -(CH2). p -(OAlk) q -R5 groups, wherein; - p indicates 1 or 2; - q represents an integer from 3 to 300; - Group -(OAlk) q - Each OAlk unit's Alk independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms; - R 5 It represents -OH or a straight-chain or branched alkoxy group containing 1 to 4 carbon atoms; - R 11 and R 12 Independently representing hydrogen or methyl; - R 13 Represents hydrogen or has the formula -COO(M) 1 / m group; - M represents an H or m-valent cation; - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M; - a is a value from 0.05 to 0.25, such that (100 × a) represents the molar percentage of units of formula (I) within the polymer; and - b is a value of 0.75 to 0.95, such that (100 × b) represents the molar percentage of units of formula (II) in the polymer.

2. The hydraulic adhesive composition according to claim 1, wherein, The guanidine salt is selected from guanidine thiocyanate, guanidine acetate, and guanidine nitrate.

3. The hydraulic adhesive composition according to claim 1, wherein, The activator is selected from calcium activators or alkaline salts.

4. The hydraulic adhesive composition according to claim 1, wherein, The activator is calcium thioate activator.

5. The hydraulic adhesive composition according to claim 1, wherein, The hydraulic binder composition comprises 75% to 99% blast furnace slag relative to the total weight of the hydraulic binder.

6. The hydraulic adhesive composition according to claim 1, wherein, The zinc salt is selected from zinc chloride and zinc nitrate.

7. The hydraulic adhesive composition according to claim 1, wherein, The polymer having a unit of formula (I) has the following formula (I'): in: - R 2 Independently representing hydrogen or methyl; - R' 4 This indicates the expression -CH2-(O-CH2-CH2). q -R5 groups, wherein: - q represents an integer from 3 to 200; - R 5 Indicates -OH or -OMe; - a is a value of 0.05 to 0.25, such that (100×a) represents the molar percentage of units with formula (I') in the polymer; The polymer having a unit of formula (II) has the following formula (II'): in: - R 12 Indicates hydrogen or methyl; - M represents an H or m-valent cation; - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M; - b is a value of 0.75 to 0.95, such that (100 × b) represents the molar percentage of units of formula (II') in the polymer.

8. The hydraulic adhesive composition according to claim 1, wherein, The amount of the guanidine salt and / or zinc salt is 0.1% to 5% dry weight relative to the total weight of the hydraulic adhesive.

9. The hydraulic adhesive composition according to claim 1, wherein, The amount of polymer is 0.1% to 3% of dry weight relative to the total weight of the hydraulic adhesive.

10. The hydraulic adhesive composition according to claim 1 further comprises at least one polyalkoxylated polyphosphonate-based polymer.

11. The hydraulic adhesive composition according to claim 1, wherein, The aluminosilicate compound is selected from fly ash and calcined clay.

12. The hydraulic adhesive composition according to claim 1, wherein, The aluminosilicate compound is blast furnace slag.

13. A hydraulic composition comprising: - A hydraulic binder comprising at least one aluminosilicate compound and an alkaline or sulfate activator and up to 10% by weight of clinker; - water; - Optionally at least one aggregate; - Guanidine salts and / or zinc salts; and - Polymers comprising units having the following formulas (I) and (II): in: - R 1 and R 2 Independently representing hydrogen or methyl; - R 3 Represents hydrogen or has the formula -COO(M) 1 / m group; - R 4 It indicates that it has the formula -(CH2). p -(OAlk) q -R5 groups, wherein; - p means 1 or 2; - q represents an integer from 3 to 300; - Group -(OAlk) q - Each OAlk unit's Alk independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms; - R 5 It represents -OH or a straight-chain or branched alkoxy group containing 1 to 4 carbon atoms; - R 11 and R 12 Independently representing hydrogen or methyl; - R 13 Represents hydrogen or has the formula -COO(M) 1 / m group; - M represents an H or m-valent cation; - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M; - a is a value from 0.05 to 0.25, such that (100 × a) represents the molar percentage of units of formula (I) within the polymer; and - b is a value of 0.75 to 0.95, such that (100 × b) represents the molar percentage of units of formula (II) in the polymer.

14. The hydraulic composition according to claim 13, wherein, The guanidine salt is selected from guanidine thiocyanate, guanidine acetate, and guanidine nitrate.

15. The hydraulic composition according to claim 13, wherein the activator is selected from calcium activators or alkaline salts.

16. The hydraulic composition according to claim 13, wherein, The hydraulic composition comprises 75% to 99% blast furnace slag relative to the total weight of the hydraulic binder.

17. The hydraulic composition according to claim 13, wherein, The zinc salt is selected from zinc chloride and zinc nitrate.

18. The hydraulic composition according to claim 13, wherein, The polymer having a unit of formula (I) has the following formula (I'): in: - R 2 Independently representing hydrogen or methyl; - R' 4 This indicates the expression -CH2-(O-CH2-CH2). q -R5 groups, wherein: - q represents an integer from 3 to 200; - R 5 Indicates -OH or -OMe; - a is a value of 0.05 to 0.25, such that (100×a) represents the molar percentage of units with formula (I') in the polymer; The polymer having a unit of formula (II) has the following formula (II'): in: - R 12 Indicates hydrogen or methyl; - M represents an H or m-valent cation; - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M; - b is a value of 0.75 to 0.95, such that (100 × b) represents the molar percentage of units of formula (II') in the polymer.

19. The hydraulic composition according to claim 13, wherein, The amount of the guanidine salt and / or zinc salt is 0.1% to 5% dry weight relative to the total weight of the hydraulic adhesive.

20. The hydraulic composition according to claim 13, wherein, The amount of polymer is 0.1% to 3% of dry weight relative to the total weight of the hydraulic adhesive.

21. The hydraulic composition of claim 13 further comprises at least one polyalkoxylated polyphosphonate-based polymer.

22. The hydraulic composition according to claim 13, wherein, The aluminosilicate compound is selected from fly ash and calcined clay.

23. The hydraulic composition according to claim 13, wherein, The aluminosilicate compound is blast furnace slag.

24. Use of a guanidine salt and / or zinc salt, and a polymer comprising units having formulas (I) and (II) below, for enhancing the flowability of hydraulic compositions: in: - R 1 and R 2 Independently representing hydrogen or methyl; - R 3 Represents hydrogen or has the formula -COO(M) 1 / m group; - R 4 It indicates that it has the formula -(CH2). p -(OAlk) q -R5 groups, wherein; - p means 1 or 2; - q represents an integer from 3 to 300; - Group -(OAlk) q - Each OAlk unit's Alk independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms; - R 5 It represents -OH or a straight-chain or branched alkoxy group containing 1 to 4 carbon atoms; - R 11 and R 12 Independently representing hydrogen or methyl; - R 13 Represents hydrogen or has the formula -COO(M) 1 / m group; - M represents an H or m-valent cation; - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M; - a is a value from 0.05 to 0.25, such that (100 × a) represents the molar percentage of units of formula (I) within the polymer; and - b is a value of 0.75 to 0.95, such that (100 × b) represents the molar percentage of units of formula (II) in the polymer; The hydraulic composition comprises a hydraulic binder comprising at least one aluminosilicate compound, an alkaline or sulfate activator, up to 10% by weight of clinker, water, and optionally at least one aggregate.

25. The use according to claim 24, wherein, The guanidine salt is selected from guanidine thiocyanate, guanidine acetate, and guanidine nitrate.

26. The use according to claim 24, wherein, The activator is selected from calcium activators or alkaline salts.

27. The use according to claim 24, wherein, The hydraulic composition comprises 75% to 99% blast furnace slag relative to the total weight of the hydraulic binder.

28. The use according to claim 24, wherein, The zinc salt is selected from zinc chloride and zinc nitrate.

29. The use according to claim 24, wherein, The polymer having a unit of formula (I) has the following formula (I'): in: - R 2 Independently representing hydrogen or methyl; - R' 4 This indicates the expression -CH2-(O-CH2-CH2). q -R5 groups, wherein: - q represents an integer from 3 to 200; - R 5 Indicates -OH or -OMe; - a is a value of 0.05 to 0.25, such that (100×a) represents the molar percentage of units with formula (I') in the polymer; The polymer having a unit of formula (II) has the following formula (II'): in: - R 12 Indicates hydrogen or methyl; - M represents an H or m-valent cation; - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M; - b is a value of 0.75 to 0.95, such that (100 × b) represents the molar percentage of units of formula (II') in the polymer.

30. The use according to claim 24, wherein, The amount of the guanidine salt and / or zinc salt is 0.1% to 5% dry weight relative to the total weight of the hydraulic adhesive.

31. The use according to claim 24, wherein, The amount of polymer is 0.1% to 3% of dry weight relative to the total weight of the hydraulic adhesive.

32. The use according to claim 24, further comprising at least one polyalkoxylated polyphosphonate-based polymer.

33. The use according to claim 24, wherein, The aluminosilicate compound is selected from fly ash and calcined clay.

34. The use according to claim 24, wherein, The aluminosilicate compound is blast furnace slag.

35. A method for enhancing the retention of flowability over time in a hydraulic composition, the hydraulic composition comprising a hydraulic binder comprising at least one aluminosilicate compound, an alkaline or sulfate activator, up to 10% by weight of clinker, water, and optionally at least one aggregate; the method comprising adding guanidine salts and / or zinc salts, and a polymer comprising units having the following formulas (I) and (II): in: - R 1 and R 2 Independently representing hydrogen or methyl; - R 3 Represents hydrogen or has the formula -COO(M) 1 / m group; - R 4 It indicates that it has the formula -(CH2). p -(OAlk) q -R5 groups, wherein; - p means 1 or 2; - q represents an integer from 3 to 300; - Group -(OAlk) q - Each OAlk unit's Alk independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms; - R 5 It represents -OH or a straight-chain or branched alkoxy group containing 1 to 4 carbon atoms; - R 11 and R 12 Independently representing hydrogen or methyl; - R 13 Represents hydrogen or has the formula -COO(M) 1 / m group; - M represents an H or m-valent cation; - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M; - a is a value from 0.05 to 0.25, such that (100 × a) represents the molar percentage of units of formula (I) within the polymer; and - b is a value of 0.75 to 0.95, such that (100 × b) represents the molar percentage of units of formula (II) in the polymer.

36. The method according to claim 35, wherein, The guanidine salt is selected from guanidine thiocyanate, guanidine acetate, and guanidine nitrate.

37. The method of claim 35, wherein, The activator is selected from calcium activators or alkaline salts.

38. The method according to claim 35, wherein, The hydraulic composition comprises 75% to 99% blast furnace slag relative to the total weight of the hydraulic binder.

39. The method according to claim 35, wherein, The zinc salt is selected from zinc chloride and zinc nitrate.

40. The method of claim 35, wherein, The polymer having a unit of formula (I) has the following formula (I'): in: - R 2 Independently representing hydrogen or methyl; - R' 4 This indicates the expression -CH2-(O-CH2-CH2). q -R5 groups, wherein: - q represents an integer from 3 to 200; - R 5 Indicates -OH or -OMe; - a is a value of 0.05 to 0.25, such that (100×a) represents the molar percentage of units with formula (I') in the polymer; The polymer having a unit of formula (II) has the following formula (II'): in: - R 12 Indicates hydrogen or methyl; - M represents an H or m-valent cation; - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M; - b is a value of 0.75 to 0.95, such that (100 × b) represents the molar percentage of units of formula (II') in the polymer.

41. The method according to claim 35, wherein, The amount of the guanidine salt and / or zinc salt is 0.1% to 5% dry weight relative to the total weight of the hydraulic adhesive.

42. The method according to claim 35, wherein, The amount of polymer is 0.1% to 3% of dry weight relative to the total weight of the hydraulic adhesive.

43. The method of claim 35 further comprises at least one polyalkoxylated polyphosphonate-based polymer.

44. The method of claim 35, wherein, The aluminosilicate compound is selected from fly ash and calcined clay.

45. The method according to claim 35, wherein, The aluminosilicate compound is blast furnace slag.

46. ​​An admixture composition comprising: - Guanidine salts and / or zinc salts; - Polymers comprising units having the following formulas (I) and (II): in: - R 1 and R 2 Independently representing hydrogen or methyl; - R 3 Represents hydrogen or has the formula -COO(M) 1 / m group; - R 4 It indicates that it has the formula -(CH2). p -(OAlk) q -R5 groups, wherein; - p means 1 or 2; - q represents an integer from 3 to 300; - Group -(OAlk) q - Each OAlk unit's Alk independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms; - R 5 It represents -OH or a straight-chain or branched alkoxy group containing 1 to 4 carbon atoms; - R 11 and R 12 Independently representing hydrogen or methyl; - R 13 Represents hydrogen or has the formula -COO(M) 1 / m group; - M represents an H or m-valent cation; - When M represents H, m represents 1, and when M represents a cation, m is the valence of the cation M; - a is a value from 0.05 to 0.25, such that (100 × a) represents the molar percentage of units of formula (I) within the polymer; and - b is a value of 0.75 to 0.95, such that (100 × b) represents the molar percentage of units of formula (II) in the polymer.

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