Improving the resistance of inorganic binder-based materials to erosion by sulfates and / or chlorides.

Abstract

Polyols and / or polyalkylene glycols are used to improve the resistance of inorganic binder compositions to sulfates and / or chlorides.

Description

[Technical Field]

[0001] The present invention relates to the use of specially selected substances to improve the resistance of cured inorganic binder compositions to sulfates and / or chlorides. Furthermore, the present invention relates to admixtures suitable for improving the resistance of cured inorganic binder compositions to sulfates and / or chlorides. [Background technology]

[0002] Structures made from hardened cementitious inorganic binder compositions, such as mortar and concrete structures, are susceptible to sulfate erosion. Specifically, sulfate erosion is a chemical decomposition mechanism in which sulfate ions react with the hydrated products of tricalcium aluminate (C3A) present in the hardened inorganic binder composition. Sulfate erosion leads to the formation of ettringite, and in some cases, further expansive products. These products cause an increase in the volume and internal pressure of the inorganic binder structure, resulting in cracks and delamination.

[0003] Sulfate erosion typically occurs when inorganic binder-based structures come into contact with water containing sulfate ions, such as soil, seawater, and wastewater treatment plants. This is also known as external erosion.

[0004] Another cause of sulfate erosion is excess gypsum in the inorganic binder composition. Excess gypsum can be introduced into the inorganic binder composition through sulfate-rich cement, aggregates containing natural gypsum, or admixtures containing small amounts of sulfate. This type of sulfate erosion is called internal erosion.

[0005] A common method for protection against sulfate attack is to reduce the alumina content by limiting the tricalcium aluminate content in the inorganic binder. Another approach to improve the resistance of inorganic binder compositions to sulfate attack is based on adding supplementary cementitious materials, such as fly ash and slag, to the inorganic binder composition.

[0006] U.S. Pat. No. 5,772,752A (New Jersey Institute of Technology) describes the use of fly ash as an additional compound in, for example, concrete and mortar mixtures to achieve excellent levels of acid and sulfate resistance while maintaining acceptable compressive strength properties.

[0007] However, known solutions for mitigating sulfate attack often depend on the availability and quality of mitigating substances (e.g., supplementary cementitious materials), and / or they may compromise other properties of the inorganic binder composition, such as setting time and compressive strength.

[0008] Similarly, when structures made from cementitious inorganic binder compositions include metallic reinforcements, chloride-induced corrosion is another degradation mechanism that impairs the long-term performance of such structures.

[0009] Although the chloride concentration in cement, mixing water, aggregates, and admixtures is strictly controlled, chloride may penetrate into structures made from the cured inorganic binder composition from external sources such as seawater, groundwater, or soil.

[0010] To protect structures based on reinforced inorganic binders from chloride attack, it is possible, for example, to coat the reinforcing members with an epoxy resin or to protect them by cathodic protection. Alternatively, it is also possible to treat the entire structure with a protective coating to reduce the penetration of chloride from external sources.

[0011] In this regard, US Patent Application Publication No. 2003 / 0168781 A1 (Kukkonen et al.) describes another method for protecting reinforcements in concrete from corrosion caused by chloride ions. Thereby, metallic copper and / or a copper compound is added to the concrete mass, and the copper reacts with chlorides to form low-solubility salts, as a result of which the risk of steel corrosion caused by chlorides is significantly reduced.

[0012] However, such measures for reducing chloride-induced attack are time-consuming and costly, or may impair other properties of the inorganic binder composition.

[0013] Accordingly, there remains a need to develop more improved solutions that have fewer or completely no such problems. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0014] An object of the present invention is to provide an improved solution for enhancing the resistance of inorganic binder compositions to sulfates and / or chlorides. In particular, this solution needs to be flexible and can be implemented as easily as possible. Desirably, this solution should have as little impact as possible on the properties of the inorganic binder composition, such as processability and setting characteristics. MEANS FOR SOLVING THE PROBLEMS

[0015] Surprisingly, it has been found that these objects can be achieved by the features of claim 1. Specifically, a polyol is used in the subject method to improve the resistance of the inorganic binder composition to sulfates and / or chlorides.

[0016] It has been found that using polyols for these purposes is highly beneficial. In particular, by simply adding polyols to an inorganic binder composition before and / or during the preparation of a processable inorganic binder composition, for example by adding polyols to mixed water, it is possible to significantly improve the resistance of the inorganic binder composition to sulfates and chlorides simultaneously in a relatively easy manner.

[0017] Therefore, to improve the resistance of inorganic binder compositions to sulfates and chlorides, only one additive is needed, and two problems can be solved at once. Thus, in a very preferred embodiment, a polyol is used to simultaneously improve the resistance of inorganic binder compositions to sulfates and chlorides.

[0018] Furthermore, it is unnecessary to use special sulfate-resistant cements with low aluminum content or specific auxiliary cementitious materials. Therefore, the solution of the present invention can be used in a highly flexible manner not only with general inorganic binder compositions but also with more specialized compositions adjusted for specific applications.

[0019] Similarly, polyols can be used in combination with most existing admixtures used in inorganic binder compositions, such as plasticizers, curing accelerators, and / or air-entraining agents, without impairing their effects.

[0020] The effective amount of polyol required to achieve the effects according to the present invention is quite low. Therefore, the polyol does not significantly alter the composition of the inorganic binder composition.

[0021] Furthermore, it was found that when polyols are used at effective additive levels, they do not significantly affect the processing properties and strength development of the inorganic binder composition.

[0022] Further aspects of the present invention are the subject of other independent claims. Particularly preferred embodiments of the present invention are the subject of dependent claims. [Modes for carrying out the invention]

[0023] A first aspect of the present invention relates to the use of polyols and / or polyalkylene glycols to improve the resistance of a cured inorganic binder composition to sulfates and / or chlorides.

[0024] Resistance to sulfates can be determined, for example, according to Annex D of standard SIA 262 / 1:2019. This test method provides a means for evaluating the resistance of cured inorganic binder samples to sulfates. In this test, the sample is subjected to a 4-week wet / dry cycle, and then immersed in a sulfate solution (5% sodium sulfate solution) for 8 weeks. The sulfates may react with a portion of the sample, changing its volume, and this is observed during the process.

[0025] Chloride resistance can be determined according to Annex B of standard SIA 262 / 1:2019. This test method allows for the determination of chloride penetration at a specific age, such as day 28.

[0026] Improving the resistance of a given inorganic binder composition to sulfates and / or chlorides by using polyols and / or polyalkylene glycols means that the resistance of the inorganic binder composition containing the polyol to sulfates and / or chlorides at a predetermined age, such as day 28, is superior to the resistance of a reference sample of the same age with the same composition but without the polyol.

[0027] As used in relation to the present invention, the term "polyol" refers to a compound containing at least two hydroxyl groups. For the applications of the present invention, polyols in pure material form or mixtures of two or more different polyols can be used.

[0028] In principle, polyols can be selected from a wide range of materials, including non-polymeric and polymeric substances.

[0029] In particular, the weight-average molecular weight (M) of polyols w The maximum molecular weight is 500 g / mol, particularly 250 g / mol, and especially 180 g / mol. Relatively low molecular weight polyols are highly effective while hardly impairing the effectiveness of other additives, such as plasticizers.

[0030] Preferably, the polyol is a diol, particularly a glycol.

[0031] More preferably, the ratio of ether groups to hydroxyl groups in the polyol is 0 to 1, particularly 0 to 0.5, particularly 0 to 0.1, and most preferably 0. Therefore, it has been found to be beneficial to use polyols containing a limited proportion of ether groups or none at all.

[0032] Particularly preferably, the polyol does not contain polymerized repeating units. In other words, the polyol is a particularly non-polymeric substance. Such polyols are very effective with respect to the objectives of the present invention, even at relatively low addition amounts. Furthermore, they have little effect on other properties of the inorganic binder composition.

[0033] In particular, polyols are, formula C n H 2n It is a polyol of (OH)2 (n=2 to 10, especially n=4 to 8, especially n=5 to 6).

[0034] Particularly suitable polyols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, pentylene glycol, neopentyl glycol, and / or hexylene glycol. In particular, the polyol is selected from neopentyl glycol, hexylene glycol, or mixtures thereof.

[0035] The term "hexylene glycol" specifically refers to 2-methyl-2,4-pentanediol.

[0036] In a particularly preferred embodiment, a combination of at least a first polyol and a second polyol is used, wherein the first and second polyols are physically and / or chemically different. In other words, in this case, the polyol is used in the form of a mixture of at least two different polyols. In particular, a combination of two polyols, especially neopentyl glycol and hexylene glycol, is used.

[0037] By combining polyols, it is possible to further adjust and / or improve resistance to sulfates and / or chlorides.

[0038] In this combination, the weight ratio of the first polyol to the second polyol is preferably 0.1 to 10, more particularly 0.3 to 2, more particularly 0.5 to 1.5, and more particularly 0.8 to 1.2.

[0039] In particular, polyols are used in the form of aqueous solutions having a proportion of water in the range of 5 to 60% by weight, especially 10 to 50% by weight, for example, 25 to 45% by weight, relative to the total weight of the aqueous solution.

[0040] In aqueous solutions, the proportion of polyols is preferably 40-95% by weight, particularly 50-90% by weight, for example 55-75% by weight. This is especially true for mixtures in which two or more different polyols are used.

[0041] According to a very preferred embodiment, the aqueous solution is, with respect to the total weight of the aqueous solution, - 10-50% by weight, especially 25-45% by weight, especially 30-40% by weight of water; - 10-40% by weight, especially 15-35% by weight, especially 20-30% by weight of a first polyol, especially neopentyl glycol; - 10-50% by weight, especially 30-50% by weight, especially 35-45% by weight of a second polyol, especially hexylene glycol; It contains or consists of these. In particular, the proportion of polyol used is 0.0001 to 10% by weight, especially 0.01 to 5% by weight, especially 0.1 to 3% by weight, and especially 0.5 to 2% by weight, relative to the weight of the inorganic binder in the inorganic binder composition.

[0042] When a mixture of different polyols is used, the proportions are relative to the total amount of all polyols.

[0043] In another preferred embodiment, the polyol is used in combination with a polyalkylene glycol. In particular, the polyalkylene glycol is chemically different from the polyol.

[0044] In particular, polyalkylene glycols have two hydroxyl groups or one hydroxyl group, especially one hydroxyl group.

[0045] In particular, one end of the polyalkylene glycol is an alkyl end, for example, an alkyl end having an alkyl group having 1 to 20 carbon atoms, especially 2 to 10 carbon atoms, and especially 3 to 8 carbon atoms.

[0046] In particular, the weight-average molecular weight (M) of polyalkylene glycols W The ) ranges from 550 to 10,000 g / mol, particularly 1,000 to 6,000 g / mol, and especially 2,000 to 5,000 g / mol.

[0047] In particular embodiments, the polyalkylene glycol is a polyalkylene glycol alkyl ether. Specifically, the polyalkylene glycol alkyl ether is (i) a reaction product of a monoalcohol with an alkylene oxide, particularly ethylene oxide and / or propylene oxide, and / or (ii) a reaction product of a diol with an alkylene oxide, particularly ethylene oxide and / or propylene oxide.

[0048] In particular, polyalkylene glycol is poly-(alkylene glycol)-monoalkyl ether, especially poly-(ethylene glycol-propylene glycol)-monoalkyl ether, for example, poly-(ethylene glycol-propylene glycol)-monobutyl ether, and / or polyalkylene glycol is polyethylene glycol neopentyl ether, especially poly(oxy-1,2-ethanediyl),α,α'-(2,2-dimethyl-1,3-propanediyl)bis[ω-hydroxy]. Poly(oxy-1,2-ethanediyl),α,α'-(2,2-dimethyl-1,3-propanediyl)bis[ω-hydroxy] is a reaction product of 2,2-dimethylpropane-1,3-diol and ethylene oxide.

[0049] Poly-(ethylene glycol-propylene glycol)-monoalkyl ethers are available, for example, from BASF under the trade name Pluriol® A520PE. Poly(oxy-1,2-ethanediyl),α,α'-(2,2-dimethyl-1,3-propanediyl)bis[ω-hydroxy] or poly(ethylene glycol) neopentyl ethers are available from Evonik under the trade name SITREN SRA L201.

[0050] The weight ratio of polyol to polyalkylene glycol is preferably 0.1 to 10, more particularly 0.3 to 2, more particularly 0.5 to 1.5, and more particularly 0.8 to 1.2. When mixtures of different polyols and / or mixtures of different polyalkylene glycols are used, this ratio is relative to the total amount of all polyols or all polyalkylene glycols, respectively.

[0051] In particular, polyalkylene glycol is used in the form of an aqueous solution, especially in the form of an aqueous solution with a water content in the range of 5 to 60% by weight, particularly 10 to 50% by weight, for example 25 to 45% by weight, relative to the total weight of the aqueous solution. Preferably, the polyalkylene glycol and the polyol are present in the same aqueous solution.

[0052] In aqueous solutions, the proportion of polyalkylene glycol is preferably 5 to 95% by weight, particularly 15 to 60% by weight, for example 30 to 50% by weight.

[0053] According to a very preferred embodiment, the aqueous solution is, with respect to the total weight of the aqueous solution, - 10-50% by weight, especially 25-45% by weight, especially 30-40% by weight of water; - 10-40% by weight, especially 15-35% by weight, especially 20-30% by weight of polyols, especially neopentyl glycol; - 10-50% by weight, especially 30-50% by weight, especially 35-45% by weight of polyalkylene glycol, especially polyalkylene glycol alkyl ether, especially poly-(ethylene glycol-propylene glycol)-monoalkyl ether and / or polyethylene glycol neopentyl ether; It includes or consists of these.

[0054] When a mixture of different polyols is used, the proportion of polyols is a proportion of the total amount of all polyols. Similarly, when a mixture of different polyalkylene glycols is used, the proportion of polyalkylene glycols is a proportion of the total amount of all polyalkylene glycols.

[0055] Very preferably, polyols are used in combination with plasticizers. While we do not wish to be bound by theory, it is thought that polyols and plasticizers functionally interact to further improve resistance to sulfates and / or chlorides, particularly to chlorides.

[0056] In particular, plasticizers are chemically different from polyols and polyalkylene glycols.

[0057] The plasticizer can be selected from naphthalene derivatives, melamine derivatives, aminosulfonic acid derivatives, lignosulfonate derivatives, polycarboxylate-based high-performance water-reducing agents, condensates of formaldehyde and polyalkoxylated aromatic compounds, and mixtures thereof. Particularly preferred is the plasticizer to be a polycarboxylate ether.

[0058] In particular, plasticizers are used in an amount of 0.0001 to 10% by weight, especially 0.01 to 5% by weight, especially 0.1 to 3% by weight, and especially 0.5 to 2% by weight, relative to the weight of the inorganic binder in the inorganic binder composition.

[0059] The weight ratio of plasticizer to polyol is 0.001 to 5, particularly 0.01 to 2, and especially 0.1 to 1. When a mixture of different polyols is used, the ratio is relative to the total amount of all polyols.

[0060] The polycarboxylate ether is preferably a comb-shaped polymer CP having the following substructure units: a) Substructure unit S1 of formula I in the a-molar part: [ka] b) Substructure unit S2 of formula II in the b-molar part: [ka] c) Substructure unit S3 of formula (III) of the c-molar part: [ka] d) Substructure unit S4 of formula (IV) of the d-molar part: [ka] (In these formulas, L is independent of H + , represents alkali metal ions, alkaline earth metal ions, divalent or trivalent metal ions, ammonium ions, or organic ammonium groups, Each Ru each independently represents hydrogen or a methyl group, each R v each independently represents hydrogen or COOM, r is 0, 1, or 2, t is 0 or 1, G 1 and G 2 are each independently a C1 to C 20 alkyl group, cycloalkyl group, alkylaryl group, or -(CH2) z -(O) z’ -[A'O] s -G 4 , z is 0, 1, 2, 3, or 4, z' is 0 or 1, A' is C2-C4 alkylene, and G 4 is H, a C1 to C 20 alkyl group, cycloalkyl group, or alkylaryl group, and s is 2 to 250, G 3 is independently NH2, -NG 5 G 6 , -OG 7 NG 8 G 9 , G 5 and G 6 are each independently a C1 to C 20 alkyl group, cycloalkyl group, or alkylaryl group, or a hydroxyalkyl group, or an acetoxyethyl group (CH3-CO-O-CH2-CH2-), or a hydroxyisopropyl group (HO-CH(CH3)-CH2-), or an acetoxyisopropyl group (CH3-CO-O-CH(CH3)-CH2-), or G 5 and G 6 together form a ring partially containing a nitrogen atom so as to constitute a morpholine ring or an imidazoline ring, G 7 is a C2-C4 alkylene group, G 8 and G 9 are each independently a C1 to C 20This represents an alkyl group, cycloalkyl group, alkylaryl group, aryl group, or hydroxyalkyl group. a, b, c, and d represent the molar ratios of their respective substructure units S1, S2, S3, and S4. a / b / c / d = (0.1~0.9) / (0.1~0.9) / (0~0.8) / (0~0.8), In particular, a / b / c / d = (0.3~0.9) / (0.1~0.7) / (0~0.6) / (0~0.4), Preferably a / b / c / d = (0.5~0.8) / (0.2~0.4) / 0 / 0 However, this is conditional on a+b+c+d=1.

[0061] A "comb-shaped polymer" is a polymer that consists of a polymer backbone and side chains bonded to it.

[0062] The arrangement of substructure units S1, S2, S3, and S4 may be alternating, blocky, or random. Furthermore, one or more substructure units S1, S2, S3, and S4 may form a gradient structure. In principle, additional structural units may be present in addition to the substructure units S1, S2, S3, and S4. In particular, the arrangement of substructure units S1, S2, S3, and S4 in the comb-type polymer CP is random or statistical.

[0063] Preferably, the substructure units S1, S2, S3, and S4 together account for at least 50% by weight, particularly at least 90% by weight, and most preferably at least 95% by weight, of the total weight of the comb-shaped polymer CP.

[0064] In comb-shaped polymer CP, R v represents hydrogen in particular, R u Preferably, it is hydrogen and / or a methyl group.

[0065] Preferably, in the comb-shaped polymer CP, r=0 and t=1. More advantageously, r=1 to 2 and t=0.

[0066] More specifically, in comb-shaped polymer CP, R v is hydrogen, R u This is a methyl group, where r=1-2 and t=0.

[0067] G in comb-shaped polymer CP 1 and / or G 2 In each case, independently and advantageously [A'O] s -G 4 Therefore, s is between 8 and 200, especially between 20 and 70, and A' is a C2-C4 alkylene. Thus, favorably, z=z'=0.

[0068] In comb-shaped polymer CP, G 4 In each case, these are, independently and preferably, hydrogen or a methyl group.

[0069] Particularly advantageous comb-shaped polymers CP are a)R u Body part and R v The part is a hydrogen atom, b) r = 0, c) t=1 d)G 1 and G 2 However, in each case, independently, -(CH2) z -(O) z’ -[A'O] s -G 4 (z=z'=0, s=20~70, A'=C2 alkylene) e) G 4 is a methyl group and / or f) a / b / c / d = (0.5~0.8) / (0.2~0.4) / (0.001~0.005) / 0 It is.

[0070] Similarly advantageous polymer CP is a) t=0, r=1~2, b) G 1 However, in each case, independently, -(CH2) z -(O) z’ -[A'O]s -G 4 (z=z'=0, s=8~200, especially 20~70), c)G 4 This represents hydrogen or a methyl group, especially hydrogen. d) and / or A' is a C2-C4 alkylene, especially a C2 alkylene. It is.

[0071] The weight-average molecular weight (Mw) of polymer CP is particularly in the range of 5,000 to 150,000 g / mol, preferably 10,000 to 100,000 g / mol, and especially 20,000 to 90,000 g / mol. The weight-average molecular weight (Mw) is determined by gel permeation chromatography (GPC) using polyethylene glycol (PEG) as a standard.

[0072] The method for preparing comb-type polymers (CPs) is known to those skilled in the art. Corresponding high-performance water-reducing agents or comb-type polymers (CPs) are also commercially available from Sika Schweiz AG under the trade name ViscoCrete®.

[0073] The polyol is preferably used in the form of an aqueous admixture comprising the polyol and one or more optional additional additives, such as plasticizers. This allows the polyol to be easily and flexibly added to the inorganic binder composition before and / or during processing.

[0074] This admixture contains, in particular, 50-100% by weight, especially 60-90% by weight, of a polyol and water. One or more additional additives, such as plasticizers, and optional additional additives may also be present.

[0075] In particular, polyols are added to the inorganic binder composition before and / or during the addition of mixing water. Therefore, polyols may be added to a single component of the inorganic binder composition, such as the inorganic binder or aggregate, or to a pre-mixed inorganic binder composition in a dry or wet state. This allows the polyols to be easily mixed and uniformly dispersed throughout the inorganic binder composition.

[0076] In particular, polyols are added to the inorganic binder composition together with plasticizers, especially before and / or during the addition of mixing water. Such a one-step addition facilitates handling and mixing.

[0077] The term "inorganic binder" refers to a binder that reacts in the presence of water during a hydration reaction to form a solid hydrate or hydrate phase. This may be, for example, a hydraulic binder, a latent hydraulic binder, and / or a pozzolanic binder. Hydraulic binders are particularly preferred. Hydraulic binders can condense in water. However, it may be advantageous for the inorganic binder to contain other binders in addition to, or instead of, a hydraulic binder. These are, in particular, latent hydraulic binders and / or pozzolanic binders. Suitable latent hydraulic binders and / or pozzolanic binders are, for example, slag, fly ash, silica dust, and / or natural pozzolanic materials.

[0078] "Inorganic binder composition" means a composition containing at least an inorganic binder and other optional components.

[0079] The inorganic binder in the inorganic binder composition includes, or comprises, cement in particular, cement of type CEM I, CEM II, CEM III, CEM IV, and / or CEM V in accordance with standard EN197-1:2011.

[0080] In another preferred embodiment, the inorganic binder in the inorganic binder composition includes slag, particularly blast furnace slag powder. Thus, the slag exists in combination with a hydraulic binder, particularly cement.

[0081] In another preferred embodiment, the inorganic binder in the inorganic binder composition includes clay, particularly calcined clay. Thus, the clay exists in combination with a hydraulic binder, particularly cement.

[0082] As a result, the solution of the present invention proved to be particularly effective for these types of inorganic binders.

[0083] In one preferred embodiment, the inorganic binder comprises, with respect to the total content of the inorganic binder, at least 5% by weight, particularly at least 20% by weight, preferably at least 35% by weight, particularly at least 65% by weight of a hydraulic binder, particularly cement, and optionally 5 to 95% by weight, particularly 5 to 65% by weight, particularly 15 to 35% by weight of a latent hydraulic binder and / or pozzolanic binder, particularly slag or clay, particularly blast furnace slag powder or calcined clay.

[0084] The inorganic binder composition may further contain aggregate. The term "aggregate" includes all types of mortar and / or concrete aggregate. In particular, the aggregate is 2.2-3 kg / dm 3 It is characterized by its density.

[0085] In particular, aggregates include stone, gravel, sand, powdered quartz, and / or limestone. However, aggregates may include or be composed of lightweight aggregates, especially foamed clay or polystyrene, or heavy aggregates, such as barite or iron ore.

[0086] In particular, the aggregate particle size is at least 0.063 mm or at least 0.125 mm.

[0087] Preferably, the aggregate particle size is a maximum of 125 mm or a maximum of 32 mm.

[0088] In particular, the aggregate particle size is 0.063 to 125 mm, especially 0.063 to 32 mm, especially 0.125 to 16 mm, for example, 0.063 to 8 mm or 0.125 to 5 mm.

[0089] In relation to the present invention, particle size is determined by sieve analysis, particularly using sieves characterized by square openings. Specifically, particle size is expressed by the opening size of the test sieve through which the coarse grains or particles of interest pass.

[0090] Furthermore, the inorganic binder composition may contain additional additives selected from those conventionally used in mortar or concrete compositions. In particular, the additional additives may be selected from accelerators, corrosion inhibitors, retarders, shrinkage inhibitors, defoamers, and / or foaming agents. Thus, the additional additives are chemically and / or physically distinct from polyols and / or plasticizers.

[0091] In particular, the proportion of additional additives is 0.0001 to 10% by weight, especially 0.001 to 5% by weight, and especially 0.01 to 2% by weight.

[0092] In particular, the inorganic binder composition is a grout, mortar, or concrete composition.

[0093] Mixing water is added to prepare the inorganic binder composition.

[0094] Preferably, the ratio of water to inorganic binder in the inorganic binder composition is 0.25 to 0.8, particularly 0.3 to 0.6, for example 0.4 to 0.5.

[0095] Another aspect of the present invention relates to an admixture for improving the resistance of an inorganic binder composition to sulfates and / or chlorides, the admixture comprising the polyol described above. In particular, the admixture further comprises one or more of the following components: a plasticizer, a polyalkylene glycol, water, and / or one or more additional additives. The polyol, plasticizer, polyalkylene glycol, and one or more additives are defined as described above.

[0096] In particular, the admixture is an aqueous solution having the water content and / or composition described above.

[0097] In this admixture, the polyol is preferably of formula C n H 2n It is either a polyol of (OH)2 (n=2~10, especially n=4~8, especially n=5~6), or one of the substances mentioned above.

[0098] Particularly preferred is the above-mentioned combination of at least a first polyol and a second polyol, especially a combination of two polyols, preferably a combination of neopentyl glycol and hexylene glycol.

[0099] The weight ratio of the first polyol to the second polyol is preferably 0.1 to 10, more particularly 0.3 to 2, more particularly 0.5 to 1.5, and more particularly 0.8 to 1.2.

[0100] In particular, the plasticizer in the admixture, if present, is a polycarboxylate ether, and preferably the comb-shaped polymer CP described above.

[0101] In particular, in this admixture, the weight ratio of the plasticizer to the polyol is 0.001 to 5, especially 0.01 to 2, and especially 0.1 to 1.

[0102] The weight ratio of polyol to polyalkylene glycol is preferably 0.1 to 10, more particularly 0.3 to 2, more particularly 0.5 to 1.5, and more particularly 0.8 to 1.2. When a mixture of different polyols is used, the ratio with respect to polyol is the ratio to the total amount of all polyols.

[0103] In a particular embodiment, admixtures for improving the resistance of the inorganic binder composition to sulfates and / or chlorides include: a) 10-50% by weight, especially 25-45% by weight, especially 30-40% by weight of water, 10-40% by weight, especially 15-35% by weight, especially 20-30% by weight of a first polyol, especially neopentyl glycol, 10-50% by weight, especially 30-50% by weight, especially 35-45% by weight of a second polyol, especially hexylene glycol, An aqueous solution containing the first and second polyols, wherein the aqueous solutions are physically and / or chemically different; or b) 10-50% by weight, especially 25-45% by weight, especially 30-40% by weight of water, 10-40% by weight, especially 15-35% by weight, especially 20-30% by weight of polyols, especially neopentyl glycol, 10-50% by weight, particularly 30-50% by weight, particularly 35-45% by weight of polyalkylene glycol, particularly polyalkylene glycol alkyl ether, particularly poly-(ethylene glycol-propylene glycol)-monoalkyl ether, and / or polyethylene glycol neopentyl ether, Aqueous solution containing; That is the case.

[0104] The admixture may be a single-component admixture. This ensures that all components of the admixture are present in a single container.

[0105] Alternatively, the admixture may be a two-component or multi-component admixture. This allows, for example, the polyol to be placed in the first container and the plasticizer in the second container. Optionally, additional additives may be placed in either the first or second container, or in one or more additional containers.

[0106] Further advantageous embodiments of the present invention are evident from the exemplary embodiments. [Examples]

[0107] Exemplary Embodiments In the first set of tests, multiple concrete compositions were prepared under identical conditions using different proportions of plasticizer and polyol. The plasticizer and polyol (if used) were added together with the mixing water used to prepare the concrete compositions. Details of the concrete compositions and their properties are shown in Table 1.

[0108] [Table 1]

[0109] As is clear from Table 1, adding 1% by weight of a polyol mixture consisting of hexylene glycol and neopentyl glycol significantly improves resistance to sulfates while simultaneously decreasing resistance to chlorides (see Example A1) compared to a similar composition without polyols (see Reference Example R1). Regarding resistance to sulfates and chlorides, lower values ​​indicate better resistance.

[0110] Furthermore, increasing the proportion of the polyol mixture and using it together with a polycarboxylate-based plasticizer can further improve resistance to sulfates and chlorides.

[0111] Notably, the addition of polyols and plasticizers does not impair compressive strength or processability (FTS).

[0112] In the second set of tests, concrete compositions with lower water content (lower w / b value) and cement content were further produced. The compositions and properties obtained in these experiments are shown in Table 2.

[0113] [Table 2]

[0114] Similar to the first set of experiments, the addition of the polyol mixture clearly improves resistance to sulfates and chlorides. This can be inferred from a comparison of Reference Example R2 and Example B2, which have essentially the same composition except for the polyol.

[0115] By increasing the plasticizer concentration while keeping the polyol content constant, resistance to chlorides can be further improved (see Experiments B2 and B3). The same is true when increasing the plasticizer concentration while simultaneously decreasing the polyol content (see Experiments B2 and B1). Therefore, by adjusting the ratio of plasticizer to polyol, resistance can be adjusted to meet specific needs.

[0116] Interestingly, using silica fume instead of polyol can also improve resistance to chlorides. However, in this case, resistance to sulfates decreases, requiring a considerably larger amount of silica fume.

[0117] In the third set of tests, further concrete compositions were prepared based on combinations of CEM I, polyol, and polyalkylene glycol alkyl ether. The compositions and properties obtained in these experiments are shown in Table 3.

[0118] [Table 3]

[0119] In the fourth set of tests, further concrete compositions were prepared based on CEM I and GGBS (blast furnace slag powder), as well as two different polyols or combinations of polyols with polyalkylene glycol alkyl ethers. The compositions and properties obtained in these experiments are shown in Table 4.

[0120] [Table 4]

[0121] In the fifth set of tests, further concrete compositions were prepared based on CEM I, GGBS, and silica fume, as well as two different polyols, or combinations of polyols with polyalkylene glycol alkyl ethers. The compositions and properties obtained in these experiments are shown in Table 5.

[0122] [Table 5]

[0123] In the sixth set of tests, further concrete compositions were prepared based on combinations of CEM II, polyols, and polyalkylene glycol alkyl ethers. The compositions and properties obtained in these experiments are shown in Table 6.

[0124] [Table 6]

[0125] The results shown in Tables 3-6 demonstrate that when polyols are used in combination with polyalkylene glycols that are chemically and / or physically different from polyols, particularly polyalkylene glycol alkyl ethers, especially poly-(ethylene glycol-propylene glycol)-monobutyl ether and / or polyethylene glycol neopentyl ether, resistance to both sulfates and chlorides can be improved.

[0126] Furthermore, by optimizing the concentration of the mixture of polyol and polyalkylene glycol alkyl ether, resistance to sulfates or chlorides can be improved based on specific requirements.

[0127] This system, which improves resistance to chlorides and / or sulfates, is applicable to various types of inorganic binders, as demonstrated by the data in Tables 1-6.

[0128] At the same time, processability (FTS) is not affected by the addition of polyols and polyalkylene glycols.

[0129] Those skilled in the art will understand that the present invention can be carried out in other specific forms without departing from its spirit or essential features. Accordingly, the embodiments disclosed herein are considered illustrative and not limiting in all respects.

Claims

1. Use of polyols and / or polyalkylene glycols for improving the resistance of a cured inorganic binder composition to sulfates and / or chlorides, wherein the polyalkylene glycol is chemically and / or physically different from the polyol.

2. The use according to claim 1, wherein the polyol is a diol, particularly a glycol.

3. The weight-average molecular weight (M) of the polyol ｗ The use according to claim 1 or 2, wherein the amount is a maximum of 500 g / mol, particularly a maximum of 250 g / mol, and particularly a maximum of 180 g / mol.

4. The use according to any one of claims 1 to 3, wherein the ratio of ether groups to hydroxyl groups in the polyol is 0 to 1, particularly 0 to 0.5, particularly 0 to 0.1, and most preferably 0.

5. The aforementioned polyol is, Formula C ｎ H ２ｎ (OH) ２ The use according to any one of claims 1 to 4, wherein the polyol is of a type n of 2 to 10, particularly n of 4 to 8, and particularly n of 5 to 6.

6. The use according to any one of claims 1 to 5, wherein the polyol is selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, pentylene glycol, neopentyl glycol, and / or hexylene glycol.

7. The use according to any one of claims 1 to 6, wherein a combination of at least a first polyol and a second polyol is used, and the first polyol and the second polyol are physically and / or chemically different, in particular a combination of neopentyl glycol and hexylene glycol.

8. The use according to claim 7, wherein in the above combination, the weight ratio of the first polyol to the second polyol is 0.1 to 10, particularly 0.3 to 2, particularly 0.5 to 1.5, and particularly 0.8 to 1.

2.

9. The use according to any one of claims 1 to 8, wherein the proportion of polyol used is 0.0001 to 10% by weight, particularly 0.01 to 5% by weight, particularly 0.1 to 3% by weight, and particularly 0.5 to 2% by weight, based on the weight of the inorganic binder in the inorganic binder composition.

10. The use according to any one of claims 1 to 9, wherein the polyalkylene glycol is a polyalkylene glycol alkyl ether, particularly poly-(ethylene glycol-propylene glycol)-monoalkyl ether and / or polyethylene glycol neopentyl ether.

11. The polyol and / or the polyalkylene glycol a) 10-50% by weight, especially 25-45% by weight, especially 30-40% by weight of water; 10 to 40% by weight, particularly 15 to 35% by weight, particularly 20 to 30% by weight, of neopentyl glycol as the first polyol; and Hexylene glycol as the second polyol in an amount of 10 to 50% by weight, particularly 30 to 50% by weight, particularly 35 to 45% by weight; or b) 10–50% by weight, especially 25–45% by weight, especially 30–40% by weight of water; 10 to 40% by weight, particularly 15 to 35% by weight, particularly 20 to 30% by weight, of neopentyl glycol as a polyol; and 10 to 50% by weight, particularly 30 to 50% by weight, particularly 35 to 45% by weight of polyalkylene glycol alkyl ethers, especially poly-(ethylene glycol-propylene glycol)-monoalkyl ethers and / or polyethylene glycol neopentyl ethers; The use according to any one of claims 7 to 10, in the form of an aqueous solution containing the above.

12. The use according to any one of claims 1 to 11, wherein the polyol and / or the polyalkylene glycol is used in combination with a plasticizer, particularly a polycarboxylate ether.

13. The use according to claim 12, wherein the plasticizer is used in the inorganic binder composition in an amount of 0.0001 to 10% by weight, particularly 0.01 to 5% by weight, particularly 0.1 to 3% by weight, and particularly 0.5 to 2% by weight, based on the weight of the inorganic binder.

14. The use according to any one of claims 1 to 13, wherein the inorganic binder in the inorganic binder composition comprises cement, particularly cement of type CEM I, CEM II, CEM III, CEM IV, and / or CEM V (in accordance with standard EN197-1:2011).

15. An admixture for improving the resistance of an inorganic binder composition in aqueous solution form to sulfates and / or chlorides, a) 10-50% by weight, especially 25-45% by weight, especially 30-40% by weight of water, 10-40% by weight, particularly 15-35% by weight, particularly 20-30% by weight of a first polyol, especially neopentyl glycol, and 10-50% by weight, especially 30-50% by weight, especially 35-45% by weight of a second polyol, especially hexylene glycol, The first polyol and the second polyol are physically and / or chemically different; or b) 10-50% by weight, especially 25-45% by weight, especially 30-40% by weight of water, 10-40% by weight, particularly 15-35% by weight, particularly 20-30% by weight of polyols, especially neopentyl glycol, and 10 to 50% by weight, especially 30 to 50% by weight, especially 35 to 45% by weight of polyalkylene glycol, especially polyalkylene glycol alkyl ether, especially poly-(ethylene glycol-propylene glycol)-monoalkyl ether and / or polyethylene glycol neopentyl ether, including; Admixture.

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