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    • 专利摘要:
    sprayable hydraulic binder composition and method for use. the present invention relates to a process for the preparation of a sprayable hydraulic binder composition containing as main components water, aggregates, hydraulic binder, setting accelerator, characterized by the fact that a component containing calcium silicate hydrate (csh) is added before and / or in the spray nozzle.
    公开号:BR112012008095B1
    申请号:R112012008095-4
    申请日:2010-08-31
    公开日:2021-04-27
    发明作者:Luc Nicoleau；Montserrat Alfonso；Elena Kolomiets
    申请人:Construction Research & Technology Gmbh；
    IPC主号:
    专利说明:

    DESCRIPTION
    [0001] The present invention relates to a process for the preparation of a sprayable hydraulic binder composition, the sprayable hydraulic binder composition and a method for using the composition. BACKGROUND OF THE INVENTION
    [0002] The application of cement compositions such as concrete to a substrate by spraying from a nozzle is a well-established technology, and is widely used in such applications as tunnel coating. It is a requirement that these compositions are capable of being transported easily (usually by pumping) to a spray nozzle. This can be achieved by adding to the cement composition that is to be pumped and sprayed, in the mixing stage, a mixture that provides improved flowability of the mixture. There is a considerable amount of such mixtures known and used in the art, for example, sulphonated melamine formaldehyde, condensed sulphonated naphthalene formaldehyde, or acrylic polymer families.
    [0003] Powdered concrete or “concrete” is used mainly in underground construction. Its application consists of transporting a mortar or concrete to a nozzle, where an accelerating mixture of handle and air is added, and its pneumatic projection at high speed on a substrate. In fact, quick pick-up and early strength development are required to allow concrete to adhere to the wall without falls and consequently additional early excavations are ensured, ensuring safety and efficient construction. For this reason, accelerators that guarantee rapid development of mechanical properties are added to the pulverized concrete or pulverized mortar.
    [0004] It is known that pickup accelerators influence the hydration process of the clinker phases such as C3A and C3S, the consumption of sulfate carriers and the chemical composition of the pore solution in the initial stage. The faster cure caused by the addition of handle accelerators is due to the large formation of hydration product such as etringite, which in some cases results in a development of poor early resistance which in the literature is correlated with a slow formation of calcium silicate hydrates. (CSH).
    [0005] Adding (1) a hardening accelerator that consists of calcium silicate hydrates and (2) an accelerator that picks up the precipitation of calcium silicate hydrate (C-S-H) can be strongly accelerated allowing the development of mechanical properties more quickly.
    [0006] A process for preparing a liquid accelerator is described in EP 08170692.1, wherein the liquid accelerator containing aluminum sulfate and / or aluminum hydroxide sulfate. EP1878713 describes an accelerator mixture that is based on 25 to 40% by weight of aluminum sulphate, at least one additional aluminum compound, so that the molar ratio of aluminum to sulphate in the dispersion is 1.35 to 0.70 and an inorganic stabilizer comprising a magnesium silicate. A process for applying a layer of cement composition to a substrate by spraying the cement composition is described in EP 0812812. An accelerator and hardening accelerator mixture for hydraulic binder according to EP 1964825 comprises sulfate, aluminum, organic acid and / or mineral acid and silicic acid. WO 2005/075381 describes a water-based accelerator mixture and a curing accelerator for hydraulic binder, comprising sulfate, aluminum and organic acid, where the molar ratio of aluminum to organic acid is less than 0.65.
    [0007] Conventional grip accelerators for concrete and other cement-containing materials are distinguished by the fact that they either result in quick grip and relatively low early strength or lead to slow grip in combination with relatively high early strength. In addition, results with respect to the performance of the concrete pick-up accelerator often vary depending on the type of cement, concrete mix design, and temperature. Although all these factors are taken into account before application, it is difficult to obtain the development of high anticipated resistance that is required today by an increasing number of tunnel designs with known grip accelerators. Therefore, the demand for more efficient and highly robust accelerator mixes, which are suitable for a wide variety of cements on a worldwide basis and which meet different specifications, is high.
    [0008] In addition, mixtures to build material mixtures that comprise hydraulic binders also typically contain hardening accelerators that increase the rate of early strength development of the hydraulic binder.
    [0009] According to WO 02/070425, calcium silicate hydrates can be used as a hardening accelerator. However, commercially available calcium silicate hydrates and dispersions of the same can only be considered as hardening accelerators that have little effect.
    [0010] The purpose of the invention is to provide a sprayable hydraulic binder composition, for example, pulverized concrete or pulverized mortar for the coating of substrates, in particular tunnel surfaces, mine surfaces, channel and well construction, with concrete or mortar.
    [0011] Surprisingly, a new chemical system has been found to accelerate the setting up and development of early strength in hydraulic binder compositions, in particular powdered concrete or powdered mortar. DETAILED DESCRIPTION OF THE INVENTION
    [0012] The disadvantage of known pick-up accelerator mixes is that the supplied quick pick results very often in a slow anticipated strength development in hydraulic binder containing compositions such as pulverized concrete.
    [0013] It is an objective of the present invention to provide a process for the preparation of a sprayable hydraulic binder composition containing as main components water, aggregates, hydraulic binder and a handle accelerator, characterized by the fact that a component containing silicate hydrate calcium (CSH) is added before and / or in the spray nozzle.
    [0014] Surprisingly, it has been found that calcium silicate hydrates improve the performance of setting accelerators in hydraulic binder compositions and thus create greater hardening of the hydraulic binder.
    [0015] The invention, therefore, provides a new chemical system to accelerate pickup and early strength development in hydraulic binder compositions, in particular pulverized concrete. It has now been found that a specific chemical system can be prepared by combining (1) a hardening mixture and (2) a setting accelerator. The (1) hardening mixture contains calcium silicate hydrates. The (2) setting accelerator consists of any type of setting accelerator for powdered concrete that is free of alkali or containing alkali based on, for example, aluminum sulphate or sodium silicate. The hardening accelerator can also be added simultaneously with the nozzle pick-up accelerator.
    [0016] Especially when sprayed on a substrate, the composition of cement, such as concrete, has to pick up very quickly. For this use, powerful accelerators that include sodium aluminate and alkali metal hydroxide have been used. However, since these accelerators are highly alkaline, their use results in very unpleasant handling and working conditions. Therefore, alkali-free and low-alkali accelerators have been proposed containing aluminum compounds.
    [0017] Usual accelerators without alkalis for pulverized concrete and other cement-containing materials are distinguished by the fact that they either result in fast grip and relatively low anticipated resistance or lead to a relatively slow grip in combination with relatively high anticipated resistance.
    [0018] In principle, the hardening accelerator contains inorganic and organic components. The inorganic component can be considered as a modified, finely dispersed calcium silicate hydrate (C-S-H) that may contain external ions, such as magnesium and aluminum. Calcium silicate hydrate (CSH) according to a preferred method is prepared by reacting a water-soluble calcium compound with a water-soluble silicate compound, in which the reaction of the water-soluble calcium compound with water-soluble silicate compound is preferably carried out in the presence of an aqueous solution containing a water-soluble comb polymer suitable as a plasticizer for hydraulic binders and / or preferably carried out in the presence of polycondensates containing, (I) at least one structural unit that it consists of an aromatic or heteroaromatic moiety supporting a polyether side chain, preferably a polyalkylene glycol side chain, more preferably a polyethylene glycol side chain, and; (II) at least one structural unit consisting of an aromatic or heteroaromatic moiety bearing at least one phosphoric acid ester group and / or its salt is present in the aqueous solution containing a water-soluble comb polymer suitable as a plasticizer for hydraulic binders.
    [0019] Preferably the aqueous solution in which the reaction is carried out contains, next to the comb polymer, a second polymer. The second polymer is a polycondensate as described in the text below of this modality and the following modalities. Preferably the comb polymer used in conjunction with the polycondensate is obtainable through radical polymerization.
    [0020] Polycondensates according to this modality are known in the prior art (US 20080108732 A1) as being effective as a superplasticizer in cement compositions. US 20080108732 A1 describes polycondensates based on an aromatic or heteroaromatic compound (A) which has 5 to 10 C atoms or heteroatoms, which has at least one oxyethylene or oxypropylene radical, and an aldehyde (C) selected from the group consisting of formaldehyde, glyoxylic acid and benzaldehyde or mixtures thereof, which result in an improved plasticizing effect of inorganic binder suspensions compared to conventionally used polycondensates and maintains this effect for a long period ("drop retention"). In a particular embodiment, these can also be polycondensed phosphates.
    [0021] Typically the polycondensate contains (I) at least one structural unit consisting of an aromatic or heteroaromatic moiety supporting a polyether side chain, preferably a polyalkylene glycol side chain, more preferably a polyethylene glycol side chain. The structural unit consisting of an aromatic or heteroaromatic moiety supporting a polyether side chain, preferably a polyethylene glycol side chain is preferably selected from the group of alkoxylates, preferably ethoxylated, hydroxy-functionalized aromatics or heteroaromatics (for example, aromatics can be selected from phenoxyethanol, phenoxypropanol, 2-alkoxyphenoxyethanols, 4-alkoxyphenoxyethanols, 2-alkylphenoxyethanols, 4-alkylphenoxyethanols) and / or alkoxylated, preferably ethoxylated, aromatic or heteroaromatic amino-functionalized (for example, N-aromatics can be selected from N-aromatics, (Dihydroxyethyl) aniline, N, - (Hydroxyethyl) aniline, N, N- (Dihydroxypropyl) aniline, N, - (Hydroxypropyl) aniline). More preferably they are alkoxylated phenol derivatives (for example, phenoxyethanol or phenoxypropanol), more preferably they are alkoxylated, especially ethoxylated phenol derivatives which have an average molecular weight between 300 g / mol and 10,000 g / mol (for example, polyphenylene glycol monophenyl ethers).
    [0022] Typically the polycondensate contains (II) at least one phosphate structural unit consisting of an aromatic or heteroaromatic moiety bearing at least one phosphoric acid ester group and / or a phosphoric acid ester salt, which is preferably selected from the group of aromatic or heteroaromatic hydroxy-functionalized alkoxylates (eg phenoxyethanol phosphate, polyethylene glycol monophenyl ether phosphates) and / or aromatic or heteroaromatic amino-functionalized alkoxylates (eg N, N- (Di-hydroxyethyl) aniline diphosphate, N, N- -hydroxyethyl) aniline phosphate, N, - (Hydroxypropyl) aniline phosphate), which support at least one phosphoric acid ester group and / or a phosphoric acid ester salt (for example through esterification with phosphoric acid and optional addition of bases) . More preferably they are alkoxylated phenols bearing at least one phosphoric acid ester group and / or a phosphoric acid ester group salt (for example, polyethylene glycol monophenyl ether phosphates with less than 25 ethylene glycol units) and more preferably they are the respective alkoxylated phenols that have weight molecular weight between 200 g / mol and 600 g / mol (eg phenoxyethanol phosphate, polyethylene glycol monophenyl ether phosphates with 2 to 10 ethylene glycol units), alkoxylated phenols bearing at least one phosphoric acid ester group and / or an acid ester group salt phosphoric (for example, by esterification with phosphoric acid and optional addition of bases).
    [0023] In another embodiment of the invention the process is characterized by the fact that in the polycondensate the structural units (I) and (II) are represented by the following general formula
    where A are identical or different and are represented by a substituted or unsubstituted aromatic or heteroaromatic compound that has 5 to 10 C atoms where B are identical or different and are represented by N, NH or O where n is 2 if B is N and is 1 if B is NH or O where R1 and R2, independently of each other, are identical or different and are represented by a direct or branched chain C1- to C10- radical alkyl, C5- to C8- radical cycloalkyl, radical aryl, heteroradical aryl or H where a are identical or different and are represented by an integer from 1 to 300 where X are identical or different and are represented by a direct or branched chain C1- to C10- radical alkyl, C5- to C8- cycloalkyl radical , radical aryl, radical heteroaryl or H, preferably H,
    where D are identical or different and are represented by a substituted or unsubstituted heteroaromatic compound that has 5 to 10 C atoms where E are identical or different and are represented by N, NH or O where m is 2 if E is N and is 1 whether E is NH or O where R3 and R4, independently of each other, are identical or different and are represented by a direct or branched chain C1- to C10-radical alkyl, C5- to C8-radical cycloalkyl, radical aryl, radical heteroaryl or H where b are identical or different and are represented by an integer from 1 to 300 where M is independently of one another an alkali metal ion, alkaline earth metal ion, ammonium ion, organic ammonium ion and / or H, a is 1 or in the case of 1/2 alkaline earth metal ions.
    [0024] Groups A and D in the general formulas (I) and (II) of the polycondensate are preferably represented by phenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, naphthyl, 2-hydroxynaphthyl, 4-hydroxynaphthyl, 2-methoxynaphthyl, 4-methoxynaphthyl, preferably phenyl, it being possible for A and D to be chosen independently of each other and also in each case to consist of a mixture of said compounds. Groups B and E, independently of each other, are preferably represented by O. The radicals R1, R2, R3 and R4 can be chosen independently of each other and are preferably represented by H, methyl, methyl or phenyl, particularly preferably by H or methyl and especially preferably by H.
    [0025] In general formula (I) a is preferably represented by an integer from 1 to 300, in particular 3 to 200 and particularly preferably 5 to 150 and b in general formula (II) by an integer from 1 to 300, preferably 1 to 50 and particularly preferably 1 to 10. The respective radicals, the size of which is defined by a and b, respectively, may here consist of uniform building blocks, but a mixture of different building blocks may also be convenient. In addition, the radicals of the general formula (I) or (II), independently of each other, can each have the same chain length, a and b each being represented by a number. As a rule, however, it will be convenient if mixtures that have different chain lengths are present in each case so that the structural moisture radicals in the polycondensate have different numerical values for a and independently for b.
    [0026] Often, the phosphate polycondensate according to the invention has an average molecular weight of 5,000 g / mol to 200,000 g / mol, preferably 10,000 to 100,000 g / mol and particularly preferably 15,000 to 55,000 g / mol.
    [0027] The polycondensate phosphate can also be present in the form of its salts, such as the sodium, potassium, organic ammonium, ammonium and / or calcium salt, preferably as the sodium and / or calcium salt.
    [0028] Typically the molar ratio of the structural units (I) :( II) is 1:10 to 10: 1, preferably 1: 8 to 1: 1. It is advantageous to have a relatively high proportion of structural units (II) in the polycondensate due to the relatively high negative charge of the polymers having a good influence on the stability of the suspensions.
    [0029] In a preferred embodiment of the invention, the polycondensate contains an additional structural unit (III) which is represented by the following formula
    where Y, independently of each other, are identical or different and are represented by (I), (II), or additional constituents of the polycondensate where R5 are identical or different and are represented by H, CH3, COOH or aromatic or a compound substituted or unsubstituted heteroaromatic having 5 to 10 C atoms, preferably H where R6 are identical or different and are represented by H, CH3, COOH or a substituted or unsubstituted aromatic or heteroaromatic compound having 5 to 10 C atoms, preferably H .
    [0030] Polycondensates are typically prepared by a process in which (I) at least one structural unit consisting of an aromatic or heteroaromatic moiety supporting a polyether side chain (e.g., poly (ethylene glycol) monophenyl ether) and (II) at least one structural unit consisting of an aromatic or heteroaromatic moiety bearing at least one phosphoric acid ester group and / or a salt of the phosphoric acid ester group (eg, phenoxyethanol phosphoric acid ester) are reacted with (IIIa) a monomer which has a keto group. Preferably the monomer that has the keto group is represented by the general formula (IIIa),
    where R7 are identical or different and are represented by H, CH3, COOH and / or a substituted or unsubstituted aromatic or heteroaromatic compound that has 5 to 10 C atoms, preferably H, where R8 are identical or different and are represented by H, CH3, COOH and / or a substituted or unsubstituted aromatic or heteroaromatic compound having 5 to 10 C atoms, preferably H.
    [0031] Preferably the monomer that has a keto group is selected from the group of ketones, being preferably an aldehyde, more preferably formaldehyde. Examples for chemicals according to the general structure (IIIa) are formaldehyde, acetaldehyde, acetone, glyoxylic acid and / or benzaldehyde. Formaldehyde is preferred.
    [0032] Typically R5 and R6 in the structural unit (III), independently of each other, are identical or different and are represented by H, COOH and / or methyl. More preferably it is H.
    [0033] In another preferred embodiment of the invention the molar ratio of the structural units [(I) + (II)]: (III) is 1: 0.8 to 3 in the polycondensate.
    [0034] Preferably, polycondensation is performed in the presence of an acidic catalyst, where this catalyst is preferably sulfuric acid, metasulfonic acid, para-toluenesulfonic acid or mixtures thereof. Polycondensation and phosphating are advantageously carried out at a temperature between 20 and 150 ° C and a pressure between 100 and 1,000 kPa. In particular, a temperature range between 80 and 130 ° C has proven to be convenient. The duration of the reaction can be between 0.1 and 24 hours, depending on the temperature, the chemical nature of the monomers used and the desired degree of crosslinking. Crosslinking can preferably occur if monosubstituted monomers of structural unit I and / or II are used because the condensation reaction can occur in two positions, ortho and the para position. Once the desired degree of polycondensation has been achieved, which can be determined, for example, by measuring the viscosity of the reaction mixture, the reaction mixture is cooled.
    [0035] The reaction mixture can be subjected to heat after treatment at a pH between 8 and 13 and a temperature between 60 and 130 ° C after the end of the condensation reaction and phosphate reaction. As a result of the heat after treatment, which advantageously takes between 5 minutes and 5 hours, it is possible to substantially reduce the content of aldehyde, in particular the content of formaldehyde, in the reaction solution. Alternatively, the reaction mixture can be subjected to vacuum treatment or other methods known in the prior art to reduce the content of (form) aldehyde.
    [0036] In order to obtain a better shelf life and better product properties, it is advantageous to treat the reaction solutions with basic compounds. Therefore, it should be considered as preferable to react to the reaction mixture after the end of the reaction with a sodium, potassium, ammonium or basic calcium compound. Sodium hydroxide, potassium hydroxide, ammonium hydroxide or calcium hydroxide have proven to be particularly convenient here, it should be considered as preferable to neutralize the reaction mixture. However, other alkali metal and alkaline earth metal salts and organic amine salts are also suitable as salts of phosphate polycondensates.
    [0037] Mixed salts of the phosphate polycondensates can also be prepared by reacting the polycondensates with at least two basic compounds.
    [0038] The used catalyst can also be separated. This can be done conveniently through the salt formed during neutralization. If sulfuric acid is used as a catalyst and the reaction solution is treated with calcium hydroxide, the formed calcium sulfate can be separated, for example, in a simple way by filtration.
    [0039] In addition, by adjusting the pH of the reaction solution to 1.0 to 4.0, in particular 1.5 to 2.0, the phosphate polycondensate can be separated from the aqueous salt solution by phase separation and can be isolated. The phosphate polycondensate can then be taken up in the desired amount of water. However, other methods known to one skilled in the art, such as dialysis, ultrafiltration or the use of an ion exchanger, are also suitable for separating the catalyst.
    [0040] In a preferred embodiment, the water-soluble comb polymer suitable as a plasticizer for hydraulic binders is present as a copolymer that contains, in the main chain, side chains that have ether and acid functions.
    [0041] In a preferred embodiment, the water-soluble comb polymer suitable as a plasticizer for hydraulic binder is present as a copolymer that is produced by free radical polymerization in the presence of acid monomer, preferably carboxylic acid monomer, and polyether macromonomer, so that altogether at least 45 mol%, preferably at least 80 mol%, of all structural units of the copolymer are produced by incorporating monomer acid, preferably carboxylic monomer acid, and polyether macromonomer in the form of polymerized units. Monomer acid is to be understood as meaning monomers that are capable of free radical copolymerization, have at least one carbon double bond, which contains at least one acid function, preferably a carboxylic acid function, and reacts as an acid in a medium aqueous. In addition, monomeric acid is also to be understood as meaning monomers that are capable of free radical copolymerization, have at least one carbon double bond, form at least one acid function, preferably a carboxylic acid function, in an aqueous medium as a result hydrolysis reaction and reacts as an acid in an aqueous medium (example: maleic anhydride or hydrolyzable esters of (meth) acrylic acid).
    [0042] In the context of the present invention, polyether macromonomers are compounds that are capable of free radical copolymerization, have at least one carbon double bond, and have at least two oxygen ether atoms, with the proviso that the polyether structural units macromonomers present in the copolymer have side chains containing at least two ether oxygen atoms, preferably at least 4 ether oxygen atoms, more preferably at least 8 ether oxygen atoms, more preferably at least 15 ether oxygen atoms.
    [0043] Structural units, which do not constitute a monomer acid or a macromonomer polyether can be, for example, styrene and derivatives of styrene (for example, substituted methyl derivatives), vinyl acetate, vinyl pyrrolidone, butadiene, vinyl propionate, unsaturated hydrocarbons such as ethylene, propylene and / or (iso) butylene. This list is a non-exhaustive list. Preferably they are monomers with no more than one carbon double bond.
    [0044] In a preferred embodiment of the invention the combination of water-soluble polymers suitable as a plasticizer for hydraulic binders is a styrene copolymer and a maleic acid ester medium with a monofunctional polyalkylene glycol. Preferably, this copolymer can be produced by free radical polymerization of the monomers styrene and maleic anhydride (or maleic acid) in a first step. In the second step, polyalkylene glycols, preferably polyalkylene alkyl glycols (preferably polyethylene alkyl glycols, more preferably polyethylene glycol methyl) are reacted with the copolymer of styrene and maleic anhydride in order to obtain an esterification of the acid groups. Styrene can be completely or partially replaced by styrene derivatives, for example, substituted methyl derivatives. Copolymers of this preferred embodiment are described in US 5,158,996, the disclosure of which is incorporated in the present patent application.
    [0045] Often, the structural unit is produced in the copolymer by incorporating the acid monomer in the form of polymerized units, a structural unit that is according to the general formula (Ia), (Ib), (Ic) and / or (Id )
    where R1 are identical or different and are represented by H and / or an unbranched chain or a branched C1 - C4 alkyl group; X are identical or different and are represented by NH- (CnH2n) where n = 1, 2, 3 or 4 and / or O- (CnH2n) where n = 1, 2, 3 or 4 and / or by a unit not present ; R2 are identical or different and are represented by OH, SO3H, PO3H2, O-PO3H2 and / or para-substituted C6H4-SO3H, with the proviso that if X is a non-present unit, R2 is represented by OH; (Ib)
    where R3 are identical or different and are represented by H and / or an unbranched chain or a branched C1 - C4 alkyl group; n = 0, 1, 2, 3 or 4 R4 are identical or different and are represented by SO3H, PO3H2, O-PO3H2 and / or para-substituted C6H4-SO3H;
    where R5 are identical or different and are represented by H and / or an unbranched chain or a branched C1 - C4 alkyl group; Z are identical or different and are represented by O and / or NH;
    where R6 are identical or different and are represented by H and / or an unbranched chain or a branched C1 - C4 alkyl group; Q are identical or different and are represented by NH and / or O; R7 are identical or different and are represented by H, (CnH2n) - SO3H where n = 0, 1, 2, 3 or 4, preferably 1, 2, 3 or 4, (CnH2n) -OH where n = 0, 1, 2, 3 or 4, preferably 1, 2, 3 or 4; (CnH2n) -PO3H2 where n = 0, 1, 2, 3 or 4, preferably 1, 2, 3 or 4, (CnH2n) -OPO3H2 where n = 0, 1, 2, 3 or 4, preferably 1, 2, 3 or 4, (C6H4) -SO3H, (C6H4) -PO3H2, (C6H4) - OPO3H2 and / or (CmH2m) eO- (A'O) α-R9 where m = 0, 1, 2, 3 or 4, preferably 1, 2, 3 or 4, e = 0, 1, 2, 3 or 4, preferably 1, 2, 3 or 4, A '= Cx'H2x' where x '= 2, 3, 4 or 5 and / or CH2C (C6HÕ) H-, a = an integer from 1 to 350 where R9 are identical or different and are represented by an unbranched chain or a branched C1 - C4 alkyl group.
    [0046] Typically, the structural unit is produced in the copolymer by incorporating the macromonomer polyether in the form of polymerized units, a structural unit that is according to the general formula (IIa), (IIb) and / or (IIc)
    where R10, R11 and R12 are in each case identical or different and, independently of each other, are represented by H and / or an unbranched chain or a branched C1 - C4 alkyl group; And they are identical or different and are represented by a branched non-chain or branched C1 - C6 alkylene group, preferably C2 - C6 alkylene group, a cyclohexylene group, CH2-C6H10, ortho, meta or para-substituted unit and / or a non-substituted unit gift; G are identical or different and are represented by O, NH and / or CO-NH, with the proviso that if E is a non-present unit, G is also present as a non-present unit; A are identical or different and are represented by CxH2x where x = 2, 3, 4 and / or 5 (preferably x = 2) and / or CH2CH (C6H5); n are identical or different and are represented by 0, 1, 2, 3, 4 and / or 5; a are identical or different and are represented by an integer from 2 to 350 (preferably 10 to 200); R13 are identical or different and are represented by H, an unbranched chain or a branched C1 - C4 alkyl group, CO-NH2, and / or COCH3;
    where R14 are identical or different and are represented by H and / or an unbranched chain or a branched C1 - C4 alkyl group; And they are identical or different and are represented by an unbranched chain or a branched C1 - C6 alkylene group, preferably a C2 - C6 alkylene group, a cyclohexylene group, CH2-C6H10, ortho-, meta- or para-substituted and / or by a unit not present; G are identical or different and are represented by a unit not present, 0, NH and / or C0-NH, with the proviso that if E is a unit not present, G is also present as a unit not present; A are identical or different and are represented by CxH2x where x = 2, 3, 4 and / or 5 and / or CH2CH (C6H5); n are identical or different and are represented by 0, 1, 2, 3, 4 and / or 5 a are identical or different and are represented by an integer from 2 to 350; D are identical or different and are represented by a non-present unit, NH and / or O, with the proviso that if D is a non-present unit: b = 0, 1, 2, 3 or 4 and c = 0, 1, 2, 3 or 4, where b + c = 3 or 4, and with the proviso that if D is NH and / or O, b = 0, 1, 2 or 3, c = 0, 1, 2 or 3, where b + c = 2 or 3; R15 are identical or different and are represented by H, an unbranched chain or branched C1 - C4 alkyl group, CO-NH2, and / or COCH3;
    where R16, R17 and R18 are in each case identical or different and, independently of each other, are represented by H and / or an unbranched chain or branched C1 - C4 alkyl group; And they are identical or different and are represented by a branched non-chain or a branched C1 - C6 alkylene group, preferably a C2-C6 alkylene group, a cyclohexylene group, CH2-C6H10, C6H4 ortho-, meta- or para-substituted and / or by a unit not present; preferably E is not a unit not present; A are identical or different and are represented by CxH2x where x = 2, 3, 4 and / or 5 and / or CH2CH (C6H5); n are identical or different and are represented by 0, 1, 2, 3, 4 and / or 5; L are identical or different and are represented by CxH2x where x = 2, 3, 4 and / or 5 and / or CH2-CH (C6H5); a are identical or different and are represented by an integer from 2 to 350; d are identical or different and are represented by an integer from 1 to 350; R19 are identical or different and are represented by H and / or an unbranched chain or a branched C1 - C4 alkyl group, R20 are identical or different and are represented by H and / or an unbranched chain C1 - C4 alkyl group.
    [0047] In a further embodiment of the invention the structural unit is produced in the copolymer through the incorporation of the polyether macromonomer in the form of polymerized units, a structural unit which is according to the general formula (IId)
    where R21, R22 and R23 are in each case identical or different and, independently of each other, are represented by H and / or an unbranched chain or branched C1 - C4 alkyl group; A are identical or different and are represented by CxH2x where x = 2, 3, 4 and / or 5 and / or CH2CH (C6H5); a are identical or different and are represented by an integer from 2 to 350; R24 are identical or different and are represented by H and / or an unbranched chain or a branched C1 - C4 alkyl group, preferably a C1 - C4 alkyl group.
    [0048] Isoxylated and / or alkoxylated hydroxybutyl vinyl ether and / or alkoxylated (meth) allyl alcohol and / or vinyl polyethylene glycol vinyl which preferably has in each case an arithmetic mean number of 4 to 340 oxyalkylene groups is preferably used as the macromonomer polyether. Methacrylic acid, acrylic acid, maleic acid, maleic anhydride, a maleic acid monoester or a mixture of a plurality of components is preferably used as the monomer acid.
    [0049] Usually, a suspension is obtained containing the calcium silicate hydrate (C-S-H) in finely dispersed form. This suspension effectively accelerates the process of hardening hydraulic binders.
    [0050] Often, the water-soluble calcium compound is present as calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium bicarbonate, calcium bromide, calcium carbonate, calcium citrate, calcium chlorate , calcium fluoride, calcium gluconate, calcium hydroxide, calcium hypochlorite, calcium iodide, calcium iodide, calcium lactate, calcium nitrite, calcium oxalate, calcium phosphate, calcium propionate, calcium silicate, stearate calcium, calcium sulfate, calcium hemihydrate sulfate, calcium dihydrate sulfate, calcium sulfide, calcium tartrate and / or calcium aluminate, tricalcium silicate and / or dicalcium silicate.
    [0051] The water-soluble calcium compound is preferably present as calcium chloride, calcium nitrate and / or calcium formate.
    [0052] Often, the water-soluble silicate compound is present as sodium silicate, potassium silicate, soluble glass, aluminum silicate, tricalcium silicate, dicalcium silicate, calcium silicate, silicic acid, sodium metasilicate and / or metasilicate of potassium.
    [0053] The water-soluble silicate compound is preferably present as sodium metasilicate, potassium metasilicate and / or soluble glass.
    [0054] In principle, a calcium silicate (as long as it is soluble) can be used both as a source of silicate and as a source of calcium. In many cases, however, this is not preferred. As a rule, species of different types are used such as the water-soluble silicate compound and the water-soluble calcium compound.
    [0055] The sprayable hydraulic binder composition prepared by the method of the invention not only improves the grip and / or early strength development in hydraulic binder compositions, but also makes it possible to reduce the cement content and obtain the same, or rather, development of early resistance.
    [0056] In a preferred embodiment of the present invention the hydraulic binder is clinker, plaster, calcium sulfate, bassanite (calcium sulfate hemihydrate), anhydride (anhydrous calcium sulfate), lime, a latent hydraulic binder (for example, fly ash, blast furnace slag or pozzolans), and mixtures thereof, preferably Portland cement.
    [0057] Cement is typically used in the construction industry as a finely ground hydraulic binder to make concrete, mortar, concrete stones and finished parts.
    [0058] Portland cement is a basic ingredient in concrete, mortar and most non-specialized mortars. The most common use for Portland cement is in the production of concrete. Concrete is an essentially composite material that consists of aggregate (gravel and sand), cement, and water. As a building material, concrete can be molded into almost any desired shape, and once hardened, it can become a structural (load-bearing) element. Portland cement can be gray or white.
    [0059] In a preferred embodiment, the aggregates are selected from the group consisting of sand, organic and / or inorganic granules, gravel, preferably with a size distribution of 0 to 16 mm, preferably 0 to 8 mm.
    [0060] In a preferred embodiment, the pickup accelerator contains as main components sulfate, aluminum in a state of oxidation +3 or mixtures thereof.
    [0061] US5340385 discloses that several chemical pick-up accelerators are well known. Alkali hydroxides, silicates, fluorosilicates, calcium formate, sodium chloride, calcium chloride, calcium nitrate and calcium nitrite are included and comprised by the present invention. In addition, the acceleration effect of setting on the cement is increased by mixing amorphous aluminum hydroxide with water-soluble sulfates, nitrates and alkali transition metal and earth shapes.
    [0062] In a preferred embodiment the handle accelerator contains sulfate in amounts between 15 and 40% by weight, referred to as the weight of said accelerator, and / or aluminum in oxidation state 3 in amounts between 3 and 10% by weight , referred to as the weight of said accelerator.
    [0063] In a preferred embodiment of the invention the component containing calcium silicate hydrate is calcium silicate hydrate itself or a mixture containing calcium silicate hydrate.
    [0064] In an additional preferred embodiment, calcium silicate hydrate is used with a calcium to silicon molar ratio (Ca / Si) of 0.5 to 2.0, preferably 0.7 to 1.9, more preferably 1, 6 to 1.8.
    [0065] In an additional preferred embodiment the component containing calcium silicate hydrate (C-S-H) is a suspension or a solid, preferably a suspension.
    [0066] In a preferred embodiment, the hydraulic binder is used in quantities of 300 to 600 kg / m3, preferably 380 to 500 kg / m3, more preferably 350 to 450 kg / m3.
    [0067] In an additional preferred mode the component containing calcium silicate hydrate (C SH) is added to the hydraulic binder in the cement plant, in the concrete plant, for the concrete mixer truck, for the transfer pump and / or in the nozzle spray, more preferably to the mixing water.
    [0068] In an additional embodiment the component containing calcium silicate hydrate (C SH) is obtainable by the reaction of a water-soluble calcium compound with a water-soluble silicate compound, in which the reaction of the soluble calcium compound in water with the water-soluble silicate compound is preferably carried out in the presence of an aqueous solution containing at least one water-soluble polymer, preferably a plasticizer or superplasticizer, more preferably a comb polymer as a dispersant preferably suitable as a plasticizer for hydraulic binders according to EN 934-2. It can contain any type of mixture such as retardants, air incorporators, or combinations thereof.
    [0069] In the context of the present invention, the term "comb polymer" is to be understood as polymers having relatively long side chains (which have a molecular weight of at least 200 g / mol in each case, particularly preferably at least 400 g / mol) in a linear main chain at more or less regular intervals. The lengths of these side chains are often approximately the same, but they can also differ quite a lot from each other (for example, when polyether macromonomers that have side chains of different lengths are incorporated in the form of polymerized units).
    [0070] An additional preferred embodiment of this invention is a composition containing sprayable hydraulic binder that can be prepared by a process.
    [0071] The invention, furthermore, comprises a composition containing sprayable hydraulic binder which further comprises a superplasticizer, preferably a polycarboxylated ether and more preferably a dispersion thereof.
    [0072] Plasticizers or dispersants are additives that increase the plasticity or fluidity of the material to which they are added, these include plastics, cement, concrete, plaster and clay bodies. Concrete plasticizers fluidize the mixture before it hardens, increasing its workability or reducing water, and usually do not intend to affect the final product after it hardens. Additionally, concrete superplasticizers are mixtures based on polycarboxylated polymer and / or condensed sulphonated melamine formaldehyde, condensed sulphonated naphthalene formaldehyde, or acrylic polymer families. It has the advantageous effect of a fall arrest ability. It is specially adapted for the production of highly durable concrete, self-compacting concrete, concrete that maintains high workability, and also concrete with a requirement for good looks.
    [0073] Finally, the invention comprises a method of using the composition for coating substrates with pulverized concrete or pulverized mortar.
    [0074] By spraying the lining under the pillar (top) its load-bearing capacity is increased. The coating can also be applied to reduce or prevent disintegration, which is the erosion of rock surfaces recently exposed by air in the tunnel or mine, to remove radon gas in a uranium mine or to stabilize landfills, for example, in a quarry, to stabilize tunnel ceilings or similar.
    [0075] According to this invention the terms "concrete" and "mortar", respectively "pulverized concrete" and "pulverized mortar", can also include other cementitious materials. For example, cement-based renders for mining and cementitious mortars for fire protection.
    [0076] The invention will be described in more detail below with reference to functional examples.
    [0077] The following examples illustrate this invention. Example 1:
    [0078] Influence on the anticipated hydration kinetics of the combination of calcium silicate hydrate (C-S-H) and (Na2Oeq <1% by weight) handle accelerators without alkalis (figure 1).
    [0079] This example shows the effect of the inventive combination of calcium silicate hydrate (CSH) and a handle accelerator (without alkali, Na2Oeq <1.0% by weight, according to EN 480-12) on the anticipated hydration kinetics of Portland cement paste.
    [0080] To measure the hydration kinetics, approximately 2g of cement was weighed in a glass ampoule which is hermetically sealed immediately after mixing with water or mixing solution water (the mixtures, if required, were dissolved in advance in water) and then placed in a TAM Air isothermal calorimeter. The measurements were performed at a temperature of 20 ° C.
    [0081] Said mixtures of cement paste are composed as follows: Table 1

    [0082] Both handle accelerators without alkali 1 and 2 are based on aluminum sulfate.
    [0083] The results are shown in figure 1. The lines are isothermal calorimetry data, and the symbols identify individual data sets. The addition of calcium silicate hydrate (CSH) has a significant acceleration effect on the second (C3S hydration) peak (the maximum rate is increased and the time to reach the peak rate decreased), so that the addition of accelerator handle has a significant acceleration effect on the first (dissolution) peak. The combination of both shows acceleration of both peaks of hydration. Example 2:
    [0084] Influence on the early hydration kinetics of the combination of calcium silicate hydrate (C-S-H) and (Na2Oeq> 1% by weight according to EN 480-12) alkali-rich handle accelerators (figure 2).
    [0085] This example shows the effect of the inventive combination of calcium silicate hydrate (CSH) and a (Na2O> 1.0% by weight according to EN 480-12) alkali-rich handle accelerator on the anticipated paste hydration kinetics Portland cement. A cement paste is prepared and the hydration kinetics measured as described in example 1.
    [0086] Said mixtures of cement paste are composed as follows: Table 2

    [0087] The pickup accelerator 3 is based on sodium silicate so that the pickup accelerator 4 is based on sodium aluminate.
    [0088] The results are shown in figure 2. The lines are isothermal calorimetry data, and the symbols identify individual data sets. As in example 1, the addition of calcium silicate hydrate (C-SH) has a significant acceleration effect on the second (C3S hydration) peak (the maximum rate is increased and the time to reach the peak rate decreased), from so that the addition of handle accelerator has a significant acceleration effect on the first (dissolution) peak. The combination of both shows acceleration of both peaks of hydration. Example 3:
    [0089] Influence of the inventive combination in the development of early strength of a Portland cement Type I (figure 3)
    [0090] In example 3 the effect of a setting accelerator without alkalis on the development of early strength of a Portland Type I cement is compared with the effect of the inventive combination (calcium silicate hydrate (CSH) + setting accelerator). Mortars prepared according to the European Standard EN 196-1 were chosen as mixtures for examination. Said mixtures are composed as follows: Table 3

    [0091] The mortar samples were examined with a penetrometer from the company LBG, which measures and records a continuous gradual increase in the consistency of the mixtures.
    [0092] The positive influence of the combination of calcium silicate hydrate (CSH) and setting accelerator on the development of early resistance is obvious and can be seen in figure 3. The addition of calcium silicate hydrate (CSH) improves performance of the conventional handle accelerator with this Type I Portland cement by a factor of 2 within 1 to 6 hours, at a lower dosage of the handle accelerator of 2% by weight of cement. Example 4:
    [0093] Influence of the inventive combination in the development of anticipated resistance of a Portland cement Type II (figure 4)
    [0094] In example 4 the effect of a setting accelerator without alkalis on the development of early strength of a Portland Type II cement is compared with the effect of the inventive combination (calcium silicate hydrate (CSH) + setting accelerator). Mortar mixtures are prepared and examined as described in example 3. Said mixtures are composed as follows: Table 4

    [0095] The positive influence of the inventive combination on the development of early strength of a Portland cement type II is obvious and is shown in figure 4. The addition of calcium silicate hydrate (CS-H) improves the performance of the conventional handle accelerator within 1 to 6 hours by a factor of 1.5 to a lower dosage of handle accelerator of 2% by weight of cement. Example 5
    [0096] The influence of the inventive combination in the development of anticipated resistance of a Portland Type II cement in different dosages of calcium silicate hydrate (C-S-H) (figure 5)
    [0097] In example 5 the effect on the development of the anticipated resistance of Portland cement type I of the inventive combination at different dosages of calcium silicate hydrate (CSH) is shown. Mortar mixtures are prepared and examined as described in example 3. Said mixtures are composed as follows: Table 5

    [0098] Increasing the dosage of the calcium silicate hydrate component (C-S-H) a proportional improvement in the anticipated resistance is shown in figure 5. Example 6:
    [0099] The influence of the inventive combination in the development of anticipated resistance of Portland cement Type II at different temperatures (figure 6)
    [0100] In example 6 the effect on the development of the anticipated resistance of Portland cement type II of the inventive combination at different temperatures is shown. Mortar mixtures are prepared and examined as described in example 3. Said mixtures are composed as follows: Table 6

    [0101] As shown in figure 6, the addition of calcium silicate hydrate (C-S-H) to an accelerated mortar can compensate for the low development of resistance at low temperatures within the first hours of hydration. The combination of calcium silicate hydrate (C-S-H) and handle accelerator at 10 ° C and the handle accelerator alone at 20 ° C has a comparable strength development in the first two hours. Example 7:
    [0102] The effect of the inventive combination on the grip and compressive strength of a Portland Type II cement when adding the calcium silicate hydrate component (C-S-H) in powder or suspension form (table 7b)
    [0103] In example 7 the effect of the inventive combination on the curing time and compressive strength of a Portland cement type I when the calcium silicate hydrate (CSH) component is added as a powder is compared with the addition of silicate hydrate of calcium (CSH) as a suspension. Mortar mixes are prepared and examined according to EN 196 1-3. Said mixtures are composed as follows: Table 7a

    [0104] The addition of calcium silicate hydrate (CSH) powder shows the comparable improvement of the performance accelerator as the addition of calcium silicate hydrate (CSH) in the form of suspension as can be seen in table 7b. Table 7b
    Example 8
    [0105] The influence of the inventive combination on the development of the compressive concrete's anticipated compressive strength at different dosages of calcium silicate hydrate (C-S-H) (table 8b)
    [0106] Powdered concrete tests were performed with the combination of calcium silicate hydrate (CSH) and setting accelerator according to the invention and comparative examples with respect to the development of compressive strength according to the European Specification EFNARC for sprayed concrete 1999. Said concrete mixes are composed as follows: Table 8a
    * percentage based on active substance
    [0107] The results of the tests of pulverized concrete with the inventive combination show a great improvement in the development of anticipated strength as can be seen in table 8b. Table 8b
    权利要求:
    Claims (15)
    [0001]
    1. Process for the preparation of a sprayable hydraulic binder composition containing as main components water, aggregates, hydraulic binder, setting accelerator, characterized by the fact that a component containing calcium silicate hydrate obtained through the reaction of a calcium compound water-soluble with a water-soluble silicate compound carried out in the presence of at least one water-soluble organic comb polymer, is added before and / or in the spray nozzle, in which the component containing calcium silicate hydrate is added to the hydraulic binder as a calcium silicate hydrate suspension, as calcium silicate hydrate powder, or with mixing water.
    [0002]
    2. Process according to claim 1, characterized by the fact that the hydraulic binder is cement, plaster, bassanite or anhydride, lime, latent hydraulic binder, preferably fly ash, blast furnace slag or pozzolans, mixtures thereof, preferably Portland cement.
    [0003]
    3. Process according to claim 1, characterized by the fact that the aggregates are selected from the group consisting of sand, granules, gravel, preferably with a size distribution of 0 to 16 mm, even more preferably 0 to 8 mm .
    [0004]
    4. Process, according to claim 1, characterized by the fact that the handle accelerator contains as main components sulfate, oxidized aluminum + 3 or mixtures thereof.
    [0005]
    5. Process according to claim 1, characterized by the fact that the handle accelerator contains sulfate in amounts between 15 and 40% by weight, referred to as the weight of said accelerator, and / or aluminum in an oxidized state 3 in amounts between 3 and 10% by weight, referred to as the weight of said accelerator.
    [0006]
    Process according to claim 1, characterized in that the component containing calcium silicate hydrate is calcium silicate hydrate or a mixture containing calcium silicate hydrate.
    [0007]
    7. Process according to claim 1, characterized by the fact that calcium silicate hydrate is used with a calcium to silicon molar ratio (Ca / Si) of 0.5 to 2.0.
    [0008]
    8. Process according to claim 1, characterized by the fact that the component containing calcium silicate hydrate is in a liquid or solid form, preferably a dispersion.
    [0009]
    9. Process according to claim 1, characterized by the fact that the hydraulic binder is used in quantities of 300 to 600 kg / m3.
    [0010]
    10. Process according to claim 1, characterized by the fact that the component containing calcium silicate hydrate is added to the hydraulic binder in the cement plant, in the concrete plant, for the mixer truck, for the transfer pump and / or for the spray nozzle.
    [0011]
    11. Process according to claim 1, characterized by the fact that the comb polymer as dispersant is suitable as a plasticizer for hydraulic binders according to EN 934-2.
    [0012]
    12. Process according to claim 1, characterized by the fact that calcium silicate hydrate is used with a calcium / silicon molar ratio (Ca / Si) of 0.7 to 1.9.
    [0013]
    13. Process according to claim 1, characterized by the fact that calcium silicate hydrate is used with a calcium to silicon molar ratio (Ca / Si) of 1.6 to 1.8.
    [0014]
    14. Process according to claim 1, characterized by the fact that the hydraulic binder is used in quantities of 380 to 500 kg / m3.
    [0015]
    15. Process according to claim 1, characterized by the fact that the hydraulic binder is used in quantities of 350 to 450 kg / m3
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    同族专利:
    公开号 | 公开日
    MX342648B|2016-10-06|
    MX2012002715A|2012-04-19|
    PE20121415A1|2012-11-17|
    AU2010291308B2|2014-08-14|
    CA2771256C|2017-02-28|
    CL2012000258A1|2012-07-06|
    SG178023A1|2012-03-29|
    BR112012008095A2|2020-07-21|
    JP2015129092A|2015-07-16|
    CN105367025A|2016-03-02|
    AU2010291308A1|2012-03-22|
    CA2771256A1|2011-03-10|
    EP2473461A2|2012-07-11|
    NZ598647A|2013-05-31|
    US20120196046A1|2012-08-02|
    JP6057712B2|2017-01-11|
    JP2013503805A|2013-02-04|
    ZA201202295B|2013-06-26|
    WO2011026825A3|2011-05-05|
    US9102568B2|2015-08-11|
    AR078261A1|2011-10-26|
    CN102482153A|2012-05-30|
    TW201124360A|2011-07-16|
    CO6491094A2|2012-07-31|
    WO2011026825A2|2011-03-10|
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    法律状态:
    2020-08-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-08-11| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-24| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-03-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 27/04/2021, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP09169299|2009-09-02|
    EP09169299.6|2009-09-02|
    PCT/EP2010/062671|WO2011026825A2|2009-09-02|2010-08-31|Sprayable hydraulic binder composition and method of use|
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