Concrete retarding water-reducing agent, its preparation method and application
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- ZHEJIANG QUZHOU DINGSHENG BUILDING MATERIALS CO LTD
- Filing Date
- 2025-09-05
- Publication Date
- 2026-06-23
Smart Images
Figure SMS_8 
Figure SMS_10 
Figure SMS_11
Abstract
Description
Technical Field
[0001] This disclosure relates to the field of concrete additives technology, and in particular to a concrete retarder and water-reducing agent, its preparation method and application. Background Technology
[0002] Concrete admixtures are commonly used reagents in the concrete preparation process. They are not only added in small amounts, but also improve concrete performance to meet practical needs. Furthermore, they can save cement, reduce energy consumption, and reduce pollutant emissions. Common admixtures include: accelerators, water-reducing agents, air-entraining agents, and retarders.
[0003] Retarder is an admixture that slows down and reduces the exothermic rate of cement hydration, thereby extending the time for concrete to fully set, maintaining the plasticity of fresh concrete for a longer period, facilitating pouring, improving construction efficiency, and without adversely affecting the later properties of the concrete. Therefore, retarders play a crucial role in the concrete industry. Currently, there are many types of retarders on the market, but they can be divided into two main categories according to their chemical composition: inorganic retarders and organic retarders. Inorganic retarders mainly include phosphates, zinc salts, ferric sulfate, copper sulfate, borates, fluorosilicates, etc.; organic retarders include lignin sulfonates, hydroxycarboxylic acids and their salts, polyols and their derivatives, sugars, and carbohydrates, etc. Inorganic retarders ionize and react with cement hydration products, forming a dense, insoluble film on the surface of cement particles, hindering normal cement hydration; organic retarders contain complex-forming groups that, in the alkaline medium of cement hydration, react with free Ca2+. 2+ The formation of unstable complexes leads to an increase in Ca in the liquid phase. 2+ The mass concentration decreases, and at the same time, complex-forming groups may also adsorb O on the surface of cement particles and hydration products. 2- Hydrogen bonds are formed, and the complex forming group associates with water molecules through hydrogen bonds, resulting in a relatively stable solvated water film on the surface of cement particles, thereby inhibiting the cement hydration process.
[0004] Water-reducing agents are concrete admixtures that reduce the amount of water used in mixing while maintaining the slump of the concrete. Most of them are anionic surfactants, such as lignin sulfonates, naphthalene sulfonates, and formaldehyde polymers. When added to concrete mixtures, they disperse cement particles, improve workability, reduce the amount of water used per unit, improve the fluidity of the concrete mixture, or reduce the amount of cement used per unit, thus saving cement.
[0005] In the existing technology, there are not many concrete-based additives that can act as both a retarder and a water-reducing agent. Therefore, there is an urgent need to develop a new type of concrete-based additive that can act as both a retarder and a water-reducing agent. Summary of the Invention
[0006] This disclosure provides a concrete retarder water-reducing agent, its preparation method, and its application, in order to address the shortcomings of related technologies.
[0007] According to a first aspect of the present disclosure, a concrete retarder water-reducing agent is provided, the concrete retarder water-reducing agent comprising compound A, component B, component C and solvent D; wherein, the structural formula of compound A includes polyphosphate segments and polyether segments; the polyphosphate segments and polyether segments are linked by residues of cyclic anhydrides.
[0008] Component B comprises the following: sodium lignosulfonate, sodium dodecyl sulfate, sodium gluconate, and at least one organic acid.
[0009] Component C contains at least two of the following: borax, calcium silicate, cellulose, magnesium sulfate, and calcium chloride.
[0010] Solvent D is a mixture of water and an organic solvent, wherein the organic solvent is selected from at least one of ethanol, n-propanol, isopropanol, n-butanol, and acetone.
[0011] In one aspect of the embodiments of this disclosure, the fiber is selected from steel fiber, polypropylene fiber, polyvinyl alcohol fiber, glass fiber, hydroxypropyl cellulose, hydroxyethyl cellulose, brucite fiber, or wollastonite fiber.
[0012] In one aspect of the embodiments of this disclosure, the mass ratio of water to organic solvent in solvent D is selected from 1:(0.25-0.75).
[0013] In one aspect of the embodiments of this disclosure, the mass ratio of compound A, component B, component C and solvent D is selected from (20-30):(5-25):(10-25):(60-80).
[0014] In one aspect of the embodiments of this disclosure, the organic acid is selected from citric acid, lactic acid, tartaric acid, or succinic acid.
[0015] In one aspect of this disclosure, compound A has the following structural formula A-1: ; where m is selected from integers from 0 to 20; L1 is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heterocyclic, substituted or unsubstituted 5-30 membered heteroaryl.
[0016] In one aspect of this disclosure, compound A has the following structural formula A-2: ; where m is selected from integers from 0 to 14; L1 is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heterocyclic, substituted or unsubstituted 5-30 membered heteroaryl.
[0017] In one aspect of this disclosure, compound A has the following structural formula A-3: L2 is selected from substituted or unsubstituted C3-C15 alkyl, substituted or unsubstituted C3-C15 alkenyl, substituted or unsubstituted C3-C15 alkynyl, substituted or unsubstituted C3-C15 alkoxy, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted 3-12 heterocyclic, and substituted or unsubstituted 5-12 heteroaryl.
[0018] In one aspect of the embodiments of this disclosure, compound A is selected from the following compounds 1-1, 1-2, or 1-3: , , .
[0019] In one aspect of this disclosure, the concrete retarder water-reducing agent comprises compound A, component B, component C, and solvent D; wherein compound A is selected from compound 1-1, compound 1-2, or compound 1-3.
[0020] Component B comprises the following: sodium lignosulfonate, sodium dodecyl sulfate, sodium gluconate and tartaric acid, wherein the mass ratio of sodium lignosulfonate, sodium dodecyl sulfate, sodium gluconate and tartaric acid is (10-15):(3-8):(2-5):(5-10).
[0021] Component C contains the following: borax, calcium silicate, brucite fiber and magnesium sulfate; wherein the mass ratio of borax, calcium silicate, brucite fiber and magnesium sulfate is (8-12):(5-10):(1-3):(3-5).
[0022] Solvent D is a mixture of water and ethanol, wherein the mass ratio of water to ethanol is selected from 1:(0.35-0.55).
[0023] The mass ratio of compound A, component B, component C and solvent D is selected from (20-30):(5-25):(10-25):(60-80).
[0024] According to a second aspect of the present disclosure, a method for preparing the aforementioned concrete retarder water-reducing agent is provided, the method comprising the following steps: Step 1: preparing compound A.
[0025] Step 2: Add compound A and component B to a mixing tank and keep mechanically stirring. Then slowly add solvent D and continue stirring for 60-90 minutes. Then add component C and continue stirring for 5-10 minutes to obtain the concrete retarder and water-reducing agent.
[0026] The compound A contains polyphosphate segments and polyether segments in its structural formula; the polyphosphate segments and polyether segments are linked by residues of cyclic anhydrides.
[0027] Component B comprises the following: sodium lignosulfonate, sodium dodecyl sulfate, sodium gluconate, and at least one organic acid.
[0028] Component C contains at least two of the following: borax, calcium silicate, cellulose, magnesium sulfate, and calcium chloride.
[0029] Solvent D is a mixture of water and an organic solvent, wherein the organic solvent is selected from at least one of ethanol, n-propanol, isopropanol, n-butanol, and acetone.
[0030] In one aspect of this disclosure, compound A has the following structural formula A-3: L2 is selected from substituted or unsubstituted C3-C15 alkyl, substituted or unsubstituted C3-C15 alkenyl, substituted or unsubstituted C3-C15 alkynyl, substituted or unsubstituted C3-C15 alkoxy, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted 3-12 heterocyclic, and substituted or unsubstituted 5-12 heteroaryl.
[0031] In one aspect of the present disclosure, compound A is prepared by the following steps: Step 1-a: providing a cyclic anhydride; reacting the cyclic anhydride with polyethylene glycol monomethyl ether to obtain the intermediate of step 1-a.
[0032] Step 2-a: React the intermediate from step 1-a with phosphorus oxychloride to obtain the intermediate from step 2-a.
[0033] Step 3-a: The intermediate from step 2-a is reacted with 1,4-butanediol to obtain compound A.
[0034] In one aspect of the embodiments of this disclosure, the cyclic anhydride is selected from phthalic anhydride, norbornene anhydride, or 7-oxobionic[2.2.1]hept-5-ene-2,3-dianhydride.
[0035] According to a third aspect of the present disclosure, the aforementioned concrete retarder water-reducing agent and / or the concrete retarder water-reducing agent prepared by the aforementioned method are provided for use in the preparation of concrete-based materials.
[0036] The technical solutions provided by the embodiments of this disclosure may include the following beneficial effects: As can be seen from the above embodiments, this disclosure provides a novel concrete-based additive that can simultaneously play a good role in retarding setting and reducing water content.
[0037] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and are not intended to limit this disclosure. Detailed Implementation
[0038] The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with this disclosure. Rather, they are merely examples of apparatuses and methods consistent with some aspects of this disclosure as detailed in the appended claims.
[0039] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions of this application will be clearly and completely described below in conjunction with embodiments. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. The embodiments described herein are illustrative in nature and are used to provide a basic understanding of this application. The embodiments of this application should not be construed as limiting this application.
[0040] For the sake of brevity, this article only discloses a few specific numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.
[0041] In this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.
[0042] In this description, unless otherwise stated, "above" and "below" include the stated number.
[0043] Unless otherwise stated, the terms used in this disclosure have their common meanings as commonly understood by those skilled in the art. Unless otherwise stated, the values of the parameters mentioned in this disclosure can be measured using various measurement methods commonly used in the art (e.g., they can be tested according to the methods given in the embodiments of this disclosure).
[0044] The term "about" is used to describe and indicate small variations. When used in conjunction with an event or situation, the term may refer to examples in which the event or situation occurred precisely or in examples in which the event or situation occurred very approximately. For example, when used in conjunction with numerical values, the term may refer to a range of variation less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. Additionally, quantities, ratios, and other numerical values are sometimes presented in range format herein. It should be understood that such range format is for convenience and brevity and should be interpreted flexibly to include not only numerical values explicitly specified as range limits but also all individual numerical values or subranges covered within the range, as if each numerical value and subrange were explicitly specified.
[0045] The list of items connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms can mean any combination of the listed items. For example, if items A and B are listed, then the phrase "at least one of A and B" means only A; only B; or A and B. In another instance, if items A, B, and C are listed, then the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may contain a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.
[0046] In this disclosure, the term "alkyl" refers to an aliphatic hydrocarbon group, which can be straight-chain or branched. Branched refers to one or more lower alkyl groups, such as methyl, ethyl, or propyl, that link a linear alkyl chain. "Lower alkyl" refers to a group containing about 1 to about 6 carbon atoms in the chain, which can be straight-chain or branched.
[0047] In this disclosure, the term "alkenyl" refers to an aliphatic hydrocarbon group containing at least one carbon-carbon double bond, which can be straight-chain or branched. Branched refers to one or more lower alkyl groups, such as methyl, ethyl, or propyl, attached to a linear alkenyl chain. "Lower alkenyl" refers to a group containing about 2 to about 6 carbon atoms in the chain, which can be straight-chain or branched.
[0048] In this disclosure, the term "alkynyl" refers to an aliphatic hydrocarbon group containing at least one carbon-carbon triple bond, which can be straight-chain or branched. Branching refers to one or more lower alkyl groups, such as methyl, ethyl, or propyl, attached to a linear alkynyl chain. "Lower alkynyl" refers to a chain containing about 2 to about 6 carbon atoms, which can be straight-chain or branched. Non-limiting examples of alkynyl groups include ethynyl, propynyl, 2-butynyl, 3-methylbutynyl, n-pentynyl, and decynyl.
[0049] In this disclosure, the term "aryl" refers to an aromatic monocyclic or polycyclic system. An aryl group may optionally be substituted with one or more "cyclic substituents," which may be the same or different, as defined herein. Non-limiting examples of suitable aryl groups include phenyl and naphthyl.
[0050] In this disclosure, the term "heteroaryl" refers to an aromatic monocyclic or polycyclic ring system, wherein one or more ring atoms are elements other than carbon, such as nitrogen, oxygen, or sulfur, either individually or in combination, and preferably a heteroaryl contains about 5 to about 6 ring atoms. A "heteroaryl" may optionally be substituted by one or more "cyclic substituents," which may be the same or different, as defined herein. The prefixes azido, oxa, or thiado preceding the name of a heteroaryl root indicate that at least one nitrogen, oxygen, or sulfur atom is present as a ring atom, respectively. The nitrogen atom of a heteroaryl may optionally be oxidized to the corresponding N-oxide. Suitable, non-limiting examples of heteroaryl groups include pyridyl, pyrazinyl, furanyl, phenylthio, pyrimidinyl, isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrroleyl, pyrazolyl, triazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl, quinoxalinyl, 2,3-diazanaphthyl, imidazo[1,2-a]pyridyl, imidazo[2,1-b]thiazolyl, benzofurazanyl, indoleyl, azaindoleyl, benzimidazolyl, benzothiopheneyl, quinolinyl, imidazolyl, thienopyridyl, quinazolinyl, thienopyrimidinyl, pyrrolopyridyl, imidazopyridyl, isoquinolinyl, benzoazaindoleyl, 1,2,4-triazinyl, benzothiazolyl, etc.
[0051] In this disclosure, the term "amino" refers to the -NR′R′′ group. The amino group may optionally be substituted. In an unsubstituted amino group, R′ and R′′ are hydrogen. In a substituted amino group, R′ and R′′ may each independently be, but not limited to, hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, alkylcycloalkyl, alkylheterocycloalkyl, alkoxy, sulfonyl, alkenyl, alkanoyl, aryl, arylalkyl, or heteroaryl, provided that R′ and R′′ are not both hydrogen. In a substituted amino group, R′ and R′′ may cyclize to form a cyclic amino group, such as pyrrolidinyl or piperidinyl. Such cyclic amino groups may incorporate other heteroatoms, for example, to form piperazine or morpholine groups. Such cyclic amino groups may optionally be substituted, for example, by an amino, hydroxyl, or oxo group.
[0052] In this disclosure, the term "alkoxy" refers to -O-alkyl. Alkoxy can refer to a straight-chain, branched, or cyclic, saturated or unsaturated oxy-hydrocarbon chain, including, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, and pentoxy. Alkoxy may optionally be substituted by one or more alkoxy substituents ("substituted alkoxy").
[0053] In this disclosure, the term "cycloalkyl" refers to a non-aromatic mono- or polycyclic ring system, preferably containing about 5 to about 7 ring atoms. The cycloalkyl group may optionally be substituted with one or more "cyclic substituents," which may be the same or different, as defined above. Suitable monocyclic cycloalkyl groups, without limitation, include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. Suitable polycyclic cycloalkyl groups, without limitation, include 1-decahydronaphthyl, norcamphenyl, adamantyl, etc. In this disclosure, the term "cycloalkoxy" refers to a group in which one or more carbon atoms in the mono- or polycyclic ring system of the "cycloalkyl" group are substituted with oxygen atoms.
[0054] In this disclosure, the term "heterocyclic group" refers to a non-aromatic saturated monocyclic or polycyclic ring system, wherein one or more ring atoms in the ring system are elements other than carbon, such as nitrogen, oxygen, or sulfur, either individually or in combination. Adjacent oxygen and / or sulfur atoms are absent in the ring system, and preferred heterocycles contain about 5 to about 6 ring atoms. The prefixes aza, oxa, or thioa preceding the name of the heterocyclic group indicate that at least one nitrogen, oxygen, or sulfur atom is present as a ring atom, respectively. The heterocyclic group may optionally be substituted with one or more "cyclic substituents," which may be the same or different, as defined herein. The nitrogen or sulfur atom of the heterocyclic group may optionally be oxidized to the corresponding N-oxide, S-oxide, or S,S-dioxide. Non-limiting examples of suitable monocyclic heterocyclic rings include piperidinyl, pyrrolyl, piperazine, morpholinyl, thiomorpholinyl, thiazolyl, 1,3-dioxolanecycloyl, 1,4-dioxacyclohexyl, tetrahydrofuranyl, tetrahydrophenylthio, tetrahydrothiopyranyl, etc.
[0055] The present disclosure will be further described below by way of specific embodiments. Unless otherwise specified, all chemical reagents used in the embodiments of the present disclosure are obtained through conventional commercial means. Unless otherwise specified, all contents mentioned below are mass contents. Unless otherwise specified, it is understood that the process is carried out at room temperature.
[0056] Examples and Comparative Examples: Example 1: Example 1 includes the following steps: 1. Preparation of compound 1-1: Under nitrogen protection, 32.8 g of norbornene adienoic anhydride (0.2 mol), 4.4 g of DMAP, and 0.21 mol (67.3 mL) of polyethylene glycol monomethyl ether (mPEG, M w=350 g / mol) and 450 mL of dichloromethane were added, and the mixture was stirred at room temperature for 48 h. After the reaction was completed, the mixture was filtered, and then washed with sufficient dichloromethane. The filtrates were combined, and deionized water was added for separation and extraction. The obtained organic phase was washed with deionized water, and then dried with anhydrous sodium sulfate. The intermediate product 1-1 was obtained by vacuum drying. The reaction process is shown below:
[0057] A double-walled glass reactor connected to a cryogenic thermostat was used as the reaction vessel. A reflux condenser equipped with a drying and HCl gas recovery device was installed on the reactor. 30.7 g (0.2 mol) of phosphorus oxychloride and 25 mL of toluene were then added. The cryogenic thermostat and magnetic stirring were turned on to lower the system temperature to below 4 °C. The intermediate product 1-1 prepared earlier was then added, and the valve opening was controlled to slowly add it to the reactor. After the addition was complete, the temperature was slowly raised to 25 °C, and the reaction continued until no more hydrogen chloride gas was released. Then, 18.1 g of 1,4-butanediol was weighed and placed in a constant-pressure dropping funnel, and the valve opening was controlled to slowly add it to the reactor. After the addition was complete, the reaction was continued at 25 °C for 1 hour, followed by a slow increase to 65 °C for 1.5 hours. Finally, the mixture was distilled under reduced pressure at 65 °C to obtain compound 1-1. The reaction process is shown below: ;
[0058] The above steps can be repeated as appropriate to prepare a sufficient amount of compound 1-1 for use in the following steps.
[0059] 2. Preparation of concrete retarder and water-reducing agent: Weigh 30 parts by weight of compound 1-1, 10 parts by weight of sodium lignosulfonate, 5 parts by weight of sodium dodecyl sulfate, 3 parts by weight of sodium gluconate, 7 parts by weight of tartaric acid, 10 parts by weight of borax, 8 parts by weight of calcium silicate, 2 parts by weight of brucite fiber, 4 parts by weight of magnesium sulfate, 55 parts by weight of water and 25 parts by weight of ethanol; add compound 1-1, sodium lignosulfonate, sodium dodecyl sulfate, sodium gluconate and tartaric acid to a mixing tank, keep mechanically stirring (150 r / min), then slowly add water and ethanol; continue stirring for 75 min, then add borax, calcium silicate, brucite fiber and magnesium sulfate, continue stirring for 10 min, to obtain the concrete retarder and water-reducing agent of Example 1.
[0060] Example 2: 1. Preparation of compounds 1-2: Under nitrogen protection, 34.2 g of 7-oxobionic[2.2.1]hept-5-en-2,3-dianhydride (0.2 mol), 4.4 g of DMAP, and 0.21 mol (67.3 mL) of polyethylene glycol monomethyl ether (mPEG, M w=350 g / mol) and 450 mL of dichloromethane were added, and the mixture was stirred at room temperature for 48 h. After the reaction was completed, the mixture was filtered, and then washed with sufficient dichloromethane. The filtrates were combined, and deionized water was added for separation and extraction. The obtained organic phase was washed with deionized water, and then dried with anhydrous sodium sulfate. The intermediate product 2-1 was obtained by vacuum drying. The reaction process is shown below:
[0061] A double-walled glass reactor connected to a cryogenic bath was used as the reaction vessel. A reflux condenser equipped with a drying and HCl gas recovery device was installed on the reactor. Then, 30.7 g (0.2 mol) of phosphorus oxychloride and 25 mL of toluene were added. The cryogenic bath and magnetic stirring were turned on to lower the system temperature to below 4 °C. Then, the intermediate product 2-1 prepared earlier was added, and the valve opening was controlled to slowly add it to the reactor. After the addition was complete, the temperature was slowly raised to 25 °C, and the reaction continued until no more hydrogen chloride gas was released. Then, 18.1 g of 1,4-butanediol was weighed and placed in a constant-pressure dropping funnel, and the valve opening was controlled to slowly add it to the reactor. After the addition was complete, the reaction was continued at 25 °C for 1 hour, then the temperature was slowly raised to 65 °C for 1.5 hours. Finally, the mixture was distilled under reduced pressure at 65 °C to obtain compound 2-2. The reaction process is shown below: ;
[0062] The above steps can be repeated as appropriate to prepare sufficient amounts of compounds 1-2 for use in the following steps.
[0063] 2. Preparation of concrete retarder and water-reducing agent: Weigh 30 parts by weight of compound 1-2, 10 parts by weight of sodium lignosulfonate, 5 parts by weight of sodium dodecyl sulfate, 3 parts by weight of sodium gluconate, 7 parts by weight of tartaric acid, 10 parts by weight of borax, 8 parts by weight of calcium silicate, 2 parts by weight of brucite fiber, 4 parts by weight of magnesium sulfate, 55 parts by weight of water and 25 parts by weight of ethanol; add compound 1-2, sodium lignosulfonate, sodium dodecyl sulfate, sodium gluconate and tartaric acid to a mixing tank and keep mechanically stirred (150 r / min), then slowly add water and ethanol; continue stirring for 75 min, then add borax, calcium silicate, brucite fiber and magnesium sulfate, and continue stirring for 10 min to obtain the concrete retarder and water-reducing agent of Example 2.
[0064] Example 3: The preparation process of Example 3 is the same as that of Example 1, except that phthalic anhydride is used instead of norbornene anhydride in equal molar amounts; compounds 1-3 with the following structural formulas are obtained. .
[0065] Comparative Example 1: Comparative Example 1 includes the following steps: 1. Preparation of intermediate product 1-1: Under nitrogen protection, 32.8 g of norbornene adienoic anhydride (0.2 mol), 4.4 g of DMAP, and 0.21 mol (67.3 mL) of polyethylene glycol monomethyl ether (mPEG, M w =350 g / mol) and 450 mL of dichloromethane were added, and the mixture was stirred at room temperature for 48 h. After the reaction was completed, the mixture was filtered, and then washed with sufficient dichloromethane. The filtrates were combined, and deionized water was added for separation and extraction. The obtained organic phase was washed with deionized water, and then dried with anhydrous sodium sulfate. The intermediate product 1-1 was obtained by vacuum drying. The reaction process is shown below:
[0066] The above steps can be repeated as appropriate to prepare a sufficient amount of intermediate product 1-1 for use in the following steps.
[0067] 2. Preparation of concrete retarder and water-reducing agent: Weigh 30 parts by weight of intermediate product 1-1, 10 parts by weight of sodium lignosulfonate, 5 parts by weight of sodium dodecyl sulfate, 3 parts by weight of sodium gluconate, 7 parts by weight of tartaric acid, 10 parts by weight of borax, 8 parts by weight of calcium silicate, 2 parts by weight of brucite fiber, 4 parts by weight of magnesium sulfate, 55 parts by weight of water and 25 parts by weight of ethanol; add intermediate product 1-1, sodium lignosulfonate, sodium dodecyl sulfate, sodium gluconate and tartaric acid to a mixing tank, keep mechanically stirring (150 r / min), then slowly add water and ethanol; continue stirring for 75 min, then add borax, calcium silicate, brucite fiber and magnesium sulfate, continue stirring for 10 min to obtain concrete retarder and water-reducing agent of Comparative Example 1.
[0068] Comparative Example 2: The preparation process of Comparative Example 2 is the same as that of Example 1, except that an equal mass of polyethylene glycol monomethyl ether (mPEG, M w (350 g / mol) replaces compound 1-1.
[0069] Performance Testing: Retarding and Water-Reducing Performance Testing: The specific retarding performance testing method is to add the test sample to ordinary concrete (in which the weight ratio of silicate cement is 30%, fly ash is 15%, manufactured sand is 25%, aggregate is 25%, and water is 5%) at 40℃, and test the initial setting time, final setting time, and compressive strength of the concrete at 3 days and 28 days; the initial setting time and final setting time testing methods are carried out in accordance with GB / T50080-2016 "Standard for Test Methods of Performance of Ordinary Concrete Mixtures", and the retarder dosage is 0.5% of the binder (in this industry, binder refers to cement and fly ash); the concrete compressive strength is tested according to the method specified in GB / T50081-2019 "Standard for Test Methods of Physical and Mechanical Properties of Concrete".
[0070] The specific water-reducing performance test method shall be carried out in accordance with the method specified in GB8076-2008 "Concrete Admixtures".
[0071] The specific values are shown in Table 1 below.
[0072] Table 1:
[0073]
[0074] As can be seen, this disclosure prepares a novel concrete retarder and water-reducing agent. The hydrophilic / charged groups (water-reducing) and coordinating groups (retarders) of compound A are located on different side chains or segments and do not affect each other. The main chain of compound A contains a hydrophobic framework; these anionic groups adsorb onto the surface of cement particles, providing electrostatic repulsion. Simultaneously, the long-chain polyether branches extend into the liquid phase, providing steric hindrance, thus "opening up" the cement particles, disintegrating the flocculated structure, releasing free water, and improving fluidity, achieving the water-reducing effect. Meanwhile, the side chain groups react with Ca in the alkaline slurry. +2 Formation of soluble chelates temporarily reduces the free Ca in the solution. +2 The concentration delays the formation of CH and CSH crystal nuclei, and the hydrophobic segments of the long-chain skeleton can also form a dynamic coating film on the surface of cement particles, further hindering crystal nucleus growth.
[0075] Other embodiments of this disclosure will readily occur to those skilled in the art upon consideration of the specification and practice of the disclosure herein. This disclosure is intended to cover any variations, uses, or adaptations of this disclosure that follow the general principles of this disclosure and include common knowledge or customary techniques in the art not disclosed herein.
Claims
1. A concrete retarder and water-reducing agent, characterized in that, The concrete retarder water-reducing agent comprises compound A, component B, component C, and solvent D; wherein, the structural formula of compound A contains polyphosphate ester segments and polyether segments; the polyphosphate ester segments and polyether segments are linked by residues of cyclic anhydrides; Component B comprises the following: sodium lignosulfonate, sodium dodecyl sulfate, sodium gluconate, and at least one organic acid; Component C contains at least two of the following: borax, calcium silicate, cellulose, magnesium sulfate, and calcium chloride; Solvent D is a mixture of water and an organic solvent, wherein the organic solvent is selected from at least one of ethanol, n-propanol, isopropanol, n-butanol, and acetone.
2. The concrete retarder and water-reducing agent according to claim 1, characterized in that, The concrete retarder and water-reducing agent meets at least one of the following conditions: (1) The fibers are selected from steel fibers, polypropylene fibers, polyvinyl alcohol fibers, glass fibers, brucite fibers or wollastonite fibers; (2) In solvent D, the mass ratio of water to organic solvent is selected from 1:(0.25-0.75); (3) The mass ratio of compound A, component B, component C and solvent D is selected from (20-30):(5-25):(10-25):(60-80); (4) The organic acid is selected from citric acid, lactic acid, tartaric acid or succinic acid.
3. The concrete retarder and water-reducing agent according to claim 1, characterized in that, The compound A has the following structural formula A-3: L2 is selected from substituted or unsubstituted C3-C15 alkyl, substituted or unsubstituted C3-C15 alkenyl, substituted or unsubstituted C3-C15 alkynyl, substituted or unsubstituted C3-C15 alkoxy, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted 3-12 heterocyclic, and substituted or unsubstituted 5-12 heteroaryl.
4. The concrete retarder and water-reducing agent according to claim 3, characterized in that, Compound A is selected from the following compounds 1-1, 1-2, or 1-3: ； ； 。 5. A method for preparing the concrete retarder and water-reducing agent according to any one of claims 1-4, characterized in that, The method includes the following steps: Step 1: Prepare compound A; Step 2: Add compound A and component B to a mixing tank and keep mechanically stirring. Then slowly add solvent D and continue stirring for 60-90 minutes. Then add component C and continue stirring for 5-10 minutes to obtain the concrete retarder water-reducing agent. The structural formula of compound A includes polyphosphate segments and polyether segments; the polyphosphate segments and polyether segments are linked by residues of cyclic anhydrides. Component B comprises the following: sodium lignosulfonate, sodium dodecyl sulfate, sodium gluconate, and at least one organic acid; Component C contains at least two of the following: borax, calcium silicate, cellulose, magnesium sulfate, and calcium chloride; Solvent D is a mixture of water and an organic solvent, wherein the organic solvent is selected from at least one of ethanol, n-propanol, isopropanol, n-butanol, and acetone.
6. The method according to claim 5, characterized in that, Compound A was prepared by the following steps: Step 1-a: Provide a cyclic anhydride; react the cyclic anhydride with polyethylene glycol monomethyl ether to obtain the intermediate of step 1-a; Step 2-a: React the intermediate from step 1-a with phosphorus oxychloride to obtain the intermediate from step 2-a; Step 3-a: The intermediate from step 2-a is reacted with 1,4-butanediol to obtain compound A.
7. The application of the concrete retarder and water-reducing agent according to any one of claims 1-4 in the preparation of concrete base materials.