CN114956653A - Coordination activator, liquid alkali-free accelerator and preparation method and application thereof - Google Patents
Coordination activator, liquid alkali-free accelerator and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
- C04B24/42—Organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/22—Esters containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
The invention discloses a coordination excitant, a liquid alkali-free accelerator, and a preparation method and application thereof. Wherein the coordination activator is a macromolecular multipolymer of a monomer of triethanolamine maleate, unsaturated amide and unsaturated silane, and the unsaturated amide is at least one of N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, N-dimethylacrylamide, N-dimethylmethacrylamide, N-diethylacrylamide, N-diethylmethacrylamide, N-dibutylacrylamide, N-isopropylacrylamide, N-phenylacrylamide, N-phenylmethylacrylamide, N- (p-hydroxyphenyl) methacrylamide; the high early strength liquid alkali-free setting accelerator provided by the invention is fluorine-free and chlorine-free, has the characteristics of rapid development of 6h compressive strength, fluorine-free and chlorine-free property, good stability, low mixing amount, rapid condensation, high later strength retention rate and the like, and can be widely applied to engineering construction applications such as traffic tunnels, mine roadway support, repair reinforcement, water prevention, leakage stoppage and the like.
Description
Technical Field
The invention belongs to the technical field of concrete accelerators, and particularly relates to a coordination activator, a high early strength liquid alkali-free accelerator, and a preparation method and application thereof.
Background
With the development of national infrastructure construction, the quality requirements of projects such as tunnel construction, mine reinforcement, urban road and waterproof facility repair and the like in China on sprayed concrete are continuously improved, and meanwhile, higher requirements are provided for the performance of the liquid accelerator for sprayed concrete. Compared with the alkali accelerating agent, the liquid alkali-free accelerating agent gradually replaces the alkali accelerating agent to become the accelerating agent with the advantages of higher long-term strength retention rate, no alkali and chlorine, safety, environmental protection, high durability and the like. However, the liquid alkali-free accelerator on the market still has the defects of poor stability, high doping amount, low 1d compressive strength, overproof alkali content, hydrofluoric acid (HF) and fluosilicic acid (H) 2 SiF 6 ) Or fluorine-containing toxic raw materials such as fluosilicate and the like. The method is formally implemented in the enterprise standard Q/CR 807-.
Patent CN 107840593A discloses an early strength type liquid alkali-free accelerator for sprayed concrete and a preparation method thereof, which consists of 60-75 wt% of modified polyaluminium sulfate solution, 5-15 wt% of modified alcohol amine solution, 0-3 wt% of performance regulator, 0-4 wt% of stabilizer and water. The patent CN 109180053A discloses a low-resilience early-strength liquid alkali-free accelerator and a preparation method thereof, wherein the raw material components comprise 60-80% of modified aluminum sulfate solution, 0.5-3% of graphene oxide, 1-5% of stabilizing agent, 1-5% of performance regulator, 0.5-3% of penetrating agent, 0.1-1% of pH buffering agent and the balance of water. The liquid alkali-free accelerator uses organic/inorganic acid stabilizers such as ethylenediamine tetraacetic acid, citric acid, salicylic acid and phosphoric acid which have retarding effect on cement hydration in order to prevent the liquid from layering and precipitating after being stored for a long time, and is not beneficial to the development of 6h strength of mortar.
In conclusion, the development of the liquid alkali-free accelerator which is free of fluorine and chlorine, low in doping amount, high in early strength and excellent in comprehensive performance is of great significance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a coordination activator, a liquid alkali-free accelerator and a preparation method and application thereof, the liquid alkali-free accelerator disclosed by the invention is fluorine-free and chlorine-free, the compressive strength of 6h is rapidly developed, various performances meet the requirements of Q/CR 807-.
The purpose of the invention is realized by the following technical scheme.
In a first aspect, the present invention provides a coordination activator, comprising a multipolymer of monomers of triethanolamine maleate, unsaturated amide and unsaturated silane, wherein the unsaturated amide is at least one of N-methylolacrylamide, N-hydroxyethyl acrylamide, N-dimethylacrylamide, N-dimethylmethacrylamide, N-diethylacrylamide, N-diethylmethacrylamide, N-dibutylacrylamide, N-isopropylacrylamide, N-phenylacrylamide, N-phenylmethylacrylamide, N- (p-hydroxyphenyl) methacrylamide; and/or 2-acrylamido-2-methylpropanesulfonic acid.
In some embodiments, the triethanolamine maleate is mono-triethanolamine maleate and/or di-triethanolamine maleate.
In some embodiments, the unsaturated silane is any one or more of alkenyl substituted silanes, preferably any one or more of triethylvinylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, acryloxytrimethylsilane, triacetoxyvinylsilane, allyltrimethylsilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, 3-methacryloxypropyltrimethoxysilane, vinyldimethylethoxysilane, methylvinyldiacetoxysilane.
In some embodiments, the mass ratio of triethanolamine maleate, unsaturated amide, and unsaturated silane is (30-100): (2-20): (1-15), preferably (40-60): (5-15): (2-10).
In some embodiments, the coordination activator is obtained by free radical copolymerization of triethanolamine maleate, unsaturated amide, and unsaturated silane in the presence of a redox initiator, a chain transfer agent, and deionized water.
In the technical scheme of the invention, the coordination activator adopts a redox initiator to initiate monomer polymerization, so that the reaction activation energy is reduced, and a higher polymerization rate can be obtained at a lower temperature, thereby realizing production under a low-temperature condition and greatly reducing the production energy consumption. Meanwhile, the self-polymerization of the monomer under the high-temperature reaction condition when a thermal decomposition type initiator is adopted can be avoided, and the generation of byproducts is reduced.
In the technical scheme of the invention, the dosage of the oxidant is 0.2-3.0 wt% of the total mass of the monomers.
In the technical scheme of the invention, the dosage of the reducing agent is 0.1-0.5 wt% of the total mass of the monomers.
In the technical scheme of the invention, the dosage of the chain transfer agent is 0.05-0.5 wt% of the total mass of the monomers.
In the technical scheme of the invention, the oxidant is at least one of hydrogen peroxide, ammonium persulfate, sodium persulfate or potassium persulfate.
In the technical scheme of the invention, the reducing agent is at least one of vitamin C, sodium formaldehyde sulfoxylate, sodium bisulfite, sodium sulfite or ferrous sulfate.
In the technical scheme of the invention, the chain transfer agent is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol and sodium methallyl sulfonate.
The coordination excitant provided by the invention can be a high-molecular mixture consisting of copolymers with different copolymerization units and different molecular weights.
In some embodiments, the host copolymer has the structural formula of any one or more of:
wherein R is 0 Is H or alkyl, R 1 、R 2 Can be the same or different and is H or one of alkyl, hydroxyalkyl and aryl; r 3 、R 4 、R 5 、R 6 Which may be the same or different, is one of alkyl, non-heteroaryl substituted alkyl, non-heteroaryl, alkyl substituted non-heteroaryl.
The number average molecular weight M of the coordination excitant provided by the invention n Has a weight average molecular weight M of 15000 to 40000, preferably 20000 to 30000 w 20000-60000, preferably 30000-50000, Z-average molecular weight M z 50000-100000, preferably 60000-80000.
In a second aspect, the present invention provides a method for preparing a coordination activator, comprising the following steps:
s1, adding triethanolamine maleate, unsaturated amide, unsaturated silane, a chain transfer agent, an oxidant and deionized water into a reactor, controlling the initial reaction temperature within the range of 10-40 ℃, and stirring and uniformly mixing;
s2, dropwise adding the aqueous solution of the reducing agent at a constant speed for 0.5-1 h, continuing to react for 1-3 h after dropwise adding is finished, and cooling to room temperature to obtain the coordination exciting agent.
In some embodiments, it is preferable that the synthesis of the coordination stimulator is initiated at a reaction temperature of 10 ℃ to 40 ℃ and the temperature during the reaction is not controlled.
In some embodiments, a method of making triethanolamine maleate comprises:
under the condition of stirring, adding maleic anhydride and triethanolamine into a reactor, adding a catalyst, heating to 110-130 ℃, and reacting at constant temperature for 3-6 hours. In the present invention, the reactor may be equipped with a stirrer, a heating device, a temperature control device and a condensing reflux device. In addition, after the reaction is finished, a proper amount of water can be added for dilution, and the reaction product is cooled to room temperature, so that the esterified product triethanolamine maleate is obtained.
In a third aspect, the invention provides a high early strength liquid alkali-free accelerator, which comprises aluminum sulfate, a stabilizer, the coordination activator, alcohol amine, an early strength agent and a neutralizer.
According to the high early strength liquid alkali-free setting accelerator provided by the invention, a detection method of Q/CR 807-.
In some embodiments, the starting materials comprise, in parts by weight: 450-600 parts of aluminum sulfate, 5-25 parts of stabilizer, 25-150 parts of coordination activator, 30-100 parts of alcohol amine, 10-100 parts of early strength agent, 0-10 parts of neutralizer and the balance of deionized water to 1000 parts. Preferably, 500-600 parts of aluminum sulfate, 10-20 parts of stabilizer, 50-100 parts of coordination activator, 40-80 parts of alcohol amine, 20-50 parts of early strength agent and 0-10 parts of neutralizer.
In some embodiments, the aluminum sulfate is technical aluminum sulfate and the formula is Al 2 (SO 4 ) 3 ·18H 2 O, and Al 2 O 3 The content is not less than 15.6 wt%.
In some embodiments, the stabilizer is at least one of sepiolite, magnesium aluminum silicate, calcium bentonite, aqueous organobentonite, aqueous polyamide wax, hectorite, nano alumina, fumed silica.
In some embodiments, the alcohol amine is at least one of ethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, diethanolisopropanolamine.
In some embodiments, the early strength agent is at least one of magnesium sulfate, magnesium sulfate hydrate, lithium carbonate, lithium sulfate hydrate, iron sulfate hydrate.
In some embodiments, the neutralizing agent is at least one of magnesium oxide, magnesium hydroxide, lithium hydroxide.
The high early strength liquid alkali-free accelerator provided by the invention has the concentration of a coordination activator of 10-50%, preferably 20-30%.
In a fourth aspect, the present invention further provides a preparation method of the high early strength liquid alkali-free setting accelerator, including the following steps:
step 1, mixing a stabilizer with water, heating and stirring to obtain a first mixed solution;
step 2, adding a coordination excitant and aluminum sulfate into the first mixed solution and stirring to obtain a second mixed solution;
and 4, adding the early strength agent and the optional neutralizing agent into the third mixed solution, and uniformly mixing to obtain the high early strength liquid alkali-free accelerator.
Wherein, the reaction temperature in the step 1 is 40-80 ℃, and the stirring time is 15-30 min; step 2, stirring for 30-60 min; step 3, the reaction time is 30-60 min; and 4, the reaction time is 30-90 min.
In a fourth aspect, the present invention provides the use of the above high early strength liquid alkali-free accelerator, in some embodiments, in tunnel construction, coal mine reinforcement, urban road and waterproofing repair.
Compared with the prior art, the invention has the beneficial effects that:
(1) the coordination activator for preparing the high early strength liquid alkali-free accelerator provided by the invention is prepared from monomer triethanolamine maleate, unsaturated amide and unsaturated silane, and the structure of the coordination activator contains induction C such as alcohol amine, amide and silane 3 S hydrated group, C can be effectively shortened 3 S incubation period of hydration, accelerated C 3 S is hydrated to generate C-S-H gel, and the strength of the gel is promoted to be rapidly developed within 6 hours. Meanwhile, it is considered that the copolymerization initiator contains carboxyl groups, amide groups and sulfonic acid in the molecular chainActive groups such as radicals, for Al 3+ Has strong chelating and solubilizing functions, and can effectively prevent the instability phenomena of crystallization, delamination, precipitation and the like when the liquid is stored for a long time.
(2) The coordination excitant provided by the invention adopts unsaturated amides of which the types are as follows: the unsaturated amide of which one or two hydrogens on the acrylamide nitrogen atom are replaced by alkyl, hydroxyalkyl, phenyl and other functional groups enables the prepared coordination activator to have stronger hydrolysis resistance when being in the cement paste alkaline environment, the hydrolysis stability of the copolymer is obviously improved compared with that of the acrylamide, and higher early strength of mortar can be obtained when the copolymer is used for an accelerator.
(3) The coordination excitant provided by the invention initiates polymerization reaction by adopting a redox initiator, compared with a thermal decomposition type initiator such as persulfate and azo initiators, the redox initiation reduces the activation energy of the reaction, and a higher polymerization rate can be obtained at a lower temperature, so that the production under the condition of a low temperature (10-40 ℃) can be realized, the reaction time is greatly shortened, and the production energy consumption is greatly reduced. Meanwhile, the self-polymerization of the monomer under the high-temperature reaction condition when a thermal decomposition type initiator is adopted can be avoided, the generation of byproducts is reduced, the high-early-strength liquid alkali-free accelerator can be prepared under the condition of a small amount of coordination excitant, and the cost is saved.
(4) The high early strength liquid alkali-free accelerator provided by the invention is fluorine-free and chlorine-free, and the fluorine-containing toxic raw materials such as hydrofluoric acid, fluosilicic acid or fluosilicate and the like are not used in the preparation process, so that compared with the existing fluorine-containing accelerator, the high early strength liquid alkali-free accelerator effectively overcomes the adverse effect of fluorine ions on the early strength of mortar and concrete doped with the alkali-free accelerator, and the early compressive strength (6h and 1d) is greatly improved.
(5) The liquid alkali-free accelerator provided by the invention does not use oxalic acid, citric acid, salicylic acid, tartaric acid and phosphoric acid. Because organic/inorganic acid stabilizers or complexing agents such as oxalic acid, citric acid, salicylic acid, tartaric acid, phosphoric acid and the like have stronger retarding effect on cement, compared with the accelerating agent added with the substances in the prior art, the organic/inorganic acid stabilizer or complexing agent is not added in the invention, thus being beneficial to early strengthAnd with early strength agents such as magnesium salt and lithium salt, etc. to promote tricalcium silicate (C) 3 S) hydration to generate calcium silicate hydrate (C-S-H) gel, so that the early strength of the cement is improved, the cement is used for quick setting of concrete mortar, and the 6-hour compressive strength is more than or equal to 1.0 MPa.
(6) The high early strength liquid alkali-free accelerator provided by the invention adopts at least one of sepiolite, magnesium aluminum silicate, calcium bentonite, water-based organic bentonite, water-based polyamide wax, hectorite, nano aluminum oxide and fumed silica as a stabilizer, so that the stability of the high early strength liquid alkali-free accelerator is further improved.
(7) The liquid alkali-free accelerator provided by the invention has the advantages of simple preparation process, strong operability, low production cost, greenness and environmental protection, and is suitable for industrial mass production.
Drawings
FIG. 1 is a GPC chart of a coordination activator provided in example 1 of the present invention;
FIG. 2 is a GPC chart of a coordination excitant provided in example 2 of the present invention;
FIG. 3 is a GPC chart of a coordination excitant provided in example 3 of the present invention;
FIG. 4 is a GPC chart of a coordination activator provided in comparative example 1 of the present invention.
Detailed Description
In order that the invention may be more readily understood, the following detailed description of the invention is given, with reference to the accompanying examples and drawings, which are given by way of illustration only and are not intended to limit the scope of the invention.
In the following examples and comparative examples, nano-alumina was purchased from Wiegmann's Degussa, model AEROXIDE Alu C; sepiolite was purchased from Tolsa, model PANGEL S9; laponite was purchased from Jiangsu Haimines New materials science and technology, Inc., model TY 220S.
Example 1
Step 1: adding 117.5g of maleic anhydride and 150g of triethanolamine into a reactor provided with a stirrer, a heating device, a temperature control device and a condensing reflux device, adding 8.0g of 98% concentrated sulfuric acid, heating to 120 ℃, reacting at constant temperature for 4 hours, adding 183.5g of deionized water for dilution, and cooling to room temperature to obtain 60% triethanolamine maleate.
Step 2: adding 125g of the 60% triethanolamine maleate obtained in the step (1), 10.0g of N-hydroxymethyl acrylamide, 7.5g of allyl trimethylsilane, 1.5g of hydrogen peroxide, 0.3g of mercaptoethanol and 100g of deionized water into a reactor, and stirring and dissolving at normal temperature; and (3) dropwise adding a mixed solution of 0.25g of sodium formaldehyde sulfoxylate and 70.5g of deionized water at constant speed at normal temperature for 60min, continuing to react for 120min after dropwise adding, and cooling to room temperature to obtain the coordination excitant with the concentration of 30%. The gel permeation chromatography (GPC spectrum) is shown in FIG. 1, and the gel permeation chromatography (GPC spectrum) is characterized in that as shown in FIG. 1, the molecular weight range is 263615-4066, and the number average molecular weight M is n 22416, weight average molecular weight M w 38142 and the main peak area was 94.87%.
And step 3: mixing 240g of deionized water and 20g of nano-alumina, heating to 60 ℃, and stirring for 15min to obtain a first mixed solution.
And 4, step 4: and adding 75g of coordination excitant and 570g of aluminum sulfate into the first mixed solution, and stirring for 30min to obtain a second mixed solution.
And 5: and adding 45g of diethanolamine and 15g of triisopropanolamine into the second mixed solution, and reacting for 60min to obtain a third mixed solution.
Step 6: and adding 25g of magnesium sulfate and 10g of ferric sulfate into the third mixed solution, and reacting for 60min to obtain the liquid alkali-free accelerator.
Example 2
Step 1: adding 110g of maleic anhydride and 150g of triethanolamine into a reactor provided with a stirrer, a heating device, a temperature control device and a condensation reflux device, adding 7.5g of p-toluenesulfonic acid, heating to 115 ℃, reacting at a constant temperature for 4 hours, adding 178g of deionized water for diluting, and cooling to room temperature to obtain an esterification product, namely the triethanolamine maleate with the concentration of 60%.
Step 2: adding 100g of the 60% triethanolamine maleate obtained in the step (1), 10.0g of N, N-dimethylacrylamide, 5.0g of vinyl triethoxysilane, 1.0g of ammonium persulfate, 0.25g of mercaptopropionic acid and 78.5g of deionized water into a reactor, and stirring and dissolving at normal temperature; at normal temperature, a mixture of 0.25g of sodium bisulfite and 60g of deionized water is dripped at constant speedAnd (3) combining the solution, dropwise adding for 30min, continuing to react for 90min after dropwise adding, and cooling to room temperature to obtain the coordination excitant with the concentration of 30%. The gel permeation chromatography (GPC spectrum) is characterized in that as shown in FIG. 2, the molecular weight ranges are 328249 and 3349, and the number average molecular weight M n Has a weight average molecular weight of 21753 w 39996, the main peak area was 95.28%.
Step 3-6: 245g of deionized water, 20g of sepiolite, 570g of aluminum sulfate, 75g of coordination excitant, 60g of diethanol amine, 25g of magnesium sulfate and 5g of magnesium oxide. The reaction temperature is 55 ℃, and the stirring time is respectively 30min, 45min and 90min, so as to obtain the liquid alkali-free accelerator.
Example 3
Step 1: triethanolamine maleate having a concentration of 60% was prepared in the same manner as in example 2.
Step 2: adding 75g of triethanolamine maleate with concentration of 60%, 8.5g of N, N-diethyl acrylamide, 5.5g of 2-acrylamide-2-methylpropanesulfonic acid, 5.75g of 3-methacryloxypropyl trimethoxy silane, 1.2g of ammonium persulfate, 0.1g of thioglycolic acid and 100g of deionized water obtained in the step 1 into a reactor, stirring for dissolving, and raising the initial reaction temperature to 40 ℃; dropping a mixed solution of 0.15g of vitamin and 50g of deionized water at a constant speed for 30min at normal temperature, continuing to react for 120min after the dropping is finished, adding 85g of deionized water, and cooling to room temperature to obtain the 20% coordination excitant. The gel permeation chromatography (GPC spectrum) is characterized in that as shown in FIG. 3, the molecular weight ranges are 299709-3294 and the number average molecular weight M n 21011 weight average molecular weight M w 36904, the main peak area was 96.77%.
Step 3-6: 210g of deionized water, 15g of hectorite, 550g of aluminum sulfate, 100g of coordination activator, 75g of diethanolamine and 50g of magnesium sulfate heptahydrate. The reaction temperature is 60 ℃, and the stirring time is 15min, 30min and 60min respectively, so as to obtain the liquid alkali-free accelerator.
Example 4
The same as example 2 except that the amount of the coordination initiator used is 25 g. Namely: 295g of deionized water, 20g of sepiolite, 570g of aluminum sulfate, 25g of coordination exciting agent, 60g of diethanol amine, 25g of magnesium sulfate and 5g of magnesium oxide.
Example 5
The same as example 2, except that the amount of the coordination initiator used was 125 g. Namely: 195g of deionized water, 20g of sepiolite, 570g of aluminum sulfate, 125g of coordination activator, 60g of diethanolamine, 25g of magnesium sulfate and 5g of magnesium oxide.
Example 6
The same as example 2, except that the early strength agent is magnesium sulfate and lithium sulfate, and the total dosage is 40 g. Namely: 230g of deionized water, 20g of sepiolite, 570g of aluminum sulfate, 75g of coordination excitant, 60g of diethanol amine, 30g of magnesium sulfate, 10g of lithium sulfate and 5g of magnesium oxide.
Comparative example 1
The same as example 2, except that no coordination booster was added. Namely: 320g of deionized water, 20g of sepiolite, 570g of aluminum sulfate, 60g of diethanol amine, 25g of magnesium sulfate and 5g of magnesium oxide.
Comparative example 2
The same as example 2, except that no early strength agent was added. Namely: 270g of deionized water, 20g of sepiolite, 570g of aluminum sulfate, 75g of coordination excitant, 60g of diethanol amine and 5g of magnesium oxide.
Comparative example 3
The same as example 2 except that the N, N-dimethylacrylamide in step 2 of example 2 was replaced with acrylamide.
Comparative example 1
The coordination excitant adopts a single thermal decomposition type initiator ammonium persulfate to initiate polymerization. The preparation method comprises the following steps:
step 1: triethanolamine maleate having a concentration of 60% was prepared in the same manner as in example 2.
Step 2: adding 100g of the 60% triethanolamine maleate obtained in the step 1, 10.0g of N, N-dimethylacrylamide, 5.0g of vinyl triethoxysilane, 0.25g of mercaptopropionic acid and 78.5g of deionized water into a reactor, stirring for dissolving, and heating to 80 ℃; at normal temperature, dropping 1.25g of mixed solution of ammonium persulfate and 60g of deionized water at constant speed for 90min, continuing to react for 150min after dropping, and cooling to room temperature to obtain the coordination excitant with the concentration of 30%. The gel permeation chromatography (GPC spectrum) is characterized as shown in FIG. 4, and the molecular weight ranges are 250272-3762 and the number average molecular weight M n Is 20752, weight average molecular weight M w 35943, the main peak area was 85.96%.
The preparation of the liquid alkali-free accelerator is the same as the step 3-6 of the example 2.
Comparative example 2
A fluorine-free high-strength liquid alkali-free accelerator manufactured by Jiangsu manufacturers has a milky yellow appearance, a solid content of 50 +/-2.5 percent, a pH value of 3.0 +/-1, and chloride ion content, total alkali content and fluoride ion content which all meet the requirements of Q/CR 807-.
Comparative example 3
Aluminum sulfate-aluminum hydroxide-hydrofluoric acid system liquid alkali-free accelerator: the aluminum sulfate-aluminum hydroxide-magnesium sulfate-aluminum mixed liquid is prepared from aluminum sulfate, aluminum hydroxide, 40% hydrofluoric acid, magnesium sulfate, diethanolamine and a stabilizer, wherein the mass fraction of the 40% hydrofluoric acid accounts for 10.0%.
Comparative example 4
Aluminum sulfate-magnesium fluosilicate system liquid alkali-free accelerator: the magnesium fluosilicate stabilizing agent is prepared from aluminum sulfate, magnesium fluosilicate, magnesium sulfate, diethanol amine and a stabilizing agent, wherein the mass fraction of the magnesium fluosilicate accounts for 4.5%.
According to the detection methods of related items in the national standard GB/T35159-2017 accelerator for sprayed concrete and the national iron enterprise standard Q/CR807-2020 accelerator for liquid alkali-free accelerator for tunnel sprayed concrete, the performance of the fluorine-free high early strength liquid alkali-free accelerator prepared in the examples 1-6 and the comparative examples 1-3, the fluorine-free liquid alkali-free accelerator obtained in the comparative examples 1-2 and the fluorine-containing liquid alkali-free accelerator obtained in the comparative examples 2-3 are tested, and the detection results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the fluoride-free high early strength liquid alkali-free setting accelerator prepared in the embodiments 1 to 6 has good stability, the compressive strength of the mortar is more than or equal to 1.0MPa in 6h, the compressive strength of the mortar is more than or equal to 10MPa in 1d, and other performance indexes meet the requirements of national iron enterprise Q/CR 807-. As is clear from comparison between example 2 and comparative example 3, the coordination initiator used in the accelerator isWhen the unsaturated amide which is synthesized by substituting one or two hydrogens on the nitrogen atom of the acrylamide with functional groups such as alkyl, hydroxyalkyl, phenyl and the like is adopted, higher compressive strength of the mortar for 6h and 1d can be obtained; as is apparent from comparison of example 2 with comparative example 1, not only can the reaction temperature be lowered and the polymerization time be shortened by redox initiation, but also the early strength is higher when used as an accelerator because the resulting polymer has a higher monomer conversion than that of thermal decomposition initiation; compared with the fluorine-free liquid alkali-free accelerator obtained in the comparative examples 1-2 and the fluorine-free liquid alkali-free accelerator sold in the comparative example 2, the fluorine-free high-early-strength liquid alkali-free accelerator provided by the invention is added with the coordination activator, so that the stability of the accelerator is improved, and meanwhile, the synergistic effect of alcohol amine, amide and silane groups on a molecular chain of the accelerator induces the cement mineral C 3 S hydration, acceleration of C 3 S is hydrated to generate C-S-H gel, so that the strength of the mortar is promoted to develop rapidly within 6 hours; the addition of the inorganic salt early strength agent has limited improvement on the 6h compressive strength of the mortar, but has very obvious effect on improving the 1d compressive strength.
Compared with comparative examples 3-4 of liquid alkali-free setting accelerators prepared from fluorine-containing raw materials such as hydrofluoric acid, fluosilicic acid or fluosilicate and the like, the high early-strength liquid alkali-free setting accelerator prepared by the invention has more obvious advantages in compressive strength of 6h and 1d due to no introduction of fluorine-containing raw materials.
In order to fully illustrate the adaptability of the high early strength liquid alkali-free setting accelerator prepared by the invention to different brands of cement, Jidong, conch, Dingxin, southwest, Emkeng, Xuanfeng and Co-creation P.O42.5 ordinary portland cement are respectively selected, the liquid alkali-free setting accelerator prepared in example 2 is adopted to carry out detection on setting time and mortar strength, and the detection results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the mixing amount of the liquid alkali-free accelerator prepared by the invention is within 6-8% of the mass of the cement, so that the net slurry setting time and the mortar strength of different brands of cement can meet the standard requirements of the national railway group company enterprise standard Q/CR807 & 2020 liquid alkali-free accelerator for tunnel shotcrete, and the liquid alkali-free accelerator has wide cement adaptability.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (11)
1. A coordination activator comprises a multipolymer of a monomer of triethanolamine maleate, an unsaturated amide and an unsaturated silane, wherein the unsaturated amide is at least one of N-methylolacrylamide, N-hydroxyethyl acrylamide, N-dimethylacrylamide, N-dimethylmethacrylamide, N-diethylacrylamide, N-diethylmethacrylamide, N-dibutylacrylamide, N-isopropylacrylamide, N-phenylacrylamide, N-phenylmethylacrylamide, N- (p-hydroxyphenyl) methacrylamide; and/or 2-acrylamido-2-methylpropanesulfonic acid; n, N-dimethylacrylamide is preferred.
2. Coordination stimulator according to claim 1, characterized in that said triethanolamine maleate is mono-and/or di-triethanolamine maleate;
and/or the unsaturated silane is any one or more of alkenyl substituted silane, preferably any one or more of triethyl vinyl silane, vinyl triethoxy silane, vinyl trimethoxy silane, acryloxy trimethyl silane, triacetoxy vinyl silane, allyl trimethyl silane, allyl triethoxy silane, allyl trimethoxy silane, diethoxy methyl vinyl silane, 3-methacryloxy propyl trimethoxy silane, vinyl dimethyl ethoxy silane and methyl vinyl diacetoxy silane.
3. Coordination activator according to claim 1 or 2, characterized in that the mass ratio of triethanolamine maleate, unsaturated amide and unsaturated silane is (30-100): (2-20): (1-15), preferably (40-60): (5-15): (2-10).
4. The coordination activator according to any one of claims 1 to 3, wherein the coordination activator is obtained by performing radical copolymerization reaction of triethanolamine maleate, unsaturated amide and unsaturated silane in the presence of a redox initiator, a chain transfer agent and deionized water;
preferably, the amount of the oxidant in the redox initiator is 0.2 wt% -3.0 wt% of the total mass of the monomers, and the amount of the reducing agent is 0.1 wt% -0.5 wt% of the total mass of the monomers;
preferably, the chain transfer agent is used in an amount of 0.05 to 0.5 wt% based on the total mass of the monomers;
more preferably, the oxidizing agent is at least one of hydrogen peroxide, ammonium persulfate, sodium persulfate, or potassium persulfate;
more preferably, the reducing agent is at least one of vitamin C, sodium formaldehyde sulfoxylate, sodium bisulfite, sodium sulfite or ferrous sulfate;
more preferably, the chain transfer agent is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, and sodium methallyl sulfonate.
5. A process for the preparation of a coordination stimulator as claimed in any one of claims 1 to 4 comprising the steps of:
s1, adding triethanolamine maleate, unsaturated amide, unsaturated silane, a chain transfer agent, an oxidant and deionized water into a reactor, and uniformly stirring;
s2, slowly adding an aqueous solution of a reducing agent into the mixture, preferably dropwise adding, more preferably dropwise adding for 0.5-1 h, and reacting for 1-3 h to obtain the coordination exciting agent;
preferably, the initial reaction temperature of the coordination activator synthesis is 10-40 ℃.
6. A high early strength liquid alkali-free accelerator, which is characterized in that raw materials comprise aluminum sulfate, a stabilizer, the coordination excitant of any one of claims 1 to 4, alcohol amine, an early strength agent and an optional neutralizer.
7. The high early strength liquid alkali-free setting accelerator as claimed in claim 6, wherein the alkali-free setting accelerator has a 6h compressive strength of 1.0MPa or more and a 1d compressive strength of 10MPa or more when used in cement mortar testing.
8. The high early strength liquid alkali-free accelerator according to claim 6 or 7, characterized in that the raw materials comprise, in parts by weight: 450-600 parts of aluminum sulfate, 5-25 parts of stabilizer, 25-150 parts of coordination activator, 30-100 parts of alcohol amine, 10-100 parts of early strength agent, 0-10 parts of neutralizer and the balance of deionized water to 1000 parts;
preferably, the starting materials comprise: 500-600 parts of aluminum sulfate, 10-20 parts of stabilizer, 50-100 parts of coordination activator, 40-80 parts of alcohol amine, 20-50 parts of early strength agent and 0-10 parts of neutralizer.
9. The high early strength liquid alkali-free accelerator as claimed in any one of claims 6 to 8, wherein the aluminum sulfate is industrial aluminum sulfate, and Al is used 2 O 3 The aluminum content is not less than 15.6 wt%; and/or
The stabilizer is at least one of sepiolite, magnesium aluminum silicate, calcium bentonite, water-based organic bentonite, water-based polyamide wax, hectorite, nano aluminum oxide and fumed silica; and/or
The alcohol amine is at least one of ethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine and diethanol monoisopropanolamine; and/or
The early strength agent is at least one of magnesium sulfate, magnesium sulfate hydrate, lithium carbonate, lithium sulfate hydrate, ferric sulfate and ferric sulfate hydrate; and/or
The neutralizing agent is at least one of magnesium oxide, magnesium hydroxide and lithium hydroxide.
10. The method for preparing the high early strength liquid alkali-free accelerator according to any one of claims 6 to 9, characterized by comprising the steps of:
s1, mixing a stabilizer with water to obtain a first mixed solution;
s2, adding a coordination excitant and aluminum sulfate into the first mixed solution, and mixing to obtain a second mixed solution;
s3, adding alcohol amine into the second mixed solution for a complexing reaction to obtain a third mixed solution;
and S4, adding the early strength agent and the neutralizing agent into the third mixed solution, and uniformly mixing to obtain the liquid alkali-free accelerator.
11. Use of a high early strength liquid alkali-free accelerator according to any one of claims 6 to 10 and/or obtained by the preparation method according to claim 10 in the field of concrete.
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