CN109369859B - Concrete tackifying type viscosity regulator and preparation method thereof - Google Patents
Concrete tackifying type viscosity regulator and preparation method thereof Download PDFInfo
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- CN109369859B CN109369859B CN201810935140.6A CN201810935140A CN109369859B CN 109369859 B CN109369859 B CN 109369859B CN 201810935140 A CN201810935140 A CN 201810935140A CN 109369859 B CN109369859 B CN 109369859B
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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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
- C04B2103/44—Thickening, gelling or viscosity increasing agents
Abstract
The invention discloses a concrete tackifying type viscosity regulator and a preparation method thereof, and the preparation method comprises the following steps: dissolving a modified polyether monomer, an unsaturated amide monomer, an unsaturated carboxylic acid monomer and a crosslinking agent in deionized water to obtain a monomer mixed solution; dissolving an unsaturated amide monomer and an unsaturated carboxylic acid monomer in deionized water, and marking as solution A; in N2And slowly dripping the initiator solution and the solution A into the monomer mixed solution at the temperature of 40-60 ℃, continuously stirring and reacting at the temperature of 60-90 ℃, adjusting the pH value, and supplementing water for dilution to obtain the viscosity regulator. The viscosity regulator disclosed by the invention has good compatibility with the polycarboxylic acid water reducing agent, can effectively regulate the cohesiveness of concrete, solves the problems of segregation and bleeding of the concrete, does not influence the slump retaining performance and the setting time of the concrete, and is favorable for the development of the compressive strength of the concrete; meanwhile, the optimized regulation and control of the polymerization process improves the stability of the product, reduces the doping amount sensitivity of the product and improves the operability of field construction.
Description
Technical Field
The invention belongs to the technical field of concrete admixtures, and particularly relates to a concrete tackifying type viscosity regulator and a preparation method thereof.
Background
With the development of large-scale and high-rise concrete structures, the demand of high-performance, high-strength and ultrahigh-strength concrete, large-fluidity concrete and the like for building construction is increasing. Under the condition of not changing the mixing proportion of the high-strength concrete, the working performance of the concrete is improved by increasing the mixing amount of the polycarboxylate superplasticizer. The polycarboxylate superplasticizer has the advantages of high water reducing rate, good slump retaining performance, low concrete shrinkage, environmental protection and the like, but can cause the problems of poor cohesiveness, bleeding, segregation and the like of concrete. In addition, the medium and low grade concrete has strong sensitivity to the addition of the water reducing agent, and segregation and bleeding phenomena can also occur to the concrete due to improper mixing proportion, poor aggregate gradation, excessive mixing of the water reducing agent and the like. These problems not only seriously affect the working performance of concrete and reduce the strength and durability of concrete, but also cause engineering accidents which bring difficulties to the construction of buildings and affect the quality and service life of concrete engineering.
Therefore, a viscosity regulator is usually added into a concrete system, so that the cohesiveness and stability of the cement-based cementing material are effectively improved, the cohesiveness and the water retention of the concrete are enhanced, and the aim of improving the overall working performance of the concrete is fulfilled. However, most viscosity modifiers, such as xanthan gum, welan gum, cyclodextrin, cellulose ether, polyacrylamide, polyvinyl alcohol, etc., have poor compatibility with polycarboxylic acid water reducing agents, are easy to precipitate if directly mixed to cause a delamination phenomenon, are not beneficial to normal construction of concrete, and have adverse effects on the maintenance performance and later strength development of concrete working performance, for example, chinese patent document CN104231152A discloses a preparation method of a concrete thickener, which has poor compatibility with polycarboxylic acid water reducing agents to cause adverse effects on the working performance of concrete.
Chinese patent document CN103554392A discloses a thickener copolymer, which is obtained by polymerizing an unsaturated polyether monomer, an unsaturated polyether carboxylic ester monomer and an unsaturated carboxylic acid monomer, has excellent water retention performance, has little influence on the fluidity of concrete, and has good compatibility with a polycarboxylate water reducing agent, but the thickener has high solid content, has larger content of the carboxylic acid monomer in a molecular structure, has larger influence on the compressive strength of the concrete, has stronger doping sensitivity, and greatly increases the working difficulty of production and quality control personnel of concrete enterprises. Chinese patent document CN106478893A discloses a preparation method of a concrete viscosity regulator, however, the viscosity regulator has strong doping sensitivity and certain viscosity reduction effect.
Therefore, the development of the high-performance viscosity regulator has very important significance, and the high-performance viscosity regulator is required to have the characteristics of obvious tackifying, anti-segregation, reduction of bleeding rate, small influence on the later-stage working performance of fresh concrete and the like, and simultaneously has no influence on the later-stage strength development of the concrete basically. The high-performance viscosity regulator can meet the current high-performance development requirement of concrete, and has important value for promoting the high performance of concrete and improving the production and application technology of concrete.
Disclosure of Invention
The invention aims to provide a preparation method of a concrete tackifying type viscosity regulator aiming at the problems in the prior art.
The invention also aims to provide the concrete viscosity-increasing type viscosity regulator prepared by the preparation method.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a concrete tackifying type viscosity regulator comprises the following steps:
(1) mixing the following components in a mass ratio of 1-20: 15-30: 10-25: dissolving 1-5 parts of modified polyether monomer, unsaturated amide monomer, unsaturated carboxylic acid monomer and cross-linking agent in deionized water with the mass of 400-600% of the total mass of the monomers to obtain a monomer mixed solution;
(2) dissolving unsaturated amide monomers and unsaturated carboxylic acid monomers with the same mass as the monomers in the monomer mixed solution into deionized water, and marking as solution A;
(3) in N2And slowly dripping an initiator solution with the mass percentage concentration of 0.1-1% and the solution A into the monomer mixed solution within 1-3 h at 40-60 ℃, keeping the temperature at 60-90 ℃, continuously stirring for reacting for 2-6 h, adding alkali liquor to adjust the pH value to 6-8, and supplementing water for dilution to obtain the tackifying type viscosity regulator with the solid content of 3-12%.
According to the method, the modified polyether monomer, the unsaturated amide monomer and the unsaturated carboxylic acid monomer are adopted for crosslinking to prepare the concrete tackifying type viscosity regulator, and the structural unit similar to the polycarboxylate superplasticizer is adopted, so that the technical problem that the traditional viscosity regulator is poor in compatibility with the polycarboxylate superplasticizer can be solved; the introduction of the modified polyether monomer not only improves the molecular weight of the polymer, but also endows the viscosity regulator with certain slump retaining performance, and reduces the influence of the product on the working performance of concrete; the amide substance has high reaction activity, can generate a high-viscosity polymer, has a certain early strength function, and is beneficial to the development of the mechanical strength of concrete; the optimized regulation and control of the polymerization process comprises the steps of preparing the unsaturated amide monomer and the unsaturated carboxylic acid monomer into the solution A, and slowly dripping the solution A into the monomer mixed solution, so that the components are fully reacted, the stability of the product is improved, the doping amount sensitivity of the product is reduced, and the operability of the site construction and quality control of the concrete is improved.
Preferably, the modified polyether monomer has the general formula R1O(EO)m(PO)nOR2Wherein R is1Is an unsaturated olefin group of 3 to 9 carbon atoms, R2H or an alkyl group having 1 to 12 carbon atoms, n is an integer of 5 to 100, and m is an integer of 0 to 100; the general formula of the unsaturated amide monomer is as follows: r3R4C＝CR5CONR6R7Wherein R is3、R4、R5Each represents H or CH3，R6、R7Each represents H, CH3、CrH2r+1、CH(CH3)2、C(CH3)2CH2SO3M or (CH)2)xNR8R9R is an integer of 1 to 5, M is H or a monovalent metal ion, x is an integer of 1 to 5, R8、R9Each represents H, CH3Or CrH2r+1(ii) a The unsaturated carboxylic acid monomer has a general formula: r10R11C＝CR12COOM，R10、R11、R12Each represents H, CH3Or COOM.
More preferably, the modified polyether monomer is one or more of allyl alcohol polyoxyethylene polyoxypropylene ether, prenol polyoxyethylene ether, 4-hydroxybutyl vinyl polyoxyethylene ether, terminal alkylene double-tail polyoxyethylene ether and allyl polyoxyalkyl epoxy ether, and the molecular weight is 300-10000; the unsaturated amide monomer is one or more of acrylamide, methacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-isopropylacrylamide, N-isopropyl methacrylamide, 2-acrylamido-2-methylpropanesulfonate, dimethylaminopropyl acrylamide and dimethylaminopropyl methacrylamide; the unsaturated carboxylic acid monomer is one or more of acrylic acid, methacrylic acid, maleic anhydride, fumaric acid and 2-methylenesuccinic acid.
Preferably, the crosslinking agent is polyethylene glycol diallyl ether or polyoxyalkylene diallyl ether.
Preferably, the initiator is a persulfate initiator or a water-soluble azo initiator, and the mass of the initiator is 0.5-2.5% of the total mass of the modified polyether monomer, the unsaturated amide monomer and the unsaturated carboxylic acid monomer in the step (1) and the step (2).
More preferably, the persulfate initiator is selected from one of sodium persulfate, ammonium persulfate and potassium persulfate; the water-soluble azo initiator is selected from one of azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid and azobisisopropylimidazoline.
Preferably, the alkali liquor is one of sodium hydroxide, potassium hydroxide and calcium hydroxide solution with the concentration of 32% by mass.
The viscosity modifier is prepared by the preparation method of the viscosity modifier, and the weight average molecular weight of the prepared viscosity modifier is 100-300 ten thousand.
The concrete tackifying type viscosity regulator disclosed by the invention has good compatibility with a polycarboxylic acid water reducing agent, is remarkable in tackifying effect, weak in sensitivity and strong in adaptability, basically has no influence on later-stage working performance, is beneficial to development of concrete strength, and can effectively solve the problems of segregation and bleeding of concrete.
Preferably, the weight average molecular weight of the viscosity modifier is 150 to 250 ten thousand.
Compared with the prior art, the invention has the beneficial effects that:
1. the modified polyether monomer, the unsaturated amide monomer and the unsaturated carboxylic acid monomer are adopted to prepare the concrete tackifying type viscosity regulator through crosslinking, the concrete tackifying type viscosity regulator has good compatibility with the polycarboxylic acid water reducing agent, obvious tackifying effect, weak sensitivity and strong adaptability, basically has no influence on later-stage working performance, is beneficial to development of concrete strength, and can effectively solve the problems of concrete segregation and bleeding.
2. The invention adopts the structural unit similar to the polycarboxylate superplasticizer, and can solve the technical problem of poor compatibility of the traditional viscosity regulator and the polycarboxylate superplasticizer; the introduction of the modified polyether monomer not only improves the molecular weight of the polymer, but also endows the viscosity regulator with certain slump retaining performance, and reduces the influence of the product on the working performance of concrete.
3. The invention adopts amide substances for polymerization reaction, has high reaction activity, can generate high-viscosity polymers, has a certain early strength function and is beneficial to the development of the mechanical strength of concrete.
4. The polymerization process is optimized, so that the components react fully, the stability of the product is improved, the doping amount sensitivity of the product is reduced, and the operability of site construction and quality control of concrete is improved.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation method of a concrete tackifying type viscosity regulator comprises the following steps:
(1) mixing the following components in a mass ratio of 1-20: 15-30: 10-25: dissolving 1-5 parts of modified polyether monomer, unsaturated amide monomer, unsaturated carboxylic acid monomer and cross-linking agent in deionized water with the mass of 400-600% of the total mass of the monomers to obtain a monomer mixed solution;
(2) dissolving unsaturated amide monomers and unsaturated carboxylic acid monomers with the same mass as the monomers in the monomer mixed solution into deionized water, and marking as solution A;
(3) in N2And slowly dripping initiator solution with the mass percentage concentration of 0.1-1% and the solution A respectively within 1-3 h at the temperature of 40-60 DEG CAnd (3) keeping the temperature of the monomer mixed solution at 60-90 ℃, continuously stirring and reacting for 2-6 h, adding alkali liquor to adjust the pH value of the monomer mixed solution to 6-8, and supplementing water to dilute the monomer mixed solution to obtain the tackifying type viscosity regulator with the solid content of 3-12%.
Preferably, the modified polyether monomer has the general formula R1O(EO)m(PO)nOR2Wherein R is1Is an unsaturated olefin group of 3 to 9 carbon atoms, R2H or an alkyl group having 1 to 12 carbon atoms, n is an integer of 5 to 100, and m is an integer of 0 to 100; the general formula of the unsaturated amide monomer is as follows: r3R4C＝CR5CONR6R7Wherein R is3、R4、R5Each represents H or CH3，R6、R7Each represents H, CH3、CrH2r+1、CH(CH3)2、C(CH3)2CH2SO3M or (CH)2)xNR8R9R is an integer of 1 to 5, M is H or a monovalent metal ion, x is an integer of 1 to 5, R8、R9Each represents H, CH3Or CrH2r+1(ii) a The unsaturated carboxylic acid monomer has a general formula: r10R11C＝CR12COOM，R10、R11、R12Each represents H, CH3Or COOM.
More preferably, the modified polyether monomer is one or more of allyl alcohol polyoxyethylene polyoxypropylene ether, prenol polyoxyethylene ether, 4-hydroxybutyl vinyl polyoxyethylene ether, terminal alkylene double-tail polyoxyethylene ether and allyl polyoxyalkyl epoxy ether, and the molecular weight is 300-10000; the unsaturated amide monomer is one or more of acrylamide, methacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-isopropylacrylamide, N-isopropyl methacrylamide, 2-acrylamido-2-methylpropanesulfonate, dimethylaminopropyl acrylamide and dimethylaminopropyl methacrylamide; the unsaturated carboxylic acid monomer is one or more of acrylic acid, methacrylic acid, maleic anhydride, fumaric acid and 2-methylenesuccinic acid.
Preferably, the crosslinking agent is polyethylene glycol diallyl ether or polyoxyalkylene diallyl ether.
Preferably, the initiator is a persulfate initiator or a water-soluble azo initiator, and the mass of the initiator is 0.5-2.5% of the total mass of the modified polyether monomer, the unsaturated amide monomer and the unsaturated carboxylic acid monomer in the step (1) and the step (2).
More preferably, the persulfate initiator is selected from one of sodium persulfate, ammonium persulfate and potassium persulfate; the water-soluble azo initiator is selected from one of azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid and azobisisopropylimidazoline.
Preferably, the alkali liquor is one of sodium hydroxide, potassium hydroxide and calcium hydroxide solution with the concentration of 32% by mass.
The viscosity modifier is prepared by the preparation method of the viscosity modifier, and the weight average molecular weight of the prepared viscosity modifier is 100-300 ten thousand.
Example 1
A preparation method of a concrete tackifying type viscosity regulator comprises the following steps:
(1) weighing 2.6g of prenyl polyoxyethylene ether, 6.4g of N, N-dimethylacrylamide, 4.65g of acrylic acid and 0.5g of polyoxyalkylene diallyl ether, dissolving in 135g of deionized water to obtain a monomer mixed solution, transferring the solution into a 1000mL four-neck flask with a stirring device, a thermometer, a constant-pressure dropping funnel and a nitrogen inlet, heating and stirring (180r/min), and introducing nitrogen;
(2) weighing 6.4g of N, N-dimethylacrylamide and 4.65g of acrylic acid, dissolving in 22g of deionized water, and uniformly mixing to obtain solution A;
(3) 0.2g of azobisisobutylamidine hydrochloride was weighed out and dissolved completely in 40g of deionized water as initiator solution in N2And slowly dropping initiator solution and solution A into the above monomer mixed solution at 50 deg.C for 1 hr, respectively, and heating to 80 deg.CKeeping the temperature and continuously stirring for reaction for 5 hours, adding a sodium hydroxide solution with the mass percentage concentration of 32% to adjust the pH value to 7.0, adding 761.5g of deionized water into the system, uniformly mixing, and naturally cooling to room temperature to obtain the tackifying type viscosity regulator with the solid content of 3%.
The weight average molecular weight of the concrete viscosity modifier prepared in the embodiment is 243 thousands, the concrete viscosity modifier is placed at room temperature for 6 months, 9 months and 12 months without layering, and the shelf life of the general concrete viscosity modifier is 6-9 months, which shows that the concrete viscosity modifier of the embodiment has good stability.
Example 2
A preparation method of a concrete tackifying type viscosity regulator comprises the following steps:
(1) weighing 3.0g of prenyl polyoxyethylene ether, 7.35g of methacrylamide, 6.15g of methacrylic acid and 0.3g of polyoxyalkylene diallyl ether, dissolving in 156g of deionized water to obtain a monomer mixed solution, transferring the solution to a 1000mL four-neck flask with a stirring device, a thermometer, a constant-pressure dropping funnel and a nitrogen inlet, heating and stirring (180r/min), and introducing nitrogen;
(2) weighing 7.35g of methacrylamide and 6.15g of methacrylic acid, dissolving in 27g of deionized water, and uniformly mixing to obtain solution A;
(3) 0.24g of azobisisobutylamidine hydrochloride was weighed out and dissolved completely in 40g of deionized water as initiator solution in N2And slowly dropping an initiator solution and the solution A into the monomer mixed solution within 1.5 hours at the temperature of 50 ℃, keeping the temperature at 70 ℃ after dropping, continuously stirring for reacting for 5 hours, adding a potassium hydroxide solution with the mass percentage concentration of 32% to adjust the pH value to 7.0, adding 728g of deionized water into the system, uniformly mixing, and naturally cooling to room temperature to obtain the tackifying type viscosity regulator with the solid content of 3.5%.
The weight average molecular weight of the concrete viscosity modifier prepared in this example is 232 ten thousand, and the concrete viscosity modifier prepared in this example has no delamination phenomenon after being placed at room temperature for 6 months, 9 months and 12 months, which indicates that the concrete viscosity modifier of this example has good stability.
Example 3
A preparation method of a concrete tackifying type viscosity regulator comprises the following steps:
(1) weighing 4g of hydroxybutyl vinyl polyoxyethylene ether, 8.33g of N-isopropyl acrylamide, 6.07g of acrylic acid and 1.0g of polyethylene glycol diallyl ether, dissolving in 168g of deionized water to obtain a monomer mixed solution, transferring the monomer mixed solution into a 1000mL four-neck flask with a stirring device, a thermometer, a constant-pressure dropping funnel and a nitrogen inlet, heating and stirring (200r/min), and introducing nitrogen;
(2) weighing 8.33g of N-isopropylacrylamide and 6.07g of acrylic acid, dissolving in 29g of deionized water, and uniformly mixing to obtain solution A;
(3) 0.34g of azobisisobutyrimidazoline hydrochloride was weighed out and dissolved completely in 66g of deionized water as initiator solution in N2And slowly dropping an initiator solution and the solution A into the monomer mixed solution within 2 hours at the temperature of 55 ℃, keeping the temperature at 80 ℃ after dropping, continuously stirring for reaction for 3 hours, adding a 32 mass percent potassium hydroxide solution to adjust the pH value to 6.0, adding 683g of deionized water into the system, uniformly mixing, and naturally cooling to room temperature to obtain the tackifying type viscosity regulator with the solid content of 4.1%.
The weight average molecular weight of the concrete viscosity modifier prepared in the embodiment is 254 ten thousand, and the concrete viscosity modifier prepared in the embodiment has no delamination phenomenon after being placed at room temperature for 6 months, 9 months and 12 months, which shows that the concrete viscosity modifier in the embodiment has good stability.
Example 4
A preparation method of a concrete tackifying type viscosity regulator comprises the following steps:
(1) 3.0g of terminal alkylene double-tail polyoxyethylene ether, 7.35g of N-isopropyl methacrylamide, 7.45g of fumaric acid and 1.2g of polyethylene glycol diallyl ether are weighed and dissolved in 185g of deionized water to obtain a monomer mixed solution, the monomer mixed solution is transferred to a 1000mL four-neck flask with a stirring device, a thermometer, a constant-pressure dropping funnel and a nitrogen inlet, and the mixture is heated and stirred (150r/min) and introduced with nitrogen;
(2) weighing 7.35g of N-isopropyl methacrylamide and 7.45g of fumaric acid, dissolving in 30g of deionized water, and uniformly mixing to obtain solution A;
(3) 0.196g of ammonium persulfate was weighed out and completely dissolved in 39g of deionized water as initiator solution in N2And slowly dropping an initiator solution and the solution A into the monomer mixed solution within 2 hours at 50 ℃, keeping the temperature at 60 ℃ after the dropping is finished, continuously stirring for reacting for 6 hours, adding a potassium hydroxide solution with the mass percentage concentration of 32% to adjust the pH value to 6.0, adding 653g of deionized water into the system, uniformly mixing, and naturally cooling to room temperature to obtain the tackifying type viscosity regulator with the solid content of 4.5%.
The weight average molecular weight of the concrete viscosity modifier prepared in this example is 283 ten thousand, and the concrete viscosity modifier prepared in this example has no delamination phenomenon after being placed at room temperature for 6 months, 9 months and 12 months, which indicates that the concrete viscosity modifier of this example has good stability.
Example 5
A preparation method of a concrete tackifying type viscosity regulator comprises the following steps:
(1) weighing 3.0g of allyl polyoxyalkyl epoxy ether, 7.35g of N, N-diethyl acrylamide, 5.80g of maleic acid and 0.6g of polyoxyalkylene diallyl ether, dissolving in 132g of deionized water to obtain a monomer mixed solution, transferring the monomer mixed solution into a 1000mL four-neck flask with a stirring device, a thermometer, a constant-pressure dropping funnel and a nitrogen inlet, heating and stirring (200r/min), and introducing nitrogen;
(2) weighing 7.35g of N, N-diethylacrylamide and 5.80g of maleic acid, dissolving in 26g of deionized water, and uniformly mixing to obtain solution A;
(3) 0.352g of potassium persulfate was weighed out and completely dissolved in 70g of deionized water as initiator solution in N2And slowly dropping an initiator solution and the solution A into the monomer mixed solution within 1 hour at the temperature of 60 ℃, keeping the temperature at 90 ℃ after dropping, continuously stirring for reacting for 2 hours, adding a potassium hydroxide solution with the mass percentage concentration of 32% to adjust the pH value to 7.0, supplementing 691g of deionized water into the system, uniformly mixing, and naturally cooling to room temperature to obtain the tackifying type viscosity regulator with the solid content of 4.0%.
The weight average molecular weight of the concrete viscosity modifier prepared in this example is 217 ten thousand, and the concrete viscosity modifier prepared in this example has no delamination phenomenon after being placed at room temperature for 6 months, 9 months and 12 months, which indicates that the concrete viscosity modifier of this example has good stability.
Example 6
A preparation method of a concrete tackifying type viscosity regulator comprises the following steps:
(1) weighing 8.0g of allyl alcohol polyoxyethylene polyoxypropylene ether, 10.6g of acrylamide, 12.8g of methacrylic acid and 2.8g of polyoxyalkylene diallyl ether, dissolving the allyl alcohol polyoxyethylene polyoxypropylene ether, the acrylamide, the methacrylic acid and the polyoxyalkylene diallyl ether in 264g of deionized water to obtain a monomer mixed solution, transferring the monomer mixed solution into a 1000mL four-neck flask with a stirring device, a thermometer, a constant-pressure dropping funnel and a nitrogen inlet, heating and stirring (200r/min), and introducing nitrogen;
(2) weighing 14.8g of N, N-dimethylacrylamide and 12.8g of methacrylic acid, dissolving in 56g of deionized water, and uniformly mixing to obtain solution A;
(3) 0.588g of azobiscyanovaleric acid was weighed out and dissolved in 117g of deionized water as initiator solution in N2And slowly dropping an initiator solution and the solution A into the monomer mixed solution within 2 hours at 40 ℃, keeping the temperature at 80 ℃ after dropping, continuously stirring for reacting for 4 hours, adding a 32 mass percent potassium hydroxide solution to adjust the pH value to 8.0, adding 462g of deionized water into the system, uniformly mixing, and naturally cooling to room temperature to obtain the tackifying type viscosity regulator with the solid content of 7.5%.
The weight average molecular weight of the concrete viscosity modifier prepared in this example is 292 million, and the concrete viscosity modifier prepared in this example has no delamination phenomenon after being placed at room temperature for 6 months, 9 months and 12 months, which indicates that the concrete viscosity modifier of this example has good stability.
Example 7
A preparation method of a concrete tackifying type viscosity regulator comprises the following steps:
(1) weighing 4.5g of prenyl alcohol polyoxyethylene ether, 9.65g of dimethylaminopropyl methacrylamide, 8.45g of acrylic acid and 0.5g of polyethylene glycol diallyl ether, dissolving in 185g of deionized water to obtain a monomer mixed solution, transferring the monomer mixed solution into a 1000mL four-neck flask with a stirring device, a thermometer, a constant-pressure dropping funnel and a nitrogen inlet, heating and stirring (150r/min), and introducing nitrogen;
(2) weighing 9.65g of dimethylamino propyl methacrylamide and 8.45g of acrylic acid, dissolving in 36g of deionized water, and uniformly mixing to obtain solution A;
(3) 0.325g of azobisisobutylamidine hydrochloride was weighed out and dissolved in 65g of deionized water as initiator solution in N2And slowly dropping an initiator solution and the solution A into the monomer mixed solution within 0.5h at the temperature of 60 ℃, keeping the temperature at 80 ℃ after dropping, continuously stirring for reacting for 5h, adding a potassium hydroxide solution with the mass percentage concentration of 32% to adjust the pH value to 7.0, supplementing 643g of deionized water into the system, uniformly mixing, and naturally cooling to room temperature to obtain the tackifying type viscosity regulator with the solid content of 5.1%.
The weight average molecular weight of the concrete viscosity modifier prepared in this example is 238 ten thousand, and the concrete viscosity modifier prepared in this example has no delamination phenomenon after being placed at room temperature for 6 months, 9 months and 12 months, which indicates that the concrete viscosity modifier of this example has good stability.
Example 8
A preparation method of a concrete tackifying type viscosity regulator comprises the following steps:
(1) weighing 1.2g of prenyl alcohol polyoxyethylene ether, 18.85g of acrylamide, 12.55g of acrylic acid and 1.2g of polyethylene glycol diallyl ether, dissolving in 185g of deionized water to obtain a monomer mixed solution, transferring the solution into a 1000mL four-neck flask with a stirring device, a thermometer, a constant-pressure dropping funnel and a nitrogen inlet, heating and stirring (150r/min), and introducing nitrogen;
(2) weighing 18.85g of acrylamide and 12.55g of acrylic acid, dissolving in 36g of deionized water, and uniformly mixing to obtain solution A;
(3) 0.325g of azobisisobutylamidine hydrochloride was weighed out and dissolved in 65g of deionized water as initiator solution in N2And slowly dripping the initiator solution and the solution A into the monomer mixed solution within 0.5h at the temperature of 60 ℃, preserving the temperature at 80 ℃ after dripping, continuously stirring for reacting for 5h, and adding 32 mass percent of the initiator solution and the solution AAdjusting the pH value of the potassium hydroxide solution to 7.0, adding 643g of deionized water into the system, uniformly mixing, and naturally cooling to room temperature to obtain the tackifying type viscosity regulator with the solid content of 5.1%.
The weight average molecular weight of the concrete viscosity modifier prepared in this example is 118 ten thousand, and the concrete viscosity modifier prepared in this example has no delamination phenomenon after being placed at room temperature for 6 months, 9 months and 12 months, which indicates that the concrete viscosity modifier of this example has good stability.
Comparative example 1
A preparation method of a concrete tackifying type viscosity regulator comprises the following steps: respectively weighing 175g of methyl allyl polyoxyethylene ether, 50g of methyl allyl polyoxyethylene ether itaconate, 50g of acrylic acid, 25g of acrylamide and 647g of deionized water, placing the weighed materials in a 1L four-neck flask with a stirrer, a thermometer and a dropping device, stirring and heating to 30 ℃, adding 2.5g of ammonium persulfate, then adding 50.5g of vitamin C aqueous solution (obtained by dissolving 0.5g of vitamin C in 50g of deionized water), continuing stirring for 5min, stopping stirring, and preserving heat at 30-50 ℃ for 4h to obtain the tackifying type viscosity regulator with the solid content of 29.6%.
The weight average molecular weight of the concrete viscosity modifier prepared in the comparative example is 96 ten thousand, the concrete viscosity modifier is free of layering phenomenon after being placed at room temperature for 6 months, 9 months and 12 months, the layering phenomenon starts to appear at 9 months, and the layering is particularly obvious at 12 months, so that the stability of the concrete viscosity modifier in the comparative example is poor.
Comparative example 2
A preparation method of a concrete tackifying type viscosity regulator comprises the following steps:
(1) weighing 2.6g of prenyl polyoxyethylene ether, 12.8g of N, N-dimethylacrylamide, 9.3g of acrylic acid and 0.5g of polyoxyalkylene diallyl ether, dissolving in 155g of deionized water to obtain a monomer mixed solution, transferring the solution into a 1000mL four-neck flask with a stirring device, a thermometer, a constant-pressure dropping funnel and a nitrogen inlet, heating and stirring (180r/min), and introducing nitrogen;
(2) 0.2g of azobisisobutylamidine hydrochloride was weighed out and dissolved completely in 40g of deionized water as initiator solutionLiquid in N2And slowly dripping an initiator solution into the monomer mixed solution within 1 hour at the temperature of 50 ℃, keeping the temperature at 80 ℃ after dripping, continuously stirring and reacting for 5 hours, adding a sodium hydroxide solution with the mass percentage concentration of 32% to adjust the pH value to 7.0, adding 761.5g of deionized water into the system, uniformly mixing, and naturally cooling to room temperature to obtain the tackifying type viscosity regulator with the solid content of 3%.
The weight average molecular weight of the concrete viscosity modifier prepared in the comparative example is 185 million, the concrete viscosity modifier is free of layering phenomenon after being placed at room temperature for 6 months, 9 months and 12 months, the layering phenomenon starts to appear at 9 months, and the layering is particularly obvious at 12 months, so that the stability of the concrete viscosity modifier in the comparative example is poor.
As comparative examples 3, 4 and 5, a commercially available tackifier specific to a polycarboxylic acid water reducing agent, a cellulose ether viscosity modifier (molecular weight: 40000) and a maltodextrin viscosity modifier were used, respectively.
Application example 1
The concrete viscosity-increasing type viscosity modifiers of examples 1 to 8 and comparative examples 1 to 5 were applied to concrete, and the influence of the standard GB/T50081-2002 on the working performance, viscosity and compressive strength of the concrete in the standard GB/T50081-2002 of the test method for mechanical properties of common concrete was tested. The workability of the concrete is represented by slump and expansion; the concrete viscosity is characterized by the time for the concrete to pass through a slump cone (slump time), and the longer the slump time, the greater the concrete viscosity.
TABLE 1C 30 and C50 concrete mixing ratio
Note: the cement is conch P.O42.5 cement; the fly ash is grade II fly ash, and the fineness is 15.0; the sand is river sand with fineness modulus of 2.7, and the mud content is less than 2%; the stone is crushed stone with 5-20 mm continuous gradation, and the mud content is less than 1%; the water reducing agent is a high-performance polycarboxylic acid water reducing agent produced by Yuanjin building material science and technology limited company, and the effective solid content is 10 percent.
The concrete performance evaluation results were as follows:
TABLE 2 Effect of different groups on the properties of C30 concrete
Note: the viscosity-increasing regulator is compounded and mixed with the high-performance polycarboxylic acid water reducing agent by adopting an external mixing method and then is directly used, and the mixing amount is the mass percentage of the water reducing agent product.
As can be seen from table 2 in combination with other experimental data of the inventor, examples 1 to 8 can significantly improve the working state of the segregated concrete, improve the slump retaining performance of the concrete, and contribute to the development of the concrete strength, wherein example 5 adopts allyl polyoxyalkyl epoxy ether as a modified polyether monomer, which has the least influence on the viscosity of the concrete, and example 7 obviously improves the compressive strength of the concrete due to the introduction of dimethylaminopropyl methacrylamide into the system; in addition, the viscosity modifier of the invention has weak mixing sensitivity, and the working performance of the concrete is not seriously influenced by slight over-mixing. However, the working performance of the concrete after 1 hour is greatly influenced by the comparative examples 1 to 5, wherein the addition amount of the viscosity regulator is the optimal addition amount of the product mark because the comparative example 4 and the comparative example 5 belong to different types of viscosity regulators, the addition amount sensitivity of the comparative example 1 is strong, and the concrete is sticky due to slight over-addition; comparative example 2 the wrapping property was poor when the blending amount was low; comparative example 3 the compressive strength of the concrete is significantly reduced; comparative example 4 has a large influence on the early compressive strength of the concrete, and has no influence on the later strength development; comparative example 5 had substantially no effect on the early compressive strength of the concrete, but had a greater effect on the later compressive strength. Therefore, the comprehensive performance of the examples 1 to 8 of the invention is obviously better than that of the comparative examples 1 to 5.
TABLE 3 Effect of different groups on the Properties of C50 concrete
As can be seen from Table 3, compared with comparative example 1, the yellowing paste phenomenon caused by the fact that the content of the glue material in the C50 concrete is increased due to the fact that the content of the glue material is high can be obviously improved in example 1 of the invention, the tackifying type viscosity regulator has a remarkable tackifying and water-retaining effect, has small influence on the workability of the concrete over time, and can improve the compressive strength of the C50 concrete 3d, 7d and 28d by 29.34%, 10.64% and 15.69% respectively, so that the concrete is beneficial to the development of the later compressive strength.
In conclusion, the viscosity-increasing type viscosity regulator disclosed by the invention is very good in compatibility with the polycarboxylic acid water reducing agent, can effectively regulate the cohesiveness of concrete, solves the problems of segregation and bleeding of the concrete, and does not influence the slump retaining performance and the setting time of the concrete and is beneficial to the development of the compressive strength of the concrete. Meanwhile, the viscosity-increasing regulator can reduce the sensitivity of the polycarboxylate water reducing agent to concrete raw materials, water consumption and mixing amount, and the concrete admixture prepared by the viscosity-increasing regulator can obtain a wider working window, thereby reducing the working difficulty of production and quality control personnel of concrete enterprises. The viscosity regulator for thickening concrete has good application prospect in the technologies of low-grade concrete, self-compacting concrete, high-fluidity concrete, sprayed concrete and the like.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The preparation method of the concrete tackifying type viscosity regulator is characterized by comprising the following steps:
(1) mixing the following components in a mass ratio of 1-20: 15-30: 10-25: dissolving 1-5 parts of modified polyether monomer, unsaturated amide monomer, unsaturated carboxylic acid monomer and cross-linking agent in deionized water with the mass of 400-600% of the total mass of the monomers to obtain a monomer mixed solution;
(2) dissolving unsaturated amide monomers and unsaturated carboxylic acid monomers with the same mass as the monomers in the monomer mixed solution into deionized water, and marking as solution A;
(3) in N2And slowly dripping an initiator solution with the mass percentage concentration of 0.1-1% and the solution A into the monomer mixed solution within 1-3 h at 40-60 ℃, keeping the temperature at 60-90 ℃, continuously stirring for reacting for 2-6 h, adding alkali liquor to adjust the pH value to 6-8, and supplementing water for dilution to obtain a tackifying type viscosity regulator with the solid content of 3-12%;
the general formula of the modified polyether monomer is R1O(EO)m(PO)nOR2Wherein R is1Is an unsaturated olefin group of 3 to 9 carbon atoms, R2H or an alkyl group having 1 to 12 carbon atoms, n is an integer of 5 to 100, and m is an integer of 0 to 100; the general formula of the unsaturated amide monomer is as follows: r3R4C＝CR5CONR6R7Wherein R is3、R4、R5Each represents H or CH3，R6、R7Each represents H, CH3、CrH2r+1、CH(CH3)2、C(CH3)2CH2SO3M or (CH)2)xNR8R9R is an integer of 1 to 5, M is H or a monovalent metal ion, x is an integer of 1 to 5, R8、R9Each represents H, CH3Or CrH2r+1(ii) a The unsaturated carboxylic acid monomer has a general formula: r10R11C＝CR12COOM，R10、R11、R12Each represents H, CH3Or COOM.
2. The method for preparing the viscosity modifier for concrete tackifying of claim 1, wherein the modified polyether monomer is one or more of allyl alcohol polyoxyethylene polyoxypropylene ether, prenol polyoxyethylene ether, 4-hydroxybutyl vinyl polyoxyethylene ether, terminal alkylene double-tail polyoxyethylene ether and allyl polyoxyalkyl epoxy ether, and the molecular weight is 300-10000; the unsaturated amide monomer is one or more of acrylamide, methacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-isopropylacrylamide, N-isopropyl methacrylamide, 2-acrylamido-2-methylpropanesulfonate, dimethylaminopropyl acrylamide and dimethylaminopropyl methacrylamide; the unsaturated carboxylic acid monomer is one or more of acrylic acid, methacrylic acid, maleic anhydride, fumaric acid and 2-methylenesuccinic acid.
3. The method of claim 1, wherein the cross-linking agent is polyethylene glycol diallyl ether or polyoxyalkylene diallyl ether.
4. The preparation method of the concrete tackifying type viscosity regulator according to claim 1, wherein the initiator is a persulfate initiator or a water-soluble azo initiator, and the mass of the initiator is 0.5-2.5% of the total mass of the modified polyether monomer, the unsaturated amide monomer and the unsaturated carboxylic acid monomer in the step (1) and the step (2).
5. The method for preparing a viscosity modifier for increasing viscosity of concrete according to claim 4, wherein the persulfate initiator is selected from one of sodium persulfate, ammonium persulfate and potassium persulfate; the water-soluble azo initiator is selected from one of azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid and azobisisopropylimidazoline.
6. The method for preparing the viscosity modifier for the thickening of concrete according to claim 1, wherein the alkali solution is one of sodium hydroxide, potassium hydroxide and calcium hydroxide solution with the concentration of 32% by mass.
7. A concrete viscosity-increasing type viscosity modifier, characterized by being prepared by the preparation method of the concrete viscosity-increasing type viscosity modifier of any one of claims 1 to 6, wherein the weight average molecular weight of the prepared viscosity modifier is 100 to 300 ten thousand.
8. The viscosity modifier for increasing viscosity of concrete according to claim 7, wherein the weight average molecular weight of the viscosity modifier is 150 to 250 ten thousand.
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