CN113637123B - Hyperbranched concrete tackifier and preparation method and application thereof - Google Patents

Hyperbranched concrete tackifier and preparation method and application thereof Download PDF

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CN113637123B
CN113637123B CN202110962118.2A CN202110962118A CN113637123B CN 113637123 B CN113637123 B CN 113637123B CN 202110962118 A CN202110962118 A CN 202110962118A CN 113637123 B CN113637123 B CN 113637123B
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concrete
unsaturated
monomer
hyperbranched
tackifier
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CN113637123A (en
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李正平
汪源
汪苏平
李祥
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Wuhan Ujoin Building Material Technology Co ltd
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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
    • 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
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses a hyperbranched concrete tackifier and a preparation method and application thereof, and belongs to the technical field of building material concrete additives, wherein the hyperbranched concrete tackifier is prepared from hyperbranched polymer A, unsaturated succinimide monoester monomer, unsaturated maleic acid diester monomer and unsaturated sulfonic acid monomer through free radical polymerization; the hyperbranched polymer A is prepared from unsaturated ternary oxygen-containing heterocyclic monomers through ring-opening polymerization, and the unsaturated ternary oxygen-containing heterocyclic monomers are allyl glycidyl ether or methallyl glycidyl ether. The tackifier can effectively improve workability of fresh concrete, solve problems of segregation, bleeding and sedimentation of concrete, has obvious water retention and tackifying effects, has good slurry wrapping effect, and has no serious retarding or air entraining phenomenon.

Description

Hyperbranched concrete tackifier and preparation method and application thereof
Technical Field
The invention belongs to the technical field of building material concrete additives, and particularly relates to a hyperbranched concrete tackifier, a preparation method and application thereof.
Background
Along with the continuous development of building structural design and super high-rise buildings, building construction also brings higher requirements on concrete, the continuous complicating of concrete members and the continuous increasing of the density of reinforcing steel bars in the building members often require that the concrete has large fluidity, but if the mixture is too thin, the concrete is easy to generate layering segregation phenomenon, the problems of pump blockage, leaking casting of construction parts, unqualified strength of a solidified body and the like are easily caused, and the quality and the service life of concrete engineering are influenced. In addition, the exploitation of natural sand is limited, the usage amount of machine-made sand is increased, but the quality of the machine-made sand is poor, the problems of poor grading, high mud content and the like exist, and the cohesiveness of concrete is poor. Therefore, an effective method is required to make fresh concrete have both good fluidity and segregation resistance. The mixing of the rheological modifier in the concrete system is a safer and more effective method for improving the viscosity of the concrete and reducing bleeding and segregation phenomena, and most of the current rheological modifiers of the concrete are natural polymers such as rice hull ash, wen Lunjiao, cellulose ether, cellulose derivatives and the like; however, the compatibility between the substances and the polycarboxylate water reducer is problematic, in addition, the rheology modifier is sensitive to the mixing amount, has good rheology modification effect when the mixing amount is low, but slightly excessive mixing can obviously increase the viscosity of the concrete, so that the fluidity of the freshly mixed concrete is reduced, the water demand is increased, and the strength of the concrete is affected;
A good concrete rheology modifier should have the following properties: firstly, the viscosity of the fresh concrete can be obviously increased when the mixing amount is low, so that the sedimentation of the fresh concrete is reduced in a plastic state, and bleeding is avoided; secondly, the additive has good compatibility with other additives; and finally, the influence on the fluidity of the concrete is small, and the concrete has certain water-retaining and tackifying capability in time. The artificially synthesized polymer concrete rheology regulator has the advantages of diversity of raw materials, rich synthesis mode, strong designability of molecular structures and the like, and becomes an important research direction of many scientific researchers. At present, part of the existing rheology modifiers can solve the technical problem of poor compatibility of the traditional rheology modifiers and the polycarboxylate water reducer, for example, chinese patent CN 109369859B discloses a concrete tackifying type viscosity modifier and a preparation method thereof, and the method comprises the following steps: dissolving a modified polyether monomer, an unsaturated amide monomer, an unsaturated carboxylic acid monomer and a cross-linking agent in deionized water to obtain a monomer mixed solution: the unsaturated amide monomer and the unsaturated carboxylic acid monomer are dissolved in deionized water and are marked as A solution: slowly dripping the initiator solution and the solution A into the monomer mixed solution at the temperature of between 40 and 60 ℃ under the conditions of N 2 and the temperature of between 40 and 90 ℃, continuously stirring the mixture for reaction, adjusting the PH value, supplementing water and diluting the mixture to obtain the viscosity regulator. The viscosity regulator has good compatibility with the polycarboxylate water reducer, can effectively regulate the cohesiveness of concrete, solves the problem of concrete segregation and bleeding, and does not influence the concrete's maintenance performance and setting time. However, the viscosity modifier adopts modified polyether monomer as raw material, the modified polyether is linear polymer, the molecular chains are easy to bend, and the molecular chains are easy to wind, so that the capability of the viscosity modifier molecules for binding water molecules, bridging cement and sand particles is weakened, and the tackifying effect of the viscosity modifier is further reduced.
Therefore, research on a tackifier capable of avoiding intermolecular entanglement of linear polymers can effectively solve the problems of segregation, bleeding and the like of fresh concrete, and has important significance in having good compatibility with a polycarboxylate water reducer.
Disclosure of Invention
Aiming at the defects of the prior art, one of the purposes of the invention is to provide a hyperbranched type concrete tackifier, which is prepared from hyperbranched polymer, unsaturated succinimide monoester monomer, unsaturated maleic acid diester monomer and unsaturated sulfonic acid monomer through free radical polymerization. The problem of intermolecular winding existing in the use of linear polyether can be avoided, the cohesiveness of concrete can be effectively regulated, and the problems of bleeding, segregation and the like of fresh concrete are solved.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
A hyperbranched concrete tackifier is prepared from hyperbranched polymer A, unsaturated succinimide monoester monomer, unsaturated maleic acid diester monomer and unsaturated sulfonic acid monomer through free radical polymerization;
the hyperbranched polymer A is prepared from unsaturated ternary oxygen-containing heterocyclic monomers through ring-opening polymerization, and the unsaturated ternary oxygen-containing heterocyclic monomers are allyl glycidyl ether or methallyl glycidyl ether.
The unsaturated ternary oxygen-containing heterocyclic monomer forms a hyperbranched polymer A with a plurality of double bonds at the tail end through ring opening multi-branching polymerization, and compared with a linear polymer, the tackifier adopts the hyperbranched polymer A as a raw material, has small fluid force turning radius and less winding among molecular chains, can effectively generate a bridging effect between cement particles and sand stones by the molecular chains, increases cohesiveness of concrete, and can effectively solve the problems of bleeding, segregation and the like of fresh concrete.
Preferably, the hyperbranched polymer a comprises a repeating unit represented by the following formula ①, or comprises a repeating unit represented by the following formula ②:
in the general formula ①, R is allyl; in the general formula ②, R' is methallyl.
Preferably, the weight average molecular weight of the hyperbranched polymer A is 3000 to 4000.
Preferably, the mass ratio of the hyperbranched polymer A to the unsaturated succinimide monoester monomer to the unsaturated maleic acid diester monomer to the unsaturated sulfonic acid monomer is as follows: 1 (0.15-0.3), 0.1-0.25 and 0.4-0.5.
Preferably, the unsaturated succinimide monoester monomer is N-hydroxysuccinimide acrylate or N-hydroxysuccinimide methacrylate.
Preferably, the unsaturated maleic acid diester monomer is one of polyethylene glycol maleic acid diester, diethylene glycol maleic acid diester and triethylene glycol maleic acid diester.
Preferably, the unsaturated sulfonic acid monomer is 2-acrylamido-2-methylpropanesulfonic acid or methacrylamidopropyl-N, N-dimethylpropanesulfonic acid.
Preferably, the weight average molecular weight of the tackifier is 10 to 100 tens of thousands.
The tackifier of the invention is obtained by free radical chain addition polymerization of monomers containing carbon-carbon double bonds, wherein-C-C-bonds are taken as the main chain of polymer molecules, and functional groups on the monomers are generally on side chains of the polymer. The polymer product has larger molecular weight, can generate a bridging effect among cement particles, sand grains and stones, and increases the cohesiveness of the concrete, namely the viscosity of the concrete. As the amide group and the ester group on the side chain can generate hydrolysis reaction in the alkaline environment of cement hydration, alcohols with water retention function are generated, and the water retention and viscosity increasing capacity of fresh concrete with time can be improved.
The inventor finds that most of the tackifier is a linear polymer at present, and the linear polymer is easy to bend in a concrete high-alkaline environment, so that tackifier molecules lose the capability of binding water molecules and bridging cement and sand particles; the unsaturated ternary oxygen-containing heterocyclic monomer can form a highly branched hydrophilic product with a plurality of double bonds at the tail end through ring opening polymerization, and C=C at the tail end can be connected with a required functional group through free radical polymerization. Compared with linear polymer, the fluid force turning radius is small, the entanglement among molecular chains is less, cement and sand particles can be effectively bridged, and the viscosity of concrete is increased.
The inventor also found that the unsaturated succinimide monoester monomer is monoester with C=C, and can generate carboxylic acid with strong adsorption capacity and alcohol with water retention performance through hydrolysis in a concrete alkaline environment, so that the tackifier has the viscosity increasing and water retention performance with time. The unsaturated maleic acid diester monomer is diester with C=C, has two or more carbon-carbon double bonds, can play a role in light crosslinking in a system, enables the polymer to form a space three-dimensional structure, combines carboxyl groups, amido groups and other groups with strong adsorptivity on the polymer, can enhance the interaction between the polymer and cement and sand particles, and endows the tackifier with better tackifying performance.
The inventors have also found that the presence of the water-soluble sulfonic acid group of the unsaturated sulfonic acid monomer, which can form hydrogen bonds with water molecules, and the presence of two s=o bonds enhances the ability of S to attract electrons from water molecules, i.e. to readily form stable hydrogen bonds with water molecules. The charge density is high, and the hydration capacity is high; in the negative ion-SO 3 -, two pi bonds and 2 oxygen atoms share a negative charge, SO that the-SO 3 -is stable and insensitive to attack of external cations, and the tackifier has good salt resistance. Three pairs of arc pair electrons on the carbonyl oxygen (c=o) in the monomer are easily adsorbed on the surface of solid particles in the cement liquid phase, providing reaction sites for forming a spatial network structure in the cement liquid phase to some extent. Meanwhile, the unsaturated sulfonic acid monomer has huge side groups, so that the rigidity of a macromolecular chain is enhanced, and the temperature resistance, salt resistance, stability and shearing resistance of the copolymer are improved; will give the tackifier good overall properties.
In general, the concrete tackifier is a cross-linked polymer, and compared with the traditional linear polymer, the concrete tackifier has the advantages of improving the tackifying and water retention performances, and simultaneously having smaller influence on the fluidity of the concrete, so that the concrete has certain viscosity and better fluidity. And the composition shows higher saturated mixing amount and more excellent dispersion performance and temperature and salt resistance in a cement/concrete system.
The invention further provides a preparation method of the hyperbranched concrete tackifier, which comprises the following steps of:
S1, dissolving 50% -70% of unsaturated ternary oxygen-containing heterocyclic monomers in a solvent, wherein the mass ratio of the monomers to the solvent is (1-2): 3, a step of; then adding an initiator to form a mixed solution, slowly dripping the rest 30-50% of unsaturated ternary oxygen-containing heterocyclic monomers into the mixed solution at the temperature of 110-120 ℃, carrying out heat preservation reaction for 3-5 h, and purifying to obtain a hyperbranched polymer A;
S2, dissolving the hyperbranched polymer A in deionized water, wherein the mass ratio of the hyperbranched polymer A to the deionized water is 1: (3-5), adding unsaturated succinimide monoester monomer, unsaturated maleic acid diester monomer and unsaturated sulfonic acid monomer into the solution, stirring uniformly, and regulating the pH value to 7-8 by using liquid alkali; slowly dripping azo initiator into the monomer mixed solution at the temperature of between 40 and 60 ℃ under the conditions of N 2, and reacting for 4 to 6 hours at the temperature of between 50 and 60 ℃ to obtain the hyperbranched concrete tackifier.
Preferably, in step S1, the mass of the initiator is 1.0-1.5% of the total mass of the unsaturated ternary oxygen-containing heterocyclic monomer, and excessive initiator consumption can cause too small branching degree of the polymerization product and adversely affect the product performance. Too little initiator can reduce the reaction rate, even stop the polymerization, the number of polymer molecules is small, and the individual molecular branching degree can be too great, affecting the adhesion-promoting properties.
Preferably, in the step S1, the initiator for the ring-opening polymerization of the unsaturated ternary oxygen-containing heterocyclic monomer is trimethylolpropane, the reaction temperature is 110-120 ℃, and the half life of the initiator can be changed when the temperature is too high or too low, so that the polymerization rate and the polymerization degree are influenced, and the comprehensive performance of a polymerization product is changed.
Preferably, in the step S2, the mass of the azo initiator is 0.5-2.0% of the sum of the mass of the hyperbranched polymer a, the mass of the unsaturated succinimide monoester monomer, the mass of the unsaturated maleic acid diester monomer and the mass of the unsaturated sulfonic acid monomer, and the amount of the initiator is insufficient, so that the generated free radicals are less, the reaction rate is slow, and even the polymerization is stopped. Excessive initiator consumption can generate excessive free radicals, so that the reaction rate is increased, the probability of double radical termination is increased, and the molecular weight of the product is reduced.
Preferably, in the step S2, firstly, azo initiator is dissolved in deionized water, the mass percentage concentration of the initiator aqueous solution is regulated to be 0.5-1.0%, and the time for dripping the azo initiator aqueous solution into the monomer mixed solution is controlled to be 1-2.5 hours.
The weight average molecular weight of the tackifier is controlled to be 10-100 ten thousand by reasonably controlling the components and the proportion of the synthetic raw materials and the synthesis conditions, and the tackifier with the molecular weight has the following beneficial effects.
It is still another object of the present invention to provide the use of the tackifier in low and medium grade strength concrete, wherein the tackifier is incorporated in an amount of 0.01 to 0.1% of the concrete binder.
Compared with the prior art, the invention has the following advantages:
(1) The tackifier can effectively improve workability of fresh concrete, solve problems of segregation, bleeding and sedimentation of concrete, has good slurry wrapping effect, obvious water retention and tackifying effects, and does not have serious retarding or air entraining phenomena.
(2) The tackifier is a cross-linked polymer, and compared with the traditional linear polymer, the tackifier has the advantages of improving the water retention and tackifying performance and simultaneously having small loss of fluidity to concrete; the method can effectively solve the contradiction between fluidity and segregation resistance and bleeding resistance of the fresh concrete, and has good fluidity while improving the viscosity of the concrete.
(3) The tackifier is insensitive to the mixing amount, and the optimal dosage is 0.01-0.1% of the dosage of the concrete cementing material.
(4) The tackifier disclosed by the invention is simple in synthesis method, good in compatibility with the polycarboxylate water reducer and free from precipitation.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by one of ordinary skill in the art without undue burden on the person of ordinary skill in the art based on embodiments of the present invention, are within the scope of the present invention.
Example 1
The hyperbranched concrete tackifier of the embodiment is prepared from hyperbranched polymer A, N-hydroxysuccinimide acrylate, polyethylene glycol maleic acid diester and 2-propionamido-2-methylpropanesulfonic acid through free radical polymerization; the hyperbranched polymer A is prepared from propenyl glycidyl ether through ring-opening polymerization reaction.
The preparation method of the concrete tackifier specifically comprises the following steps:
s1, adding 150ml of DMAC solution and 68.48g of propenyl glycidyl ether into a four-neck flask with an electric stirrer, a dripping device, a thermometer and nitrogen circulation, setting the temperature of an oil bath at 60 ℃, and uniformly stirring; 1.14g of trimethylolpropane is then added, and after complete dissolution 2.85g of potassium carbonate is added; the temperature was raised to 120 ℃, then 45.66g of propenyl glycidyl ether was slowly added dropwise to the four-necked flask using a peristaltic pump; after the completion of the dropwise addition, stirring was continued for 3 hours. The reaction product was dissolved with anhydrous methanol, then neutralized by cation exchange resin, and the solution was transferred to 10-fold volume of acetone for precipitation, and the crude product was dissolved with methanol, which was removed using a rotary evaporator at 45 ℃ to obtain hyperbranched polymer a.
S2, adding 51.75g of hyperbranched polymer A and 160ml of deionized water into a four-neck flask with an electric stirrer, a dripping device, a thermometer and nitrogen circulation, stirring and dissolving, adding 14.51g N-hydroxysuccinimide acrylate, 12.47g of polyethylene glycol maleic acid diester and 24.75g of 2-propionamido-2-methylpropanesulfonic acid into the solution, stirring uniformly, and regulating the pH value to 7-8 by using 14.8g of sodium hydroxide solution with the mass concentration of 32%; purging the inside of the four-necked flask by using nitrogen, and raising the temperature of the water bath to 50 ℃ while stirring; 0.72g of azodiisobutylamidine hydrochloride was dissolved in deionized water to prepare a 0.5% by mass solution, which was added dropwise to a four-necked flask over 2 hours. After the completion of the dropwise addition, the temperature was raised to 60℃and the reaction was continued for 4 hours, and aged at 40℃for 1 hour. Finally 666ml of water are added to obtain a polymerization product with a solids content of 10%.
Example 2
The hyperbranched concrete tackifier of the embodiment is prepared from hyperbranched polymer A, N-hydroxysuccinimide methacrylic acid, diethylene glycol maleic acid diester and methacrylamidopropyl-N, N dimethyl propane sulfonic acid through free radical polymerization; the hyperbranched polymer A is prepared from propenyl glycidyl ether through ring-opening polymerization reaction.
The preparation method of the concrete tackifier specifically comprises the following steps:
S1, adding 150ml of DMAC solution and 57.07g of propenyl glycidyl ether into a four-neck flask with an electric stirrer, a dripping device, a thermometer and nitrogen circulation, setting the temperature of an oil bath at 60 ℃, and uniformly stirring; 1.71g of trimethylolpropane is then added, and after complete dissolution 2.85g of potassium carbonate is added; the temperature was raised to 120 ℃, then 57.07g of propenyl glycidyl ether was slowly added dropwise to the four-necked flask using a peristaltic pump; after the completion of the dropwise addition, stirring was continued for 3 hours. The reaction product was dissolved with anhydrous methanol, then neutralized by cation exchange resin, and the solution was transferred to 10-fold volume of acetone for precipitation, and the crude product was dissolved with methanol, which was removed using a rotary evaporator at 45 ℃ to obtain hyperbranched polymer a.
S2, adding 51.75g of hyperbranched polymer A and 160ml of deionized water into a four-neck flask with an electric stirrer, a dripping device, a thermometer and nitrogen circulation, stirring for dissolution, adding 10.07g N-hydroxysuccinimide methacrylate, 6.31g of diethylene glycol maleate diester and 24.75g of methacrylamidopropyl-N, N-dimethylpropanesulfonic acid into the solution, stirring uniformly, and adjusting the pH value to 7-8 by using 14.8g of sodium hydroxide solution with the mass concentration of 32%; purging the inside of the four-necked flask by using nitrogen, and raising the temperature of the water bath to 50 ℃ while stirring; 0.56g of azodiisobutylamidine hydrochloride was dissolved in deionized water to prepare a 0.5% by mass solution, which was added dropwise to a four-necked flask over 2 hours. After the completion of the dropwise addition, the temperature was raised to 50℃and the reaction was continued for 4 hours, and aged at 40℃for 1 hour. Finally 601ml of water were fed in to give a polymerization product with a solids content of 10%.
Example 3
The hyperbranched concrete tackifier of the embodiment is prepared from hyperbranched polymer A, N-hydroxysuccinimide methacrylic acid, diethylene glycol maleic acid diester and methacrylamidopropyl-N, N dimethyl propane sulfonic acid through free radical polymerization; the hyperbranched polymer A is prepared from propenyl glycidyl ether through ring-opening polymerization reaction.
The preparation method of the concrete tackifier specifically comprises the following steps:
S1, adding 150ml of DMAC solution and 89.69g of methylpropenyl glycidyl ether into a four-neck flask with an electric stirrer, a dripping device, a thermometer and nitrogen circulation, setting the temperature of an oil bath at 60 ℃, and uniformly stirring; 1.71g of trimethylolpropane is then added, and after complete dissolution 2.85g of potassium carbonate is added; the temperature was raised to 120 ℃, then 38.44g of methylpropenyl glycidyl ether was slowly added dropwise to the four-necked flask using a peristaltic pump; after the completion of the dropwise addition, stirring was continued for 3 hours. The reaction product was dissolved with anhydrous methanol, then neutralized by cation exchange resin, and the solution was transferred to 10-fold volume of acetone for precipitation, and the crude product was dissolved with methanol, which was removed using a rotary evaporator at 45 ℃ to obtain hyperbranched polymer a.
S2, adding 35.2g of hyperbranched polymer A and 160ml of deionized water into a four-neck flask with an electric stirrer, a dripping device, a thermometer and nitrogen circulation, stirring for dissolution, adding 10.55g N-hydroxysuccinimide methacrylate, 3.52g of diethylene glycol maleic acid diester and 17.59g of methacrylamidopropyl-N, N-dimethylpropanesulfonic acid into the solution, stirring uniformly, and regulating the pH value to 7-8 by using 10.56g of sodium hydroxide solution with the mass concentration of 32%; purging the inside of the four-necked flask by using nitrogen, and raising the temperature of the water bath to 50 ℃ while stirring; 0.48g of azodiisobutylamidine hydrochloride was dissolved in deionized water to prepare a 0.5% by mass solution, which was added dropwise to a four-necked flask over 2 hours. After the completion of the dropwise addition, the temperature was raised to 50℃and the reaction was continued for 4 hours, and aged at 40℃for 1 hour. Finally 373ml of water was added to give a polymerization product with a solids content of 10%.
Comparative example 1
The concrete tackifier of the comparative example is prepared from methylallyl polyoxyethylene ether, N-hydroxysuccinimide methacrylic acid, diethylene glycol maleic acid diester and methacrylamidopropyl-N, N-dimethylpropanesulfonic acid through free radical polymerization;
The preparation method of the concrete tackifier specifically comprises the following steps:
51.75g of methyl allyl polyoxyethylene ether and 160ml of deionized water are added into a four-neck flask with an electric stirrer, a dripping device, a thermometer and nitrogen circulation, stirred and dissolved, 14.51g N-hydroxysuccinimide acrylate, 12.47g of polyethylene glycol maleic acid diester and 24.75g of 2-propionamido-2-methylpropanesulfonic acid are added into the solution, stirred evenly, the interior of the four-neck flask is purged with nitrogen, and the water bath temperature is raised to 50 ℃ while stirring; 0.72g of azodiisobutylamidine hydrochloride was dissolved in deionized water to prepare a 0.5% by mass solution, which was added dropwise to a four-necked flask over 2 hours. After the completion of the dropwise addition, the temperature was raised to 50℃and the reaction was continued for 4 hours, followed by aging at 40℃for 1 hour. Then adjusting the pH value to 7-8 by using 14.8g of sodium hydroxide solution with the mass concentration of 32%; finally 666ml of water are added to obtain a polymerization product with a solids content of 10%.
Comparative example 2
The concrete tackifier of this comparative example was a commercially available hydroxypropyl methylcellulose ether, available from Hubei Xingzhou scientific Co., ltd., model 172, 10 ten thousand viscosity.
Comparative example 3
The concrete tackifier of this comparative example was commercially available diutan, available from Jiangsu-Violet, biotechnology Inc., industrial grade.
Test examples
① The concrete tackifiers of examples 1 to 3 and comparative examples 1 to 3 were applied to a mortar system, and the mortar system was tested for bleeding over time. The test method is as follows: 450g of cement, 1350g of standard sand, 180g of water, 1.2g of water reducer and 0.23g of tackifier with the solid content of 10% are mixed, stirred uniformly and then placed in a square container; recording the total mass M1 of the gum sand and the container, standing, removing the water secreted from the surface by using water absorbing paper at 15min and 30min, measuring the total mass M2 and M3 of the gum sand and the container respectively, calculating to obtain the bleeding amount at 15min and 30min, and specifically testing the bleeding amount, wherein the specific test results are shown in Table 1.
TABLE 1 bleeding amount (g) of the mortar system
Group of Bleeding amount for 15min Bleeding amount for 30min
Blank group 6 8
Example 1 0 0
Example 2 0 0
Example 3 0 1
Comparative example 1 2 3
Comparative example 2 2 5
Comparative example 3 1 3
As can be seen from the data in table 1, the tackifiers of examples 1 to 3 effectively improved bleeding problems of the gum sand and had a remarkable water retention effect as compared with the blank and comparative examples 1 to 3.
② Concrete tackifiers of examples 1 to 3 and comparative examples 1 to 3 were applied to C30 concrete, and the mixing ratios of the concrete are shown in table 2, and performance test of the concrete was performed.
Table 2 shows the proportions of C30 concrete (kg/m 3)
Cement and its preparation method Fly ash Sand and sand Stone Water and its preparation method Water reducing agent
265 80 870 1000 170 5.6
Wherein the cement is Huaxin P.O42.5 grade cement; the fly ash is class II fly ash; the fineness modulus of the sand is 2.8, and the mud content is less than 2%; the stone is 5-25 mm continuous graded broken stone, and the water reducing agent is Ujion-PC polycarboxylate water reducing agent produced by Wu Hanyuan brocade building materials Co.
The working properties of the fresh concrete of the blank group, examples 1 to 3 and comparative examples 1 to 3 were examined according to the specifications in GB/T50080-2016 Standard for Performance test methods for common concrete mixtures; detecting the mechanical properties of the concrete according to the specification in GB/T50081-2002 general concrete mechanical property test method Standard; testing the emptying time of the concrete mixture in the inverted slump cone according to the test method of annex A of JGJ/T281-2012 technical regulations for high-strength concrete application; the test results are shown in Table 3.
TABLE 3 concrete Performance test results
Wherein the mixing amount of the tackifier is the mass percentage of the cementing material; the more ". V" indicates the degree of bleeding, the more ". V" indicates the more serious the bleeding.
From the test results in Table 3, it can be seen that: compared with blank groups and comparative examples, the tackifier of the embodiments 1 to 3 of the invention can obviously improve the bleeding segregation problem of concrete, has obvious water retention and tackifying effects, has no obvious air entraining phenomenon, has no negative effect on the compressive strength of concrete, and can effectively improve the workability of freshly mixed concrete; the comparative examples show that the adhesion promoters of comparative examples 1 to 3 significantly reduce the expansion and slump of concrete and affect the workability of the concrete. Comparative example 1 has a lower evacuation time than the examples, indicating that the adhesion-promoting effect is poorer than the examples, and the slump and expansion are smaller than the examples; the tackifying effect of comparative example 2 was also poorer than that of the examples, and bleeding phenomenon occurred; the tackifying effect of comparative example 3 was better, but the slump and expansion loss was large. In conclusion, the tackifier of the embodiments 1 to 3 has better compatibility with other additives, can effectively solve the problems of poor wrapping property, segregation, bleeding and the like of the low-strength grade fresh concrete, can effectively improve the viscosity of the concrete, can effectively improve the workability of the concrete, and does not influence the working performance of the concrete; in addition, the tackifier of the invention has low sensitivity to the doping amount, does not cause the rapid increase of viscosity after the doping amount is increased, and does not reduce the slump and the expansion degree of concrete.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (9)

1. The hyperbranched concrete tackifier is characterized by being prepared from a polymer A, an unsaturated succinimide monoester monomer, an unsaturated maleic acid diester monomer and an unsaturated sulfonic acid monomer through a free radical polymerization reaction;
The polymer A is prepared from unsaturated ternary oxygen-containing heterocyclic monomers through ring-opening polymerization, wherein the unsaturated ternary oxygen-containing heterocyclic monomers are allyl glycidyl ether or methallyl glycidyl ether;
The polymer a comprises a repeating unit represented by the following general formula ① or a repeating unit represented by the following general formula ②:
in the general formula ①, R is allyl; in the general formula ②, R' is methallyl.
2. The hyperbranched type concrete tackifier according to claim 1, wherein the mass ratio of the polymer A, the unsaturated succinimide monoester monomer, the unsaturated maleic acid diester monomer and the unsaturated sulfonic acid monomer is 1 (0.15-0.3): 0.1-0.25): 0.4-0.5.
3. The hyperbranched concrete adhesion promoter of claim 1, wherein the unsaturated succinimide monoester monomer is N-hydroxysuccinimide acrylate or N-hydroxysuccinimide methacrylate.
4. The hyperbranched type concrete adhesion promoter according to claim 1, wherein the unsaturated maleic acid diester monomer is one of polyethylene glycol maleic acid diester, diethylene glycol maleic acid diester, triethylene glycol maleic acid diester.
5. The hyperbranched type concrete adhesion promoter according to claim 1, wherein the unsaturated sulfonic acid monomer is 2-acrylamido-2-methylpropanesulfonic acid or methacrylamidopropyl-N, N-dimethylpropanesulfonic acid.
6. The hyperbranched concrete adhesion promoter of claim 1, wherein the adhesion promoter has a weight average molecular weight ranging from 10 to 100 tens of thousands.
7. The method for preparing the hyperbranched concrete tackifier according to any one of claims 1 to 6, comprising the following steps:
S1, dissolving a part of unsaturated ternary oxygen-containing heterocyclic monomers in a solvent, then adding an initiator to form a mixed solution, slowly dripping the other part of unsaturated ternary oxygen-containing heterocyclic monomers into the mixed solution at 110-120 ℃, carrying out heat preservation reaction for 3-5 h, and purifying to obtain a polymer A;
S2, dissolving the polymer A, the unsaturated succinimide monoester monomer, the unsaturated maleic acid diester monomer and the unsaturated sulfonic acid monomer in deionized water to form a monomer mixed solution, and regulating the pH value to 7-8; slowly dripping azo initiator into the monomer mixed solution at the temperature of between 40 and 60 ℃ under the conditions of N 2, and reacting for 4 to 6 hours at the temperature of between 50 and 60 ℃ to obtain the hyperbranched concrete tackifier.
8. The method for preparing a hyperbranched concrete thickener according to claim 7, wherein in the step S1, the mass of the initiator is 1.0 to 1.5% of the total mass of the unsaturated ternary oxygen-containing heterocyclic monomer.
9. The hyperbranched concrete tackifier according to any one of claims 1 to 6 or the application of the tackifier prepared by the preparation method of claim 7 or 8 in medium-low grade strength concrete, wherein the mixing amount of the tackifier is 0.01-0.1% of the concrete cementing material.
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