CN109678403B - Application of viscosity-reducing polycarboxylic acid water reducer in preparation of C100 concrete - Google Patents

Application of viscosity-reducing polycarboxylic acid water reducer in preparation of C100 concrete Download PDF

Info

Publication number
CN109678403B
CN109678403B CN201811605781.1A CN201811605781A CN109678403B CN 109678403 B CN109678403 B CN 109678403B CN 201811605781 A CN201811605781 A CN 201811605781A CN 109678403 B CN109678403 B CN 109678403B
Authority
CN
China
Prior art keywords
integer
viscosity
parts
reducing
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811605781.1A
Other languages
Chinese (zh)
Other versions
CN109678403A (en
Inventor
张小富
白淑英
赵利华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangxi Redwall New Material Co ltd
Original Assignee
Guangxi Redwall New Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangxi Redwall New Material Co ltd filed Critical Guangxi Redwall New Material Co ltd
Priority to CN201811605781.1A priority Critical patent/CN109678403B/en
Publication of CN109678403A publication Critical patent/CN109678403A/en
Application granted granted Critical
Publication of CN109678403B publication Critical patent/CN109678403B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • 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
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
    • 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
    • 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
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers

Landscapes

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

Abstract

The invention provides concrete, which contains the synthesized viscosity-reducing polycarboxylic acid water reducing agent, and also provides application of the viscosity-reducing polycarboxylic acid water reducing agent shown in the formula (I) in preparation of C100 concrete. Compared with the prior art, the C100 concrete prepared by using the viscosity-reducing polycarboxylate superplasticizer has the advantages of no segregation, no bleeding, no bottom scraping, good slump retentivity with time, good flowing property, good workability, soft material, no bottom scraping and proper viscosity. The strength of the concrete is high.

Description

Application of viscosity-reducing polycarboxylic acid water reducer in preparation of C100 concrete
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to application of a viscosity-reducing polycarboxylic acid water reducer in preparation of C100 concrete.
Background
In recent years, with the increase of the infrastructure of China, high-grade concrete gradually enters the building material market by virtue of the characteristics of high strength, good integrity and small self weight, and is particularly used in bridge engineering in large quantities. However, due to the adoption of a large amount of gel materials and a low water-gel ratio, the high-grade concrete has the problems of high viscosity and low flowing speed, so that the problems of concrete stirring, transportation, pumping and construction are caused, and the popularization and application of the high-strength and ultrahigh-strength concrete are limited to a great extent.
For engineering technicians, the problem of high viscosity of high-strength and ultrahigh-strength concrete is a long-standing technical problem. At present, the viscosity reduction method of high-strength concrete mainly adopts the steps of increasing the mixing amount of a water reducing agent and optimizing superfine powder to optimize the particle grading. The problems of bleeding, bottom scraping and the like of fresh concrete can occur when the mixing amount of the water reducing agent is increased and the viscosity of the concrete is reduced, so that certain difficulty is caused to construction, the concrete is excessively delayed to be coagulated, the formwork removal period is prolonged, and the production cost of the concrete is increased. Although many researches are carried out on the optimization of particle gradation by the optimized ultrafine powder to reduce the viscosity of concrete, the method has certain limitations, and the actual problem cannot be fundamentally solved by optimizing the particle gradation mainly depending on the strong adsorption and dispersion effects of the high-efficiency water reducing agent on the flowability of fresh concrete.
The polycarboxylic acid water reducing agent serving as a third-generation product of the concrete water reducing agent has the advantages of low mixing amount, high water reducing rate, good slump retaining performance, small shrinkage, environmental friendliness and the like, and becomes one of essential components of high-performance concrete. The high performance of the polycarboxylate-type water reducing agent is realized by selecting monomers with different structures and functions, setting the molecular structure of a specific polycarboxylate-type water reducing agent and optimally combining and controlling the polymerization degree of a main chain, the length of a side chain and the types of functional groups, and the polycarboxylate-type water reducing agent with low shrinkage and viscosity reduction functions is prepared and obtained, so that the problems of high concrete viscosity, low flowing speed, high shrinkage and the like are solved.
In recent years, viscosity-reducing polycarboxylic acid water reducing agents gradually become a research hotspot in the field of concrete admixtures, however, in the light of documents and patents of viscosity-reducing polycarboxylic acid water reducing agents, researchers mostly adopt (1) reducing the molecular weight of the water reducing agent, (2) reducing the length of PEG side chains, (3) introducing hydrophobic functional groups, such as methyl and ester groups, into the molecular structure of the water reducing agent, so as to increase the hydrophobicity of the product, thereby achieving the purposes of reducing the combination with water, releasing free water to the maximum extent, indirectly improving the water-cement ratio and further reducing the viscosity of concrete slurry. The molecular weight of the water reducing agent and the length of a PEG side chain are reduced, and the water reducing agent has the advantages that the viscosity reduction type water reducing agent has higher freedom of movement in free water than a common water reducing agent, and can extend molecular chains of the water reducing agent more quickly, so that cement particles are quickly adsorbed and dispersed, and the viscosity of cement paste is reduced. The disadvantages are that the molecular weight of the water reducing agent is small, and the absorption and dispersion group-COO-The quantity of the water reducing agent is small, the adsorption and dispersion effects of the water reducing agent molecules on cement particles are reduced, the length of PEG side chains is reduced, and the steric hindrance effect is reduced, so that the water reducing rate of the polycarboxylate water reducing agent is greatly reduced. Hydrophobic methyl and ester groups are introduced into the molecular structure of the water reducing agent, for example, methacrylate, hydroxy methacrylate and the like are introduced into the molecular structure, so that the synthesized polymer has a certain viscosity reduction effectHowever, there are disadvantages in that the hydrophobic functional group is located on the main chain, the content of the hydrophobic functional group is limited, and if the proportion of the hydrophobic polymeric small monomer substituted for methacrylic acid in the copolymer is too high, the dispersing group-COO is adsorbed-The content of (A) is reduced, the adsorption and dispersion of cement particles and hydration products thereof are influenced, the water reduction rate is reduced, and if the proportion of hydrophobic polymerized small monomers in the copolymer for substituting methacrylic acid is too low, the viscosity reduction effect is not obvious, and the aim of reducing the viscosity is not achieved. Therefore, the research and development of the polycarboxylic acid water reducing agent with good viscosity reduction effect and higher water reducing rate have important social and economic significance for the production and research and development of high-grade concrete, especially the production and research and development of ultrahigh-grade concrete with more than C100 and low-slump pipe pile concrete.
Disclosure of Invention
Aiming at the technical defects, the invention provides concrete, which contains the viscosity-reducing polycarboxylic acid water reducer designed by the invention. Because the hydrophobic alkyl and the ester group are positioned on the PEG side chain, the water reducing agent has the following 4 main advantages: 1. the content of the copolymer does not influence the adsorption and dispersion of-COO in the copolymer-The content of the groups does not influence the adsorption and dispersion effects of the water reducing agent; 2. the content of hydrophobic alkyl and ester groups can be adjusted at will according to the actual requirement of the viscosity reduction effect, so as to achieve the purpose of effectively solving the problems of high viscosity and low flow rate of high-grade concrete; 3. because the PEG side chain contains a large amount of hydrophobic viscosity-reducing alkyl and ester groups, the water reducing agent molecules cannot form a complete water layer film on the surface of cement particles, but form a defective collapsed water layer film, and the defective collapsed water layer film endows the water reducing agent with the following characteristics: (1) more free water can be released, and the viscosity of cement paste is reduced; (2) the molecular weight of the water reducing agent is not limited by the viscosity reduction requirement; (3) the length of the PEG side chain is not limited by the viscosity reduction requirement; 4. a large number of hydrophobic alkyl and ester groups introduced in the PEG side chainThe surface tension of the product is greatly reduced, and the shrinkage force of water evaporation is reduced, so that the shrinkage cracking of concrete is reduced, and a good shrinkage reducing effect is achieved. The invention also provides application of the viscosity reduction type polycarboxylate superplasticizer shown in the formula (I) in preparation of C100 concrete.
In order to realize the purpose, the technical scheme is as follows: the concrete comprises the following raw materials in parts by weight:
150 parts of water (120), 500 parts of cement (370), 80-120 parts of fly ash, 80-120 parts of mineral powder, 0-60 parts of silica fume, 680 parts of sand (600), 1100 parts of stone (900) and 20-23 parts of admixture; the additive comprises a viscosity-reducing polycarboxylate water reducer shown in formula (I), and the structural formula of the viscosity-reducing polycarboxylate water reducer shown in formula (I) is as follows:
Figure GDA0001986528900000031
a is an integer of 10 to 80, b is an integer of 1 to 60, c is an integer of 1 to 80, d is an integer of 1 to 60,
a is
Figure GDA0001986528900000032
R1Is H or CH3；
B is
Figure GDA0001986528900000033
R2Is H or CH3，R3Is CH2、CH2CH2Or OCH2CH2CH2CH2，m1M is an integer of 0 to 502Is an integer of 5 to 50;
c is
Figure GDA0001986528900000041
R4Is H or CH3，R5Is CH2、CH2CH2Or OCH2CH2CH2CH2N is an integer of 1 to 80;
d is
Figure GDA0001986528900000042
，R6Is H or CH3，R7Is CH2、CH2CH2Or OCH2CH2CH2CH2M is an integer of 2-6; y is1Is an integer of 0 to 60, y2Is an integer of 0 to 60, y1、y2Cannot be 0 at the same time; preferably, y1、y2Are all not 0, y1：y2＝2:8～8:2。
Preferably, the concrete comprises the following raw materials in parts by weight: 122-148 parts of water, 390-480 parts of cement, 90-115 parts of fly ash, 90-115 parts of mineral powder, 20-50 parts of silica fume, 610-660 parts of sand, 960-1080 parts of stone and 21-23 parts of admixture; more preferably, the concrete comprises the following raw materials in parts by weight: 140 parts of water, 420 parts of cement, 100 parts of fly ash, 80 parts of mineral powder, 30 parts of silica fume, 620 parts of sand, 1011 parts of stones and 22 parts of additives.
Preferably, the preparation method of the viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
dissolving a reaction monomer B, a reaction monomer C, a reaction monomer D and an oxidant in water to obtain a solution 1, dissolving a reaction monomer A and a chain transfer agent in water to obtain a solution 2, dissolving a reducing agent in water to obtain a solution 3, dropwise adding the solution 2 and the solution 3 into the solution 1 to react under the condition of normal temperature, starting dropwise adding the solution 2 and the solution 3 simultaneously, dropwise adding the solution 2 within 2-3 h, dropwise adding the solution 3 for 10-30 min more than the solution 2, dropwise adding the solution 3 within 2.5-3.5 h, continuing to react for 4-8 h, and adjusting the pH of the reacted solution to 7-8 to obtain the viscosity-reducing polycarboxylic acid water reducer;
the reaction monomer A is at least one of acrylic acid and methacrylic acid;
the reaction monomer B is at least one of APEG/PPG, HAPEG/PPG, VAPEG/PPG and TAPEG/PPG;
the reaction monomer C is at least one of APEG, HPEG, VPEG and TPEG;
the reaction monomer D is a viscosity-reducing active macromonomer shown in a formula (II), and the structural formula of the viscosity-reducing active macromonomer shown in the formula (II) is as follows:
Figure GDA0001986528900000051
wherein R is6H or CH3，R7＝CH2、CH2CH2Or OCH2CH2CH2CH2(ii) a m is an integer of 2-6;
y1is an integer of 0 to 60, y2Is an integer of 0 to 60, y1、y2Cannot be 0, y simultaneously1：y22: 8-8: 2; preferably, y1、y2Are all not 0, y1：y2＝2:8～8:2。
Preferably, the molar ratio of the reaction monomer A to the reaction monomer B to the reaction monomer C to the reaction monomer D is 4-10: 0.4-1.0: 0.6-1.2: 0.2 to 1.6.
Preferably, the addition amount of the chain transfer agent is 0.05-5% of the total mole number of the reaction monomers, the addition amount of the oxidant is 0.05-5% of the total mole number of the reaction monomers, and the addition amount of the reducing agent is 20-100% of the oxidant. The total reactive monomer moles refer to the sum of the moles of reactive monomer A, reactive monomer B, reactive monomer C and reactive monomer D.
Preferably, the oxidizing agent is hydrogen peroxide, the reducing agent is one or two of ascorbic acid and sodium bisulfite, and the chain transfer agent is one or two of thioglycolic acid and mercaptopropionic acid.
Preferably, the preparation method of the viscosity-reducing active macromonomer comprises the following steps:
mixing an initiator enol and a catalyst, dropwise adding at least one of epoxy alkane and glycidic butyrate at a constant speed at 80-120 ℃ in a protective gas atmosphere, continuously reacting for 6-12 hours at 90-110 ℃ after dropwise adding is finished within 2-4 hours, and obtaining a viscosity-reducing active macromonomer;
the structural formula of the alkylene oxide is shown as a formula (III),
Figure GDA0001986528900000061
m is an integer of 2 to 6.
The reaction formula is as follows:
Figure GDA0001986528900000062
preferably, the enol is at least one of allyl alcohol, isobutenol, 4-hydroxybutyl vinyl ether and isopentenol, the catalyst is sodium hydride or sodium, and the protective gas is nitrogen.
Preferably, the molar ratio of the starter enol, the alkylene oxide and the glycidyl butyrate is 1: y is1：y2，y1Is an integer of 0 to 60, y2Is an integer of 0 to 60, y1、y2Cannot be 0, y simultaneously1：y22: 8-8: 2; preferably, y1、y2Are all not 0, y1：y2＝2:8～8:2。
The invention provides application of the viscosity-reducing polycarboxylate superplasticizer shown in the formula (I) in preparation of C100 concrete.
The viscosity-reducing polycarboxylate superplasticizer is synthesized, and has remarkable viscosity-reducing and shrinkage-reducing effects while keeping a high water-reducing rate;
according to the invention, a PEG active macromonomer D containing alkyl and ester-based double-hydrophobic viscosity reduction functional groups is synthesized by using initiators such as prenol, glycidyl butyrate and alkyl epoxide, the macromonomer is copolymerized with a reactive monomer A, B, C to synthesize a polycarboxylic acid water reducing agent, the hydrophobic functional groups are positioned on PEG side chains, and the content of the hydrophobic functional groups in the whole molecular structure can be randomly adjusted according to the actual requirement of the viscosity reduction effect under the condition of not influencing the water reduction rate, so that the requirement on the viscosity reduction effect is met, and the technical defect that the content of the ester-based functional groups influences the water reduction rate in the prior art is avoided; meanwhile, because a large amount of hydrophobic alkyl and ester groups are introduced into the PEG side chain of the water reducing agent, water reducing agent molecules cannot form a complete water layer film on the surface of cement particles, but form a defective collapsed water layer film, and the defective collapsed water layer film endows the water reducing agent with the following characteristics: (1) more free water can be released, and the viscosity of cement paste is reduced; (2) the molecular weight of the water reducing agent is not limited by the viscosity reduction requirement; (3) the PEG side chain of the water reducer molecule is not limited by viscosity reduction requirements, and the technical defect that the water reduction rate of the product is influenced by reducing the polymer molecular weight and the PEG side chain of the viscosity reduction type polycarboxylate water reducer for realizing the viscosity reduction effect in the prior art is overcome.
On the other hand, in the molecular structure of the water reducing agent, hydrophobic viscosity reduction group methyl (from a macromonomer B), alkyl and ester groups (from a macromonomer D) are introduced on a PEG side chain in the molecular structure of the water reducing agent, so that the synthesized water reducing agent has a good viscosity reduction effect, and simultaneously has the capability of reducing surface tension, and the contractility of water evaporation is reduced, thereby reducing the shrinkage cracking of concrete.
Has the advantages that:
compared with the viscosity reduction type polycarboxylate superplasticizer synthesized by the prior art, the viscosity reduction type polycarboxylate superplasticizer synthesized by the method disclosed by the invention has the following advantages that the components and functional groups have mutual synergistic effect:
1. the viscosity-reducing hydrophobic group functional group is positioned on the side chain, the viscosity-reducing effect of the water reducer can be adjusted by adjusting the content of the viscosity-reducing functional group, but the content of the dispersing group and the dispersing effect on cement particles are not influenced, so that the dispersing and water-reducing effects of the water reducer are not influenced;
2. the molecular weight of the water reducing agent is not limited by the viscosity reduction effect of the water reducing agent;
3. the length of the PEG side chain in the molecular structure of the water reducing agent is not limited by the viscosity reduction effect of the water reducing agent;
4. the viscosity reduction effect is excellent, and the water reduction rate is not influenced.
5. Has better adaptability to cement.
6. Has good viscosity reduction effect.
7. Has good water reducing rate and slump retaining capacity
8. The concrete with the product has low shrinkage rate and no cracking.
Compared with the prior art, the C100 concrete prepared by using the viscosity-reducing polycarboxylate superplasticizer has the following advantages:
1. original production equipment and process are not changed.
2. The fresh concrete has no segregation, bleeding and bottom scraping.
3. The fresh concrete has good slump retentivity with time, and the slump loss within 3 hours is not more than 10 mm.
4. The fresh concrete has good flow property, and the expansion loss is not more than 20mm within 3 hours.
5. The fresh concrete has good workability, soft material, proper viscosity, and the emptying time of 8-12 ″, and is neither sticky nor weeping.
6. The concrete has high strength, and the 28-day and 56-day compressive strength can reach 130% of the designed strength.
7. Due to the use of the viscosity-reducing polycarboxylic acid water reducer, the concrete has proper viscosity, good cement dispersibility and good concrete compactness, so that admixtures such as fly ash, mineral powder and the like can be added to reach 35 percent without influencing the compressive strength and durability of the concrete.
8. 50-80 kg of silica fume is usually added in the prepared C100 concrete, the silica fume has the functions of improving the compactness of the concrete and reducing the viscosity of high-grade concrete, and by adopting the viscosity-reducing polycarboxylic acid water reducing agent, a small amount of silica fume is added to improve the grain composition of a cementing material, and the reduction of the viscosity of the concrete mainly depends on the viscosity-reducing polycarboxylic acid water reducing agent.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The preparation method of the viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
(1) and (3) synthesizing a viscosity-reducing active macromonomer D:
1mol of methallyl alcohol and 2g of sodium hydride are added into a four-neck glass flask with a stirrer, a thermometer, a reflux condenser tube and a dropping device, stirred under the protection of nitrogen, 30mol of alkylene oxide is dropped at a uniform speed at 90 ℃, after dropping for 3h, reaction is continued for 8h at 100 ℃, and the viscosity-reducing active macromonomer D is obtained.
(2) Synthesis of viscosity-reducing polycarboxylic acid water reducer
Dissolving a reaction monomer B, a reaction monomer C, a reaction monomer D and an oxidant in water to obtain a solution 1, dissolving a reaction monomer A and a chain transfer agent in water to obtain a solution 2, dissolving a reducing agent in water to obtain a solution 3, dropwise adding the solution 2 and the solution 3 into the solution 1 to react under the normal temperature condition, starting dropwise adding the solution 2 and the solution 3 simultaneously, dropwise adding the solution 2 within 3h, dropwise adding the solution 3 for 30min more than the solution 2, dropwise adding within 3.5h, continuing to react for 6h, and adjusting the pH of the reacted solution to 7 to obtain the viscosity-reducing polycarboxylic acid water reducer.
The reaction monomer A is methacrylic acid, the reaction monomer B is HPEG/PPG, the reaction monomer C is HPEG, and the reaction monomer D is the viscosity-reducing active macromonomer D obtained in the step (1). The molar ratio of the reaction monomer A to the reaction monomer B to the reaction monomer C to the reaction monomer D is 6:0.8: 1.
the oxidant is hydrogen peroxide, the reducing agent is sodium bisulfite, and the chain transfer agent is thioglycolic acid. The adding amount of the chain transfer agent is 2 percent of the total mole number of the reaction monomers, the adding amount of the oxidizing agent is 2 percent of the total mole number of the reaction monomers, and the adding amount of the reducing agent is 80 percent of the oxidizing agent.
Example 2
The preparation method of the viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
(1) and (3) synthesizing a viscosity-reducing active macromonomer D:
adding 1mol of methallyl alcohol and 2g of sodium hydride into a four-neck glass flask with a stirrer, a thermometer, a reflux condenser tube and a dripping device, stirring under the protection of nitrogen, dripping 30mol of glycidol butyrate at a uniform speed at 90 ℃, continuously reacting for 8 hours at 100 ℃ after finishing dripping for 3 hours, and thus obtaining the viscosity-reducing active macromonomer D.
(2) Synthesis of viscosity-reducing polycarboxylic acid water reducer
Dissolving a reaction monomer B, a reaction monomer C, a reaction monomer D and an oxidant in water to obtain a solution 1, dissolving a reaction monomer A and a chain transfer agent in water to obtain a solution 2, dissolving a reducing agent in water to obtain a solution 3, dropwise adding the solution 2 and the solution 3 into the solution 1 to react under the normal temperature condition, starting dropwise adding the solution 2 and the solution 3 simultaneously, dropwise adding the solution 2 within 3h, dropwise adding the solution 3 for 30min more than the solution 2, dropwise adding within 3.5h, continuing to react for 6h, and adjusting the pH of the reacted solution to 7 to obtain the viscosity-reducing polycarboxylic acid water reducer.
The reaction monomer A is methacrylic acid, the reaction monomer B is HPEG/PPG, the reaction monomer C is HPEG, and the reaction monomer D is the viscosity-reducing active macromonomer D obtained in the step (1). The molar ratio of the reaction monomer A to the reaction monomer B to the reaction monomer C to the reaction monomer D is 6:0.8: 1.
the oxidant is hydrogen peroxide, the reducing agent is sodium bisulfite, and the chain transfer agent is thioglycolic acid. The adding amount of the chain transfer agent is 2 percent of the total mole number of the reaction monomers, the adding amount of the oxidizing agent is 2 percent of the total mole number of the reaction monomers, and the adding amount of the reducing agent is 80 percent of the oxidizing agent.
Example 3
The preparation method of the viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
(1) and (3) synthesizing a viscosity-reducing active macromonomer D:
adding 1mol of methallyl alcohol and 2g of sodium hydride into a four-neck glass flask with a stirrer, a thermometer, a reflux condenser tube and a dripping device, stirring under the protection of nitrogen, dripping 15mol of alkylene oxide and 15mol of glycidyl butyrate at a uniform speed at 90 ℃, after finishing dripping for 3 hours, continuing to react for 8 hours at 100 ℃ to obtain the viscosity-reducing active macromonomer D.
(2) Synthesis of viscosity-reducing polycarboxylic acid water reducer
Dissolving a reaction monomer B, a reaction monomer C, a reaction monomer D and an oxidant in water to obtain a solution 1, dissolving a reaction monomer A and a chain transfer agent in water to obtain a solution 2, dissolving a reducing agent in water to obtain a solution 3, dropwise adding the solution 2 and the solution 3 into the solution 1 to react under the normal temperature condition, starting dropwise adding the solution 2 and the solution 3 simultaneously, dropwise adding the solution 2 within 3h, dropwise adding the solution 3 for 30min more than the solution 2, dropwise adding within 3.5h, continuing to react for 6h, and adjusting the pH of the reacted solution to 7 to obtain the viscosity-reducing polycarboxylic acid water reducer.
The reaction monomer A is methacrylic acid, the reaction monomer B is HPEG/PPG, the reaction monomer C is HPEG, and the reaction monomer D is the viscosity-reducing active macromonomer D obtained in the step (1). The molar ratio of the reaction monomer A to the reaction monomer B to the reaction monomer C to the reaction monomer D is 6:0.8: 1.
the oxidant is hydrogen peroxide, the reducing agent is sodium bisulfite, and the chain transfer agent is thioglycolic acid. The adding amount of the chain transfer agent is 2 percent of the total mole number of the reaction monomers, the adding amount of the oxidizing agent is 2 percent of the total mole number of the reaction monomers, and the adding amount of the reducing agent is 80 percent of the oxidizing agent.
Example 4
The preparation method of the viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
(1) and (3) synthesizing a viscosity-reducing active macromonomer D:
adding 1mol of methallyl alcohol and 2g of sodium hydride into a four-neck glass flask with a stirrer, a thermometer, a reflux condenser tube and a dripping device, stirring under the protection of nitrogen, dripping 6mol of alkylene oxide and 24mol of glycidyl butyrate at a uniform speed at 90 ℃, after finishing dripping for 3 hours, continuing to react for 8 hours at 100 ℃ to obtain the viscosity-reducing active macromonomer D.
(2) Synthesis of viscosity-reducing polycarboxylic acid water reducer
Dissolving a reaction monomer B, a reaction monomer C, a reaction monomer D and an oxidant in water to obtain a solution 1, dissolving a reaction monomer A and a chain transfer agent in water to obtain a solution 2, dissolving a reducing agent in water to obtain a solution 3, dropwise adding the solution 2 and the solution 3 into the solution 1 to react under the normal temperature condition, starting dropwise adding the solution 2 and the solution 3 simultaneously, dropwise adding the solution 2 within 3h, dropwise adding the solution 3 for 30min more than the solution 2, dropwise adding within 3.5h, continuing to react for 6h, and adjusting the pH of the reacted solution to 7 to obtain the viscosity-reducing polycarboxylic acid water reducer.
The reaction monomer A is methacrylic acid, the reaction monomer B is HPEG/PPG, the reaction monomer C is HPEG, and the reaction monomer D is the viscosity-reducing active macromonomer D obtained in the step (1). The molar ratio of the reaction monomer A to the reaction monomer B to the reaction monomer C to the reaction monomer D is 6:0.8: 1.
the oxidant is hydrogen peroxide, the reducing agent is sodium bisulfite, and the chain transfer agent is thioglycolic acid. The adding amount of the chain transfer agent is 2 percent of the total mole number of the reaction monomers, the adding amount of the oxidizing agent is 2 percent of the total mole number of the reaction monomers, and the adding amount of the reducing agent is 80 percent of the oxidizing agent.
Example 5
The preparation method of the viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
(1) and (3) synthesizing a viscosity-reducing active macromonomer D:
adding 1mol of methallyl alcohol and 2g of sodium hydride into a four-neck glass flask with a stirrer, a thermometer, a reflux condenser tube and a dripping device, stirring under the protection of nitrogen, dripping 24mol of alkylene oxide and 6mol of glycidyl butyrate at a uniform speed at 90 ℃, after finishing dripping for 3 hours, continuing to react for 8 hours at 100 ℃ to obtain the viscosity-reducing active macromonomer D.
(2) Synthesis of viscosity-reducing polycarboxylic acid water reducer
Dissolving a reaction monomer B, a reaction monomer C, a reaction monomer D and an oxidant in water to obtain a solution 1, dissolving a reaction monomer A and a chain transfer agent in water to obtain a solution 2, dissolving a reducing agent in water to obtain a solution 3, dropwise adding the solution 2 and the solution 3 into the solution 1 to react under the normal temperature condition, starting dropwise adding the solution 2 and the solution 3 simultaneously, dropwise adding the solution 2 within 3h, dropwise adding the solution 3 for 30min more than the solution 2, dropwise adding within 3.5h, continuing to react for 6h, and adjusting the pH of the reacted solution to 7 to obtain the viscosity-reducing polycarboxylic acid water reducer.
The reaction monomer A is methacrylic acid, the reaction monomer B is HPEG/PPG, the reaction monomer C is HPEG, and the reaction monomer D is the viscosity-reducing active macromonomer D obtained in the step (1). The molar ratio of the reaction monomer A to the reaction monomer B to the reaction monomer C to the reaction monomer D is 6:0.8: 1.
the oxidant is hydrogen peroxide, the reducing agent is sodium bisulfite, and the chain transfer agent is thioglycolic acid. The adding amount of the chain transfer agent is 2 percent of the total mole number of the reaction monomers, the adding amount of the oxidizing agent is 2 percent of the total mole number of the reaction monomers, and the adding amount of the reducing agent is 80 percent of the oxidizing agent.
Example 6
Parameters of examples 1 to 5 of the invention are shown in Table 1, C100 concrete is prepared by using the viscosity-reducing polycarboxylate superplasticizer synthesized in examples 1 to 5 of the invention, and a commercially available viscosity-reducing polycarboxylate superplasticizer is used as a comparative example. Then, C100 concrete was prepared according to the formulation shown in Table 2 below, and the properties of the C100 concrete were measured.
TABLE 1 parameters of examples 1 to 5 of the present invention
Figure GDA0001986528900000121
TABLE 2C 100 concrete mixing ratio
Figure GDA0001986528900000131
The admixture of the present invention was a mixture (solid content: 20%) of the early-strength viscosity-reducing type polycarboxylic acid water-reducing agent of examples 1 to 5 and a conventional water-reducing type polycarboxylic acid water-reducing agent (weight ratio: 60: 40).
The admixture of the comparative example was a mixture (20% in solid content) of a commercially available early strength type polycarboxylic acid water reducing agent and a conventional water reducing type polycarboxylic acid water reducing agent (60: 40 by weight).
The effect comparison of the C100 concrete prepared by the viscosity-reducing polycarboxylic acid water reducer of the embodiments 1-5 of the invention and the commercially available viscosity-reducing polycarboxylic acid water reducer is shown in Table 3:
TABLE 3C 100 concrete Effect
Figure GDA0001986528900000132
As can be seen from Table 3, compared with the C100 concrete doped with the commercial viscosity-reducing polycarboxylate superplasticizer, the C100 concrete prepared by using the viscosity-reducing polycarboxylate superplasticizer of the invention has the following advantages:
1. original production equipment and process are not changed.
2. The fresh concrete has no segregation, bleeding and bottom scraping.
3. The fresh concrete has good slump retentivity with time, and the slump loss within 3 hours is not more than 10 mm.
4. The fresh concrete has good flow property, and the expansion loss is not more than 20mm within 3 hours.
5. The fresh concrete has good workability, soft material, proper viscosity, and the emptying time of 8-12 ″, and is neither sticky nor weeping.
6. The concrete has high strength, and the 28-day and 56-day compressive strength can reach 130% of the designed strength.
7. Due to the use of the viscosity-reducing polycarboxylic acid water reducer, the concrete has proper viscosity, good cement dispersibility and good concrete compactness, so that admixtures such as fly ash, mineral powder and the like can be added to reach 35 percent without influencing the compressive strength and durability of the concrete.
8. 50-80 kg of silica fume is usually added in the prepared C100 concrete, the silica fume has the functions of improving the compactness of the concrete and reducing the viscosity of high-grade concrete, and by adopting the viscosity-reducing polycarboxylic acid water reducing agent, a small amount of silica fume is added to improve the grain composition of a cementing material, and the reduction of the viscosity of the concrete mainly depends on the viscosity-reducing polycarboxylic acid water reducing agent.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (14)

1. The concrete is characterized by comprising the following raw materials in parts by weight:
150 parts of water (120), 500 parts of cement (370), 80-120 parts of fly ash, 80-120 parts of mineral powder, 0-60 parts of silica fume, 680 parts of sand (600), 1100 parts of stone (900) and 20-23 parts of admixture; the additive comprises a viscosity-reducing polycarboxylate water reducer shown in formula (I), and the structural formula of the viscosity-reducing polycarboxylate water reducer shown in formula (I) is as follows:
Figure 136864DEST_PATH_IMAGE001
（Ⅰ）；
a is an integer of 10 to 80, b is an integer of 1 to 60, c is an integer of 1 to 80, d is an integer of 1 to 60,
a is
Figure 687931DEST_PATH_IMAGE002
，R1Is H or CH3；
B is
Figure 752839DEST_PATH_IMAGE003
，R2Is H or CH3，R3Is CH2、CH2CH2Or OCH2CH2CH2CH2，m1M is an integer of 0 to 502Is an integer of 5 to 50;
c is
Figure 276224DEST_PATH_IMAGE004
，R4Is H or CH3，R5Is CH2、CH2CH2Or OCH2CH2CH2CH2N is 1 to 8An integer of 0;
d is
Figure 706068DEST_PATH_IMAGE005
，
R6Is H or CH3，R7Is CH2、CH2CH2Or OCH2CH2CH2CH2M = an integer of 2 to 6; y is1Is an integer of 0 to 60, y2Is an integer of 0 to 60, y1、y2Cannot be 0 at the same time.
2. The concrete of claim 1, wherein y is1、y2Are all not 0, y1：y2=2:8～8:2。
3. The concrete according to claim 1, wherein the concrete comprises the following raw materials in parts by weight: 148 parts of water 122-.
4. The concrete according to claim 3, wherein the concrete comprises the following raw materials in parts by weight: 140 parts of water, 420 parts of cement, 100 parts of fly ash, 80 parts of mineral powder, 30 parts of silica fume, 620 parts of sand, 1011 parts of stones and 22 parts of additives.
5. The concrete according to claim 1, wherein the preparation method of the viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
dissolving a reaction monomer B, a reaction monomer C, a reaction monomer D and an oxidant in water to obtain a solution 1, dissolving a reaction monomer A and a chain transfer agent in water to obtain a solution 2, dissolving a reducing agent in water to obtain a solution 3, dropwise adding the solution 2 and the solution 3 into the solution 1 to react under the condition of normal temperature, starting dropwise adding the solution 2 and the solution 3 simultaneously, dropwise adding the solution 2 within 2-3 h, dropwise adding the solution 3 for 10-30 min more than the solution 2, dropwise adding the solution 3 within 2.5-3.5 h, continuing to react for 4-8 h, and adjusting the pH of the reacted solution to 7-8 to obtain the viscosity-reducing polycarboxylic acid water reducer;
the reaction monomer A is at least one of acrylic acid and methacrylic acid;
the reaction monomer B is at least one of APEG/PPG, HPEG/PPG, VPEG/PPG and TPEG/PPG;
the reaction monomer C is at least one of APEG, HPEG, VPEG and TPEG;
the reaction monomer D is a viscosity-reducing active macromonomer shown in a formula (II), and the structural formula of the viscosity-reducing active macromonomer shown in the formula (II) is as follows:
Figure 744432DEST_PATH_IMAGE006
（Ⅱ），
wherein R is6= H or CH3，R7 = CH2、CH2CH2Or OCH2CH2CH2CH2(ii) a m = an integer of 2 to 6;
y1is an integer of 0 to 60, y2Is an integer of 0 to 60, y1、y2Cannot be 0 at the same time.
6. Concrete according to claim 5, characterized in that, in formula (II), y1、y2Are all not 0, y1：y2=2:8～8:2。
7. The concrete according to claim 5, wherein the molar ratio of the reactive monomer A to the reactive monomer B to the reactive monomer C to the reactive monomer D is 4-10: 0.4-1.0: 0.6-1.2: 0.2 to 1.6.
8. The concrete according to claim 5, wherein the addition amount of the chain transfer agent is 0.05-5% of the total mole number of the reaction monomers, the addition amount of the oxidant is 0.05-5% of the total mole number of the reaction monomers, and the addition amount of the reducing agent is 20-100% of the oxidant.
9. The concrete according to claim 5, wherein the oxidizing agent is hydrogen peroxide,
the reducing agent is one or two of ascorbic acid and sodium bisulfite, and the chain transfer agent is one or two of thioglycolic acid and mercaptopropionic acid.
10. The concrete according to claim 5, wherein the preparation method of the viscosity-reducing active macromonomer comprises the following steps:
mixing an initiator enol and a catalyst, dropwise adding at least one of epoxy alkane and glycidic butyrate at a constant speed at 80-120 ℃ in a protective gas atmosphere, continuously reacting for 6-12 hours at 90-110 ℃ after dropwise adding is finished within 2-4 hours, and obtaining a viscosity-reducing active macromonomer;
the structural formula of the alkylene oxide is shown as a formula (III),
Figure 19555DEST_PATH_IMAGE007
(III) m is an integer of 2-6.
11. The concrete of claim 10, wherein the enol is at least one of allyl alcohol, isobutenol, 4-hydroxybutyl vinyl ether, and isopentenol, the catalyst is sodium hydride or sodium, and the protective gas is nitrogen.
12. The concrete according to claim 10, wherein the molar ratio of the starter enol, the alkylene oxide and the glycidyl butyrate is 1: y is1：y2Wherein, y1Is an integer of 0 to 60, y2Is an integer of 0 to 60, y1、y2Cannot be 0 at the same time.
13. The concrete according to claim 12, wherein the molar ratio of the starter enols, alkylene oxides and glycidyl butyrate is y1、y2Are all not 0, y1：y2=2:8～8:2。
14. The application of the viscosity-reducing polycarboxylate superplasticizer in preparing C100 concrete is characterized in that the structure of the viscosity-reducing polycarboxylate superplasticizer is shown as a formula (I):
Figure 663026DEST_PATH_IMAGE008
（Ⅰ）；
a is an integer of 10 to 80, b is an integer of 1 to 60, c is an integer of 1 to 80, d is an integer of 1 to 60,
a is
Figure 60509DEST_PATH_IMAGE002
，R1Is H or CH3；
B is
Figure 789431DEST_PATH_IMAGE003
，R2Is H or CH3，R3Is CH2、CH2CH2Or OCH2CH2CH2CH2，m1M is an integer of 0 to 502Is an integer of 5 to 50;
c is
Figure 694677DEST_PATH_IMAGE009
，R4Is H or CH3，R5Is CH2、CH2CH2Or OCH2CH2CH2CH2N is an integer of 1 to 80;
d is
Figure 192654DEST_PATH_IMAGE005
，
R6Is H or CH3，R7Is CH2、CH2CH2Or OCH2CH2CH2CH2M = an integer of 2 to 6; y is1Is an integer of 0 to 60, y2Is an integer of 0 to 60, y1、y2Cannot be 0 at the same time.
CN201811605781.1A 2018-12-26 2018-12-26 Application of viscosity-reducing polycarboxylic acid water reducer in preparation of C100 concrete Active CN109678403B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811605781.1A CN109678403B (en) 2018-12-26 2018-12-26 Application of viscosity-reducing polycarboxylic acid water reducer in preparation of C100 concrete

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811605781.1A CN109678403B (en) 2018-12-26 2018-12-26 Application of viscosity-reducing polycarboxylic acid water reducer in preparation of C100 concrete

Publications (2)

Publication Number Publication Date
CN109678403A CN109678403A (en) 2019-04-26
CN109678403B true CN109678403B (en) 2021-07-20

Family

ID=66189833

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811605781.1A Active CN109678403B (en) 2018-12-26 2018-12-26 Application of viscosity-reducing polycarboxylic acid water reducer in preparation of C100 concrete

Country Status (1)

Country Link
CN (1) CN109678403B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102993432A (en) * 2012-10-19 2013-03-27 江苏博特新材料有限公司 Water reducer midbody, preparation method thereof and water reducer prepared by using preparation method
CN102532435B (en) * 2011-12-21 2013-10-30 湖北恒利建材科技有限公司 Polycarboxylene high-performance water reducing agent and preparation method thereof
CN106883355A (en) * 2017-03-28 2017-06-23 中建商品混凝土有限公司 A kind of low entraining viscosity reduction type polycarboxylate water-reducer and preparation method thereof
CN107400188A (en) * 2017-08-14 2017-11-28 联泓(江苏)新材料研究院有限公司 A kind of unsaturated polyether monomer and preparation method thereof, using and obtained polymer
CN108003301A (en) * 2017-11-14 2018-05-08 佳化化学（茂名）有限公司 A kind of preparation method of viscosity reduction type polycarboxylate water-reducer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102532435B (en) * 2011-12-21 2013-10-30 湖北恒利建材科技有限公司 Polycarboxylene high-performance water reducing agent and preparation method thereof
CN102993432A (en) * 2012-10-19 2013-03-27 江苏博特新材料有限公司 Water reducer midbody, preparation method thereof and water reducer prepared by using preparation method
CN106883355A (en) * 2017-03-28 2017-06-23 中建商品混凝土有限公司 A kind of low entraining viscosity reduction type polycarboxylate water-reducer and preparation method thereof
CN107400188A (en) * 2017-08-14 2017-11-28 联泓(江苏)新材料研究院有限公司 A kind of unsaturated polyether monomer and preparation method thereof, using and obtained polymer
CN108003301A (en) * 2017-11-14 2018-05-08 佳化化学（茂名）有限公司 A kind of preparation method of viscosity reduction type polycarboxylate water-reducer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
樊俊江等.预制构件用C100高强混凝土配合比研究.《混凝土与水泥制品》.2017,(第10期),24-28页. *

Also Published As

Publication number Publication date
CN109678403A (en) 2019-04-26

Similar Documents

Publication Publication Date Title
JP6074517B2 (en) Method for producing slump retention type polycarboxylate-based high performance fluidizing agent
CA2605186C (en) Concrete and mortar admixture
CN109627397B (en) Polycarboxylate superplasticizer for improving rheological property of cement paste and preparation method thereof
CN107652405B (en) Polycarboxylate superplasticizer with amide/imide structure and preparation method thereof
JP2005089193A (en) Cement admixture having high water-reducing effect and method for producing the same
CN111100253A (en) Concrete anti-sensitive polycarboxylate superplasticizer and preparation method thereof
CN111349199B (en) Steady-state polycarboxylic acid superplasticizer with core-shell structure and preparation method thereof
CN111378083A (en) Polycarboxylic acid dispersant with star structure and preparation method and application thereof
JP2007063090A (en) Super-quick hardening cement composition and dispersing agent for super-quick hardening cement composition
CN109734847B (en) Viscosity reduction type polycarboxylate superplasticizer containing three viscosity reduction functional groups, and preparation method and application thereof
JP4947856B2 (en) Cement dispersant and cement composition using the same
CN112979214B (en) Polyether water-retaining agent, preparation method thereof and cement-based building material
CN114230726A (en) Polycarboxylate superplasticizer with strong adsorption and fast dispersion and preparation method thereof
CN108192010B (en) Viscosity-reducing polycarboxylic acid water reducer and preparation method thereof
CN109762114B (en) Early-strength viscosity-reduction type polycarboxylate superplasticizer containing double viscosity-reduction functional groups and preparation method thereof
CN109776034B (en) Application of viscosity-reducing water reducer containing alkyl in preparation of C100 concrete
CN109485323B (en) Application of early-strength viscosity-reduction type polycarboxylate superplasticizer in preparation of precast concrete
CN113072666B (en) Preparation method and application of high-water-reduction type polycarboxylic acid superplasticizer
CN109721722B (en) Viscosity-reducing type polycarboxylate superplasticizer containing double viscosity-reducing functional groups, and preparation method and application thereof
CN112194762A (en) Preparation method of non-crosslinked reticular polycarboxylic acid water reducing agent
CN109678403B (en) Application of viscosity-reducing polycarboxylic acid water reducer in preparation of C100 concrete
WO2014059766A1 (en) Super plasticizer for precast concrete component
CN113773457B (en) Low-creep high-efficiency polycarboxylate superplasticizer and preparation method thereof
CN109749020B (en) Alkyl-containing early-strength viscosity-reduction type polycarboxylate superplasticizer and preparation method thereof
CN109749074B (en) Alkyl-containing viscosity-reducing polycarboxylate superplasticizer and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant