CN113912842A - Ligand, conductive early-strength polycarboxylate superplasticizer, conductive early-strength graphene dispersion slurry and preparation method thereof - Google Patents

Ligand, conductive early-strength polycarboxylate superplasticizer, conductive early-strength graphene dispersion slurry and preparation method thereof Download PDF

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CN113912842A
CN113912842A CN202111076864.8A CN202111076864A CN113912842A CN 113912842 A CN113912842 A CN 113912842A CN 202111076864 A CN202111076864 A CN 202111076864A CN 113912842 A CN113912842 A CN 113912842A
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strength
early
conductive
deionized water
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CN113912842B (en
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邵幼哲
李格丽
吴传灯
林志群
方云辉
钟丽娜
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Hunan Kezhijie New Material Co ltd
Kezhijie New Material Group Co Ltd
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Kezhijie New Material Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0627—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
    • 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
    • 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
    • C04B30/00—Compositions for artificial stone, not containing binders
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

The invention relates to the field of polycarboxylic acid water reducing agents, and provides a ligand, a conductive early-strength polycarboxylic acid water reducing agent, conductive early-strength graphene dispersion slurry and a preparation method thereof. The ligand is formed by the polycondensation of a first polymer, thionyl chloride, 4-hydroxy-2, 2', 6', 2' -terpyridine and dichloromethane. The first polymer is prepared by free radical polymerization of methoxy polyethylene glycol acrylate, unsaturated monocarboxylic acid and acrylamide monomers. The conductive early-strength polycarboxylate superplasticizer is prepared from a ligand, zinc nitrate and deionized water. The conductive early-strength graphene dispersion slurry is prepared by mixing graphene, graphene oxide, a conductive early-strength polycarboxylate superplasticizer and deionized water. The conductive early-strength polycarboxylate superplasticizer and the conductive early-strength graphene dispersion slurry prepared by the invention have excellent conductivity and early strength.

Description

Ligand, conductive early-strength polycarboxylate superplasticizer, conductive early-strength graphene dispersion slurry and preparation method thereof
Technical Field
The invention relates to the field of polycarboxylic acid water reducing agents, and particularly relates to a ligand, a conductive early-strength polycarboxylic acid water reducing agent, conductive early-strength graphene dispersion slurry and a preparation method thereof.
Background
The polycarboxylate superplasticizer has the characteristics of high water reducing rate, high slump retention, low alkali, environmental protection and the like, and is widely applied to concrete engineering. However, the early strength development of the common polycarboxylic acid water reducing agent is slow, and particularly under the low-temperature condition, the use of the common polycarboxylic acid water reducing agent in winter construction and cold environment is limited, so that the early hydration of cement is promoted, and the development of the early strength polycarboxylic acid water reducing agent has obvious technical and economic benefits.
In recent years, along with the rapid development of economy in China, in many projects, in order to accelerate the progress of the project and shorten the construction period, an early strength water reducing agent is needed to accelerate the hydration speed of cement, increase the early strength of concrete and ensure the smooth completion of the project.
The conductive concrete is prepared by adding a conductive component into common concrete, has conductive performance, and generally has a conductive mechanism that a network is formed by the conductive component materials dispersed in a matrix and is conducted by connecting insulators among the networks through a tunnel effect. The conductive concrete has very wide application in snow melting and deicing of cold area engineering (such as road engineering, reservoir dams, airport runways and the like), engineering piezoelectric sensor manufacturing, thermodynamic parameter monitoring and the like.
At present, in the preparation of conductive concrete, the high conductivity and the high strength of the concrete are difficult to be organically combined, some of the concrete are mainly focused on improving the conductivity of the concrete, and some of the concrete are mainly focused on improving the strength of the concrete, which is also a key technical bottleneck for limiting the development of the conductive concrete.
The existing conductive concrete is mostly prepared by compounding conductive materials in concrete, such as iron slag, steel fibers, carbon nanotubes, graphite powder, graphene and the like, but because the substances are dispersed in the concrete, the probability of contact conduction is not high, the iron slag and the steel fibers are easy to generate corrosion in the concrete, and the carbon fibers, the carbon nanotubes, the graphite powder and the graphene are easy to generate agglomeration in the concrete or are incompatible with the concrete, so that the conductivity of the concrete and even the mechanical property of the concrete are further influenced.
The existing concrete with both electric conduction and early strength functions is mostly compounded by a non-conductive polycarboxylic acid water reducing agent with the early strength function and a conductive component with the electric conduction function, and the conductive component is dispersed in the concrete and has low contact electric conduction probability and poor electric conduction performance.
The prior Chinese patent with the reference publication number of CN103304181A discloses an early-strength polycarboxylic acid high-performance water reducing agent, which comprises the following components in percentage by weight: 10-20% of a polycarboxylic acid water reducing agent, 10-17% of calcium chloride, 10-20% of sodium nitrite, 1-3% of triethanolamine and the balance of water. However, the calcium chloride is added into the water reducing agent, so that the reaction between alkali and aggregate is aggravated, the corrosion of the concrete is aggravated, in addition, the calcium ions in the concrete are increased due to the addition of the calcium chloride, the probability of producing calcium sulfate through the reaction of the calcium ions and sulfate is increased, the concrete is cracked, and the performance of the concrete for resisting the sulfate corrosion is reduced. And the concrete is not conductive.
Another chinese patent publication No. CN112708048A discloses an ester-based anti-mud type super-early-strength polycarboxylate superplasticizer and a preparation method thereof, wherein the ester-based anti-mud type super-early-strength polycarboxylate superplasticizer comprises the following preparation raw materials: methoxy polyethylene glycol acrylate, 3-chloro-1-propanol, N-methyl allyl amine, unsaturated carboxylic acid, allyl amine, acrylamide, an oxidizing agent, a reducing agent, a chain transfer agent and methanol. The ester anti-mud type super early strength polycarboxylate superplasticizer disclosed by the invention is good in workability, and the density of early strength groups contained in short side chains is high, so that the early strength of concrete is greatly improved, and the ester anti-mud type super early strength polycarboxylate superplasticizer has good mud resistance. However, the concrete is not conductive, and the 3-chloro-1-propanol reacts with amine substances to generate quaternary ammonium salt, which makes the synthetic reaction process more complicated, increases the uncertainty of the synthetic result and weakens the water reducing capacity of the polycarboxylic acid water reducing agent.
Another Chinese patent with publication number CN111268978A discloses a carbon fiber doped conductive cement-based material, which comprises, by weight, 85-90 parts of cement, 200 parts of sand 125-containing sand, 10-15 parts of mineral powder, 1-3 parts of redispersible latex powder, 40-50 parts of water, 0.5-0.8 part of water reducing agent and 0.03-0.06 part of defoaming agent; and carbon fibers, wherein the volume of the carbon fibers accounts for 0.6-1% of the volume of the mixture. The preparation method of the conductive cement-based material comprises the following steps of S1, preparing carbon fiber dispersion liquid; s2, preparing cement-based mortar; and S3, forming the conductive cement-based material. The conductive cement-based material has the properties of early strength and quick hardening, and is suitable for repair engineering; the durability and the toughness are higher, the resistivity is lower, and the shrinkage of the cement-based material is effectively reduced; has the functions of repairing and conducting electricity. However, the water reducing agent and the conductive carbon fiber are compounded into the material by adopting a compounding means, the conductive component is dispersed in the cement-based material, and the contact conductivity probability is not high, and the conductivity is not good.
Disclosure of Invention
In order to solve the defect of poor conductivity of the concrete with early strength in the prior art, the invention provides a ligand, which is prepared by polycondensation of a first polymer, thionyl chloride, 4-hydroxy-2, 2':6',2 '-terpyridine and dichloromethane, wherein the mass ratio of the first polymer to the 4-hydroxy-2, 2':6', 2' -terpyridine is (10-12): (1-1.5); the first polymer is prepared by free radical polymerization of methoxy polyethylene glycol acrylate, unsaturated monocarboxylic acid and acrylamide monomers, the molecular weight of the methoxy polyethylene glycol acrylate is 2000-5000, and the mass ratio of the methoxy polyethylene glycol acrylate to the unsaturated monocarboxylic acid to the acrylamide monomers is (110-120): (10-15): (1-1.5).
In one embodiment, the preparation method of the first polymer comprises the following specific steps in parts by mass:
putting 80-100 parts of deionized water, 110-120 parts of methoxy polyethylene glycol acrylate and 0.15-0.25 part of oxidant into a reaction kettle, stirring and dissolving uniformly, wherein the reaction temperature is 25-60 ℃; dissolving 10-15 parts of unsaturated monocarboxylic acid and 1-1.5 parts of acrylamide monomer in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.5-0.8 part of chain transfer agent in 20 parts of deionized water to prepare a material B for later use; dissolving 0.15-0.2 part of reducing agent in 20 parts of deionized water to prepare a material C for later use;
simultaneously, dropwise adding the prepared material A, material B and material C into the reaction kettle, dropwise adding the material A for 3.5-4 h, dropwise adding the material B for 3.5-4 h, dropwise adding the material C for 3-3.5 h, and carrying out heat preservation reaction for 1-2 h; and neutralizing until the pH value is 6-7, and removing water by reduced pressure distillation to obtain a first polymer.
In one embodiment, the unsaturated monocarboxylic acid is one or both of methacrylic acid and acrylic acid; the acrylamide monomer is one or more of N, N-dimethylacrylamide, N-isopropylacrylamide and acrylamide.
In one embodiment, the oxidant is one or more of ammonium persulfate, potassium persulfate, sodium persulfate and hydrogen peroxide; the chain transfer agent is one or more of 3-mercaptopropionic acid, thioglycolic acid, mercaptoethanol, thioglycerol and dodecyl mercaptan; the reducing agent is one or more of L-ascorbic acid, sodium bisulfite, sodium hypophosphite and sodium formaldehyde sulfoxylate; the pH was neutralized with sodium hydroxide.
The invention also provides a preparation method of the ligand, which comprises the following specific steps in parts by mass:
weighing 100-120 parts of a first polymer, adding the first polymer into a first reaction container, adding 150-250 parts of thionyl chloride, dropwise adding 0.5-1 part of N, N-dimethylformamide, heating and refluxing, and reacting t1Distilling to remove unreacted thionyl chloride, adding 100-200 parts of redistilled toluene, and distilling under reduced pressure to remove residual thionyl chloride; weighing 10-15 parts of 4-hydroxy-2, 2', 6', 2' -terpyridine, adding into a second reaction container, adding 10-30 parts of dry dichloromethane and 2-5 parts of triethylamine, stirring, and heating to reflux to obtain a material D;
diluting the material D with 400-500 parts of dry dichloromethane at t2Dropping into the first reaction container for continuous reaction t3(ii) a The solvent was removed by rotary evaporation to give the ligand.
In one embodiment, t1Is 5 to 7 hours, t21 to 1.5h, t3Is 20 to 28 hours.
The invention also provides a conductive early-strength polycarboxylate superplasticizer which is prepared from the ligand, zinc nitrate and deionized water in the technical scheme, wherein the mass ratio of the ligand to the zinc nitrate is 15: (2-3).
The invention also provides a preparation method of the conductive early-strength polycarboxylate superplasticizer, which comprises the following specific preparation steps in parts by mass:
weighing 150 parts of the ligand in a third reaction container, dissolving with equivalent deionized water to prepare a material E, weighing 20-30 parts of zinc nitrate in a fourth reaction container, adding equivalent deionized water to dissolve, transferring to a fifth reaction container, stirring for 5-10 min, adding the material E into the fifth reaction container, and supplementing water until the solid content is 35-45%, thus preparing the conductive early-strength polycarboxylate superplasticizer.
The invention also provides conductive early-strength graphene dispersion slurry which is prepared by mixing graphene, graphene oxide, the conductive early-strength polycarboxylate water reducer and deionized water in the technical scheme, wherein the mass ratio of the graphene to the graphene oxide to the conductive early-strength polycarboxylate water reducer to the deionized water is (1-4): (1-4): 5:50.
The invention also provides a preparation method of the conductive early-strength graphene dispersion slurry, which comprises the following specific steps: mixing graphene, graphene oxide, the conductive early-strength type polycarboxylate superplasticizer and deionized water, stirring at the speed of 500-540 r/min for 1-2 min, and then carrying out ultrasonic treatment for 20-60 min to obtain the conductive early-strength type graphene dispersion slurry.
Based on the above, compared with the prior art, the ligand provided by the invention introduces terpyridine groups, and because terpyridine is highly conjugated and stable, and N atoms on a ring are very active, the ligand is easy to react with Zn2+The coordination of metal ions forms a complex with novel and stable structure. The metal supermolecule polymer generated by coordination and complexation of the organic macromolecules containing the ligand and the metal ions introduces the metal into the polymer, so that the polymer has the properties of the polymer, and can obtain the characteristics of light, electricity, magnetism and the like which are unique to the metal ions, and the electric activity is obviously improved. The invention creatively applies the principle of matching of free radical polymerization activity and introduces polyether macromonomer with ultrahigh molecular weight, so that the molecular structure of the synthesized polymer is long in side chain and short in main chain, the shape of the molecule is changed from the traditional comb shape into an inverted T shape, the length of the side chain is far beyond the main chain, the structure not only has strong steric hindrance dispersion effect, but also has good hydrophilicity, the hydration process is accelerated, and simultaneously the development of the early strength of the concrete can be greatly promoted.
The invention adopts nitrate capable of accelerating the hydration speed of cement, introduces acrylamide functional small monomer with early strength effect in a polycarboxylic acid structure, and further promotes the development of early strength in coagulation by coordinating with the nitrate.
According to the invention, the conductive early-strength type graphene dispersion slurry prepared by mixing the conductive early-strength type polycarboxylate superplasticizer, the graphene oxide and the graphene and combining a dispersion process has the advantages of strong stability, excellent conductivity and early strength, steric hindrance generated by a long side chain structure of the conductive early-strength type polycarboxylate superplasticizer, prevention of graphene particle coagulation, and electrostatic repulsion provided by anionic polar groups such as carboxyl groups and the like to improve the dispersion effect.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; the technical features designed in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be noted that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs, and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The invention provides the following examples and comparative examples:
example 1
1. First Polymer Synthesis
Putting 80 parts of deionized water, 110 parts of methoxy polyethylene glycol acrylate (with the molecular weight of 5000) and 0.15 part of ammonium persulfate into a reaction kettle, and uniformly stirring and dissolving at the reaction temperature of 25 ℃;
dissolving 10 parts of methacrylic acid and 1 part of N, N-dimethylacrylamide in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.5 part of 3-mercaptopropionic acid in 20 parts of deionized water to prepare a material B for later use; 0.15 portion of L-ascorbic acid is dissolved in 20 portions of deionized water to prepare a material C for standby.
Simultaneously dropwise adding the prepared material A, material B and material C into the reaction kettle at a constant speed, dropwise adding the material A for 3.5 hours, dropwise adding the material B for 3 hours, and carrying out heat preservation reaction for 1 hour; adding 32% sodium hydroxide solution to neutralize until the pH value is 6, and distilling under reduced pressure to remove water to obtain a first polymer.
2. Ligand preparation
100 parts of the first polymer are weighed and added into a 1000ml three-necked flask, 200 parts of thionyl chloride is added, 0.5 part of N, N-dimethylformamide is added dropwise, heating reflux is carried out, and the reaction is carried out for 5 hours. Distilling to remove unreacted thionyl chloride, adding 150 parts by weight of distilled toluene, and distilling under reduced pressure to remove residual thionyl chloride.
Weighing 10 parts of 4-hydroxy-2, 2', 6', 2' -terpyridine, adding into a 100ml three-neck flask, adding 20 parts of dry dichloromethane and 3 parts of triethylamine, stirring, heating to reflux and obtaining material D. Diluting the obtained material D with 400 parts of dry dichloromethane, slowly dropwise adding the diluted material D into a 1000ml three-neck flask at a constant speed within 1h, and continuously reacting for 24 h. The solvent was removed by rotary evaporation to give the ligand.
3. Preparation of conductive early-strength polycarboxylate superplasticizer
Weighing 150 parts of ligand in a 500ml beaker, dissolving with equivalent deionized water to prepare a material E, weighing 20 parts of zinc nitrate in a 100ml beaker, adding equivalent deionized water to dissolve, transferring to the 100ml beaker, putting a rotary magneton on a magnetic stirrer to carry out magnetic stirring, dripping the material E into a zinc nitrate solution in the beaker at a constant speed for 5min, and replenishing water until the solid content is 40%, thus preparing the conductive early-strength polycarboxylate superplasticizer.
4. Preparation of conductive early-strength graphene dispersion slurry
Mixing 1 part of graphene, 4 parts of graphene oxide, 5 parts of conductive early-strength polycarboxylate superplasticizer and 50 parts of deionized water, mechanically stirring at the speed of 500r/min for 1min, and then moving into an ultrasonic instrument for ultrasonic treatment for 30min to obtain the conductive early-strength graphene dispersion slurry.
Example 2
1. First Polymer Synthesis
Putting 90 parts of deionized water, 110 parts of methoxy polyethylene glycol acrylate (molecular weight is 3000) and 0.2 part of sodium persulfate into a reaction kettle, and uniformly stirring and dissolving at the reaction temperature of 40 ℃;
dissolving 6 parts of methacrylic acid, 6 parts of acrylic acid and 1.2 parts of N-isopropylacrylamide in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.6 part of mercaptoethanol in 20 parts of deionized water to prepare a material B for later use; 0.18 part of sodium hypophosphite is dissolved in 20 parts of deionized water to prepare a material C for standby.
Simultaneously, dropwise adding the prepared material A, material B and material C into the reaction kettle at a constant speed for 3.5 hours, dropwise adding the material B for 3 hours, and carrying out heat preservation reaction for 1.5 hours; adding 32% sodium hydroxide solution to neutralize until the pH value is 6, and distilling under reduced pressure to remove water to obtain a first polymer.
2. Ligand preparation
110 parts of the first polymer are weighed and added into a 1000ml three-necked flask, 200 parts of thionyl chloride is added, 0.8 part of N, N-dimethylformamide is added dropwise, heating reflux is carried out, and the reaction is carried out for 6 hours. Distilling to remove unreacted thionyl chloride, adding 150 parts by weight of distilled toluene, and distilling under reduced pressure to remove residual thionyl chloride.
Weighing 12 parts of 4-hydroxy-2, 2', 6', 2' -terpyridine, adding into a 100ml three-neck flask, adding 20 parts of dry dichloromethane and 3 parts of triethylamine, stirring, heating to reflux and obtaining material D. Diluting the obtained material D with 400 parts of dry dichloromethane, slowly dropwise adding the diluted material D into a 1000ml three-neck flask at a constant speed within 1.5h, and continuously reacting for 24 h. The solvent was removed by rotary evaporation to give the ligand.
3. Preparation of conductive early-strength polycarboxylate superplasticizer
Weighing 150 parts of ligand in a 500ml beaker, dissolving with equivalent deionized water to prepare a material E, weighing 25 parts of zinc nitrate in a 100ml beaker, adding equivalent deionized water to dissolve, transferring to the 100ml beaker, putting a rotary magneton on a magnetic stirrer to carry out magnetic stirring, dripping the material E into a zinc nitrate solution in the beaker at a constant speed for 7min, and replenishing water until the solid content is 40%, thus preparing the conductive early-strength polycarboxylate superplasticizer.
4. Preparation of conductive early-strength graphene dispersion slurry
Mixing 2 parts of graphene, 3 parts of graphene oxide, 5 parts of conductive early-strength polycarboxylate superplasticizer and 50 parts of deionized water, mechanically stirring at the speed of 520r/min for 1.5min, and then moving into an ultrasonic instrument for ultrasonic treatment for 40min to obtain the conductive early-strength graphene dispersion slurry.
Example 3
1. First Polymer Synthesis
Putting 100 parts of deionized water, 120 parts of methoxy polyethylene glycol acrylate (molecular weight 2000) and 0.25 part of hydrogen peroxide into a reaction kettle, stirring and dissolving uniformly, wherein the reaction temperature is 60 ℃;
dissolving 15 parts of acrylic acid and 1.5 parts of acrylamide in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.8 part of dodecyl mercaptan in 20 parts of deionized water to prepare a material B for later use; 0.2 part of sodium formaldehyde sulfoxylate is dissolved in 20 parts of deionized water to prepare a material C for standby.
Simultaneously dropwise adding the prepared material A, material B and material C into the reaction kettle at a constant speed, dropwise adding the material A for 4 hours, dropwise adding the material B for 3.5 hours, and carrying out heat preservation reaction for 2 hours; adding 32% sodium hydroxide solution to neutralize until the pH value is 7, and distilling under reduced pressure to remove water to obtain a first polymer.
2. Ligand preparation
120 parts of the first polymer is weighed and added into a 1000ml three-necked flask, 200 parts of thionyl chloride is added, 1 part of N, N-dimethylformamide is added dropwise, heating reflux is carried out, and the reaction is carried out for 7 hours. Distilling to remove unreacted thionyl chloride, adding 150 parts by weight of distilled toluene, and distilling under reduced pressure to remove residual thionyl chloride.
Weighing 15 parts of 4-hydroxy-2, 2', 6', 2' -terpyridine, adding into a 100ml three-neck flask, adding 20 parts of dry dichloromethane and 3 parts of triethylamine, stirring, heating to reflux and obtaining material D. Diluting the obtained material D with 400 parts of dry dichloromethane, slowly dropwise adding the diluted material D into a 1000ml three-neck flask at a constant speed within 1.5h, and continuously reacting for 24 h. The solvent was removed by rotary evaporation to give the ligand.
3. Preparation of conductive early-strength polycarboxylate superplasticizer
Weighing 150 parts of ligand in a 500ml beaker, dissolving with equivalent deionized water to prepare a material E, weighing 30 parts of zinc nitrate in a 100ml beaker, adding equivalent deionized water to dissolve, transferring to the 100ml beaker, putting a rotary magneton on a magnetic stirrer to carry out magnetic stirring, dripping the material E into a zinc nitrate solution in the beaker at a constant speed within 10min, and replenishing water until the solid content is 40%, thus preparing the conductive early-strength polycarboxylate superplasticizer.
4. Preparation of conductive early-strength graphene dispersion slurry
Mixing 2.5 parts of graphene, 2.5 parts of graphene oxide, 5 parts of conductive early-strength polycarboxylate superplasticizer and 50 parts of deionized water, mechanically stirring for 2min at the speed of 540r/min, and then moving into an ultrasonic instrument for ultrasonic treatment for 60min to obtain the conductive early-strength graphene dispersion slurry.
Example 4
1. First Polymer Synthesis
Putting 80 parts of deionized water, 110 parts of methoxy polyethylene glycol acrylate (with the molecular weight of 5000) and 0.15 part of ammonium persulfate into a reaction kettle, and uniformly stirring and dissolving at the reaction temperature of 25 ℃;
dissolving 10 parts of methacrylic acid and 1 part of N, N-dimethylacrylamide in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.5 part of 3-mercaptopropionic acid in 20 parts of deionized water to prepare a material B for later use; 0.15 portion of L-ascorbic acid is dissolved in 20 portions of deionized water to prepare a material C for standby.
Simultaneously dropwise adding the prepared material A, material B and material C into the reaction kettle at a constant speed, dropwise adding the material A for 3.5 hours, dropwise adding the material B for 3 hours, and carrying out heat preservation reaction for 1 hour; adding 32% sodium hydroxide solution to neutralize until the pH value is 6, and distilling under reduced pressure to remove water to obtain a first polymer.
2. Ligand preparation
100 parts of the first polymer are weighed and added into a 1000ml three-necked flask, 200 parts of thionyl chloride is added, 0.5 part of N, N-dimethylformamide is added dropwise, heating reflux is carried out, and the reaction is carried out for 5 hours. Distilling to remove unreacted thionyl chloride, adding 150 parts by weight of distilled toluene, and distilling under reduced pressure to remove residual thionyl chloride.
Weighing 15 parts of 4-hydroxy-2, 2', 6', 2' -terpyridine, adding into a 100ml three-neck flask, adding 20 parts of dry dichloromethane and 3 parts of triethylamine, stirring, heating to reflux and obtaining material D. Diluting the obtained material D with 400 parts of dry dichloromethane, slowly dropwise adding the diluted material D into a 1000ml three-neck flask at a constant speed within 1h, and continuously reacting for 24 h. The solvent was removed by rotary evaporation to give the ligand.
3. Preparation of conductive early-strength polycarboxylate superplasticizer
Weighing 150 parts of ligand in a 500ml beaker, dissolving with equivalent deionized water to prepare a material E, weighing 20 parts of zinc nitrate in a 100ml beaker, adding equivalent deionized water to dissolve, transferring to the 100ml beaker, putting a rotary magneton on a magnetic stirrer to carry out magnetic stirring, dripping the material E into a zinc nitrate solution in the beaker at a constant speed for 5min, and replenishing water until the solid content is 40%, thus preparing the conductive early-strength polycarboxylate superplasticizer.
4. Preparation of conductive early-strength graphene dispersion slurry
Mixing 1 part of graphene, 4 parts of graphene oxide, 5 parts of conductive early-strength polycarboxylate superplasticizer and 50 parts of deionized water, mechanically stirring at the speed of 500r/min for 1min, and then moving into an ultrasonic instrument for ultrasonic treatment for 30min to obtain the conductive early-strength graphene dispersion slurry.
Example 5
1. First Polymer Synthesis
Putting 80 parts of deionized water, 110 parts of methoxy polyethylene glycol acrylate (with the molecular weight of 5000) and 0.15 part of ammonium persulfate into a reaction kettle, and uniformly stirring and dissolving at the reaction temperature of 25 ℃;
dissolving 10 parts of methacrylic acid and 1 part of N, N-dimethylacrylamide in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.5 part of 3-mercaptopropionic acid in 20 parts of deionized water to prepare a material B for later use; 0.15 portion of L-ascorbic acid is dissolved in 20 portions of deionized water to prepare a material C for standby.
Simultaneously dropwise adding the prepared material A, material B and material C into the reaction kettle at a constant speed, dropwise adding the material A for 3.5 hours, dropwise adding the material B for 3 hours, and carrying out heat preservation reaction for 1 hour; adding 32% sodium hydroxide solution to neutralize until the pH value is 6, and distilling under reduced pressure to remove water to obtain a first polymer.
2. Ligand preparation
100 parts of the first polymer are weighed and added into a 1000ml three-necked flask, 200 parts of thionyl chloride is added, 0.5 part of N, N-dimethylformamide is added dropwise, heating reflux is carried out, and the reaction is carried out for 5 hours. Distilling to remove unreacted thionyl chloride, adding 150 parts by weight of distilled toluene, and distilling under reduced pressure to remove residual thionyl chloride.
Weighing 15 parts of 4-hydroxy-2, 2', 6', 2' -terpyridine, adding into a 100ml three-neck flask, adding 20 parts of dry dichloromethane and 3 parts of triethylamine, stirring, heating to reflux and obtaining material D. Diluting the obtained material D with 400 parts of dry dichloromethane, slowly dropwise adding the diluted material D into a 1000ml three-neck flask at a constant speed within 1h, and continuously reacting for 24 h. The solvent was removed by rotary evaporation to give the ligand.
3. Preparation of conductive early-strength polycarboxylate superplasticizer
Weighing 150 parts of ligand in a 500ml beaker, dissolving with equivalent deionized water to prepare a material E, weighing 30 parts of zinc nitrate in a 100ml beaker, adding equivalent deionized water to dissolve, transferring to the 100ml beaker, placing a rotary magneton on a magnetic stirrer to carry out magnetic stirring, dripping the material E into a zinc nitrate solution in the beaker at a constant speed for 5min, and replenishing water until the solid content is 40%, thus preparing the conductive early-strength polycarboxylate superplasticizer.
4. Preparation of conductive early-strength graphene dispersion slurry
Mixing 1 part of graphene, 4 parts of graphene oxide, 5 parts of conductive early-strength polycarboxylate superplasticizer and 50 parts of deionized water, mechanically stirring at the speed of 500r/min for 1min, and then moving into an ultrasonic instrument for ultrasonic treatment for 30min to obtain the conductive early-strength graphene dispersion slurry.
Example 6
1. First Polymer Synthesis
Putting 80 parts of deionized water, 110 parts of methoxy polyethylene glycol acrylate (with the molecular weight of 5000) and 0.15 part of ammonium persulfate into a reaction kettle, and uniformly stirring and dissolving at the reaction temperature of 25 ℃;
dissolving 10 parts of methacrylic acid and 1 part of N, N-dimethylacrylamide in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.5 part of 3-mercaptopropionic acid in 20 parts of deionized water to prepare a material B for later use; 0.15 portion of L-ascorbic acid is dissolved in 20 portions of deionized water to prepare a material C for standby.
Simultaneously dropwise adding the prepared material A, material B and material C into the reaction kettle at a constant speed, dropwise adding the material A for 3.5 hours, dropwise adding the material B for 3 hours, and carrying out heat preservation reaction for 1 hour; adding 32% sodium hydroxide solution to neutralize until the pH value is 6, and distilling under reduced pressure to remove water to obtain a first polymer.
2. Ligand preparation
100 parts of the first polymer are weighed and added into a 1000ml three-necked flask, 200 parts of thionyl chloride is added, 0.5 part of N, N-dimethylformamide is added dropwise, heating reflux is carried out, and the reaction is carried out for 5 hours. Distilling to remove unreacted thionyl chloride, adding 150 parts by weight of distilled toluene, and distilling under reduced pressure to remove residual thionyl chloride.
Weighing 10 parts of 4-hydroxy-2, 2', 6', 2' -terpyridine, adding into a 100ml three-neck flask, adding 20 parts of dry dichloromethane and 3 parts of triethylamine, stirring, heating to reflux and obtaining material D. Diluting the obtained material D with 400 parts of dry dichloromethane, slowly dropwise adding the diluted material D into a 1000ml three-neck flask at a constant speed within 1h, and continuously reacting for 24 h. The solvent was removed by rotary evaporation to give the ligand.
3. Preparation of conductive early-strength polycarboxylate superplasticizer
Weighing 150 parts of ligand in a 500ml beaker, dissolving with equivalent deionized water to prepare a material E, weighing 30 parts of zinc nitrate in a 100ml beaker, adding equivalent deionized water to dissolve, transferring to the 100ml beaker, placing a rotary magneton on a magnetic stirrer to carry out magnetic stirring, dripping the material E into a zinc nitrate solution in the beaker at a constant speed for 5min, and replenishing water until the solid content is 40%, thus preparing the conductive early-strength polycarboxylate superplasticizer.
4. Preparation of conductive early-strength graphene dispersion slurry
Mixing 1 part of graphene, 4 parts of graphene oxide, 5 parts of conductive early-strength polycarboxylate superplasticizer and 50 parts of deionized water, mechanically stirring at the speed of 500r/min for 1min, and then moving into an ultrasonic instrument for ultrasonic treatment for 30min to obtain the conductive early-strength graphene dispersion slurry.
Comparative example 1
1 part of graphene, 4 parts of graphene oxide, 5 parts of a commercially available early strength water reducing agent (the solid content is 40%) and 50 parts of deionized water are mixed, mechanically stirred at the speed of 500r/min for 1min, and then moved into an ultrasonic instrument for 30min to prepare slurry.
Comparative example 2
Mixing 2 parts of graphene, 3 parts of graphene oxide, 5 parts of a commercial early strength water reducing agent (the solid content is 40%) and 50 parts of deionized water, mechanically stirring at the speed of 520r/min for 1.5min, and then moving into an ultrasonic instrument for ultrasonic treatment for 40min to obtain the slurry.
Comparative example 3
Mixing 2.5 parts of graphene, 2.5 parts of graphene oxide, 5 parts of a commercial early strength water reducing agent (the solid content is 40%) and 50 parts of deionized water, mechanically stirring at the speed of 540r/min for 2min, and then moving into an ultrasonic instrument for ultrasonic treatment for 60min to obtain the slurry.
Comparative example 4
1. First Polymer Synthesis
Putting 80 parts of deionized water, 110 parts of methoxy polyethylene glycol acrylate (with the molecular weight of 5000) and 0.15 part of ammonium persulfate into a reaction kettle, and uniformly stirring and dissolving at the reaction temperature of 25 ℃;
dissolving 10 parts of methacrylic acid and 1 part of N, N-dimethylacrylamide in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.5 part of 3-mercaptopropionic acid in 20 parts of deionized water to prepare a material B for later use; 0.15 portion of L-ascorbic acid is dissolved in 20 portions of deionized water to prepare a material C for standby.
Simultaneously dropwise adding the prepared material A, material B and material C into the reaction kettle at a constant speed, dropwise adding the material A for 3.5 hours, dropwise adding the material B for 3 hours, and carrying out heat preservation reaction for 1 hour; adding 32% sodium hydroxide solution to neutralize until the pH value is 6, and distilling under reduced pressure to remove water to obtain a first polymer.
2. Ligand preparation
100 parts of the first polymer are weighed and added into a 1000ml three-necked flask, 200 parts of thionyl chloride is added, 0.5 part of N, N-dimethylformamide is added dropwise, heating reflux is carried out, and the reaction is carried out for 5 hours. Distilling to remove unreacted thionyl chloride, adding 150 parts of redistilled toluene, and distilling under reduced pressure to remove residual thionyl chloride to obtain the ligand.
3. Preparation of conductive early-strength polycarboxylate superplasticizer
Weighing 150 parts of ligand in a 500ml beaker, dissolving with equivalent deionized water to prepare a material E, weighing 20 parts of zinc nitrate in a 100ml beaker, adding equivalent deionized water to dissolve, transferring to the 100ml beaker, putting a rotary magneton on a magnetic stirrer to carry out magnetic stirring, dripping the material E into a zinc nitrate solution in the beaker at a constant speed for 5min, and replenishing water until the solid content is 40%, thus preparing the conductive early-strength polycarboxylate superplasticizer.
4. Preparation of conductive early-strength graphene dispersion slurry
Mixing 1 part of graphene, 4 parts of graphene oxide, 5 parts of conductive early-strength polycarboxylate superplasticizer and 50 parts of deionized water, mechanically stirring at the speed of 500r/min for 1min, and then moving into an ultrasonic instrument for ultrasonic treatment for 30min to obtain the conductive early-strength graphene dispersion slurry.
Comparative example 5
1. First Polymer Synthesis
Putting 80 parts of deionized water, 110 parts of methoxy polyethylene glycol acrylate (with the molecular weight of 5000) and 0.15 part of ammonium persulfate into a reaction kettle, and uniformly stirring and dissolving at the reaction temperature of 25 ℃;
dissolving 10 parts of methacrylic acid and 1 part of N, N-dimethylacrylamide in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.5 part of 3-mercaptopropionic acid in 20 parts of deionized water to prepare a material B for later use; 0.15 portion of L-ascorbic acid is dissolved in 20 portions of deionized water to prepare a material C for standby.
Simultaneously dropwise adding the prepared material A, material B and material C into the reaction kettle at a constant speed, dropwise adding the material A for 3.5 hours, dropwise adding the material B for 3 hours, and carrying out heat preservation reaction for 1 hour; adding 32% sodium hydroxide solution to neutralize until the pH value is 6, and distilling under reduced pressure to remove water to obtain a first polymer.
2. Ligand preparation
100 parts of the first polymer are weighed and added into a 1000ml three-necked flask, 200 parts of thionyl chloride is added, 0.5 part of N, N-dimethylformamide is added dropwise, heating reflux is carried out, and the reaction is carried out for 5 hours. Distilling to remove unreacted thionyl chloride, adding 150 parts by weight of distilled toluene, and distilling under reduced pressure to remove residual thionyl chloride.
Weighing 20 parts of 4-hydroxy-2, 2', 6', 2' -terpyridine, adding into a 100ml three-neck flask, adding 20 parts of dry dichloromethane and 3 parts of triethylamine, stirring, heating to reflux and obtaining material D. Diluting the obtained material D with 400 parts of dry dichloromethane, slowly dropwise adding the diluted material D into a 1000ml three-neck flask at a constant speed within 1h, and continuously reacting for 24 h. The solvent was removed by rotary evaporation to give the ligand.
3. Preparation of conductive early-strength polycarboxylate superplasticizer
Weighing 150 parts of ligand in a 500ml beaker, dissolving with equivalent deionized water to prepare a material E, weighing 20 parts of zinc nitrate in a 100ml beaker, adding equivalent deionized water to dissolve, transferring to the 100ml beaker, putting a rotary magneton on a magnetic stirrer to carry out magnetic stirring, dripping the material E into a zinc nitrate solution in the beaker at a constant speed for 5min, and replenishing water until the solid content is 40%, thus preparing the conductive early-strength polycarboxylate superplasticizer.
4. Preparation of conductive early-strength graphene dispersion slurry
Mixing 1 part of graphene, 4 parts of graphene oxide, 5 parts of conductive early-strength polycarboxylate superplasticizer and 50 parts of deionized water, mechanically stirring at the speed of 500r/min for 1min, and then moving into an ultrasonic instrument for ultrasonic treatment for 30min to obtain the conductive early-strength graphene dispersion slurry.
Comparative example 6
1. First Polymer Synthesis
Putting 80 parts of deionized water, 110 parts of methoxy polyethylene glycol acrylate (with the molecular weight of 5000) and 0.15 part of ammonium persulfate into a reaction kettle, and uniformly stirring and dissolving at the reaction temperature of 25 ℃;
dissolving 10 parts of methacrylic acid and 1 part of N, N-dimethylacrylamide in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.5 part of 3-mercaptopropionic acid in 20 parts of deionized water to prepare a material B for later use; 0.15 portion of L-ascorbic acid is dissolved in 20 portions of deionized water to prepare a material C for standby.
Simultaneously dropwise adding the prepared material A, material B and material C into the reaction kettle at a constant speed, dropwise adding the material A for 3.5 hours, dropwise adding the material B for 3 hours, and carrying out heat preservation reaction for 1 hour; adding 32% sodium hydroxide solution to neutralize until the pH value is 6, and distilling under reduced pressure to remove water to obtain a first polymer.
2. Ligand preparation
100 parts of the first polymer are weighed and added into a 1000ml three-necked flask, 200 parts of thionyl chloride is added, 0.5 part of N, N-dimethylformamide is added dropwise, heating reflux is carried out, and the reaction is carried out for 5 hours. Distilling to remove unreacted thionyl chloride, adding 150 parts by weight of distilled toluene, and distilling under reduced pressure to remove residual thionyl chloride.
Weighing 7 parts of 4-hydroxy-2, 2', 6', 2' -terpyridine, adding into a 100ml three-neck flask, adding 20 parts of dry dichloromethane and 3 parts of triethylamine, stirring, heating to reflux and obtaining material D. Diluting the obtained material D with 400 parts of dry dichloromethane, slowly dropwise adding the diluted material D into a 1000ml three-neck flask at a constant speed within 1h, and continuously reacting for 24 h. The solvent was removed by rotary evaporation to give the ligand.
3. Preparation of conductive early-strength polycarboxylate superplasticizer
Weighing 150 parts of ligand in a 500ml beaker, dissolving with equivalent deionized water to prepare a material E, weighing 20 parts of zinc nitrate in a 100ml beaker, adding equivalent deionized water to dissolve, transferring to the 100ml beaker, putting a rotary magneton on a magnetic stirrer to carry out magnetic stirring, dripping the material E into a zinc nitrate solution in the beaker at a constant speed for 5min, and replenishing water until the solid content is 40%, thus preparing the conductive early-strength polycarboxylate superplasticizer.
4. Preparation of conductive early-strength graphene dispersion slurry
Mixing 1 part of graphene, 4 parts of graphene oxide, 5 parts of conductive early-strength polycarboxylate superplasticizer and 50 parts of deionized water, mechanically stirring at the speed of 500r/min for 1min, and then moving into an ultrasonic instrument for ultrasonic treatment for 30min to obtain the conductive early-strength graphene dispersion slurry.
Comparative example 7
1. First Polymer Synthesis
Putting 80 parts of deionized water, 110 parts of methoxy polyethylene glycol acrylate (with the molecular weight of 5000) and 0.15 part of ammonium persulfate into a reaction kettle, and uniformly stirring and dissolving at the reaction temperature of 25 ℃;
dissolving 10 parts of methacrylic acid and 1 part of N, N-dimethylacrylamide in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.5 part of 3-mercaptopropionic acid in 20 parts of deionized water to prepare a material B for later use; 0.15 portion of L-ascorbic acid is dissolved in 20 portions of deionized water to prepare a material C for standby.
Simultaneously dropwise adding the prepared material A, material B and material C into the reaction kettle at a constant speed, dropwise adding the material A for 3.5 hours, dropwise adding the material B for 3 hours, and carrying out heat preservation reaction for 1 hour; adding 32% sodium hydroxide solution to neutralize until the pH value is 6, and distilling under reduced pressure to remove water to obtain a first polymer.
2. Ligand preparation
100 parts of the first polymer are weighed and added into a 1000ml three-necked flask, 200 parts of thionyl chloride is added, 0.5 part of N, N-dimethylformamide is added dropwise, heating reflux is carried out, and the reaction is carried out for 5 hours. Distilling to remove unreacted thionyl chloride, adding 150 parts by weight of distilled toluene, and distilling under reduced pressure to remove residual thionyl chloride.
Weighing 10 parts of 4-hydroxy-2, 2', 6', 2' -terpyridine, adding into a 100ml three-neck flask, adding 20 parts of dry dichloromethane and 3 parts of triethylamine, stirring, heating to reflux and obtaining material D. Diluting the obtained material D with 400 parts of dry dichloromethane, slowly dropwise adding the diluted material D into a 1000ml three-neck flask at a constant speed within 1h, and continuously reacting for 24 h. The solvent was removed by rotary evaporation to give the ligand.
3. Preparation of conductive early-strength polycarboxylate superplasticizer
Weighing 150 parts of ligand in a 500ml beaker, dissolving with equivalent deionized water to prepare a material E, weighing 10 parts of zinc nitrate in a 100ml beaker, adding equivalent deionized water to dissolve, transferring to the 100ml beaker, putting a rotary magneton on a magnetic stirrer to carry out magnetic stirring, dripping the material E into a zinc nitrate solution in the beaker at a constant speed for 5min, and replenishing water until the solid content is 40%, thus preparing the conductive early-strength polycarboxylate superplasticizer.
4. Preparation of conductive early-strength graphene dispersion slurry
Mixing 1 part of graphene, 4 parts of graphene oxide, 5 parts of conductive early-strength polycarboxylate superplasticizer and 50 parts of deionized water, mechanically stirring at the speed of 500r/min for 1min, and then moving into an ultrasonic instrument for ultrasonic treatment for 30min to obtain the conductive early-strength graphene dispersion slurry.
Comparative example 8
1. First Polymer Synthesis
Putting 80 parts of deionized water, 110 parts of methoxy polyethylene glycol acrylate (with the molecular weight of 5000) and 0.15 part of ammonium persulfate into a reaction kettle, and uniformly stirring and dissolving at the reaction temperature of 25 ℃;
dissolving 10 parts of methacrylic acid and 1 part of N, N-dimethylacrylamide in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.5 part of 3-mercaptopropionic acid in 20 parts of deionized water to prepare a material B for later use; 0.15 portion of L-ascorbic acid is dissolved in 20 portions of deionized water to prepare a material C for standby.
Simultaneously dropwise adding the prepared material A, material B and material C into the reaction kettle at a constant speed, dropwise adding the material A for 3.5 hours, dropwise adding the material B for 3 hours, and carrying out heat preservation reaction for 1 hour; adding 32% sodium hydroxide solution to neutralize until the pH value is 6, and distilling under reduced pressure to remove water to obtain a first polymer.
2. Ligand preparation
100 parts of the first polymer are weighed and added into a 1000ml three-necked flask, 200 parts of thionyl chloride is added, 0.5 part of N, N-dimethylformamide is added dropwise, heating reflux is carried out, and the reaction is carried out for 5 hours. Distilling to remove unreacted thionyl chloride, adding 150 parts by weight of distilled toluene, and distilling under reduced pressure to remove residual thionyl chloride.
Weighing 10 parts of 4-hydroxy-2, 2', 6', 2' -terpyridine, adding into a 100ml three-neck flask, adding 20 parts of dry dichloromethane and 3 parts of triethylamine, stirring, heating to reflux and obtaining material D. Diluting the obtained material D with 400 parts of dry dichloromethane, slowly dropwise adding the diluted material D into a 1000ml three-neck flask at a constant speed within 1h, and continuously reacting for 24 h. The solvent was removed by rotary evaporation to give the ligand.
3. Preparation of conductive early-strength polycarboxylate superplasticizer
Weighing 150 parts of ligand in a 500ml beaker, dissolving with equivalent deionized water to prepare a material E, weighing 40 parts of zinc nitrate in a 100ml beaker, adding equivalent deionized water to dissolve, transferring to the 100ml beaker, putting a rotary magneton on a magnetic stirrer to carry out magnetic stirring, dripping the material E into a zinc nitrate solution in the beaker at a constant speed for 5min, and replenishing water until the solid content is 40%, thus preparing the conductive early-strength polycarboxylate superplasticizer.
4. Preparation of conductive early-strength graphene dispersion slurry
Mixing 1 part of graphene, 4 parts of graphene oxide, 5 parts of conductive early-strength polycarboxylate superplasticizer and 50 parts of deionized water, mechanically stirring at the speed of 500r/min for 1min, and then moving into an ultrasonic instrument for ultrasonic treatment for 30min to obtain the conductive early-strength graphene dispersion slurry.
Comparative example 9
1. First Polymer Synthesis
Putting 80 parts of deionized water, 110 parts of methoxy polyethylene glycol acrylate (with the molecular weight of 5000) and 0.15 part of ammonium persulfate into a reaction kettle, and uniformly stirring and dissolving at the reaction temperature of 25 ℃;
dissolving 10 parts of methacrylic acid and 1 part of N, N-dimethylacrylamide in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.5 part of 3-mercaptopropionic acid in 20 parts of deionized water to prepare a material B for later use; 0.15 portion of L-ascorbic acid is dissolved in 20 portions of deionized water to prepare a material C for standby.
Simultaneously dropwise adding the prepared material A, material B and material C into the reaction kettle at a constant speed, dropwise adding the material A for 3.5 hours, dropwise adding the material B for 3 hours, and carrying out heat preservation reaction for 1 hour; adding 32% sodium hydroxide solution to neutralize until the pH value is 6, and distilling under reduced pressure to remove water to obtain a first polymer.
2. Ligand preparation
100 parts of the first polymer are weighed and added into a 1000ml three-necked flask, 200 parts of thionyl chloride is added, 0.5 part of N, N-dimethylformamide is added dropwise, heating reflux is carried out, and the reaction is carried out for 5 hours. Distilling to remove unreacted thionyl chloride, adding 150 parts by weight of distilled toluene, and distilling under reduced pressure to remove residual thionyl chloride.
Weighing 10 parts of 4-hydroxy-2, 2', 6', 2' -terpyridine, adding into a 100ml three-neck flask, adding 20 parts of dry dichloromethane and 3 parts of triethylamine, stirring, heating to reflux and obtaining material D. Diluting the obtained material D with 400 parts of dry dichloromethane, slowly dropwise adding the diluted material D into a 1000ml three-neck flask at a constant speed within 1h, and continuously reacting for 24 h. The solvent was removed by rotary evaporation to give the ligand.
3. Preparation of polycarboxylic acid water reducing agent
And weighing 150 parts of ligand in a 500ml beaker, and supplementing water until the solid content is 40% to obtain the polycarboxylic acid water reducing agent.
4. Preparation of conductive early-strength graphene dispersion slurry
Mixing 1 part of graphene, 4 parts of graphene oxide, 5 parts of conductive early-strength polycarboxylate superplasticizer and 50 parts of deionized water, mechanically stirring at the speed of 500r/min for 1min, and then moving into an ultrasonic instrument for ultrasonic treatment for 30min to obtain the conductive early-strength graphene dispersion slurry.
Comparative example 10
1. First Polymer Synthesis
Putting 80 parts of deionized water, 110 parts of methoxy polyethylene glycol acrylate (with the molecular weight of 5000) and 0.15 part of ammonium persulfate into a reaction kettle, and uniformly stirring and dissolving at the reaction temperature of 25 ℃;
dissolving 10 parts of methacrylic acid and 1 part of N, N-dimethylacrylamide in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.5 part of 3-mercaptopropionic acid in 20 parts of deionized water to prepare a material B for later use; 0.15 portion of L-ascorbic acid is dissolved in 20 portions of deionized water to prepare a material C for standby.
Simultaneously dropwise adding the prepared material A, material B and material C into the reaction kettle at a constant speed, dropwise adding the material A for 3.5 hours, dropwise adding the material B for 3 hours, and carrying out heat preservation reaction for 1 hour; adding 32% sodium hydroxide solution to neutralize until the pH value is 6, and distilling under reduced pressure to remove water to obtain a first polymer.
2. Ligand preparation
100 parts of the first polymer are weighed and added into a 1000ml three-necked flask, 200 parts of thionyl chloride is added, 0.5 part of N, N-dimethylformamide is added dropwise, heating reflux is carried out, and the reaction is carried out for 5 hours. Distilling to remove unreacted thionyl chloride, adding 150 parts by weight of distilled toluene, and distilling under reduced pressure to remove residual thionyl chloride.
Weighing 10 parts of 4-hydroxy-2, 2', 6', 2' -terpyridine, adding into a 100ml three-neck flask, adding 20 parts of dry dichloromethane and 3 parts of triethylamine, stirring, heating to reflux and obtaining material D. Diluting the obtained material D with 400 parts of dry dichloromethane, slowly dropwise adding the diluted material D into a 1000ml three-neck flask at a constant speed within 1h, and continuously reacting for 24 h. The solvent was removed by rotary evaporation to give the ligand.
3. Preparation of conductive early-strength polycarboxylate superplasticizer
Weighing 150 parts of ligand in a 500ml beaker, dissolving with equivalent deionized water to prepare a material E, weighing 20 parts of zinc nitrate in a 100ml beaker, adding equivalent deionized water to dissolve, transferring to the 100ml beaker, putting a rotary magneton on a magnetic stirrer to carry out magnetic stirring, dripping the material E into a zinc nitrate solution in the beaker at a constant speed for 5min, and replenishing water until the solid content is 40%, thus preparing the conductive early-strength polycarboxylate superplasticizer.
4. Preparation of conductive early-strength graphene dispersion slurry
Mixing 8 parts of graphene, 4 parts of graphene oxide, 5 parts of conductive early-strength polycarboxylate superplasticizer and 50 parts of deionized water, mechanically stirring at the speed of 500r/min for 1min, and then moving into an ultrasonic instrument for ultrasonic treatment for 30min to obtain the conductive early-strength graphene dispersion slurry.
The grade and other technical indexes of the raw materials adopted in the preparation method, the examples and the comparative examples can be selected according to the prior art, and if the technical indexes are specified in the invention, the technical indexes are selected within the range specified in the invention, so that the technical effect of the invention is not influenced.
The performances of the conductive early-strength polycarboxylate water reducer synthesized in the examples 1 to 3 were compared with the commercially available early-strength polycarboxylate water reducer (solid content: 40%) and the water reducer obtained in the comparative examples 4 to 9, and the water-reducing rate, gas content and strength of the concrete were measured according to GB 8076 + 2008 "concrete admixture" using red lion cement with a water reducer addition amount of 0.40% by mass of the cement (converted into solid content). And when the test piece is cured to the corresponding age, directly testing the resistivity of the test piece by using a resistivity meter. The test method comprises the following steps: selecting a certain non-molding surface of the test piece as a test surface, wetting the molding surface by using wet cloth, simultaneously plugging wetted sponge into an electrode of the resistivity meter, opening a switch of the resistivity meter, and tightly attaching the electrode of the resistivity meter on the test surface for testing. The concrete mixing proportion is as follows: cement 360kg/m3790kg/m of sand3Stone 1060kg/m3175kg/m of water3The results are shown in Table 1. Comparing the performances of the conductive early-strength graphene dispersion slurry obtained by compounding in the examples 1 to 3 with those of the comparative examples 1 to 10, and keeping the mixing amount of the water reducing agentThe cement mortar is 0.38 percent (by weight) of the mass of the cement, the mixing amount of the slurry is 0.5 percent of the mass of the cement, and the mixing ratio of the concrete is as follows: cement 360kg/m3790kg/m of sand3Stone 1060kg/m3173.5kg/m of water3The results of the tests on the air content, strength and resistivity of the concrete are shown in the attached table 2.
TABLE 1 comparison of Water reducing agent Properties
Figure 3
TABLE 2 comparison of slurry Properties
Figure RE-GDA0003411391570000232
As shown in the test results of examples 1-3 and the commercially available early strength type water reducing agent in the attached Table 1, the conductive early strength type polycarboxylate water reducing agent disclosed by the invention has a conductive effect while maintaining excellent water reducing and early strength properties; examples 4-6, comparative example 4 (no terpyridine group) and comparative example 9 (no zinc nitrate) show that the terpyridine group and the zinc nitrate play a mutual supporting and mutual influencing role in the conductivity of the water reducing agent, and the generated conductivity effect is superior to the conductivity when the terpyridine group and the zinc nitrate are used independently; and when no zinc nitrate exists, the early strength performance of the conductive early strength type polycarboxylate water reducer is reduced because the synergistic effect of the zinc nitrate and the acrylamide monomer disappears. Comparative examples 5 to 8 show that the electric conduction effect of the water reducing agent is reduced when the content of the terpyridine group and the zinc nitrate is not within the range disclosed by the technical scheme of the invention. The test results of examples 1-3 and comparative examples 1-3 in the attached table 2 show that the conductive early-strength graphene dispersion slurry provided by the invention can further improve the early and later strength of concrete and enhance the conductivity of the concrete; examples 4-6, comparative example 4 and comparative example 9 show that terpyridine groups and zinc nitrate play a role in mutual support and influence on the conductivity of the conductive early-strength graphene dispersion slurry, and the generated conductive effect is superior to the conductivity when terpyridine groups and zinc nitrate are used alone; comparative examples 5-8 show that the conductive effect of the conductive early-strength type graphene dispersion slurry is reduced when the content of the terpyridine group and the zinc nitrate is not within the disclosure range of the technical scheme, and comparative example 10 shows that the conductive early-strength type polycarboxylate superplasticizer has a dispersion effect on graphene, when the content of graphene is increased, graphene agglomeration is caused and the conductive capability is reduced because the mass ratio of the conductive early-strength type polycarboxylate superplasticizer to graphene is reduced and graphene cannot be effectively dispersed.
It is obvious to those skilled in the art that the technical solutions of the present invention can still obtain the same or similar technical effects as the above embodiments when changed within the following ranges, and still fall within the protection scope of the present invention.
In conclusion, compared with the prior art, the ligand provided by the invention introduces terpyridine groups, and because terpyridine is highly conjugated and stable, and N atoms on a ring are very active, the ligand is easy to react with Zn2+The coordination of metal ions forms a complex with novel and stable structure. The metal supermolecule polymer generated by coordination and complexation of the organic macromolecules containing the ligand and the metal ions introduces the metal into the polymer, so that the polymer has the properties of the polymer, and can obtain the characteristics of light, electricity, magnetism and the like which are unique to the metal ions, and the electric activity is obviously improved. The invention creatively applies the principle of matching of free radical polymerization activity and introduces polyether macromonomer with ultrahigh molecular weight, so that the molecular structure of the synthesized polymer is long in side chain and short in main chain, the shape of the molecule is changed from the traditional comb shape into an inverted T shape, the length of the side chain is far beyond the main chain, the structure not only has strong steric hindrance dispersion effect, but also has good hydrophilicity, the hydration process is accelerated, and simultaneously the development of the early strength of the concrete can be greatly promoted.
The synthetic method of the first polymer is simple, side reactions are few, and the water reducing agent synthesized by the first polymer is high in water reducing rate because the water reducing agent does not contain interfering components such as quaternary ammonium salt and the like.
The invention adopts nitrate capable of accelerating the hydration speed of cement, introduces acrylamide functional small monomer with early strength effect in a polycarboxylic acid structure, and further promotes the development of early strength in coagulation by coordinating with the nitrate.
According to the invention, the conductive early-strength type graphene dispersion slurry prepared by mixing the conductive early-strength type polycarboxylate superplasticizer, the graphene oxide and the graphene and combining a dispersion process has the advantages of strong stability, excellent conductivity and early strength, steric hindrance generated by a long side chain structure of the conductive early-strength type polycarboxylate superplasticizer, prevention of graphene particle coagulation, and electrostatic repulsion provided by anionic polar groups such as carboxyl groups and the like to improve the dispersion effect.
In addition, it will be appreciated by those skilled in the art that, although there may be many problems with the prior art, each embodiment or aspect of the present invention may be improved only in one or several respects, without necessarily simultaneously solving all the technical problems listed in the prior art or in the background. It will be understood by those skilled in the art that nothing in a claim should be taken as a limitation on that claim.
Although terms such as the first polymer, the unsaturated monocarboxylic acid, the ligand, the conductive early strength type polycarboxylate water reducer, the conductive early strength type graphene dispersion slurry, the acrylamide-based monomer, and the like are used more frequently herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention; the terms "first," "second," and the like in the description and in the claims, if any, of the embodiments of the invention are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A ligand, characterized by:
the adhesive is prepared by polycondensing a first polymer, thionyl chloride, 4-hydroxy-2, 2':6',2 '-terpyridine and dichloromethane, wherein the mass ratio of the first polymer to the 4-hydroxy-2, 2':6', 2' -terpyridine is (10-12): (1-1.5);
the first polymer is prepared by free radical polymerization of methoxy polyethylene glycol acrylate, unsaturated monocarboxylic acid and acrylamide monomers, the molecular weight of the methoxy polyethylene glycol acrylate is 2000-5000, and the mass ratio of the methoxy polyethylene glycol acrylate to the unsaturated monocarboxylic acid to the acrylamide monomers is (110-120): (10-15): (1-1.5).
2. The ligand of claim 1, wherein:
the preparation method of the first polymer comprises the following specific steps in parts by mass:
putting 80-100 parts of deionized water, 110-120 parts of methoxy polyethylene glycol acrylate and 0.15-0.25 part of oxidant into a reaction kettle, stirring and dissolving uniformly, wherein the reaction temperature is 25-60 ℃; dissolving 10-15 parts of unsaturated monocarboxylic acid and 1-1.5 parts of acrylamide monomer in 40 parts of deionized water to prepare a material A for later use, and dissolving 0.5-0.8 part of chain transfer agent in 20 parts of deionized water to prepare a material B for later use; dissolving 0.15-0.2 part of reducing agent in 20 parts of deionized water to prepare a material C for later use;
simultaneously, dropwise adding the prepared material A, material B and material C into the reaction kettle, dropwise adding the material A for 3.5-4 h, dropwise adding the material B for 3.5-4 h, dropwise adding the material C for 3-3.5 h, and carrying out heat preservation reaction for 1-2 h; and neutralizing until the pH value is 6-7, and removing water by reduced pressure distillation to obtain a first polymer.
3. The ligand of claim 2, wherein: the unsaturated monocarboxylic acid is one or all of methacrylic acid and acrylic acid; the acrylamide monomer is one or more of N, N-dimethylacrylamide, N-isopropylacrylamide and acrylamide.
4. The ligand of claim 2, wherein: the oxidant is one or more of ammonium persulfate, potassium persulfate, sodium persulfate and hydrogen peroxide; the chain transfer agent is one or more of 3-mercaptopropionic acid, thioglycolic acid, mercaptoethanol, thioglycerol and dodecyl mercaptan; the reducing agent is one or more of L-ascorbic acid, sodium bisulfite, sodium hypophosphite and sodium formaldehyde sulfoxylate; the pH was neutralized with sodium hydroxide.
5. A process for the preparation of a ligand according to any one of claims 1 to 4, characterized in that:
the method comprises the following specific steps of:
weighing 100-120 parts of a first polymer, adding the first polymer into a first reaction container, adding 150-250 parts of thionyl chloride, dropwise adding 0.5-1 part of N, N-dimethylformamide, heating and refluxing, and reacting t1Distilling to remove unreacted thionyl chloride, adding 100-200 parts of redistilled toluene, and distilling under reduced pressure to remove residual thionyl chloride; weighing 10-15 parts of 4-hydroxy-2, 2', 6', 2' -terpyridine, adding into a second reaction container, adding 10-30 parts of dry dichloromethane and 2-5 parts of triethylamine, stirring, and heating to reflux to obtain a material D;
diluting the material D with 400-500 parts of dry dichloromethane at t2Dropping into the first reaction container for continuous reaction t3(ii) a The solvent was removed by rotary evaporation to give the ligand.
6. The method for preparing the ligand according to claim 5, wherein: t is t1Is 5 to 7 hours, t21 to 1.5h, t3Is 20 to 28 hours.
7. The conductive early-strength polycarboxylate superplasticizer is characterized by comprising the following components in parts by weight: prepared by using the ligand of any one of claims 1 to 4, zinc nitrate and deionized water, wherein the mass ratio of the ligand to the zinc nitrate is 15: (2-3).
8. The preparation method of the conductive early-strength polycarboxylate superplasticizer according to claim 7 is characterized by comprising the following steps:
the preparation method comprises the following specific preparation steps in parts by mass:
weighing 150 parts of the ligand in a third reaction container, dissolving with equivalent deionized water to prepare a material E, weighing 20-30 parts of zinc nitrate in a fourth reaction container, adding equivalent deionized water to dissolve, transferring to a fifth reaction container, stirring for 5-10 min, adding the material E into the fifth reaction container, and supplementing water until the solid content is 35-45%, thus preparing the conductive early-strength polycarboxylate superplasticizer.
9. The utility model provides a conductive early strong type graphite alkene dispersion thick liquids which characterized in that: the conductive early-strength polycarboxylate water reducer is prepared by mixing graphene, graphene oxide, the conductive early-strength polycarboxylate water reducer of claim 7 and deionized water, wherein the mass ratio of the graphene to the graphene oxide to the conductive early-strength polycarboxylate water reducer to the deionized water is (1-4): (1-4): 5:50.
10. A method for preparing the conductive early-strength graphene dispersion paste according to claim 9, wherein the conductive early-strength graphene dispersion paste comprises:
the method comprises the following specific steps:
mixing graphene, graphene oxide, the conductive early-strength type polycarboxylate superplasticizer and deionized water, stirring at the speed of 500-540 r/min for 1-2 min, and then carrying out ultrasonic treatment for 20-60 min to obtain the conductive early-strength type graphene dispersion slurry.
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