CN113637125A - Cucurbituril compound modified composite functional polycarboxylate superplasticizer and preparation method and application thereof - Google Patents
Cucurbituril compound modified composite functional polycarboxylate superplasticizer and preparation method and application thereof Download PDFInfo
- Publication number
- CN113637125A CN113637125A CN202111194807.XA CN202111194807A CN113637125A CN 113637125 A CN113637125 A CN 113637125A CN 202111194807 A CN202111194807 A CN 202111194807A CN 113637125 A CN113637125 A CN 113637125A
- Authority
- CN
- China
- Prior art keywords
- vpeg
- cucurbituril
- polyether macromonomer
- substituted
- cucurbituril compound
- 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.)
- Granted
Links
Classifications
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
-
- 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
Abstract
The invention discloses a cucurbituril compound modified composite functional polycarboxylate water reducer and a preparation method and application thereof, and belongs to the technical field of concrete admixtures. According to the invention, the cucurbituril compound capable of including various heavy metal ions is introduced to the VPEG polyether macromonomer of the polymer molecular main chain, so that the polymer has the high water reducing function of the polycarboxylic acid water reducing agent, and also has the function of including various heavy metal ions to better inhibit the exosmosis of the polycarboxylic acid water reducing agent, and the prepared concrete containing the water reducing agent has high strength and better environment-friendly effect.
Description
Technical Field
The invention relates to the field of concrete admixtures, in particular to a cucurbituril compound modified polycarboxylic acid water reducing agent and a preparation method and application thereof.
Background
With the enhancement of environmental awareness throughout the society, the cement and concrete industries use a large amount of waste byproducts of other industries every year to reduce environmental load and make the best use of solid wastes. However, there are many heavy metal ions or toxic metal ions in the industrial waste, which are released again by dissolution under certain conditions, resulting in secondary environmental pollution.
Mainly in the analysis of the environmental impact of cement and concrete materialsConsidering the problem of dissolution of its inorganic harmful components. These inorganic harmful components are mainly heavy metals and toxic metal ions, such as Pb2+、Hg2+、Cd2+、Cr2+And As2+、Cr6+And the like. Heavy metals and toxic ions in cement are mainly derived from raw fuel, refractory bricks in the kiln and grinding media. The content of heavy metal and toxic ion in the fly ash and the dissolution problem are very complex, and the heavy metal and toxic ion are greatly influenced by the formation age, producing area and mineral site of a coal bed, the depth of a mineral bed, the type of a combustion furnace, the combustion temperature and the like. In order to reduce the environmental impact that may occur, various countries have actively studied measures for reducing harmful components in cement and concrete, and have made measures for controlling elution and studied elution test methods suitable for the measures.
The method has the advantages that the method is wide in breadth in China, cement production kilns are multiple, mineral sources and sources of raw materials, fuels, mixed materials and the like for producing cement and concrete are complex, the difference between the climate in south and north, particularly the rainfall is large, the content and the dissolution amount of harmful components in the cement concrete are influenced, and the difficulty in prediction, evaluation and analysis and effective control is increased. Cement and fly ash are extremely large and difficult to reverse and eliminate if there is a substantial problem with the dissolution of the harmful components. Therefore, China also pays attention to the problem at present, and actively develops related researches to develop various strategies for reducing or controlling the elution amount of the toxic heavy metal ions so as to finally control the content of the toxic heavy metal ions in the material within a safe range.
Patent CN109574582 discloses pervious concrete with the capability of adsorbing heavy metal ions and a preparation method thereof, wherein the pervious concrete consists of the following raw materials: 20.89-21.18% of cement, 55.14-56.49% of recycled concrete aggregate with the grain diameter of 2.35-4.75mm, 18.38-18.55% of recycled concrete aggregate with the grain diameter of 4.76-9.5mm, 1.31-1.35% of silica fume, 1.27-1.67% of adsorbing material, 0.45-0.74% of water reducing agent and 0.43-2.07% of waterborne epoxy resin. The pervious concrete prepared by the simple process method has the advantages of high strength, good water permeability and low cost, and the adsorbing material of the ethylenediamine tetraacetic acid magnesium-aluminum intercalated hydrotalcite is adopted as the heavy metal ion chelating agent to carry out chelating treatment on Cd2+Ions have good adsorption performance, and Cd is reduced to a certain extent2+And (4) dissolving out. However, in the present invention, only a single pair of Cd2+The heavy metal ions have adsorption effect, the problem that various heavy metal ions contained in cement and concrete are dissolved out cannot be solved, the actual molecular weight of the ethylene diamine tetraacetic acid magnesium-aluminum intercalated hydrotalcite is not large, and the ethylene diamine tetraacetic acid magnesium-aluminum intercalated hydrotalcite is used as a heavy metal ion chelating agent, so that a chelated complex can be dissolved out, and the dissolution of the heavy metal ions is actually reduced only to a certain extent.
Disclosure of Invention
Based on the problems in the prior art, the invention provides a cucurbituril compound modified composite functional polycarboxylate superplasticizer and a preparation method thereof. The cucurbituril compound is creatively used as a substituent and suspended on the main chain of the polycarboxylate water reducer macromolecule, so that the water reducing performance and the dispersing performance of the polycarboxylate water reducer are improved, and the cucurbituril compound is better fixed through polymer molecules, so that the heavy metal ions are more difficult to dissolve out by utilizing the inclusion effect of the cucurbituril compound on the heavy metal ions, the phenomenon of heavy metal ion extravasation is obviously improved, the environment-friendly effect of concrete is obviously improved, and the environment and the human health are more benefited by using the concrete in a long term. The invention makes a contribution to the prior art, and the melon ring compound modified polycarboxylate water reducer is found to improve the dissolution of heavy metals in concrete for the first time and improve the alkaline water performance and the dispersing performance of the polycarboxylate water reducer.
Specifically, the invention provides a cucurbituril compound modified composite functional polycarboxylate superplasticizer which is mainly characterized in that: the water reducer is prepared by the polymerization of active controllable free radicals, and the preparation raw materials comprise a 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG) macromonomer, a cucurbituril compound substituted VPEG polyether macromonomer, an acrylic acid or acrylate derivative small monomer, a chain transfer agent, an initiator and a solvent.
The cucurbituril compound modified composite functional polycarboxylate superplasticizer is characterized in that the cucurbituril compound in the VPEG polyether macromonomer substituted by the cucurbituril compound is one or more of hydroxyl substituted multi-component cucurbituril compounds; preferably, the compound is one or more of monohydroxy substituted quinary cucurbituril, monohydroxy substituted hexahydric cucurbituril and monohydroxy substituted heptatomic cucurbituril.
The cucurbituril compound modified composite functional polycarboxylate superplasticizer comprises the following preparation raw materials in parts by mass: 50-800 parts of VPEG polyether macromonomer, 10-300 parts of cucurbit compound substituted VPEG polyether macromonomer, 10-100 parts of acrylic acid or acrylate derivative small monomer, 1-10 parts of chain transfer agent, 0.1-5 parts of initiator and 100-1500 parts of solvent; preferably, 100-300 parts of VPEG polyether macromonomer, 10-200 parts of cucurbit compound substituted VPEG polyether macromonomer, 10-70 parts of acrylic acid or acrylate derivative small monomer, 1-5 parts of chain transfer agent, 0.5-3 parts of initiator and 1000 parts of solvent.
The invention also provides a preparation method of the cucurbituril compound modified composite functional polycarboxylate superplasticizer, which is characterized by comprising the following steps:
1) preparing a cucurbituril compound substituted VPEG polyether macromonomer;
2) Dissolving VPEG polyether macromonomer and an initiator in a solvent, stirring and mixing, vacuumizing, heating to 60-90 ℃ in an oil bath, and stirring and reacting for 0.1-1 hour under the protection of nitrogen;
3) continuously dropwise adding a mixed aqueous solution of acrylic acid and/or acrylic ester derivative small monomers, stirring and reacting for 1-48 hours under the protection of nitrogen, wherein a cucurbituril compound substituted VPEG polyether large monomer is added in stages;
4) and (3) dropwise adding a chain transfer agent, continuing to react for 0.5-1 hour, cooling in an ice bath to terminate the reaction after the reaction is finished, precipitating to obtain a polymer, washing the polymer with a solvent, precipitating again, and drying in vacuum to obtain the target product.
In the preparation method of the cucurbituril compound modified composite functional polycarboxylate superplasticizer, the solvent is one or more selected from N, N-Dimethylformamide (DMF), acetone, toluene, chloroform, dimethyl sulfoxide (DMSO), ethyl acetate, methanol and ethylene glycol.
In the preparation method of the cucurbituril compound modified composite functional polycarboxylate superplasticizer, the initiator is selected from azo compounds or organic peroxides, preferably azobisisobutyric acidNitrile (AIBN), dibenzoyl peroxide (BPO) or potassium persulfate (K)2S2O8)。
In the preparation method of the cucurbituril compound modified composite functional polycarboxylate water reducer, the chain transfer agent is selected from dithioester, alpha-dithionaphthoic acid isobutyronitrile ester (CPDN), dithiobenzoic acid-2-nitrile isopropyl ester (CPDB), dithiobenzoic acid tert-butyl ester (CDB), dithiobenzoic acid (2-ethoxycarbonyl) propyl-2-Ester (EPDB) and dithiobenzoic acid 2- (ethoxyformyl) -2-propyl ester.
In the preparation method of the cucurbituril compound modified polycarboxylate superplasticizer, the preparation steps of the cucurbituril compound substituted VPEG polyether macromonomer are as follows:
1) dissolving a VPEG monomer in a dichloromethane solution, introducing nitrogen, stirring uniformly, then dropwise adding thionyl chloride in an ice-water bath, keeping dropwise adding reaction for 1-3 hours, then heating to more than 50 ℃, stirring and reacting for 1-2 hours, finishing the reaction, and carrying out rotary evaporation to obtain the chlorinated polyether macromonomer.
2) Dissolving a chlorinated polyether macromonomer in water, dropwise adding a cucurbituril compound at 40-60 ℃ to obtain an alkaline water solution, stirring while dropwise adding, reacting for 1-4 hours, adjusting the pH value of a reaction system to be neutral, removing a byproduct and an unreacted cucurbituril compound through precipitation, and distilling and concentrating to obtain the cucurbituril compound modified polyether macromonomer.
In the preparation method for substituting the cucurbituril compound for the VPEG polyether macromonomer, the VPEG polyether macromonomer is selected from one or more VPEG polyether macromonomers with different molecular weights; one or more of VPEG polyether macromonomer (2400), VPEG polyether macromonomer (3000), and VPEG polyether macromonomer (4000) are preferred.
The invention also provides concrete, which mainly comprises the following components of cement, sand, stones, fly ash, an admixture, the cucurbituril compound modified polycarboxylate superplasticizer and water. The concrete comprises the following components in parts by mass: sand: stone: fly ash: blending materials: cucurbituril compound modified polycarboxylic acid water reducing agent: water =1: 1-3: 3-5: 0.2-0.4: 0.01-0.1: 0.01-0.05: 0.3-0.5.
According to the invention, by introducing the cucurbituril compound structure on the main chain of the polymer molecule, the product can promote the water reducing effect of the polycarboxylate superplasticizer, and can better prevent the heavy metal ions in the concrete from being leaked, so that the product has a better compound function, and the prepared concrete has a better environment-friendly effect. The product of the invention has simple preparation method, controllable structure and low cost, and the product performance can be adjusted by flexibly regulating and controlling the characteristics and the use amount of the cucurbituril compound according to the actual industrial requirements, thereby having important economic value.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments. The experimental raw materials are all commercial products and are not subjected to secondary processing.
Example 1
The embodiment prepares a cucurbituril compound modified composite functional polycarboxylate superplasticizer, and comprises two steps:
Step one, preparing cucurbituril compound substituted VPEG polyether macromonomer
1) Dissolving 100g of VPEG (2400) monomer in 200ml of dichloromethane solution, introducing nitrogen, stirring uniformly, then dropwise adding 5g of thionyl chloride in ice-water bath, keeping dropwise adding reaction for 1-3 hours, then heating to above 50 ℃, stirring for reaction for 1-2 hours, finishing the reaction, and carrying out rotary evaporation to obtain the chlorinated polyether macromonomer.
2) Dissolving 50g of chlorinated polyether macromonomer in water, dropwise adding 4.5g of monohydroxy substituted quinary melon ring compound at 40-60 ℃ to obtain an aqueous alkali solution, stirring while dropwise adding, reacting for 1-4 hours, adjusting the pH value of a reaction system to be neutral, removing by-products and unreacted melon ring compound by precipitation, and distilling and concentrating to obtain the monohydroxy substituted quinary melon ring compound modified polyether macromonomer.
Step two, preparing cucurbituril compound modified polycarboxylate superplasticizer
100 parts of 4-hydroxybutyl alkenyl polyoxyethylene ether (VPEG) and 0.5 part of Azobisisobutyronitrile (AIBN) are dissolved in 1000 parts of deionized water, stirred at room temperature to be uniformly dissolved, vacuumized, heated to 70 ℃ in an oil bath, and stirred to react for 0.5 hour under the protection of nitrogen. And then continuously dropwise adding 10 parts of methyl acrylate small monomer, stirring and reacting for 2.5 hours under the protection of nitrogen, adding 2 parts of monohydroxy substituted quinary melon ring compound substituted VPEG polyether large monomer obtained in the step one every 20 minutes from the dropwise adding of methyl acrylate in the dropwise adding process of methyl acrylate, adding 10 parts of melon ring compound substituted VPEG polyether large monomer and 1 part of dithioester chain transfer agent, continuing to react for half an hour, cooling in an ice bath to terminate the reaction, precipitating the polymer in n-hexane, washing the polymer with methanol for three times, precipitating again, and drying in vacuum to obtain the target product.
Example 2
The other conditions are the same as the example 1, except that 5g of the full-hydroxy-substituted five-membered cucurbituril compound is adopted to replace the monohydroxy-substituted five-membered cucurbituril in the substep 2) of the first step to prepare the full-hydroxy-substituted five-membered cucurbituril compound-substituted VPEG polyether macromonomer, and the full-hydroxy-substituted five-membered cucurbituril compound-substituted VPEG polyether macromonomer is correspondingly added in the second step to replace the monohydroxy-substituted five-membered cucurbituril compound-substituted VPEG polyether macromonomer.
Example 3
The other conditions are the same as example 1, except that 0.5g of full-hydroxy substituted quinary melon ring compound is adopted to replace monohydroxy substituted quinary melon ring in substep 2) of the first step to prepare the full-hydroxy substituted quinary melon ring compound substituted VPEG polyether macromonomer, and the full-hydroxy substituted quinary melon ring compound substituted VPEG polyether macromonomer is correspondingly added to replace the monohydroxy substituted quinary melon ring compound substituted VPEG polyether macromonomer in the second step.
Example 4
The other conditions are the same as example 1, except that 5.5g of monohydroxy-substituted six-membered cucurbituril compound is adopted in substep 2) of step one instead of monohydroxy-substituted five-membered cucurbituril to prepare the monohydroxy-substituted six-membered cucurbituril compound-substituted VPEG polyether macromonomer, and the monohydroxy-substituted six-membered cucurbituril compound-substituted VPEG polyether macromonomer is correspondingly added in step two instead of monohydroxy-substituted five-membered cucurbituril compound-substituted VPEG polyether macromonomer.
Example 5
The other conditions are the same as example 1, except that 6g of the full-hydroxy-substituted six-membered cucurbituril compound is adopted in substep 2) of step one to replace the monohydroxy-substituted five-membered cucurbituril to obtain the full-hydroxy-substituted six-membered cucurbituril compound-substituted VPEG polyether macromonomer, and the full-hydroxy-substituted six-membered cucurbituril compound-substituted VPEG polyether macromonomer is correspondingly added in step two to replace the monohydroxy-substituted five-membered cucurbituril compound-substituted VPEG polyether macromonomer.
Example 6
The other conditions were the same as in example 1, except that 6.5g of monohydroxy-substituted heptatomic cucurbituril compound was used in the substep 2) of the first step instead of monohydroxy-substituted pentacyclic cucurbituril to obtain monohydroxy-substituted heptatomic cucurbituril compound-substituted VPEG polyether macromonomer, and in the second step, the monohydroxy-substituted heptatomic cucurbituril compound-substituted VPEG polyether macromonomer was added in place of monohydroxy-substituted pentacyclic compound-substituted VPEG polyether macromonomer.
Example 7
The other conditions were the same as in example 1 except that 6 parts of a monohydroxy-substituted pentacyclic compound-substituted VPEG polyether macromonomer and a total of 30 parts of a cucurbitacin compound-substituted VPEG polyether macromonomer were added at 20 minute intervals in step two.
Example 8
The other conditions were the same as in example 1 except that 10 parts of the monohydroxy-substituted pentacyclic compound-substituted VPEG polyether macromonomer and a total of 50 parts of the cucurbitacin compound-substituted VPEG polyether macromonomer were added every 20 minutes in step two.
Example 9
The other conditions were the same as in example 4 except that 6 parts of the VPEG polyether macromonomer substituted with a monohydroxy-substituted six-membered cucurbituril compound was added in step two every 20 minutes, and a total of 30 parts was added.
Example 10
The other conditions were the same as in example 4 except that 10 parts of the VPEG polyether macromonomer substituted with a monohydroxy-substituted six-membered cucurbituril compound was added in step two every 20 minutes, and a total of 50 parts was added.
Example 11
The other conditions were the same as in example 6 except that 6 parts of the monohydroxy-substituted heptatomic cucurbituril compound-substituted VPEG polyether macromonomer was added in step two every 20 minutes, and a total of 30 parts was added.
Example 12
The other conditions were the same as in example 6 except that 10 parts of the monohydroxy-substituted heptatomic cucurbituril compound-substituted VPEG polyether macromonomer was added in step two every 20 minutes, and 50 parts in total were added.
Application examples 1 to 12
The concrete mainly comprises 360kg of cement (PO 42.5), 800kg of sand, 1250kg of stones, 90kg of fly ash, 3kg of admixture (sodium carboxymethylcellulose) and 4kg of water reducing agent. The water reducing agents used in application examples 1 to 12 were the water reducing agents prepared in the foregoing examples 1 to 12, respectively.
Comparative example 1
The preparation method of the polycarboxylate water reducer comprises the specific steps of dissolving 100 parts of 4-hydroxybutyl alkenyl polyoxyethylene ether (VPEG) and 0.5 part of Azobisisobutyronitrile (AIBN) in 1000 parts of deionized water, stirring at room temperature to enable the solutions to be uniform, vacuumizing, heating the oil bath to 70 ℃, and stirring and reacting for 0.5 hour under the protection of nitrogen. Then dripping 10 parts of methyl acrylate monomer at a constant speed, reacting for 2.5 hours under the protection of nitrogen, dripping 1 part of dithioester chain transfer agent, continuing to react for half an hour, cooling in an ice bath to terminate the reaction after the reaction is ended, precipitating the polymer in n-hexane, washing the polymer for three times by using methanol, precipitating again, and drying in vacuum to obtain the target product.
Comparative example 2
The other conditions were the same as in comparative example 1 except that 30 parts of methyl acrylate monomer was added dropwise.
Comparative example 3
The other conditions were the same as in comparative example 1 except that 50 parts of methyl acrylate monomer was added dropwise.
Application of comparative examples 1 to 3
The concrete mainly comprises 360kg of cement (PO 42.5), 800kg of sand, 1250kg of stones, 90kg of fly ash, 3kg of admixture (sodium carboxymethylcellulose) and 4kg of water reducing agent. The water reducing agents used in the application comparative examples 1 to 3 are the water reducing agents prepared in the comparative examples 1 to 3 respectively.
The application examples 1 to 12 and the application comparative examples 1 to 3 of the present invention were subjected to water-reducing rate, net slurry fluidity, compressive strength and heavy metal ion leaching experimental tests, respectively. The water reducing rate refers to GB8076-2008 concrete admixture, the net slurry fluidity refers to GB/T8077-2012 concrete admixture homogeneity test method, the compressive strength measurement refers to GB/T50081-2019 common concrete mechanical property test method, and the heavy metal ion leaching test refers to HJ 557-. The performance results are detailed in table 1.
From the results in the table, the polycarboxylate water reducing agents modified by the cucurbiturils can obviously reduce the release amount of heavy metal ions, wherein the monohydroxy quinary cucurbituril modified water reducing agent is used for Pb2+、Hg2+And Cr3+Has obvious dissolution inhibiting effect, and the monohydroxy six-membered cucurbituril modified water reducing agent has Pb-free performance2+And Cd2+ Has obvious dissolution inhibiting effect, and the seven-element cucurbituril modified water reducing agent has less dissolution inhibiting effect on the four heavy metal ions than five-element cucurbituril and six-element cucurbituril. In general, the water reducing rate and the net slurry fluidity of the polycarboxylate superplasticizers modified by the monohydroxy cucurbituril compounds are slightly improved. The results show that the polycarboxylate water reducer modified by the monohydroxy cucurbituril compound has good water reducing effect and Pb 2+、Cr3+、Cd2+ 、Hg2+Inhibiting the dissolution of heavy metal ions.
The foregoing embodiments and examples are merely illustrative of the present invention, which is not to be construed as limiting, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The cucurbituril compound modified composite functional polycarboxylate superplasticizer is characterized in that: the water reducer is prepared by the polymerization of active controllable free radicals, and the preparation raw materials comprise a 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG) macromonomer, a cucurbituril compound substituted VPEG polyether macromonomer, an acrylic acid and/or acrylate derivative small monomer, a chain transfer agent, an initiator and a solvent.
2. The cucurbituril compound modified multifunctional polycarboxylate water reducer as claimed in claim 1, wherein the cucurbituril compound in the cucurbituril compound substituted VPEG polyether macromonomer is one or more of hydroxyl substituted multi-component cucurbituril compounds.
3. The cucurbituril compound modified composite functional polycarboxylate superplasticizer according to claim 1, wherein the raw materials for preparation comprise, in parts by weight: 50-800 parts of VPEG polyether macromonomer, 10-300 parts of cucurbit compound substituted VPEG polyether macromonomer, 10-100 parts of acrylic acid or acrylate derivative small monomer, 1-10 parts of chain transfer agent, 0.1-5 parts of initiator and 100-1500 parts of solvent.
4. The preparation method of the cucurbituril compound modified multifunctional polycarboxylate superplasticizer according to any one of claims 1 to 3, characterized by comprising the following steps:
1) preparing a cucurbituril compound substituted VPEG polyether macromonomer;
2) dissolving VPEG polyether macromonomer and an initiator in a solvent, stirring and mixing, vacuumizing, heating to 60-90 ℃ in an oil bath, and stirring and reacting for 0.1-1 hour under the protection of nitrogen;
3) continuously dropwise adding an aqueous solution of acrylic acid and/or acrylate derivative small monomers, stirring and reacting for 1-48 hours under the protection of nitrogen, wherein a cucurbituril compound substituted VPEG polyether large monomer is added in stages;
4) and (3) dropwise adding a chain transfer agent, continuing to react for 0.5-1 hour, cooling in an ice bath to terminate the reaction after the reaction is finished, precipitating to obtain a polymer, washing the polymer with a solvent, precipitating again, and drying in vacuum to obtain the target product.
5. The preparation method of the cucurbituril compound modified composite functional polycarboxylate superplasticizer according to claim 4, wherein the solvent in step 2) and step 4) is one or more selected from N, N-Dimethylformamide (DMF), acetone, toluene, chloroform, dimethyl sulfoxide (DMSO), ethyl acetate, methanol and ethylene glycol.
6. The preparation method of the cucurbit uril compound modified multifunctional polycarboxylate superplasticizer according to claim 4, wherein the initiator is selected from azo compounds or organic peroxides.
7. The method for preparing the cucurbituril compound modified multifunctional polycarboxylate water reducer as claimed in claim 4, wherein the chain transfer agent is selected from the group consisting of dithioester, α -dithionaphthoic acid isobutyronitrile ester (CPDN), dithiobenzoic acid-2-cyanoisopropyl ester (CPDB), dithiobenzoic acid tert-butyl ester (CDB), dithiobenzoic acid (2-ethoxycarbonyl) propyl-2-Ester (EPDB), dithiobenzoic acid 2- (ethoxyformyl) -2-propyl ester.
8. The preparation method of the cucurbituril compound modified polycarboxylate water reducer as claimed in claim 4, wherein the preparation steps of the cucurbituril compound substituted VPEG polyether macromonomer are as follows:
1) dissolving a VPEG monomer in a dichloromethane solution, introducing nitrogen, stirring uniformly, then dropwise adding thionyl chloride in an ice-water bath, keeping dropwise adding reaction for 1-3 hours, then heating to more than 50 ℃, stirring and reacting for 1-2 hours, finishing the reaction, and carrying out rotary evaporation to obtain a chlorinated polyether macromonomer;
dissolving a chlorinated polyether macromonomer in water, dropwise adding an alkaline water solution of a cucurbit uril compound at 40-60 ℃, stirring while dropwise adding, reacting for 1-4 hours, adjusting the pH value of a reaction system to be neutral, removing a byproduct and an unreacted cucurbit uril compound through precipitation, and distilling and concentrating to obtain the cucurbituril compound modified polyether macromonomer.
9. The method of claim 8, wherein the VPEG polyether macromonomer is selected from the group consisting of a VPEG polyether macromonomer with a weight average molecular weight of 2400, a VPEG polyether macromonomer with a weight average molecular weight of 3000, and a VPEG polyether macromonomer with a weight average molecular weight of 4000.
10. The concrete mainly comprises cement, sand, stones, fly ash, admixtures, water and a polycarboxylic acid water reducing agent, and is characterized in that the polycarboxylic acid water reducing agent is the cucurbituril compound modified polycarboxylic acid water reducing agent in any one of claims 1 to 3 or the cucurbituril compound modified polycarboxylic acid water reducing agent obtained by the preparation method in any one of claims 4 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111194807.XA CN113637125B (en) | 2021-10-14 | 2021-10-14 | Cucurbituril compound modified composite functional polycarboxylate superplasticizer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111194807.XA CN113637125B (en) | 2021-10-14 | 2021-10-14 | Cucurbituril compound modified composite functional polycarboxylate superplasticizer and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113637125A true CN113637125A (en) | 2021-11-12 |
| CN113637125B CN113637125B (en) | 2022-01-25 |
Family
ID=78426701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111194807.XA Active CN113637125B (en) | 2021-10-14 | 2021-10-14 | Cucurbituril compound modified composite functional polycarboxylate superplasticizer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113637125B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116514437A (en) * | 2023-07-04 | 2023-08-01 | 北京鼎瀚中航建设有限公司 | Composite anti-mud water reducer and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008127430A (en) * | 2006-11-17 | 2008-06-05 | Nippon Shokubai Co Ltd | Manufacturing method for polycarboxylic acid-based concrete admixture |
| CN103483473A (en) * | 2013-09-17 | 2014-01-01 | 中国科学院南京土壤研究所 | Method for preparing immobilized cucurbiturils |
| WO2014059674A1 (en) * | 2012-10-19 | 2014-04-24 | 江苏博特新材料有限公司 | Water reducer intermediate, preparation method therefor, and water reducer prepared by using the same |
| CN112876619A (en) * | 2021-02-05 | 2021-06-01 | 江苏奥莱特新材料股份有限公司 | Anti-mud polycarboxylate superplasticizer and preparation method thereof |
| CN113024151A (en) * | 2021-03-30 | 2021-06-25 | 北京慕湖外加剂有限公司 | Polycarboxylate superplasticizer composite material, use method and concrete |
| CN113336902A (en) * | 2021-08-09 | 2021-09-03 | 北京慕湖外加剂有限公司 | Tea saponin modified compound water reducing agent and preparation method and application thereof |
-
2021
- 2021-10-14 CN CN202111194807.XA patent/CN113637125B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008127430A (en) * | 2006-11-17 | 2008-06-05 | Nippon Shokubai Co Ltd | Manufacturing method for polycarboxylic acid-based concrete admixture |
| WO2014059674A1 (en) * | 2012-10-19 | 2014-04-24 | 江苏博特新材料有限公司 | Water reducer intermediate, preparation method therefor, and water reducer prepared by using the same |
| CN103483473A (en) * | 2013-09-17 | 2014-01-01 | 中国科学院南京土壤研究所 | Method for preparing immobilized cucurbiturils |
| CN112876619A (en) * | 2021-02-05 | 2021-06-01 | 江苏奥莱特新材料股份有限公司 | Anti-mud polycarboxylate superplasticizer and preparation method thereof |
| CN113024151A (en) * | 2021-03-30 | 2021-06-25 | 北京慕湖外加剂有限公司 | Polycarboxylate superplasticizer composite material, use method and concrete |
| CN113336902A (en) * | 2021-08-09 | 2021-09-03 | 北京慕湖外加剂有限公司 | Tea saponin modified compound water reducing agent and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116514437A (en) * | 2023-07-04 | 2023-08-01 | 北京鼎瀚中航建设有限公司 | Composite anti-mud water reducer and preparation method thereof |
| CN116514437B (en) * | 2023-07-04 | 2023-08-25 | 北京鼎瀚中航建设有限公司 | Composite anti-mud water reducer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113637125B (en) | 2022-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107337766B (en) | High-adaptability polycarboxylate superplasticizer and preparation method thereof | |
| US5840114A (en) | High early-strength-enhancing admixture for precast hydraulic cement and compositions containing same | |
| CA2605186C (en) | Concrete and mortar admixture | |
| CA2107267C (en) | Cement dispersion agents | |
| CN114195421A (en) | Preparation method of polycarboxylic acid admixture for machine-made sand concrete | |
| CN109790261B (en) | Preparation method of block slow-release concrete admixture | |
| CN112694574A (en) | Novel high-mud-resistance high-slump-resistance polycarboxylic acid water reducer and preparation method thereof | |
| CN113637125B (en) | Cucurbituril compound modified composite functional polycarboxylate superplasticizer and preparation method and application thereof | |
| CN111777722A (en) | Anti-mud slump-retaining polycarboxylate superplasticizer and preparation method thereof | |
| Ma et al. | Sodium gluconate as a retarder modified sewage sludge ash-based geopolymers: Mechanism and environmental assessment | |
| CN113336902B (en) | Tea saponin modified compound water reducing agent and preparation method and application thereof | |
| CN111533495A (en) | Industrial production process of high-strength self-compacting concrete | |
| CN109650762B (en) | Phosphate type polycarboxylate superplasticizer and preparation method thereof | |
| CN110643003B (en) | Preparation method of retarding type ester polycarboxylate superplasticizer | |
| Massarweh et al. | Performance evaluation of heavy oil fly ash as a retarder of Portland cement hydration | |
| CN113321776B (en) | Mud-resistant polycarboxylate water reducer | |
| CN109626860B (en) | Preparation method of block viscosity-reducing concrete admixture | |
| CN108191289B (en) | Carbon black modified polycarboxylate superplasticizer and preparation method and application thereof | |
| JP4994056B2 (en) | Cement admixture, cement composition, and cement concrete | |
| CN115521102A (en) | Full-solid-waste self-compacting concrete and preparation method thereof | |
| CN109535347B (en) | Preparation method of block water-retaining concrete admixture | |
| CN108586663B (en) | Concrete synergist containing amide group and preparation method thereof | |
| CN110891988B (en) | Aqueous polymer compositions and copolymers | |
| CN116063634B (en) | High slump-retaining polycarboxylate superplasticizer and preparation method thereof | |
| CN112175148A (en) | Crosslinking type early-strength carboxylic acid water reducing agent, 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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220107 Address after: 529000 Chunhe Wei, the sixth villager group, Lianhe village, Sanjiang Town, Xinhui District, Jiangmen City, Guangdong Province Applicant after: Jiangmen Qiaoshi New Building Materials Co.,Ltd. Address before: 101408 Fangkou Village No. 543, Huaibei Town, Huairou District, Beijing Applicant before: BEIJING MUHU CONCRETE ADMIXTURE Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |