CN112062894A - Preparation method of silicon-based modified oleic acid polycarboxylic acid water reducing agent - Google Patents
Preparation method of silicon-based modified oleic acid polycarboxylic acid water reducing agent Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
- C04B24/42—Organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The invention relates to the field of building material preparation, in particular to a method for preparing enol polyether from ethylene oxide and propylene oxide by using a block copolymerization method, and then copolymerizing the enol polyether with silicon-based modified oleic acid containing double building to prepare modified polyether molecules with a plurality of molecular chain segments in a molecular chain. The water reducing agent can obtain higher fluidity and reduce the using amount of water under the condition of low mixing amount, thereby avoiding the phenomenon of drying shrinkage of concrete, improving the compactness of the concrete, further improving the working performance of the concrete and prolonging the service life of the concrete.
Description
Technical Field
The invention relates to the field of preparation of building materials, in particular to a preparation method of a silicon-based modified oleic acid polycarboxylic acid water reducing agent.
Background
The polycarboxylic acid high-performance water reducing agent has the characteristics of obvious characteristics and strong superiority, namely the polycarboxylic acid water reducing agent can form product serialization, and the characteristic is the key for distinguishing the polycarboxylic acid high-performance water reducing agent from the traditional high-performance water reducing agent. The polycarboxylic acid high-efficiency water reducing agent applied to the concrete not only can greatly improve the technical performance of the concrete, but also can greatly promote the development of building construction technology by taking the polycarboxylic acid high-performance water reducing agent as a new technical means, and can produce and develop cement-based composite materials with better performance.
The main components of the straw are cellulose, hemicellulose, lignin and other bio-based macromolecules, the molecules contain ether groups, carbon-carbon double bonds, propenol hydroxyl groups, phenolic hydroxyl groups, carbonyl groups, methoxyl groups, carboxyl groups, benzene rings and other functional groups and chemical bonds, graft copolymerization and cross-linking copolymerization reactions such as etherification, esterification, sulfonation, amidation and the like can be carried out, and the obtained product has special performance.
CN111154046A discloses a polycarboxylic acid water reducing agent. The polycarboxylic acid water reducing agent is prepared by the method comprising the following steps: 1) mixing modified polyether, special ester macromonomer and water to obtain a first aqueous solution; 2) adding an oxidant into the first aqueous solution, and respectively dripping a second aqueous solution and a third aqueous solution at the temperature of 20-70 ℃; 3) and after the second aqueous solution and the third aqueous solution are dripped, stirring, controlling the temperature of the system to be 0-30 ℃ and not to include 0 ℃, adding water, and adjusting the pH value of the system to be 6.5 +/-1.0 to obtain the polycarboxylic acid water reducing agent with the solid content of 40-50 wt%. The polycarboxylate superplasticizer disclosed by the invention is low in doping amount sensitivity, good in slump retaining property, good in adaptability, particularly good in concrete workability, easy to control preparation conditions, simple to operate, high in application cost performance and capable of realizing mass production.
CN110041468A discloses a viscosity-reducing polycarboxylic acid water-reducing composition and a preparation method thereof, wherein the composition comprises the following components in parts by weight: 200-220 parts of unsaturated polyether macromonomer, 25-35 parts of styrene, 25-35 parts of unsaturated anhydride, 200-250 parts of butyl acetate, 750-800 parts of n-heptane, 2-4 parts of initiator, 1.5-2.2 parts of chain transfer agent and a proper amount of deionized water. According to the invention, the ester viscosity-reducing polycarboxylate water reducer is synthesized by using a two-step method, the synthesized intermediate has better reaction activity with MPEG, the conversion rate is high, the process is simpler compared with that of a common ester polycarboxylate water reducer, the production efficiency is improved, the cost price is reduced, the energy is saved, the environment is protected, the polycarboxylate water reducer is synthesized by using styrene, maleic anhydride and 2000 molecular weight polyethylene glycol monomethyl ether, and the benzene ring and the anhydride are introduced into the side chain of the water reducer to adjust the hydrophilic oleophylic value of the polycarboxylate water reducer.
CN109250945A provides a polycarboxylic acid type water reducing agent, which comprises the following components in percentage by weight: 14-21 parts of unsaturated polyoxyethylene ether, 2.8-3.5 parts of slow-release high-efficiency water reducing agent, 3.8-12.5 parts of sodium dodecyl sulfate, 5.5-8.5 parts of acrylic acid, 5-10 parts of crosslinking monomer, 11-26 parts of diethanol monoisopropanolamine, 8-20 parts of sodium gluconate, 1.6-3.0 parts of maleic anhydride, 8-16 parts of mercaptopropionic acid, 1-2 parts of N-dimethylcyclohexylamine, 3.5-7.5 parts of carboxylic ester, 7-9 parts of sodium methallylsulfonate, 8-13 parts of sodium hypophosphite, 3-5 parts of initiator and 6-12 parts of preservative. The water reducing agent provided by the production method of the high-performance water reducing agent can reduce the water amount added in the concrete construction process, is beneficial to shortening the setting time of concrete and improving the strength of the concrete.
Although the polycarboxylic acid water reducing agent has many good performances, the polycarboxylic acid water reducing agent provided by the above patents and the prior art still has the problem of unstable application effect on different cement materials in practical application and production due to the complexity of the use environment.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a silicon-based modified oleic acid polycarboxylic acid ethanol reducer.
A preparation method of a silicon-based modified oleic acid polycarboxylic acid ethanol reducer comprises the following specific preparation scheme:
according to the mass portion, evenly mixing 40-48 portions of acrylic acid, 5-8 portions of hydroxyethyl methacrylate, 1-5 portions of mercaptopropionic acid and 2-7 portions of diallyl dimethyl ammonium chloride, slowly adding the mixture into a reaction kettle, adding 20-28 portions of silicon-based modified oleic acid, 1.5-3.6 portions of 2-acrylamido-2-methyl-1-propane sodium sulfonate, 0.1-0.5 portion of surfactant, 0.2-0.7 portion of ferric acrylate, 1.6-3.4 portions of initiator and 300 portions of water into the reaction kettle in advance, stirring and evenly mixing, heating under the protection of nitrogen, reacting for 60-120min at 70-75 ℃, adding 300 portions of 400 portions of aqueous solution containing 13-18 portions of sodium hydroxide, continuously stirring and reacting for 180-240min, evaporating to remove water, thus obtaining the silicon-based modified oleic acid polycarboxylic acid water reducing agent.
The preparation method of the silicon-based modified oleic acid comprises the following steps:
putting 100-200 parts of oleic acid and 300-400 parts of ethanol into a reaction kettle, stirring and mixing uniformly to obtain oil emulsion, adjusting the pH to 8-11, and then adding 4-10 parts of vinyldimethylsilane; after uniform mixing, adding azobisisobutyronitrile, reacting for 150-75 min at 70-75 ℃, adjusting the pH value to 7.0-8.5 by using dilute hydrochloric acid, then adding 0.7-4 parts of myrcenol ether, 0.003-0.02 part of chloroplatinic acid, reacting for 60-120min at 70-75 ℃, and controlling the pH of the reaction system to 7.0-8.5 by using 1-5% of sodium hydroxide solution; and (3) terminating the reaction after the reaction is finished, washing, distilling to remove ethanol, and drying to obtain the silicon-based modified oleic acid.
The oleic acid and the vinyl dimethyl silane are co-grafted to obtain oleic acid containing silicon-hydrogen bonds, the lauryl enol ether and the oleic acid containing the silicon-hydrogen bonds are subjected to hydrosilylation reaction to obtain silicon-based modified oleic acid containing double structures,
the main reaction mechanism can be represented by the following schematic equation:
the preparation method of the myrcenol ether comprises the following steps:
adding 16-28 parts of myrcenol and 0.05-0.1 part of sodium alkoxide in parts by mass into a high-pressure reaction kettle, then replacing the materials with dry nitrogen for three times, finally vacuumizing, filling 22-36 parts of ethylene oxide gas into the reaction kettle, controlling the temperature to be 90-110 ℃, stirring and reacting for 60-120min, filling 12-28 parts of propylene oxide gas into the high-pressure reaction kettle, controlling the temperature to be 80-100 ℃, continuing to react for 90-180min, and obtaining the myrcenol ether after the reaction is completed.
Part of the reaction mechanism can be represented by the following schematic equation:
the sodium alkoxide is sodium methoxide or sodium ethoxide.
The surfactant is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.
The initiator is ammonium persulfate or potassium persulfate or azobisisobutyronitrile.
According to the preparation method of the silicon-based modified oleic acid polycarboxylic acid ethanol reducer, oleic acid containing silicon-hydrogen bonds is obtained by co-grafting oleic acid and vinyl dimethylsilane, the lauryl enol ether and the oleic acid containing the silicon-hydrogen bonds are subjected to silicon-hydrogen addition reaction to obtain the silicon-based modified oleic acid containing double structures, and the silicon-based modified oleic acid is applied to synthesis of the polycarboxylic acid ethanol reducer, so that molecular steric hindrance can be increased, the interaction force among macromolecular chains can be reduced, the solution viscosity can be reduced, the surface tension of the synthesized polycarboxylic acid ethanol reducer can be reduced, ethanol mud particles can be effectively dispersed, the condensation phenomenon of the ethanol mud particles can be reduced, and the fluidity of concrete can be improved. The ethanol reducer can obtain higher fluidity and reduce the dosage of ethanol under the condition of low doping amount, thereby avoiding the phenomenon of dry shrinkage of concrete, improving the compactness of the concrete, further improving the working performance of the concrete and prolonging the service life of the concrete.
Drawings
FIG. 1 is a Fourier infrared spectrum of a silicon-based modified starch polycarboxylate superplasticizer product prepared in example 1;
at 1781cm-1The absorption peak of carboxyl carbonyl exists nearby and is 2929cm-1An absorption peak of carbon hydrogen exists nearby, which indicates that acrylic acid participates in the reaction; at 806cm-1An absorption peak of silicon carbon exists nearby, and is 1173cm-1An absorption peak of ether bond exists nearby, which indicates that the silicon-based modified starch participates in the reaction; at 1065cm-1An absorption peak of an ester carbon-oxygen single bond exists nearby, which indicates that hydroxyethyl methacrylate participates in the reaction; at 973cm-1An absorption peak of a carbon-nitrogen single bond exists nearby, which indicates that diallyl dimethyl ammonium chloride participates in the reaction; at 745cm-1An absorption peak of a carbon-sulfur bond exists nearby, which indicates that mercaptopropionic acid participates in the reaction; at 655cm-1A telescopic absorption peak of a sulfur-oxygen single bond exists nearby, which indicates that 2-acrylamido-2-methyl-1-propane sodium sulfonate participates in the reaction; at 1625cm-1And an absorption peak of carboxylate ions exists nearby, which indicates that the iron acrylate participates in the reaction.
Detailed Description
The invention is further illustrated by the following specific examples:
the percentages in the examples are percentages by mass.
Example 1
A preparation method of a silicon-based modified oleic acid polycarboxylic acid ethanol reducer comprises the following specific preparation scheme:
uniformly mixing 40kg of acrylic acid, 5kg of hydroxyethyl methacrylate, 1kg of mercaptopropionic acid and 2kg of diallyl dimethyl ammonium chloride, slowly adding the mixture into a reaction kettle, adding 20kg of silicon-based modified oleic acid, 1.5kg of 2-acrylamido-2-methyl-1-propane sodium sulfonate, 0.1kg of surfactant, 0.2kg of ferric acrylate, 1.6kg of initiator and 300kg of water into the reaction kettle in advance, uniformly stirring, heating under the protection of nitrogen, reacting at 70 ℃ for 60-120min, adding 300kg of ethanol solution containing 13kg of sodium hydroxide, continuously stirring, continuously reacting for 180min, and evaporating to remove water to obtain the silicon-based modified polycarboxylic acid ethanol reducer.
The preparation method of the silicon-based modified oleic acid comprises the following steps:
putting 100kg of oleic acid and 300kg of ethanol into a reaction kettle, stirring and mixing uniformly to obtain oil emulsion, adjusting the pH to 8, and then adding 4kg of vinyldimethylsilane; after uniform mixing, adding azobisisobutyronitrile, reacting for 150min at 70 ℃, adjusting the pH value to 7.0 by using dilute hydrochloric acid, then adding 0.7kg of lauryl enol ether and 0.003kg of chloroplatinic acid, reacting for 60min at 70 ℃, and controlling the pH value of a reaction system to 7.0 by using 1% sodium hydroxide solution; and (3) terminating the reaction after the reaction is finished, washing, distilling to remove ethanol, and drying to obtain the silicon-based modified oleic acid.
The preparation method of the myrcenol ether comprises the following steps:
adding 16kg of myrcenol and 0.05kg of sodium alkoxide into a high-pressure reaction kettle, then replacing with dry nitrogen for three times, finally vacuumizing, filling 22kg of ethylene oxide gas into the reaction kettle, controlling the temperature to be 90 ℃, stirring for reaction for 60min, then filling 12kg of propylene oxide gas into the high-pressure reaction kettle, controlling the temperature to be 80 ℃, continuing to react for 90min, and obtaining myrcenol ether after the reaction is finished;
the sodium alkoxide is sodium methoxide.
The surfactant is sodium dodecyl sulfate.
The initiator is ammonium persulfate.
Example 2
A preparation method of a silicon-based modified oleic acid polycarboxylic acid ethanol reducer comprises the following specific preparation scheme:
uniformly mixing 44kg of acrylic acid, 6kg of hydroxyethyl methacrylate, 3kg of mercaptopropionic acid and 3kg of diallyl dimethyl ammonium chloride, slowly adding the mixture into a reaction kettle, adding 24kg of silicon-based modified oleic acid, 2kg of 2-acrylamido-2-methyl-1-propane sodium sulfonate, 0.3kg of surfactant, 0.4kg of ferric acrylate and 1.9kg of initiator into the reaction kettle in advance, stirring and uniformly mixing, heating under the protection of nitrogen, reacting for 90min at 72 ℃, adding 350kg of ethanol solution containing 15kg of sodium hydroxide, continuously stirring and reacting for 200min, and evaporating to remove water to obtain the silicon-based modified oleic acid polycarboxylic acid ethanol reducer.
The preparation method of the silicon-based modified oleic acid comprises the following steps:
putting 150kg of oleic acid and 380kg of ethanol into a reaction kettle, stirring and mixing uniformly to obtain oil emulsion, adjusting the pH to 9, and then adding 5kg of vinyl dimethylsilane; after uniform mixing, adding azobisisobutyronitrile, reacting for 180min at 72 ℃, adjusting the pH value to 7.5 by using dilute hydrochloric acid, then adding 3kg of myrcenol ether and 0.007kg of chloroplatinic acid, reacting for 80min at 72 ℃, and controlling the pH value of a reaction system to 7.5 by using a 4% sodium hydroxide solution; and (3) terminating the reaction after the reaction is finished, washing, distilling to remove ethanol, and drying to obtain the silicon-based modified oleic acid.
The preparation method of the myrcenol ether comprises the following steps:
adding 19kg of myrcenol and 0.07kg of sodium alkoxide into a high-pressure reaction kettle, then replacing with dry nitrogen for three times, finally vacuumizing, filling 28kg of ethylene oxide gas into the reaction kettle, controlling the temperature to be 95 ℃, stirring for reaction for 80min, then filling 17kg of propylene oxide gas into the high-pressure reaction kettle, controlling the temperature to be 87 ℃, continuing to react for 120min, and obtaining myrcenol ether after the reaction is finished;
the sodium alkoxide is sodium ethoxide.
The surfactant is sodium dodecyl benzene sulfonate.
The initiator is potassium persulfate.
Example 3
A preparation method of a silicon-based modified oleic acid polycarboxylic acid ethanol reducer comprises the following specific preparation scheme:
uniformly mixing 48kg of acrylic acid, 8kg of hydroxyethyl methacrylate, 5kg of mercaptopropionic acid and 7kg of diallyl dimethyl ammonium chloride, slowly adding the mixture into a reaction kettle, adding 28kg of silicon-based modified oleic acid, 3.6kg of 2-acrylamido-2-methyl-1-propane sodium sulfonate, 0.5kg of surfactant, 0.7kg of ferric acrylate and 3.4kg of initiator into the reaction kettle in advance, stirring and uniformly mixing, heating under the protection of nitrogen, reacting at 75 ℃ for 60-120min, adding 400kg of ethanol solution containing 18kg of sodium hydroxide, continuously stirring for continuing to react for 240min, and evaporating to remove water to obtain the silicon-based modified oleic acid polycarboxylic acid ethanol reducer.
The preparation method of the silicon-based modified oleic acid comprises the following steps:
putting 200kg of oleic acid and 400kg of ethanol into a reaction kettle, stirring and mixing uniformly to obtain oil emulsion, adjusting the pH to 11, and then adding 10kg of vinyldimethylsilane; after uniform mixing, adding azobisisobutyronitrile, reacting for 300min at 75 ℃, adjusting the pH value to 8.5 by using dilute hydrochloric acid, then adding 4kg of lauryl enol ether and 0.02kg of chloroplatinic acid, reacting for 120min at 75 ℃, and controlling the pH of a reaction system to 8.5 by using a 5% sodium hydroxide solution; and (3) terminating the reaction after the reaction is finished, washing, distilling to remove ethanol, and drying to obtain the silicon-based modified oleic acid.
The preparation method of the myrcenol ether comprises the following steps:
adding 28kg of myrcenol and 0.1kg of sodium alkoxide into a high-pressure reaction kettle, then replacing with dry nitrogen for three times, finally vacuumizing, filling 36kg of ethylene oxide gas into the reaction kettle, controlling the temperature to be 110 ℃, stirring for reaction for 120min, then filling 28kg of propylene oxide gas into the high-pressure reaction kettle, controlling the temperature to be 100 ℃, continuing to react for 180min, and obtaining myrcenol ether after the reaction is finished;
the sodium alkoxide is sodium ethoxide.
The surfactant is sodium dodecyl benzene sulfonate.
The initiator is azobisisobutyronitrile.
The concrete slump of the experiment is measured according to the standard of GB/T50080-2002 'common concrete mixture performance test method'. And (3) filling the prepared concrete into a slump cone, and vibrating. In the vibrating process, the test sample is ensured to be filled in the whole slump cone all the time, and if concrete is vibrated out of the test cone, the concrete needs to be added. After the vibration is finished, scraping redundant mixture to ensure that the concrete is flush with the top surface of the slump cone. And (3) stably and vertically lifting the slump cone upwards, finishing the whole process within 10s, and measuring the height difference between the highest point of the slump mixture sample and the cone to obtain the slump of the mixture. The mixture comprises the following raw materials in percentage by weight: ethanol sludge: mineral powder: fly ash: ethanol: river sand: the crushed stone is 1.0:0.36:0.44:0.68:3.4:5.4, the mixing amount of the synthetic ethanol reducing agent is 0.15%, and a blank experiment is carried out at the same time.
The test method of the experiment is carried out according to GB/T8077-2000, the surface tension of the solution doped with the polycarboxylic acid ethanol reducer is measured, and the influence of the silicon-based modified oleic acid polycarboxylic acid ethanol reducer on the surface tension of the solution when the mass concentration is 2 percent (conversion value) is researched. The results of the measurements are shown in the following table:
| surface tension (mN/m) | Slump (mm) | |
| Blank group | 72.4 | 110 |
| Example 1 | 38.7 | 175 |
| Example 2 | 36.2 | 180 |
| Example 3 | 35.8 | 195 |
Comparative example 1
A preparation method of a silicon-based modified oleic acid polycarboxylic acid ethanol reducer comprises the following specific preparation scheme:
uniformly mixing 40kg of acrylic acid, 5kg of hydroxyethyl methacrylate, 1kg of mercaptopropionic acid and 2kg of diallyl dimethyl ammonium chloride, slowly adding the mixture into a reaction kettle, adding 20kg of silicon-based modified oleic acid, 1.5kg of 2-acrylamido-2-methyl-1-propane sodium sulfonate, 0.1kg of surfactant, 0.2kg of ferric acrylate, 1.6kg of initiator and 300kg of water into the reaction kettle in advance, uniformly stirring, heating under the protection of nitrogen, reacting at 70 ℃ for 60-120min, adding 300kg of ethanol solution containing 13kg of sodium hydroxide, continuously stirring, continuously reacting for 180min, and evaporating to remove water to obtain the silicon-based modified polycarboxylic acid ethanol reducer.
The preparation method of the silicon-based modified oleic acid comprises the following steps:
putting 100kg of oleic acid and 300kg of ethanol into a reaction kettle, stirring and mixing uniformly to obtain oil emulsion, adjusting the pH to 8, and then adding 4kg of vinyldimethylsilane; after uniform mixing, adding azobisisobutyronitrile, reacting for 150min at 70 ℃, adjusting the pH value to 7.0 by using dilute hydrochloric acid, reacting for 60min at 70 ℃ by using 0.003kg of chloroplatinic acid, and controlling the pH value of a reaction system to 7.0 by using 1% sodium hydroxide solution; and (3) terminating the reaction after the reaction is finished, washing, distilling to remove ethanol, and drying to obtain the silicon-based modified oleic acid.
The sodium alkoxide is sodium methoxide.
The surfactant is sodium dodecyl sulfate.
The initiator is ammonium persulfate.
Comparative example 2
A preparation method of a silicon-based modified oleic acid polycarboxylic acid ethanol reducer comprises the following specific preparation scheme:
uniformly mixing 40kg of acrylic acid, 5kg of hydroxyethyl methacrylate, 1kg of mercaptopropionic acid and 2kg of diallyl dimethyl ammonium chloride, slowly adding the mixture into a reaction kettle, adding 1.5kg of 2-acrylamido-2-methyl-1-propane sodium sulfonate, 0.1kg of surfactant, 0.2kg of ferric acrylate, 1.6kg of initiator and 300kg of water into the reaction kettle in advance, stirring and uniformly mixing, heating under the protection of nitrogen, reacting at 70 ℃ for 60-120min, adding 300kg of ethanol solution containing 13kg of sodium hydroxide, continuously stirring and continuously reacting for 180min, and evaporating to remove water to obtain the silicon-based modified oleic acid polycarboxylic acid ethanol reducer.
The sodium alkoxide is sodium methoxide.
The surfactant is sodium dodecyl sulfate.
The initiator is ammonium persulfate.
Comparative example 3
A preparation method of a silicon-based modified oleic acid polycarboxylic acid ethanol reducer comprises the following specific preparation scheme:
uniformly mixing 40kg of acrylic acid, 5kg of hydroxyethyl methacrylate, 1kg of mercaptopropionic acid and 2kg of diallyl dimethyl ammonium chloride, slowly adding the mixture into a reaction kettle, adding 20kg of silicon-based modified oleic acid, 1.5kg of 2-acrylamido-2-methyl-1-propane sodium sulfonate, 0.1kg of surfactant, 0.2kg of ferric acrylate, 1.6kg of initiator and 300kg of water into the reaction kettle in advance, uniformly stirring, heating under the protection of nitrogen, reacting at 70 ℃ for 60-120min, adding 300kg of ethanol solution containing 13kg of sodium hydroxide, continuously stirring, continuously reacting for 180min, and evaporating to remove water to obtain the silicon-based modified polycarboxylic acid ethanol reducer.
The preparation method of the silicon-based modified oleic acid comprises the following steps:
putting 100kg of oleic acid and 300kg of ethanol into a reaction kettle, stirring and mixing uniformly to obtain oil emulsion, adjusting the pH to 8, and then adding 4kg of vinyldimethylsilane; after uniform mixing, adding azobisisobutyronitrile, reacting for 150min at 70 ℃, adjusting the pH value to 7.0 by using dilute hydrochloric acid, then adding 0.7kg of lauryl enol ether and 0.003kg of chloroplatinic acid, reacting for 60min at 70 ℃, and controlling the pH value of a reaction system to 7.0 by using 1% sodium hydroxide solution; and (3) terminating the reaction after the reaction is finished, washing, distilling to remove ethanol, and drying to obtain the silicon-based modified oleic acid.
The preparation method of the myrcenol ether comprises the following steps:
adding 16kg of myrcenol and 0.05kg of sodium alkoxide into a high-pressure reaction kettle, then replacing with dry nitrogen for three times, finally vacuumizing, filling 22kg of ethylene oxide gas into the reaction kettle, controlling the temperature to be 90 ℃, stirring for reaction for 60min, then filling 12kg of propylene oxide gas into the high-pressure reaction kettle, controlling the temperature to be 80 ℃, continuing to react for 90min, and obtaining myrcenol ether after the reaction is finished;
the sodium alkoxide is sodium methoxide.
The surfactant is sodium dodecyl sulfate.
The initiator is ammonium persulfate.
The ethanol-reducing agent performance of the comparative example was tested in the same manner as in the above example, and the test results are as follows.
| Surface tension (mN/m) | Slump (mm) | |
| Comparative example 1 | 45.9 | 155 |
| Comparative example 2 | 57.6 | 135 |
| Comparative example 3 | 41.5 | 160 |
Claims (6)
1. A preparation method of a silicon-based modified oleic acid polycarboxylic acid water reducing agent comprises the following specific preparation scheme:
according to the mass portion, evenly mixing 40-48 portions of acrylic acid, 5-8 portions of hydroxyethyl methacrylate, 1-5 portions of mercaptopropionic acid and 2-7 portions of diallyl dimethyl ammonium chloride, slowly adding the mixture into a reaction kettle, adding 20-28 portions of silicon-based modified oleic acid, 1.5-3.6 portions of 2-acrylamido-2-methyl-1-propane sodium sulfonate, 0.1-0.5 portion of surfactant, 0.2-0.7 portion of ferric acrylate, 1.6-3.4 portions of initiator and 300 portions of water into the reaction kettle in advance, stirring and evenly mixing, heating under the protection of nitrogen, reacting for 60-120min at 70-75 ℃, adding 300 portions of 400 portions of aqueous solution containing 13-18 portions of sodium hydroxide, continuously stirring and reacting for 180-240min, evaporating to remove water, thus obtaining the silicon-based modified oleic acid polycarboxylic acid water reducing agent.
2. The preparation method of the silicon-based modified oleic acid polycarboxylic acid water reducing agent according to claim 1, characterized in that: the preparation method of the silicon-based modified oleic acid comprises the following steps:
putting 100-200 parts of oleic acid and 300-400 parts of ethanol into a reaction kettle, stirring and mixing uniformly to obtain oil emulsion, adjusting the pH to 8-11, and then adding 4-10 parts of vinyldimethylsilane; after uniform mixing, adding azobisisobutyronitrile, reacting for 150-75 min at 70-75 ℃, adjusting the pH value to 7.0-8.5 by using dilute hydrochloric acid, then adding 0.7-4 parts of myrcenol ether, 0.003-0.02 part of chloroplatinic acid, reacting for 60-120min at 70-75 ℃, and controlling the pH of the reaction system to 7.0-8.5 by using 1-5% of sodium hydroxide solution; and (3) terminating the reaction after the reaction is finished, washing, distilling to remove ethanol, and drying to obtain the silicon-based modified oleic acid.
3. The preparation method of the silicon-based modified oleic acid polycarboxylic acid water reducing agent according to claim 2, characterized in that: the preparation method of the myrcenol ether comprises the following steps:
adding 16-28 parts of myrcenol and 0.05-0.1 part of sodium alkoxide in parts by mass into a high-pressure reaction kettle, then replacing the materials with dry nitrogen for three times, finally vacuumizing, filling 22-36 parts of ethylene oxide gas into the reaction kettle, controlling the temperature to be 90-110 ℃, stirring and reacting for 60-120min, filling 12-28 parts of propylene oxide gas into the high-pressure reaction kettle, controlling the temperature to be 80-100 ℃, continuing to react for 90-180min, and obtaining the myrcenol ether after the reaction is completed.
4. The preparation method of the silicon-based modified oleic acid polycarboxylic acid water reducing agent according to claim 2, characterized in that: the sodium alkoxide is sodium methoxide or sodium ethoxide.
5. The preparation method of the silicon-based modified oleic acid polycarboxylic acid water reducing agent according to claim 1, characterized in that: the surfactant is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.
6. The preparation method of the silicon-based modified oleic acid polycarboxylic acid water reducing agent according to claim 1, characterized in that: the initiator is ammonium persulfate or potassium persulfate or azobisisobutyronitrile.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115259893A (en) * | 2022-08-08 | 2022-11-01 | 广东广垠建设股份有限公司 | Light environment-friendly building material |
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| CN103709396A (en) * | 2013-12-26 | 2014-04-09 | 四川石达化学股份有限公司 | Dihydromyrcenol polyoxyethylene ether and synthetic method thereof |
| CN105017491A (en) * | 2015-08-24 | 2015-11-04 | 科之杰新材料集团有限公司 | Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN110003402A (en) * | 2019-04-23 | 2019-07-12 | 四川同舟化工科技有限公司 | A kind of anti-mud collapse protective poly-carboxylic acid water reducing agent and its low temperature preparation method of lower shrinkage high-adaptability |
| US20210040002A1 (en) * | 2019-08-09 | 2021-02-11 | Radi Al-Rashed | Multiple Crystallization Enhance (MCE) Intermix for Portland Cement Concrete |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103709396A (en) * | 2013-12-26 | 2014-04-09 | 四川石达化学股份有限公司 | Dihydromyrcenol polyoxyethylene ether and synthetic method thereof |
| CN105017491A (en) * | 2015-08-24 | 2015-11-04 | 科之杰新材料集团有限公司 | Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN110003402A (en) * | 2019-04-23 | 2019-07-12 | 四川同舟化工科技有限公司 | A kind of anti-mud collapse protective poly-carboxylic acid water reducing agent and its low temperature preparation method of lower shrinkage high-adaptability |
| US20210040002A1 (en) * | 2019-08-09 | 2021-02-11 | Radi Al-Rashed | Multiple Crystallization Enhance (MCE) Intermix for Portland Cement Concrete |
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| CN115259893A (en) * | 2022-08-08 | 2022-11-01 | 广东广垠建设股份有限公司 | Light environment-friendly building material |
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Application publication date: 20201211 |