CN111333829A - Unsaturated polyether monomer, polycarboxylate superplasticizer and preparation method thereof - Google Patents
Unsaturated polyether monomer, polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN111333829A CN111333829A CN202010339503.7A CN202010339503A CN111333829A CN 111333829 A CN111333829 A CN 111333829A CN 202010339503 A CN202010339503 A CN 202010339503A CN 111333829 A CN111333829 A CN 111333829A
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- 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
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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
Abstract
The invention relates to an unsaturated polyether monomer, a polycarboxylic acid water reducing agent and a preparation method thereof. The unsaturated polyether monomers of the present invention have the following formula I. The polycarboxylate superplasticizer is a copolymer of the unsaturated polyether monomer and unsaturated carboxylic acid, and comprises a monomer unit derived from the unsaturated polyether monomer and a monomer unit derived from the unsaturated carboxylic acid. The polycarboxylate superplasticizer obtained by the unsaturated polyether monomer can well solve the problem of soil in concrete, which means that the clay does not change the adsorption capacity of corresponding PCE (Poly-ester-carbonate) to cement, and can well contain sandstoneThe concrete field with high mud content (5% -10%) and the gypsum dispersant field.
Description
Technical Field
The invention relates to the field of cement or gypsum-based building materials, in particular to a macromonomer serving as a key component of a mud-resistant water reducing agent, a polycarboxylic acid water reducing agent obtained by the macromonomer and a preparation method of the polycarboxylic acid water reducing agent.
Background
The impurities of the sand, gravel and mud (clay) in the sand used for concrete production are becoming more and more difficult for concrete manufacturers and constructors. The deterioration of the concrete properties is due to the undesired adsorption of the ethylene oxide based water reducing agent in the clay interlayer. The mud appears to have a particle size of less than 2 μm. The slurry not only destroys the properties of the fresh concrete, but also the strength (due to less water reduction), shrinkage, impermeability, frost resistance and abrasion resistance of the concrete. The national sandstone standard requires that a washing process is adopted before use. Although this may improve the quality of the aggregate, it may also create economic and environmental problems, among others. If the water reducing agent can be prevented from adsorbing the inner surface of the clay, obvious benefits can be brought about on the performance of fresh concrete, the engineering performance of hardened concrete and economic and environmental problems.
The common slurries (clays) in gravel are montmorillonite, kaolinite, muscovite and illite, chemically characterized by a silicon tetrahedral and alumina octahedral structure. Depending on the composition of the clay, different types of clay may be formed. The influence of clay on the working properties of concrete is related to the amount and type of clay, of which the type of clay mineral plays a decisive role. The polycarboxylic acid high-efficiency water reducing agent is widely applied to the fields of high-speed railways, water conservancy and hydropower, nuclear power, highways, port wharfs and the like. It has been widely used in the field of high speed railways, and water reducing agents in the high speed railway department are more sensitive to collapse of sandy soil than polycarboxylate water reducing agents.
The clay mineral has obvious expansion performance and water absorption performance, and has important influence on the working performance and the mechanical property of concrete. The adsorption capacity of the clay reduces the effective adsorption of the PCE to the surface of the cement particles. Therefore, the EO-containing PCE is very sensitive to the amount of clay containing sand and gravel in the concrete. The initial flow of the concrete is reduced and the flow loss is accelerated.
CN 104891853A discloses a composition for reducing the viscosity of pumped concrete and increasing the mud resistance and a preparation method of a polycarboxylic acid type pumping aid. The mud pumping resistant agent is a liquid polycarboxylate water reducing agent, the solid content of the water reducing agent is 40%, the retarder is a conventional retarder, and the air entraining group is a synthetic anionic surfactant. In addition, a viscosity reducer combination based on a mixture of calcium nitrate, polyethylene glycol, dextrin and dimethyldiallylammonium chloride is described.
CN 104479084A discloses a novel environment-friendly polycarboxylate-based shear resistant agent and a preparation method thereof, belonging to the field of building material concrete. The polycarboxylate anti-sludge agent is prepared by polymerizing unsaturated oxygen-containing polyoxyethylene ether, unsaturated ester and derivatives thereof serving as monomers, unsaturated carboxylic acid and derivatives thereof and redox initiator through free radicals and the like, and the polycarboxylate anti-sludge water reducing agent prevents concrete from adsorbing the polycarboxylate water reducing agent in soil in the using process, so that the using amount of the water reducing agent is reduced, the cost is saved, and the performance of the concrete is improved.
CN 102276181A discloses a concrete slurry inhibitor, which comprises 50-75% of alkylene amine ether, 5-15% of (methyl) acrylate, 0.1-1% of DA, 0.5-5% of alkylene sulfonate, 0.1-1% of EA and 5-15% of vinyl ester by mass percent of a monomer composition and a polymer mother liquor. The anti-mud agent is introduced into the polymer monomer lipid monomer, so that the water absorption of the mud particles can be reduced by the adsorbent and the surfaces of the mud particles, and the water demand of the concrete can reach a proper amount.
CN 106810099A states that a single conventional polycarboxylate water reducing agent cannot solve the clay problem. According to the invention, by constructing a high-adaptability mud-resisting system with nesting and sealing hydrophobic synergistic effects, the design of multi-component matching of the mud-resisting agent is a difficult point, so that the key is how to design the multi-component matching of the mud-resisting agent.
CN108250429A discloses a preparation method of a high-efficiency water reducing agent with relatively low molecular weight and anti-sticking property and phosphate. Polyamine is used as a leavening agent, ring opening is carried out, an intermediate product is purified, and then phosphorization is carried out to obtain the anti-adhesive phosphate type high-efficiency water reducing agent with the molecular weight of 5000-14000. The method adopts the ring-opening reaction of the alkyl oxide, the production condition and the equipment requirement are high, two-step purification operation is needed in the preparation process, and the industrialization difficulty is high; the macrocyclic polyamine used in the method has high cost and is easy to cause environmental pollution. Patent No. CN107312507A discloses a preparation method of a clay stabilizer. The cationic clay stabilizer with the molecular weight of 250-5000-. The clay stabilizer has good performance, but amine substances used in the process are inflammable and volatile, and have larger potential safety hazard and environmental problems. CN108047396A discloses a cationic polycarboxylate anti-mud water reducing agent and a preparation method thereof. Polymerizing a cationic monomer A, an unsaturated carboxylic acid/unsaturated anhydride B and an unsaturated monomer C solution to prepare the cationic side chain mud-resistant polycarboxylate superplasticizer. The cationic side chain is an amine salt hydrochloride, the stability of the concrete under alkaline conditions has a great problem, and the compatibility with the anionic polycarboxylic acid water reducing agent needs to be further concerned.
Disclosure of Invention
The invention provides a special functional polymer monomer based on ethylene glycol divinyl ether, which is a key component of a cement (clay) resistant dispersing agent in an inorganic solid suspension and is a high-efficiency water reducing agent for concrete.
The present invention provides an unsaturated polyether monomer having the following formula I:
wherein R isAIdentical or different and represent a hydrogen atom, a linear or branched C1-C12Alkyl radical, C5-C8Cycloalkyl, phenyl, C7-C12Aralkyl group;
a is identical or different and represents a group consisting of CXH2XAlkylene group represented by wherein x is 2, 3, 6 or 7;
b are identical or different and represent an integer between 6 and 450.
In one embodiment, RARepresents a hydrogen atom.
In one embodiment, a represents CH2CH2Ethylene and CH2CH2CH2One or two of the propylene groups represented.
The present invention also provides a method of preparing an unsaturated polyether monomer comprising:
reacting vinyl glycol ether with an epoxy compound in the presence of a catalyst to obtain the unsaturated polyether monomer.
In one embodiment, the catalyst is one or more of sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide in an amount of 0.5% to 2.0% by weight of the vinyl glycol ether.
The invention also provides a polycarboxylate water reducing agent which is a copolymer of the unsaturated polyether monomer and the unsaturated carboxylic acid, and comprises a monomer unit derived from the unsaturated polyether monomer and a monomer unit derived from the unsaturated carboxylic acid.
In one embodiment, the copolymer has a weight average molecular weight of 4 to 7 ten thousand and a molecular weight distribution of 1 to 5.
In one embodiment, in the copolymer, the molar ratio of the monomer unit derived from the unsaturated polyether monomer to the monomer unit derived from the unsaturated carboxylic acid is 1: 3.0-5.0.
In one embodiment, the unsaturated carboxylic acid is selected from one or more of acrylic acid, methacrylic acid, and maleic anhydride.
The invention also provides a method for preparing the polycarboxylate superplasticizer, which comprises the following steps:
reacting the unsaturated polyether monomer of any one of claims 1-3 with an unsaturated carboxylic acid in the presence of a chain transfer agent to obtain the polycarboxylate water reducer.
In one embodiment, the method comprises:
dissolving the unsaturated polyether monomer in deionized water to obtain reaction base solution;
adding the unsaturated carboxylic acid, a reducing agent and a chain transfer agent into deionized water in sequence for dissolving to obtain a dropping liquid;
controlling the temperature of the reaction base solution to be 15-25 ℃, adding an oxidant into the reaction base solution, and then dripping the dripping liquid into the reaction base solution;
and (3) carrying out heat preservation reaction on the reaction mixture at the temperature of 15-25 ℃ to obtain the polycarboxylic acid water reducer.
In one embodiment, the unsaturated carboxylic acid is one or more of acrylic acid, methacrylic acid, and maleic anhydride, and the molar ratio of the unsaturated polyether monomer to the unsaturated carboxylic acid is from 1:3.0 to 5.0.
In one embodiment, the chain transfer agent is one or more of mercaptopropionic acid, mercaptoacetic acid, and mercaptoethanol, and is added in an amount of 0.5% to 1% by weight of the unsaturated polyether monomer.
In one embodiment, the oxidant is hydrogen peroxide, and the addition amount of the oxidant is 0.1-0.5% of the mass of the unsaturated polyether monomer.
In one embodiment, the reducing agent is one or more of sodium formaldehyde sulfoxylate, vitamin C, E51, FF6M and sodium bisulfite, and the mass ratio of the oxidizing agent to the reducing agent is 1.5-2.5: 1.
in another aspect, the present invention also provides the use of a polycarboxylate water reducer according to the invention or obtained by the method according to any one of claims 10-15 as a water reducer in concrete having a sand mud content of 5-10 wt%.
The polycarboxylate superplasticizer obtained by the unsaturated polyether monomer can well solve the problem of soil in concrete, which means that the clay does not change the adsorption capacity of corresponding PCE to cement, and can well solve the concrete field with high sand and stone content (5-10%) and the gypsum dispersant field. This is probably due to the special structure obtained from the vinyl macromonomer by the polycarboxylate water reducer of the present invention, which can reduce or even stop the adsorption of PCE to the clay interlayer.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
In one aspect, the present invention provides an unsaturated polyether monomer having the following formula I:
wherein R isAIdentical or different and represent a hydrogen atom, a linear or branched C1-C12Alkyl radical, C5-C8Cycloalkyl, phenyl, C7-C12Aralkyl group;
a is identical or different and represents a group consisting of CXH2XAlkylene group represented by wherein x is 2, 3, 6 or 7;
b are identical or different and represent an integer between 6 and 450.
In one embodiment, RAMay represent a hydrogen atom. In one embodiment, a may represent CH2CH2Ethylene and CH2CH2CH2One or two of the propylene groups represented.
The unsaturated polyether monomer has a double bond and can be copolymerized with other comonomers so as to be introduced into a polymer chain. And the unsaturated polyether monomer also has-O-CH2CH2-O-(AO)b-RAThe chain can exist in a side chain form in a polymer chain, and because the O atom in the side chain is directly connected with the double bond to have stronger electron effect, the softness of the side chain is better and has better workability in the application of concrete.
In another aspect, the present invention provides a method of preparing the unsaturated polyether monomer, comprising:
reacting vinyl glycol ether with an epoxy compound in the presence of a catalyst to obtain the unsaturated polyether monomer.
Specifically, it can be performed as follows: and injecting the mixed solution of the vinyl glycol ether and the catalyst into the closed high-pressure kettle, stirring and heating the reaction kettle to the temperature of 100 ℃ and 135 ℃, continuously introducing the epoxy compound for 6-9 hours, and cooling to obtain the unsaturated polyether monomer.
The AO units in the unsaturated polyether monomer may vary depending on the epoxy compound used. When ethylene oxide is used, the AO unit may be-CH2CH2An O (EO) unit; when propylene oxide is used, the AO unit may be-CH2CH2CH2An O (PO) unit; when ethylene oxide and propylene oxide are used, the AO units can be a combination of EO units and PO units.
The addition number b of the AO unit in the unsaturated polyether monomer can be controlled by reaction conditions such as reaction time and reaction temperature. B may be an integer from 6 to 450, preferably an integer from 8 to 120.
In one embodiment, the catalyst is one or more of sodium alkoxide (e.g., sodium methoxide, etc.), potassium alkoxide, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, and is used in an amount of 0.5% to 2.0% by weight of the vinyl glycol ether.
In another aspect, the present invention provides a polycarboxylic acid water reducing agent which is a copolymer of the unsaturated polyether monomer of the present invention and an unsaturated carboxylic acid, comprising a monomer unit derived from the unsaturated polyether monomer and a monomer unit derived from the unsaturated carboxylic acid. In the copolymer, the monomer unit derived from the unsaturated polyether monomer and the monomer unit derived from the unsaturated carboxylic acid may be present in a random manner.
In one embodiment, in the copolymer, the molar ratio of the monomer unit derived from the unsaturated polyether monomer to the monomer unit derived from the unsaturated carboxylic acid is 1: 3.0-5.0.
In one embodiment, the copolymer has a weight average molecular weight of 4 to 7 ten thousand and a molecular weight distribution of 1 to 5.
In one embodiment, the unsaturated carboxylic acid is selected from one or more of acrylic acid, methacrylic acid, and maleic anhydride.
The invention provides a method for preparing a polycarboxylic acid water reducing agent, which comprises the following steps:
the unsaturated polyether monomer and the unsaturated carboxylic acid react in the presence of a chain transfer agent to obtain the polycarboxylic acid water reducing agent.
Specifically, the method comprises the following steps:
dissolving the unsaturated polyether monomer in deionized water to obtain reaction base solution;
adding the unsaturated carboxylic acid, a reducing agent and a chain transfer agent into deionized water in sequence for dissolving to obtain a dropping liquid;
controlling the temperature of the reaction base solution to be 15-25 ℃, adding an oxidant into the reaction base solution, and then dripping the dripping liquid into the reaction base solution;
and (3) carrying out heat preservation reaction on the reaction mixture at the temperature of 15-25 ℃ to obtain the polycarboxylic acid water reducer.
In one embodiment, the unsaturated carboxylic acid is one or more of acrylic acid, methacrylic acid, and maleic anhydride, and the molar ratio of the unsaturated polyether monomer to the unsaturated carboxylic acid is from 1:3.0 to 5.0.
In one embodiment, the chain transfer agent is one or more of mercaptopropionic acid, mercaptoacetic acid, and mercaptoethanol, and is added in an amount of 0.5% to 1% by weight of the unsaturated polyether monomer.
In one embodiment, the oxidant is hydrogen peroxide, and the addition amount of the oxidant is 0.1-0.5% of the mass of the unsaturated polyether monomer.
In one embodiment, the reducing agent is one or more of sodium formaldehyde sulfoxylate, vitamin C, E51, FF6M and sodium bisulfite, and the mass ratio of the oxidizing agent to the reducing agent is 1.5-2.5: 1.
the polycarboxylate superplasticizer disclosed by the invention has special comonomer unit distribution in a polymer chain, so that the PCE is beneficial to cement adsorption and can be prevented from being adsorbed on clay, and the polycarboxylate superplasticizer can be applied to the fields of concrete with high sand and stone content (5% -10%) and gypsum dispersing agents.
The clay in China takes feldspar, mica, kaolin and the like as main components, and the montmorillonite is used as a mineral with strong interlayer adsorption capacity and is mostly present in the north. The montmorillonite has the most serious influence on the polycarboxylic acid water reducing agent (PCE), the workability is greatly influenced when the content of the sandstone material reaches 2 percent or even is less than 2 percent, and the workability is obviously influenced when the contents of the feldspar, the kaolinite and the muscovite are 4 to 5 percent and the content of the sericite is 5 to 6 percent. The clay content in the field of application of the present invention is between 1 and 25% by weight of the mineral binder (such as cement or gypsum). In one embodiment, the polycarboxylic acid water reducer containing functional macromers of the present invention may be used in an amount of 2.5% solids by mass of cement.
The technical solution of the present invention will be further explained with reference to the following examples.
Example 1
(1) Macromonomer synthesis
220g of vinyl glycol ether and 3g of sodium methoxide are added into a beaker and stirred uniformly. A1.8L closed autoclave was charged with a mixed solution of vinyl glycol ether and sodium methoxide. The reaction kettle is sealed, the temperature is raised to 100 ℃, and ethylene oxide gas is introduced. Controlling the temperature of the reaction kettle to be not higher than 135 ℃, continuously reacting for 9 hours, cumulatively introducing about 7.5Kg of ethylene oxide gas, then stopping introducing the ethylene oxide gas, and reducing the temperature of the reaction kettle. And (3) discharging the product after cooling, and obtaining white waxy solid after cooling, namely the EPEG macromonomer with the number average molecular weight of 3000.
(2) PCE synthesis
In a 1L four-neck flask provided with a stirrer and a condenser, 364g of EPEG-3000 macromonomer is added into 238g of deionized water, and the mixture is properly heated and fully dissolved to prepare reaction bottom liquid; adding 1.7g of vitamin C, 30.79g of acrylic acid and 1.98g of thioglycolic acid into 78g of deionized water at one time, mixing and stirring uniformly to prepare a dropping liquid; controlling the reaction temperature to be 20-25 ℃, and adding 2.97g of H into the reaction base solution2O2Then dripping the dropping liquid at a constant speed for 2 hours; and (3) after continuing the heat preservation reaction for 1 hour, adding a solution prepared from 30.80g of NaOH and 246g of water, and uniformly stirring to obtain the polycarboxylate superplasticizer, wherein the weight average molecular weight of the polycarboxylate superplasticizer is 40000, and the molecular weight distribution of the polycarboxylate superplasticizer is 2.5.
Example 2
(1) Macromonomer synthesis
220g of vinyl glycol ether and 5g of sodium methoxide are added into a beaker and stirred uniformly. A1.8L closed autoclave was charged with a mixed solution of vinyl glycol ether and sodium methoxide. The reaction kettle is sealed, the temperature is raised to 100 ℃, and ethylene oxide gas is introduced. Controlling the temperature of the reaction kettle to be not higher than 135 ℃, continuously reacting for 9 hours, cumulatively introducing about 10Kg of ethylene oxide gas, then stopping introducing the ethylene oxide gas, and reducing the temperature of the reaction kettle. And (3) discharging the product after cooling, and obtaining white waxy solid after cooling, namely the EPEG macromonomer with the number average molecular weight of 4000.
(2) PCE synthesis
In a 1L four-neck flask provided with a stirrer and a condenser, 364g of EPEG-4000 macromonomer is added into 238g of deionized water, and the mixture is properly heated and fully dissolved to prepare reaction bottom liquid; adding 1.7g of vitamin C, 30.79g of acrylic acid and 1.98g of thioglycolic acid into 78g of deionized water at one time, mixing and stirring uniformly to prepare a dropping liquid; controlling the reaction temperature to be 10-15 ℃, and adding 2.97g of H into the reaction base solution2O2Then dripping the dropping liquid at a constant speed for 2 hours; and (3) after the heat preservation reaction is continued for 1 hour, adding a solution prepared from 30.80g of NaOH and 246g of water, and uniformly stirring to obtain the polycarboxylate superplasticizer, wherein the average weight average molecular weight is 45000 and the molecular weight distribution is 3.1.
Example 3
(1) Macromonomer synthesis
220g of vinyl glycol ether and 6g of sodium methoxide are added into a beaker and stirred uniformly. A1.8L closed autoclave was charged with a mixed solution of vinyl glycol ether and sodium methoxide. The reaction kettle is sealed, the temperature is raised to 100 ℃, and ethylene oxide gas is introduced. Controlling the temperature of the reaction kettle to be not higher than 135 ℃, continuously reacting for 9 hours, cumulatively introducing 12.5Kg of ethylene oxide gas, then stopping introducing the ethylene oxide gas, and reducing the temperature of the reaction kettle. And (3) cooling, discharging the product, and cooling to obtain a white waxy solid, namely the EPEG macromonomer with the number average molecular weight of 5000.
(2) PCE synthesis
384g of EPEG-5000 macromonomer is added into 238g of deionized water in a 1L four-neck flask provided with a stirrer and a condenser, and the mixture is properly heated and fully dissolved to prepare reaction bottom liquid; 1.7g of sodium formaldehyde sulfoxylate,30.79g of acrylic acid and 1.98g of thioglycollic acid are added into 78g of deionized water at a time, mixed and stirred uniformly to prepare a dropping liquid; controlling the reaction temperature to be 10-15 ℃, and adding 2.97g of H into the reaction base solution2O2Then dripping the dropping liquid at a constant speed for 2 hours; and (3) after continuing the heat preservation reaction for 1 hour, adding a solution prepared from 30.80g of NaOH and 246g of water, and uniformly stirring to obtain the polycarboxylate superplasticizer, wherein the weight average molecular weight of the polycarboxylate superplasticizer is 50000, and the molecular weight distribution of the polycarboxylate superplasticizer is 3.5.
Comparative example 1
(1) Macromonomer synthesis
220g of isopentenol and 3g of sodium methoxide are added into a beaker and stirred uniformly. A mixed solution of prenol and sodium methoxide was charged into a closed 1.8L autoclave. The reaction kettle is sealed, the temperature is raised to 100 ℃, and ethylene oxide gas is introduced. Controlling the temperature of the reaction kettle to be not higher than 135 ℃, continuously reacting for 9 hours, cumulatively introducing about 1500g of ethylene oxide gas, then stopping introducing the ethylene oxide gas, and reducing the temperature of the reaction kettle. And (3) discharging the product after cooling, and obtaining white waxy solid after cooling, namely the TPEG macromonomer with the number average molecular weight of 3000.
(2) PCE synthesis
In a 1L four-neck flask provided with a stirrer and a condenser, 364g of TPEG-3000 macromonomer is added into 238g of deionized water, and the mixture is properly heated and fully dissolved to prepare reaction bottom liquid; adding 1.7g of vitamin C, 30.79g of acrylic acid and 1.98g of thioglycolic acid into 78g of deionized water at one time, mixing and stirring uniformly to prepare a dropping liquid; controlling the reaction temperature to be 35-40 ℃, and adding 2.97g of H into the reaction base solution2O2Then dripping the dropping liquid at a constant speed for 3 hours; and (3) after continuing the heat preservation reaction for 1h, adding a solution prepared from 30.80g of NaOH and 246g of water, and uniformly stirring to obtain the polycarboxylate superplasticizer, wherein the weight average molecular weight of the polycarboxylate superplasticizer is 36000, and the molecular weight distribution is 3.6.
Application example
The influence of the anti-mud polycarboxylate superplasticizer disclosed by the invention on fresh concrete is detected according to a method specified in GB 8076-2008. The fixed water-gel ratio is 0.40, the polycarboxylic acid bending and fixing mixing amount is 0.17%, the test temperature is 25 ℃, the humidity is 80%, the concrete mixing ratio is 267, mineral powder 53, fly ash 60, sand 767, large stone 800 and small stone 260, and the concrete test results are shown in table 1.
TABLE 1
As can be seen from the data in the above table, if the mud content in the comparative example exceeds 2%, the concrete has no flow property, while the concrete with the mud content of 8% in the example still has better flow property, which indicates that the polycarboxylate water reducer of the invention can well solve the problem of mud in the concrete, which means that the clay does not change the adsorption capacity of the corresponding PCE to the cement. This is probably due to the special structure obtained from the vinyl macromonomer by the polycarboxylate water reducer of the present invention, which can reduce or even stop the adsorption of PCE to the clay interlayer.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (16)
1. An unsaturated polyether monomer having the following formula I:
wherein R isAIdentical or different and represent a hydrogen atom, a linear or branched C1-C12Alkyl radical, C5-C8Cycloalkyl, phenyl, C7-C12Aralkyl group;
a is identical or different and represents a group consisting of CXH2XAlkylene group represented by wherein x is 2, 3, 6 or 7;
b are identical or different and represent an integer between 6 and 450.
2. The unsaturated polyether monomer of claim 1, wherein RARepresents a hydrogen atom.
3. An unsaturated polyether monomer according to claim 1 or 2, wherein a represents CH2CH2Ethylene and CH2CH2CH2One or two of the propylene groups represented.
4. A method of preparing the unsaturated polyether monomer of any one of claims 1-3, comprising:
reacting vinyl glycol ether with an epoxy compound in the presence of a catalyst to obtain the unsaturated polyether monomer.
5. The process of claim 4, wherein the catalyst is one or more of sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, and is used in an amount of 0.5% to 2.0% by mass of the vinyl glycol ether.
6. A polycarboxylic acid water reducing agent which is a copolymer of the unsaturated polyether monomer and the unsaturated carboxylic acid as described in any one of claims 1 to 3, comprising a monomer unit derived from the unsaturated polyether monomer and a monomer unit derived from the unsaturated carboxylic acid.
7. The polycarboxylate water reducer of claim 6 wherein the weight average molecular weight of said copolymer is 4-7 ten thousand and the molecular weight distribution is 1-5.
8. The polycarboxylic acid water reducing agent according to claim 6 or 7, wherein, in the copolymer, the molar ratio of the monomer unit derived from the unsaturated polyether monomer to the monomer unit derived from the unsaturated carboxylic acid is 1: 3.0-5.0.
9. A polycarboxylate water reducer as claimed in claim 6 or 7 wherein said unsaturated carboxylic acid is selected from one or more of acrylic acid, methacrylic acid and maleic anhydride.
10. A method for preparing a polycarboxylic acid water reducing agent comprises the following steps:
reacting the unsaturated polyether monomer of any one of claims 1-3 with an unsaturated carboxylic acid in the presence of a chain transfer agent to obtain the polycarboxylate water reducer.
11. The method of claim 10, wherein the method comprises:
dissolving the unsaturated polyether monomer in deionized water to obtain reaction base solution;
adding the unsaturated carboxylic acid, a reducing agent and a chain transfer agent into deionized water in sequence for dissolving to obtain a dropping liquid;
controlling the temperature of the reaction base solution to be 15-25 ℃, adding an oxidant into the reaction base solution, and then dripping the dripping liquid into the reaction base solution;
and (3) carrying out heat preservation reaction on the reaction mixture at the temperature of 15-25 ℃ to obtain the polycarboxylic acid water reducer.
12. The method of claim 10 or 11, wherein the unsaturated carboxylic acid is one or more of acrylic acid, methacrylic acid, and maleic anhydride, and the molar ratio of the unsaturated polyether monomer to the unsaturated carboxylic acid is 1: 3.0-5.0.
13. The method of claim 10 or 11, wherein the chain transfer agent is one or more of mercaptopropionic acid, mercaptoacetic acid, mercaptoethanol, added in an amount of 0.5% to 1% by mass of the unsaturated polyether monomer.
14. The method of claim 11, wherein the oxidant is hydrogen peroxide, and the addition amount of the oxidant is 0.1-0.5% of the mass of the unsaturated polyether monomer.
15. The method of claim 11, wherein the reducing agent is one or more of sodium formaldehyde sulfoxylate, vitamin C, E51, FF6M, and sodium bisulfite, and the mass ratio of the oxidizing agent to the reducing agent is 1.5-2.5: 1.
16. use of a polycarboxylate water reducer according to any of the claims 6-9 or obtained by the method according to any of the claims 10-15 as a water reducer in concrete having a sand content of 5-10 wt%.
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| CN112812288A (en) * | 2021-02-03 | 2021-05-18 | 湖北工业大学 | Preparation method of nano-alumina dispersant and nano-alumina dispersant |
| WO2021217762A1 (en) * | 2020-04-26 | 2021-11-04 | 辽宁奥克化学股份有限公司 | Unsaturated polyether monomer, and polycarboxylate superplasticizer and preparation method therefor |
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| CN116284603A (en) * | 2023-03-24 | 2023-06-23 | 辽宁奥克化学股份有限公司 | Water reducer suitable for fly ash and slag type concrete and preparation method thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011084459A (en) * | 2009-09-18 | 2011-04-28 | Nippon Shokubai Co Ltd | Cement admixture, cement composition, and polycarboxylic acid copolymer for cement admixture |
| CN108102085A (en) * | 2017-12-22 | 2018-06-01 | 上海东大化学有限公司 | Polyether monomer, polycarboxylate water-reducer and its methods for making and using same from it |
| CN111333829A (en) * | 2020-04-26 | 2020-06-26 | 辽宁奥克化学股份有限公司 | Unsaturated polyether monomer, polycarboxylate superplasticizer and preparation method thereof |
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| WO2021217762A1 (en) * | 2020-04-26 | 2021-11-04 | 辽宁奥克化学股份有限公司 | Unsaturated polyether monomer, and polycarboxylate superplasticizer and preparation method therefor |
| CN112812288A (en) * | 2021-02-03 | 2021-05-18 | 湖北工业大学 | Preparation method of nano-alumina dispersant and nano-alumina dispersant |
| CN112812288B (en) * | 2021-02-03 | 2023-03-28 | 湖北工业大学 | Preparation method of nano-alumina dispersant and nano-alumina dispersant |
| CN113980203A (en) * | 2021-11-22 | 2022-01-28 | 山东交通学院 | Polycarboxylate superplasticizer with controllable structure based on EPEG polyether macromonomer and preparation method thereof |
| WO2023184786A1 (en) * | 2022-03-30 | 2023-10-05 | 佳化化学科技发展（上海）有限公司 | Template agent, and preparation method therefor and use thereof |
| CN116284603A (en) * | 2023-03-24 | 2023-06-23 | 辽宁奥克化学股份有限公司 | Water reducer suitable for fly ash and slag type concrete and preparation method thereof |
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