CN112708140B - Early-strength cement dispersion polymer and preparation method thereof - Google Patents
Early-strength cement dispersion polymer and preparation method thereof Download PDFInfo
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- 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
- C08F220/10—Esters
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- 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
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
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- 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
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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Abstract
The invention relates to the technical field of building additives, in particular to an early strength cement dispersion polymer and a preparation method thereof, wherein the early strength cement dispersion polymer comprises the following components: a) an ester group-containing polymer comprising a polymer or copolymer derived from monomers comprising: 1) an unsaturated carboxylic acid ester monomer; and 2) at least one of unsaturated acid monomer and unsaturated silane monomer; and b) carboxymethyl starch; and c) polyethylene glycol monomethyl ether. The early strength cement dispersion polymer provided by the invention adopts a method of low-temperature copolymerization and high-temperature esterification, reduces the damage of double bonds of reaction monomers, improves the copolymerization degree, has high water reducing rate, can improve the workability of concrete and improve the early strength of the concrete, thereby improving the compactness of the concrete and reducing the cracking risk of the concrete; meanwhile, the operation process is simple, and large-scale industrial production is facilitated.
Description
Technical Field
The invention relates to the technical field of building additives, in particular to an early strength cement dispersion polymer and a preparation method thereof.
Background
With the continuous popularization of national key engineering projects and the complexity of the structure and the badness of conditions of the structure, great challenges are provided for the quality and the durability of a concrete structure, the temperature inside the concrete rises due to a large amount of hydration heat generated by cement hydration, the hydration heat is accumulated inside the concrete and is not easy to dissipate, and when the tensile stress generated by the internal and external temperature difference at the initial stage of concrete setting exceeds the compressive strength of the concrete, the concrete cracks, so that the strength and the durability of the concrete are seriously affected.
The current possible effective solution is to add materials such as a polycarboxylate water reducer, a hydration regulator and the like to regulate the state and the hydration heat of concrete, but the polycarboxylate water reducer and a sand material have adaptability problem. Therefore, in order to ensure the smooth construction and the engineering quality of the structure, the water reducer which has a good dispersion function and can obviously reduce the hydration heat release rate of the cement is developed, and the water reducer has a wide market prospect.
The starch has the advantages of wide source, high yield, no toxicity and low price, and the molecular chain of the natural starch contains hydrophobic chains and hydrophilic hydroxyl groups, so that the basic structural framework of the starch is very suitable for being used as the raw material of the water reducing agent. And the glycosidic bond and the hydroxyl on the molecular structure of the starch are active in chemical property, so that the starch can be chemically modified to introduce a multi-purpose acting group on the molecular structure of the starch. Therefore, the modified starch can replace a part of polyether macromonomer to synthesize the water reducing agent.
In the prior art, starch substances are introduced into a polycarboxylic acid water reducing agent, so that the problems of poor dispersing performance, overlarge product viscosity and adaptability of the water reducing agent, or the problems of concrete durability and the like caused by the hydration heat release rate of cement cannot be solved.
The publication No. CN104558215A discloses a double-modified maltodextrin high-efficiency water reducing agent, which is prepared by diluting concentrated sulfuric acid by an organic solvent, sulfonating maltodextrin at low temperature, carrying out esterification reaction on a sulfonated product by using dibasic acid anhydride, and finally dissolving the product in water and adding alkali for neutralization.
The publication No. CN108440762A discloses a hyperbranched starch-based water reducing agent, and the adopted hyperbranched polymers with polyamide-amine at the tail end are prepared by the reaction of polybasic acid and amine substances and are reacted with starch to synthesize the hyperbranched starch-based water reducing agent, so that the water reducing efficiency of the water reducing agent can be better improved, the retardation performance is improved, but the preparation process is too complex, the conversion rate of a target product is low, and the industrial production is not facilitated.
The publication No. CN109776022A discloses a composite controllable hydration heat cement-based material, which achieves the purpose of controlling the hydration heat release rate of cement by physically compounding a certain amount of cross-linking agent, organic acid and starch-based macromolecular organic matter, but the product does not have the water reducing effect, and the product is compounded in a liquid-solid manner, so that the actual application process is complex, and the popularization is not facilitated.
The publication No. CN110606922A discloses a preparation method of a polycarboxylate water reducer with hydration heat regulation and control effects, wherein carboxymethyl starch with a substitution degree of 0.3-0.5 and better water solubility is introduced, and is subjected to series of treatments such as pyrolysis, acidolysis and enzymolysis, and then is subjected to esterification reaction with unsaturated hydroxy ester monomers to obtain modified CMS monomers for synthesizing the polycarboxylate water reducer, but the preparation process is too complex and is not beneficial to industrial production.
The publication No. CN111592619A discloses a starch-based polycarboxylic acid water reducer mate and a preparation and use method thereof, wherein modified starch containing unsaturated double bonds, unsaturated polyoxyethylene ether and acrylic monomers are used for preparing the starch-based polycarboxylic acid water reducer mate under the action of an initiator, but the water reduction rate is low, the starch-based polycarboxylic acid water reducer mate needs to be compounded with other water reducers for use, the starch-based polycarboxylic acid water reducer mate has the problem of adaptability to the water reducers, and the starch-based polycarboxylic acid water reducer mate is not beneficial to popularization and application.
Disclosure of Invention
In order to solve the problem mentioned in the above background art that the existing water reducing agent is insufficient in early strength, the present invention provides an early strength cement dispersion polymer comprising:
a) an ester group-containing polymer comprising a polymer or copolymer derived from monomers comprising: 1) an unsaturated carboxylic acid ester monomer; and 2) at least one of unsaturated acid monomer and unsaturated silane monomer; and
b) a carboxymethyl starch; and
c) polyethylene glycol monomethyl ether.
On the basis of the above scheme, further, the unsaturated carboxylic ester monomer comprises one or more of the following monomers:
CH2＝CR1-COOR2；
wherein, R is1Is H or CH3，R2Is CH3Or CH2CH3(ii) a The unsaturated carboxylic acid ester monomer accounts for 35 mol% to 50 mol% of the total amount of the polymerized monomers.
On the basis of the above scheme, further, the unsaturated acid monomer comprises one or more of the following monomers:
CH2＝CH-Ar-R3-COOH；
wherein, R is3Represents an alkyl group having 0 to 2 carbon atoms, Ar represents an aryl group-containing structure of an aryl group having a para-oriented linking group, and the unsaturated acid monomer accounts for 35 to 45 mol% of the total amount of the polymerized monomers.
On the basis of the scheme, further, the unsaturated silane monomer is vinyl trimethoxy silane or gamma- (methacryloyloxy) propyl trimethoxy silane.
On the basis of the scheme, the molecular weight of the polyethylene glycol monomethyl ether is 3000-5000.
On the basis of the scheme, the mass ratio of the carboxymethyl starch to the ester group-containing polymer is 1: 10-20.
The invention provides a preparation method of an early strength cement dispersion polymer, which comprises the following steps:
(1) preparing an ester group-containing polymer comprising a polymer or copolymer derived from monomers comprising: 1) an unsaturated carboxylic acid ester monomer; and 2) at least one of unsaturated acid monomer and unsaturated silane monomer;
(2) carboxymethyl starch, polyethylene glycol monomethyl ether and ester group-containing polymer are subjected to ester exchange under the condition of a catalyst to prepare the early strength cement dispersion polymer.
On the basis of the above scheme, further, the polymerization reaction is carried out under redox initiation conditions.
On the basis of the scheme, the oxidant in the redox initiation system is at least one selected from hydrogen peroxide, potassium persulfate, sodium persulfate and ammonium persulfate.
On the basis of the scheme, the reducing agent in the redox initiation system is selected from at least one of sodium hypophosphite, L-ascorbic acid, sodium bisulfite and sodium formaldehyde sulfoxylate.
On the basis of the scheme, the oxidant in the redox initiation system accounts for 2-5% of the total mass of the polymerization monomers, and the reducing agent accounts for 0.5-2% of the total mass of the polymerization monomers.
On the basis of the scheme, the catalyst is rare earth solid super acid SO4 2-/TiO2/Mo6+。
On the basis of the scheme, the catalyst accounts for 0.1-1% of the total mass of the polymerized monomers.
On the basis of the scheme, the temperature of the polymerization reaction is 30-40 ℃, and the temperature of the esterification reaction is 120-160 ℃.
Compared with the prior art, the early strength cement dispersion polymer and the preparation method thereof provided by the invention have the following beneficial effects:
1. the early strength type cement dispersion polymer for concrete, which is synthesized by the invention, can improve the workability of concrete and the early strength of the concrete by introducing the unsaturated silane monomer, thereby improving the compactness of the concrete and reducing the cracking risk of the concrete;
2. the carboxymethyl starch is adopted to replace partial polyether monomer for esterification modification, so that the cost is reduced, the cohesiveness and the water-retaining property of the concrete are improved, the problems of concrete quality and durability caused by poor bleeding, segregation and compactness of the concrete are solved, and the carboxymethyl starch has excellent adaptability to different cements, admixtures, artificial sand, environmental temperature and concrete mixing ratio fluctuation.
3. The invention adopts the method of low-temperature copolymerization and high-temperature esterification, reduces the damage of double bonds of reaction monomers, improves the copolymerization degree, and produces the cement dispersion polymer with high water reducing rate and good workability.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of an early strength cement dispersion polymer, which comprises the following steps:
adding an ester-containing polymer and polyethylene glycol monomethyl ether into a reaction kettle, heating to 105 ℃, continuously introducing nitrogen, adding carboxymethyl starch and a catalyst after all water is distilled, heating to 120-160 ℃, simultaneously vacuumizing to react for 2-4 hours under the vacuum degree of 40-80 mbar, slicing the polymer in a molten state, or cooling to below 70 ℃, adding a certain amount of water and sodium hydroxide with the mass concentration of 30% for neutralization to ensure that the pH is 6-7, thus preparing the cement dispersed polymer with the mass concentration of 50%, wherein the molecular weight of the cement dispersed polymer is 600120000-00.
Wherein the preparation method of the polymer containing ester groups comprises the following steps:
1) adding 50 parts of deionized water into a reaction kettle;
2) when the temperature is raised to 30-40 ℃, respectively dripping 15-45 parts of an oxidant aqueous solution A with the mass concentration of 10% and 20-40 parts of a reducing agent aqueous solution B with the mass concentration of 5%, and after 10min, dripping a mixed solution C of 30-50 parts of unsaturated carboxylic ester monomers, 35-45 parts of unsaturated acid monomers, 10-30 parts of unsaturated silane monomers and 30 parts of deionized water within 90-120 min;
3) and after the dripping is finished, adding 5 parts of oxidant aqueous solution A with the mass concentration of 10%, finishing the dripping within 20min, and curing for 0.5 hour to obtain the polymer solution with the solid content of 40-50%, the viscosity of 350-450 cps and the weight-average molecular weight of 5000-8000.
To this end, the invention provides the following examples and comparative examples:
example 1
1) Adding 50g of deionized water into a reaction kettle, respectively dropwise adding 25g of 10% hydrogen peroxide aqueous solution A and 20g of 5% L-ascorbic acid aqueous solution B when the temperature is raised to 30 ℃, dropwise adding a mixed solution C of 35g of methyl acrylate, 40g of 4-vinyl phenylacetic acid, 25g of gamma- (methacryloyloxy) propyl trimethoxy silane and 30g of deionized water after 10min, and completing dripping within 100 min;
2) after the dropwise addition is finished, 5g of hydrogen peroxide aqueous solution A with the mass concentration of 10% is added, the dropwise addition is finished within 10min, and the mixture is cured for 0.5 hour to obtain a copolymer solution with the solid content of 45.2%, the viscosity of 500cps and the weight-average molecular weight of 7700;
3) adding 200g of copolymer and 50g of polyethylene glycol monomethyl ether into a reaction kettle, heating to 105 ℃, continuously introducing nitrogen, adding 20g of carboxymethyl starch and 0.7g of rare earth solid super acid SO after water is distilled4 2-/TiO2/Mo6+And raising the reaction temperature to 150 ℃, simultaneously vacuumizing to enable the mixture to react for 2 hours under the vacuum degree of 50mbar, cooling to below 70 ℃, adding 60g of water and 33g of sodium hydroxide with the mass concentration of 30% for neutralization, and enabling the pH value to be 6-7, so that the cement dispersed polymer with the mass concentration of 50% is prepared, and the molecular weight is 87600.
Example 2
1) Adding 50g of deionized water into a reaction kettle, respectively dropwise adding 15g of 10% ammonium persulfate aqueous solution A and 20g of 5% sodium hypophosphite aqueous solution B when the temperature is raised to 35 ℃, and dropwise adding a mixed solution C of 40g of ethyl acrylate, 45g of 4-vinyl phenylacetic acid, 15g of vinyl trimethoxy silane and 30g of deionized water within 100min after 10 min;
2) after the dropwise addition is finished, 5g of ammonium persulfate aqueous solution A with the mass concentration of 10% is added, the dropwise addition is finished within 10min, and the mixture is cured for 0.5 hour to obtain a copolymer solution with the solid content of 46.3%, the viscosity of 450cps and the weight-average molecular weight of 6800;
3) adding 200g of copolymer and 60g of polyethylene glycol monomethyl ether into a reaction kettle, heating to 105 ℃, continuously introducing nitrogen, adding 10g of carboxymethyl starch and 0.5g of rare earth solid super acid SO after water is distilled4 2-/TiO2/Mo6+And raising the reaction temperature to 130 ℃, simultaneously vacuumizing to enable the mixture to react for 2 hours under the vacuum degree of 50mbar, cooling to below 70 ℃, adding 75g of water and 35g of sodium hydroxide with the mass concentration of 30% for neutralization, and enabling the pH value to be 6-7, so that the cement dispersed polymer with the mass concentration of 50% is prepared, and the molecular weight is 75400.
Example 3
1) Adding 50g of deionized water into a reaction kettle, when the temperature is raised to 40 ℃, respectively dropwise adding 45g of 10% sodium persulfate aqueous solution A and 30g of 5% sodium bisulfite aqueous solution B, after 10min, dropwise adding a mixed solution C of 40g of methyl methacrylate, 35g of 4-vinyl benzoic acid, 25g of vinyl trimethoxy silane and 30g of deionized water, and completing dripping within 100 min;
2) after the dropwise addition, 5g of sodium persulfate aqueous solution A with the mass concentration of 10% is added, the dropwise addition is completed within 10min, and the mixture is cured for 0.5 hour to obtain a copolymer solution with the solid content of 48.3%, the viscosity of 600cps and the weight-average molecular weight of 6100;
3) adding 200g of copolymer and 70g of polyethylene glycol monomethyl ether into a reaction kettle, heating to 105 ℃, and continuously introducing nitrogen until water is containedAfter all the distillation, 15g of carboxymethyl starch and 0.2g of rare earth solid super acidic SO are added4 2-/TiO2/Mo6+And raising the reaction temperature to 160 ℃, simultaneously vacuumizing to enable the mixture to react for 4 hours under the vacuum degree of 50mbar, cooling to below 70 ℃, adding 83g of water and 35g of sodium hydroxide with the mass concentration of 30% for neutralization, and enabling the pH value to be 6-7, so that the cement dispersed polymer with the mass concentration of 50% is prepared, and the molecular weight is 73600.
Example 4
1) Adding 50g of deionized water into a reaction kettle, when the temperature is raised to 35 ℃, respectively dropwise adding 35g of 10% potassium persulfate aqueous solution A and 35g of 5% sodium bisulfite aqueous solution B, after 10min, dropwise adding a mixed solution C of 37g of ethyl methacrylate, 50g of 4-vinyl phenylacetic acid, 13g of gamma- (methacryloyloxy) propyl trimethoxy silane and 30g of deionized water, and completing dripping within 100 min;
2) after the dripping is finished, 5g of potassium persulfate aqueous solution A with the mass concentration of 10 percent is added, and the mixture is dripped within 10min and cured for 0.5 hour to obtain copolymer solution with the solid content of 46.7 percent, the viscosity of 560cps and the weight-average molecular weight of 7300;
3) adding 200g of copolymer and 40g of polyethylene glycol monomethyl ether into a reaction kettle, heating to 105 ℃, continuously introducing nitrogen, adding 12g of carboxymethyl starch and 1g of rare earth solid super acidic SO after water is distilled4 2-/TiO2/Mo6+And raising the reaction temperature to 120 ℃, simultaneously vacuumizing to enable the mixture to react for 3 hours under the vacuum degree of 50mbar, cooling to below 70 ℃, adding 65g of water and 37g of sodium hydroxide with the mass concentration of 30% for neutralization, and enabling the pH value to be 6-7, so that the cement dispersed polymer with the mass concentration of 50% is prepared, and the molecular weight is 97300.
Comparative example 1
1) Adding 50g of deionized water into a reaction kettle, when the temperature is raised to 35 ℃, respectively dropwise adding 35g of 10% potassium persulfate aqueous solution A and 35g of 5% sodium bisulfite aqueous solution B, after 10min, dropwise adding a mixed solution C of 37g of ethyl methacrylate, 50g of 4-vinyl phenylacetic acid, 13g of gamma- (methacryloyloxy) propyl trimethoxy silane and 30g of deionized water, and completing dripping within 100 min;
2) after the dripping is finished, 5g of potassium persulfate aqueous solution A with the mass concentration of 10 percent is added, and the mixture is dripped within 10min and cured for 0.5 hour to obtain copolymer solution with the solid content of 46.7 percent, the viscosity of 560cps and the weight-average molecular weight of 7300;
3) adding 200g of copolymer and 40g of polyethylene glycol monomethyl ether into a reaction kettle, heating to 105 ℃, continuously introducing nitrogen, and adding 1g of rare earth solid super acid SO after water is distilled4 2-/TiO2/Mo6+And raising the reaction temperature to 120 ℃, simultaneously vacuumizing to enable the mixture to react for 3 hours under the vacuum degree of 50mbar, cooling to below 70 ℃, adding 25g of water and 37g of sodium hydroxide with the mass concentration of 30% to neutralize, and enabling the pH value to be 6-7, so that the cement dispersed polymer with the mass concentration of 50% is prepared, and the molecular weight is 47300.
Comparative example 2
1) Adding 200g of polyethylene glycol monomethyl ether and 37g of ethyl methacrylate into a reaction kettle, heating to 105 ℃, continuously introducing nitrogen, and adding 1g of rare earth solid super acid SO after water is distilled4 2-/TiO2/Mo6+The reaction temperature is raised to 120 ℃, vacuum pumping is carried out simultaneously to enable the reaction to be carried out for 3 hours under the vacuum degree of 50mbar, the temperature is cooled to be lower than 70 ℃, and 23g of water is added to obtain the polyethylene glycol monomethyl ether methacrylate.
2) Adding 50g of deionized water into a reaction kettle, when the temperature is raised to 35 ℃, respectively dropwise adding 35g of 10% potassium persulfate aqueous solution A and 35g of 5% sodium bisulfite aqueous solution B, after 10min, dropwise adding a mixed solution C of 100g of polyethylene glycol monomethyl ether methacrylate, 50g of 4-vinyl phenylacetic acid, 13g of gamma- (methacryloyloxy) propyl trimethoxy silane and 30g of deionized water, and completing dripping within 100 min;
3) after the dropwise addition, 5g of a 10% potassium persulfate aqueous solution A was added and the mixture was added within 10min, followed by aging for 0.5 hour, and 37g of 30% sodium hydroxide was added to neutralize the mixture to adjust the pH to 6 to 7, thereby obtaining a 50% cement-dispersed polymer having a molecular weight of 37300.
Comparative example 3
1) Adding 200g of polyethylene glycol monomethyl ether and 37g of ethyl methacrylate into a reaction kettle, heating to 105 ℃, continuously introducing nitrogen, and adding 1g of rare earth solid super acid SO after water is distilled4 2-/TiO2/Mo6+The reaction temperature is raised to 120 ℃, vacuum pumping is carried out simultaneously to enable the reaction to be carried out for 3 hours under the vacuum degree of 50mbar, the temperature is cooled to be lower than 70 ℃, and 60g of water is added to obtain the polyethylene glycol monomethyl ether methacrylate.
2) Adding 50g of deionized water into a reaction kettle, when the temperature is raised to 35 ℃, respectively dropwise adding 35g of 10% potassium persulfate aqueous solution A and 35g of 5% sodium bisulfite aqueous solution B, after 10min, dropwise adding a mixed solution C of 200g of polyethylene glycol monomethyl ether methacrylate, 50g of 4-vinyl phenylacetic acid, 13g of acryloyloxyethyl trimethyl ammonium chloride and 30g of deionized water, and completing dripping within 100 min;
3) after the dropwise addition, 5g of a 10% potassium persulfate aqueous solution A was added and the mixture was added within 10min, followed by aging for 0.5 hour, and 37g of 30% sodium hydroxide was added to neutralize the mixture to adjust the pH to 6 to 7, thereby obtaining a 50% cement-dispersed polymer having a molecular weight of 35300.
Comparative example 4
1) Adding 200g of polyethylene glycol monomethyl ether and 37g of methacrylic acid into a reaction kettle, heating to 105 ℃, continuously introducing nitrogen, and adding 1g of rare earth solid super acid SO after water is distilled4 2-/TiO2/Mo6+The reaction temperature is raised to 120 ℃, vacuum pumping is carried out simultaneously to enable the reaction to be carried out for 3 hours under the vacuum degree of 50mbar, the temperature is cooled to be lower than 70 ℃, and 60g of water is added to obtain the polyethylene glycol monomethyl ether methacrylate.
2) Adding 50g of deionized water into a reaction kettle, when the temperature is raised to 35 ℃, respectively dropwise adding 35g of 10% potassium persulfate aqueous solution A and 35g of 5% sodium bisulfite aqueous solution B, after 10min, dropwise adding a mixed solution C of 200g of polyethylene glycol monomethyl ether methacrylate, 40g of acrylic acid and 30g of deionized water, and completing dripping within 100 min;
3) after the dropwise addition, 5g of a 10% potassium persulfate aqueous solution a was added and the mixture was added within 10min, followed by aging for 0.5 hour, and 37g of 30% sodium hydroxide was added to neutralize the mixture to adjust the pH to 6 to 7, thereby obtaining a 50% cement-dispersed polymer having a molecular weight of 28300.
It should be noted that the specific parameters or some common reagents in the above embodiments are specific examples or preferred embodiments of the present invention, and are not limited thereto; those skilled in the art can adapt the same within the spirit and scope of the present invention.
Samples synthesized in examples 1 to 4 and comparative examples 1 to 4 were tested for water-reducing rate, slump loss with time, workability and the like of concrete by using standard cement according to GB8076-2008 "concrete admixture". The concrete mixing proportion is as follows: cement 360kg/m3780kg/m of sand3Stone 1050kg/m3The slump was controlled to 210. + -.10 mm, and the results are shown in Table 1.
TABLE 1 test results of various examples and comparative examples
As can be seen from Table 1, the workability of the synthesized examples 1-4 is better than that of the comparative examples 1-4, the bleeding rate is lower than that of the comparative examples 1-4, the compressive strength of 1d of the examples 1-4 is better than that of the comparative examples 1-4, and the compressive strength of 3d and 28d is equivalent to or even better than that of the comparative examples 1-4.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (12)
1. An early strength cement dispersing polymer prepared by a process comprising:
(1) preparing an ester group-containing polymer comprising a polymer or copolymer derived from monomers comprising: 1) an unsaturated carboxylic acid ester monomer; and 2) unsaturated acid monomers, unsaturated silane monomers;
(2) performing ester exchange on carboxymethyl starch, polyethylene glycol monomethyl ether and an ester-group-containing polymer under the condition of a catalyst to prepare an early-strength cement dispersion polymer;
the unsaturated acid monomers include one or more of the monomers having the following structures:
CH2=CH-Ar-R3-COOH；
wherein, R is3Represents an alkyl group having 0 to 2 carbon atoms, Ar represents an aryl group-containing structure of an aryl group having a para-oriented linking group, and the unsaturated acid monomer accounts for 35 to 45 mol% of the total amount of the polymerized monomers;
the mass ratio of the carboxymethyl starch to the ester group-containing polymer is 1: 10-20.
2. The early strength cement dispersion polymer of claim 1, wherein the unsaturated carboxylic acid ester monomer comprises one or more of the monomers having the following structures:
CH2=CR1-COOR2；
wherein, R is1Is H or CH3，R2Is CH3Or CH2CH3(ii) a The unsaturated carboxylic acid ester monomer accounts for 35 mol% to 50 mol% of the total amount of the polymerized monomers.
3. The early strength cement dispersion polymer of claim 1, wherein the unsaturated silane monomer is vinyl trimethoxysilane or gamma- (methacryloyloxy) propyl trimethoxysilane.
4. The early strength cement-dispersed polymer according to claim 1, characterized in that: the molecular weight of the polyethylene glycol monomethyl ether is 3000-5000.
5. A method of preparing an early strength cement dispersing polymer, the method comprising:
(1) preparing an ester group-containing polymer comprising a polymer or copolymer derived from monomers comprising: 1) an unsaturated carboxylic acid ester monomer; and 2) unsaturated acid monomers, unsaturated silane monomers;
(2) performing ester exchange on carboxymethyl starch, polyethylene glycol monomethyl ether and an ester-group-containing polymer under the condition of a catalyst to prepare an early-strength cement dispersion polymer;
the unsaturated acid monomers include one or more of the monomers having the following structures:
CH2=CH-Ar-R3-COOH；
wherein, R is3Represents an alkyl group having 0 to 2 carbon atoms, Ar represents an aryl group-containing structure of an aryl group having a para-oriented linking group, and the unsaturated acid monomer accounts for 35 to 45 mol% of the total amount of the polymerized monomers;
the mass ratio of the carboxymethyl starch to the ester group-containing polymer is 1: 10-20.
6. The method for producing an early strength cement-dispersed polymer according to claim 5, characterized in that: the polymerization reaction is carried out under redox-initiated conditions.
7. The method for producing an early strength cement-dispersed polymer according to claim 6, characterized in that: the oxidant in the redox initiation system is at least one selected from hydrogen peroxide, potassium persulfate, sodium persulfate or ammonium persulfate.
8. The method for producing an early strength cement-dispersed polymer according to claim 6, characterized in that: the reducing agent in the redox initiation system is at least one selected from sodium hypophosphite, L-ascorbic acid, sodium bisulfite and sodium formaldehyde sulfoxylate.
9. The method for producing an early strength cement-dispersed polymer according to claim 6, characterized in that: the oxidant in the redox initiation system accounts for 2-5% of the total mass of the polymerization monomers, and the reducing agent accounts for 0.5-2% of the total mass of the polymerization monomers.
10. The method for producing an early strength cement-dispersed polymer according to claim 5, characterized in that: the catalyst is rare earth solid super acid SO4 2-/TiO2/ Mo6+。
11. The method for producing an early strength cement-dispersed polymer according to claim 5, characterized in that: the catalyst accounts for 0.1-1% of the total mass of the polymerization monomers.
12. The method for producing an early strength cement-dispersed polymer according to claim 5, characterized in that: the temperature of the polymerization reaction is 30-40 ℃, and the temperature of the esterification reaction is 120-160 ℃.
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