CN112851879A - Polycarboxylate superplasticizer for concrete and preparation method thereof - Google Patents
Polycarboxylate superplasticizer for concrete and preparation method thereof Download PDFInfo
- Publication number
- CN112851879A CN112851879A CN202110032912.7A CN202110032912A CN112851879A CN 112851879 A CN112851879 A CN 112851879A CN 202110032912 A CN202110032912 A CN 202110032912A CN 112851879 A CN112851879 A CN 112851879A
- Authority
- CN
- China
- Prior art keywords
- concrete
- parts
- polycarboxylic acid
- reducing agent
- mixed solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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 a polycarboxylic acid water reducing agent for concrete, which comprises the following components in parts by weight: 30-50 parts of polyether macromonomer; 4-8 parts of unsaturated acid; 8-15 parts of small monomers; 0.15-0.3 part of an initiator; 0.1-0.3 part of sulfonated chain transfer agent; 48-72 parts of water, the polycarboxylate water reducing agent for concrete provided by the invention has good water reducing performance, and can enable concrete to have good workability, in the using process of the polycarboxylate water reducing agent, the polycarboxylate water reducing agent can increase the fluidity of concrete, and the polycarboxylate water reducing agent can increase the viscosity of concrete, so that the rebound rate of concrete is reduced, the water consumption of concrete in the construction process of concrete can be reduced, the water-cement ratio in concrete is reduced, the using amount of an accelerator is effectively reduced, and the construction cost of concrete is reduced.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a polycarboxylic acid water reducing agent for concrete and a preparation method thereof.
Background
When concrete on the current market is subjected to on-site spray construction, an accelerator is usually required to be added to shorten the setting time and improve the compressive strength, but because the performance of a sand-stone material on the current market is not stable enough and the mud content of the sand-stone material is high, the fluidity of concrete spray is poor when the accelerator is added to the concrete for on-site construction, and further the concrete spray construction is subjected to resistance, in order to increase the fluidity of the concrete and ensure the smooth running of the concrete spray, in the concrete construction process, on-site construction workers usually add a large amount of water to the concrete to increase the fluidity of the concrete, however, the water-cement ratio in the concrete is overlarge, so that the concrete setting time is long, the compressive strength is too low, and the rebound rate is large.
Therefore, in the process of concrete spraying construction, in order to increase the fluidity of concrete and reduce the water-cement ratio of concrete, so that the setting time of concrete is shortened, the compressive strength is improved, and the rebound rate is reduced, a construction unit usually adds a certain amount of water reducing agent into concrete, which plays a good role in concrete spraying construction.
However, the water reducing agents in the current market are various in types, and after the water reducing agents are used for concrete spraying construction engineering, the water reducing rate of the water reducing agents is low; the concrete still has poor fluidity and high rebound rate, and the workability of the concrete is not obviously improved after the water reducing agent is used in concrete spraying construction engineering, so that the water reducing agent which can increase the fluidity of the concrete, shorten the setting time of the concrete, improve the compressive strength of the concrete and reduce the rebound rate of the concrete has great significance.
Disclosure of Invention
Therefore, a polycarboxylic acid water reducing agent for concrete and a preparation method thereof are needed, wherein the polycarboxylic acid water reducing agent can increase the fluidity of concrete, shorten the setting time of concrete, improve the compressive strength of concrete and reduce the rebound rate of concrete.
A polycarboxylic acid water reducing agent for concrete comprises the following components in parts by weight:
polyether macromonomer: 30-50 parts of a solvent;
unsaturated acid: 4-8 parts;
small monomers: 8-15 parts;
initiator: 0.15-0.3 part;
sulfonated chain transfer agent: 0.1-0.3 part;
water: 48-72 parts.
Preferably, the polycarboxylic acid water reducing agent for concrete further comprises one or more of 1-3 parts of a neutralizing agent and 0.2-0.8 part of a strength regulator.
Preferably, the polyether macromonomer comprises one or more of type 2+2 vinyl polyglycol ether and type 2+4 vinyl polyglycol ether.
Preferably, the structure of the 2+2 type vinyl polyglycol ether is as follows:
wherein n is an integer of 45 to 105.
Preferably, the structure of the 2+4 type vinyl polyglycol ether is as follows:
wherein n is an integer of 45 to 105.
Preferably, the unsaturated acid comprises one or more of acrylic acid, methacrylic acid and fumaric acid.
Preferably, the small monomer comprises one or more of maleic anhydride glyceride, maleic anhydride monomethyl ether polyethylene glycol ester and methylene amide phosphate.
Preferably, the initiator comprises one or more of cumene hydroperoxide, peroxyacetic acid and tert-butyl hydroperoxide.
Preferably, the sulfonated chain transfer agent comprises one or more of sulfonated thioglycolic acid and sulfonated thioglycolic acid.
The invention also provides a preparation method of the polycarboxylic acid water reducing agent for concrete, which comprises the following steps in parts by weight:
adding 30-45 parts of water into a reactor, putting the reactor filled with 30-45 parts of water into a low-temperature constant-temperature reaction bath, and adjusting the temperature of the low-temperature constant-temperature reaction bath to control the temperature of the low-temperature constant-temperature reaction bath to be-20-15 ℃;
adding 30-50 parts of polyether macromonomer, the first mixed solution, the second mixed solution and the third mixed solution into a reactor, and preserving the temperature for 1-2 hours to obtain a polycarboxylic acid water reducer;
wherein the first mixed solution is a mixture of 4-8 parts of unsaturated acid and 8-15 parts of small monomer;
the second mixed solution is a mixture of 0.15-0.3 part of initiator and 8-12 parts of water;
the third mixed solution is a mixture of 0.1-0.3 parts of sulfonated chain transfer agent and 10-15 parts of water.
The polycarboxylic acid water reducer for concrete in the embodiment of the invention has the following beneficial effects:
the polycarboxylate superplasticizer obtained through the free radical copolymerization reaction among the components has good water reducing performance, and can enable concrete to have good workability, the polycarboxylate superplasticizer can increase the fluidity of the concrete in the using process of the polycarboxylate superplasticizer, and the polycarboxylate superplasticizer can increase the viscosity of the concrete, so that the concrete is easy to adhere to a steel arch in the spraying construction process of the concrete to the steel arch, the rebound rate of the concrete is reduced, the water consumption of the concrete in the construction process of the concrete can be reduced, the water-cement ratio in the concrete is reduced, and the consumption of a quick-setting admixture is effectively reduced, so that the construction cost of the concrete is reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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 experimental procedures in the following examples are conventional unless otherwise specified. Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified. In the quantitative tests in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.
In addition, "and/or" in the whole text includes three schemes, taking a and/or B as an example, including a technical scheme, and a technical scheme that a and B meet simultaneously; in addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides a polycarboxylate superplasticizer which comprises the following components in parts by weight:
polyether macromonomer: 30-50 parts of a solvent;
unsaturated acid: 4-8 parts;
small monomers: 8-15 parts;
initiator: 0.15-0.3 part;
sulfonated chain transfer agent: 0.1-0.3 part;
water: 48-72 parts.
The polycarboxylate superplasticizer for concrete provided by the invention has good water reducing performance, can enable concrete to have good workability after being added into concrete, can increase the fluidity of concrete in the using process of the polycarboxylate superplasticizer, can increase the viscosity of concrete, enables concrete to be easily adhered to a steel arch in the spraying construction process of the concrete to the steel arch, reduces the rebound rate of the concrete, can reduce the water consumption of the concrete in the construction process of the concrete, reduces the water-cement ratio in the concrete, effectively reduces the using amount of an accelerator, and reduces the construction cost of the concrete.
In some embodiments, the concrete may be, but is not limited to, shotcrete.
In some embodiments, the polycarboxylic acid water reducer for concrete further comprises one or more of 1-3 parts of a neutralizing agent and 0.2-0.8 part of an intensity regulator, and when the polycarboxylic acid water reducer comprises 1-3 parts of the neutralizing agent, 1-3 parts of the neutralizing agent can regulate the pH value of the polycarboxylic acid water reducer to ensure the workability of the polycarboxylic acid water reducer; when the polycarboxylate water reducer comprises 0.2-0.8 parts of strength regulator, the strength of the polycarboxylate water reducer can be better regulated by 0.2-0.8 parts of strength regulator, so that the workability of the polycarboxylate water reducer is guaranteed.
In some embodiments, the pH of the polycarboxylic acid water reducing agent for concrete is 5-7, so that the stability of the polycarboxylic acid water reducing agent is improved.
Preferably, the pH of the polycarboxylic acid water reducing agent for concrete is 6.
In some embodiments, the neutralizing agent comprises one or more of sodium hydroxide, potassium hydroxide, and sodium acetate.
In some embodiments, when the neutralizing agent comprises a plurality of sodium hydroxide, potassium hydroxide, and sodium acetate, the neutralizing agent is a mixture of a plurality of sodium hydroxide, potassium hydroxide, and sodium acetate mixed in any ratio.
In some embodiments, the strength-modifying agent comprises one or more of ethanolamine, diethanolamine, triethanolamine, and N-methyldiethanolamine to further modify the strength of the polycarboxylate water reducer.
Specifically, when the strength adjusting agent includes a plurality of kinds of ethanolamine, diethanolamine, triethanolamine and N-methyldiethanolamine, the strength adjusting agent includes a mixture in which a plurality of kinds of ethanolamine, diethanolamine, triethanolamine and N-methyldiethanolamine are mixed in an arbitrary ratio.
In some embodiments, the polyether macromonomer comprises one or more of 2+2 type vinyl polyglycol ether and 2+4 type vinyl polyglycol ether, and the polyether macromonomer is introduced to obtain the polycarboxylate superplasticizer which can enable concrete to have better workability, adjust the fluidity, cohesiveness and slurry encapsulation of concrete, and increase the fluidity of concrete.
Specifically, when the polyether macromonomer includes a plurality of types of 2+2 type vinyl polyglycol ether and 2+4 type vinyl polyglycol ether, the polyether macromonomer includes a mixture of a plurality of types of 2+2 type vinyl polyglycol ether and 2+4 type vinyl polyglycol ether mixed in an arbitrary ratio.
In some embodiments, the structure of the 2+2 type vinyl polyglycol ether is as follows:
wherein n is an integer of 45 to 105.
Specifically, n is preferably 48, 65 and 96.
In particular, the 2+2 type means that the vinyl group is bonded to-CH through an oxygen atom2—CH2-connecting.
In some embodiments, the structure of the type 2+4 vinyl polyglycol ether is as follows:
wherein n is an integer of 45 to 105.
Specifically, n is preferably 48, 65 and 96.
The 2+2 type vinyl polyglycol ether and the 2+4 type vinyl polyglycol ether with the structural formula are introduced into the molecular structure of the polycarboxylic acid water reducer for sprayed concrete, the vinyl in the 2+2 type vinyl polyglycol ether and the 2+4 type vinyl polyglycol ether is directly connected with oxygen atoms, the reaction activities of the 2+2 type vinyl polyglycol ether and the 2+4 type vinyl polyglycol ether and unsaturated acid are more suitable due to the strong electron pushing effect of the oxygen atoms, and when the vinyl in the 2+2 type vinyl polyglycol ether and the 2+4 type vinyl polyglycol ether forms a main chain in the polycarboxylic acid water reducer through free radical copolymerization reaction, the side chain of the polycarboxylic acid water reducer has large swing amplitude due to few groups around the vinyl and long chain lengths in the 2+2 type vinyl polyglycol ether and the 2+4 type vinyl polyglycol ether, when the polycarboxylate superplasticizer is added into concrete, the wrapping property and the winding property of the side chain of the polycarboxylate superplasticizer in the concrete are improved, and the fluidity, the cohesiveness and the slurry wrapping property of the concrete can be adjusted, so that the construction performance of the concrete in the injection construction process is guaranteed.
In particular, the 2+4 type means that the vinyl group is bonded to-CH through an oxygen atom2—CH2—CH2—CH2-connecting.
In some embodiments, the molecular weight of the polyether macromonomer includes any one of 3000, 4000 and 6000, and the polycarboxylate superplasticizer prepared from the polyether macromonomer with the molecular weight has good dispersibility, so that the polycarboxylate superplasticizer is relatively uniform, and in the use process of the polycarboxylate superplasticizer, the polycarboxylate superplasticizer with good dispersibility can exert the performance of the polycarboxylate superplasticizer to the maximum extent, so that the fluidity of concrete is increased.
In some embodiments, the unsaturated acid includes one or more of acrylic acid, methacrylic acid, and fumaric acid to promote the formation of a polycarboxylic acid water reducer for concrete.
Specifically, when the unsaturated acid includes a plurality of acrylic acid, methacrylic acid, and fumaric acid, the unsaturated acid includes a mixture in which a plurality of acrylic acid, methacrylic acid, and fumaric acid are mixed in an arbitrary ratio.
In some embodiments, the small monomer includes one or more of maleic anhydride glyceride, maleic anhydride monomethyl ether polyethylene glycol ester, and methylene amide phosphate ester to improve the workability of the polycarboxylic acid water reducer for concrete.
Specifically, when the small monomer includes a plurality of maleic anhydride glyceride, maleic anhydride monomethyl ether polyethylene glycol ester and methylene amide phosphate, the small monomer includes a mixture in which a plurality of maleic anhydride glyceride, maleic anhydride monomethyl ether polyethylene glycol ester and methylene amide phosphate are mixed in any ratio.
In some embodiments, the glycerol maleate is of the formula:
the maleic anhydride glyceride with the structural formula is introduced into the molecular structural formula of the polycarboxylic acid water reducing agent for concrete, so that the polycarboxylic acid water reducing agent for concrete with better workability is obtained.
In some embodiments, the structure of the maleic anhydride monomethyl ether polyethylene glycol ester is as follows:
wherein n is an integer of 5 to 9.
In some embodiments, the structure of the methylene amide phosphate is as follows:
the small monomer with the molecular structural formula is introduced into the polycarboxylic acid water reducing agent for concrete, so that the polycarboxylic acid water reducing agent for concrete has the advantages that the wrapping performance of slurry in concrete on stones is good, the workability of concrete is good, and the fluidity of concrete is increased.
In some embodiments, the initiator includes one or more of cumene hydroperoxide, peracetic acid, and tert-butyl hydroperoxide to initiate free radical copolymerization to promote formation of a polycarboxylic acid water reducer for concrete having good workability.
Specifically, when the initiator includes a plurality of cumene hydroperoxide, peracetic acid, and t-butyl hydroperoxide, the initiator includes a mixture in which a plurality of cumene hydroperoxide, peracetic acid, and t-butyl hydroperoxide are mixed in any ratio.
In some embodiments, the sulfonated chain transfer agent comprises one or more of sulfonated thioglycolic acid and sulfonated thioglycolic alcohol, such that the polycarboxylate water reducer undergoes chain transfer and chain termination, thereby adjusting the relative molecular mass of the polycarboxylate water reducer and obtaining a concrete polycarboxylate water reducer with an appropriate relative molecular mass.
Specifically, when the sulfonated chain transfer agent includes a plurality of sulfonated thioglycolic acid and sulfonated thioglycol, the sulfonated chain transfer agent includes a mixture of a plurality of sulfonated thioglycolic acid and sulfonated thioglycol mixed in an arbitrary ratio.
In some embodiments, the sulfonated thioglycolic acid has the following structural formula:
wherein R is- (CH)2nN is an integer of 1 to 3.
In some embodiments, the structure of the sulfonated thioalcohols is as follows:
wherein R is- (CH)2nN is an integer of 1 to 3.
Specifically, the sulfonated thioglycolic acid and the sulfonated thioglycolic alcohol with the above configurations can adjust the molecular weight of the polycarboxylic acid water reducer for concrete in the process of free radical copolymerization, and have the performance of low corrosivity and harmfulness.
The invention also provides a preparation method of the polycarboxylic acid water reducing agent for concrete, which comprises the following steps in parts by weight:
adding 30-45 parts of water into a reactor, putting the reactor filled with 30-45 parts of water into a low-temperature constant-temperature reaction bath, and adjusting the temperature of the low-temperature constant-temperature reaction bath to control the temperature of the low-temperature constant-temperature reaction bath to be-20-15 ℃;
adding 30-50 parts of polyether macromonomer, the first mixed solution, the second mixed solution and the third mixed solution into the reactor, and preserving the temperature for 1-2 hours to obtain the polycarboxylic acid water reducer;
wherein the first mixed solution is a mixture of 4-8 parts of unsaturated acid and 8-15 parts of small monomer;
the second mixed solution is a mixture of 0.15-0.3 part of initiator and 8-12 parts of water;
the third mixed solution is a mixture of 0.1-0.3 part of sulfonated chain transfer agent and 10-15 parts of water.
According to the preparation method of the polycarboxylic acid water reducer for concrete, in the presence of an initiator and a sulfonated chain transfer agent, polyether macromonomers, small monomers and unsaturated acid are added into a polymer reaction system and subjected to free radical copolymerization reaction, so that the polyether macromonomers, the small monomers and the unsaturated acid are introduced into a molecular structure of the polycarboxylic acid water reducer for concrete, and the obtained polycarboxylic acid water reducer for concrete can increase the workability of concrete in the construction process, increase the fluidity of concrete, reduce the water consumption of concrete in the concrete construction process, avoid the overhigh water-cement ratio of concrete, reduce the consumption of an accelerator, reduce the setting time under the condition of reducing the consumption of the accelerator and enhance the compressive strength of concrete; in addition, in the invention, the initiator and the sulfonated chain transfer agent are pre-dissolved with water in advance, so that the initiator and the sulfonated chain transfer agent are fully dissolved, and the generation of the polycarboxylic acid water reducing agent for concrete is promoted.
In some embodiments, the reactor may be, but is not limited to, a reaction flask.
In some embodiments, the preparation method of the polycarboxylic acid water reducer for concrete further comprises the following steps: and after the temperature of the reaction system of the polycarboxylic acid water reducing agent for the concrete is kept for 1 to 2 hours, adding 1 to 3 parts of neutralizing agent and 0.2 to 0.8 part of strength regulator into the reactor, and reacting for 0.5 hour to obtain the polycarboxylic acid water reducing agent for the concrete.
Specifically, the solid content of the prepared polycarboxylic acid water reducer for concrete is 50%.
In some embodiments, the temperature of the cryostat reaction bath is preferably controlled to between-20 ℃ and 10 ℃ to facilitate the rate and yield of the polycarboxylic acid water reducer for concrete.
In some embodiments, the first mixed solution, the second mixed solution and the third mixed solution are added, and then the temperature is kept for 1h, so that the preparation rate and the yield of the polycarboxylic acid water reducing agent for concrete are improved.
In some embodiments, the first mixture, the second mixture, and the third mixture are added to the reactor simultaneously with the polyether macromonomer.
In some embodiments, the first mixed solution, the second mixed solution and the third mixed solution are all added into the reactor dropwise to promote the dispersibility of the polycarboxylic acid water reducing agent reaction system for concrete.
Specifically, the dropping time of the first mixed solution is 2 to 3 hours, so that the reaction is fully performed.
More specifically, the second mixed solution and the third mixed solution are added dropwise for 2.5h to 3.5h, so that the reaction is sufficiently performed.
In some embodiments, the weight average molecular weight of the prepared polycarboxylic acid water reducer for concrete is 20000-60000, so that the polycarboxylic acid water reducer for concrete has good construction performance.
In some embodiments, the water may be, but is not limited to, deionized water.
The technical solution of the present invention will be further described with reference to the preferred embodiments.
Example 1
2+2 type vinyl polyglycol ether: 38 parts of (B);
acrylic acid: 4 parts of a mixture;
maleic anhydride glyceride: 8 parts of a mixture;
peroxyacetic acid: 0.15 part;
sulfonated thioglycolic acid: 0.1 part;
sodium hydroxide: 1 part;
n-methyldiethanolamine: 0.2 part;
deionized water: 52 parts.
Preparing a polycarboxylic acid water reducing agent for concrete:
adding 35 parts of deionized water into a reaction bottle, placing the reaction bottle filled with 35 parts of deionized water into a low-temperature constant-temperature reaction bath, and adjusting the temperature of the low-temperature constant-temperature reaction bath to control the temperature of the low-temperature constant-temperature reaction bath to be-20 ℃;
adding 38 parts of 2+2 type vinyl polyglycol ether into a reaction bottle, simultaneously dropwise adding the first mixed solution, the second mixed solution and the third mixed solution, and keeping the temperature for 1 hour;
adding 1 part of sodium hydroxide and 0.2 part of N-methyldiethanolamine into a reaction bottle, and reacting for 0.5h to obtain a polycarboxylic acid water reducer for concrete;
wherein the first mixed solution is obtained by mixing 4 parts of acrylic acid and 8 parts of maleic anhydride glyceride in a beaker, and the dripping time of the first mixed solution is 2.5 hours;
the second mixed solution is obtained by mixing 0.15 part of peroxyacetic acid and 8 parts of deionized water in a beaker, and the dripping time of the second mixed solution is 3 hours;
the third mixed solution is obtained by mixing 0.1 part of sulfonated thioglycolic acid and 9 parts of deionized water in a beaker, and the dropping time of the third mixed solution is 3 hours.
Example 2
2+2 type vinyl polyglycol ether: 37 parts of;
acrylic acid: 5 parts of a mixture;
maleic anhydride monomethyl ether polyethylene glycol ester: 8 parts of a mixture;
t-butyl hydroperoxide: 0.25 part;
sulfonated thioglycolic acid: 0.15 part;
sodium hydroxide: 1 part;
ethanolamine: 0.25 part;
deionized water: 51 parts.
Preparing a polycarboxylic acid water reducing agent for concrete:
adding 32 parts of deionized water into a reaction bottle, putting the reaction bottle filled with 32 parts of deionized water into a low-temperature constant-temperature reaction bath, and adjusting the temperature of the low-temperature constant-temperature reaction bath to control the temperature of the low-temperature constant-temperature reaction bath to be-15 ℃;
adding 37 parts of 2+2 type vinyl polyglycol ether into a reaction bottle, simultaneously dropwise adding the first mixed solution, the second mixed solution and the third mixed solution, and keeping the temperature for 1 hour;
adding 1 part of sodium hydroxide and 0.25 part of ethanolamine into a reaction bottle, and reacting for 0.5h to obtain a polycarboxylic acid water reducer for concrete;
wherein the first mixed solution is obtained by mixing 5 parts of acrylic acid and 8 parts of maleic anhydride monomethyl ether polyethylene glycol ester in a beaker, and the dripping time of the first mixed solution is 2.5 hours;
the second mixed solution is obtained by mixing 0.25 part of tert-butyl hydroperoxide and 7 parts of deionized water in a beaker, and the dripping time of the second mixed solution is 3 hours;
the third mixed solution was obtained by mixing 0.15 part of sulfonated thioglycolic acid and 12 parts of deionized water in a beaker, and the third mixed solution was added dropwise for 3 hours.
Example 3
2+4 type vinyl polyglycol ether: 37 parts of;
methacrylic acid: 5 parts of a mixture;
methylene amide phosphate ester: 9 parts of (1);
peroxyacetic acid: 0.2 part;
sulfonated thio-ethanol: 0.15 part;
sodium hydroxide: 2 parts of (1);
n-methyldiethanolamine: 0.3 part;
deionized water: 54 parts of a binder;
preparing a polycarboxylic acid water reducing agent for concrete:
adding 32 parts of deionized water into a reaction bottle, putting the reaction bottle filled with 32 parts of deionized water into a low-temperature constant-temperature reaction bath, and adjusting the temperature of the low-temperature constant-temperature reaction bath to control the temperature of the low-temperature constant-temperature reaction bath to be-10 ℃;
adding 37 parts of 2+4 type vinyl polyglycol ether into a reaction bottle, simultaneously dropwise adding the first mixed solution, the second mixed solution and the third mixed solution, and keeping the temperature for 1 hour;
adding 2 parts of sodium hydroxide and 0.3 part of N-methyldiethanolamine into a reaction bottle, and reacting for 0.5h to obtain a polycarboxylic acid water reducer for concrete;
the first mixed solution is obtained by mixing 5 parts of methacrylic acid and 9 parts of methylene amide phosphate in a beaker, and the dripping time of the first mixed solution is 2 hours;
the second mixed solution is obtained by mixing 0.2 part of peroxyacetic acid and 10 parts of deionized water in a beaker, and the dripping time of the second mixed solution is 2.5 hours;
the third mixed solution is obtained by mixing 0.15 part of sulfonated thioglycol and 12 parts of deionized water in a beaker, and the dropping time of the third mixed solution is 2.5 hours.
Example 4
2+4 type vinyl polyglycol ether: 31 parts of (B);
methacrylic acid: 6 parts of (1);
maleic anhydride glyceride: 12 parts of (1);
t-butyl hydroperoxide: 0.25 part;
sulfonated thioglycolic acid: 0.1 part;
potassium hydroxide: 3 parts of a mixture;
ethanolamine: 0.2 part;
deionized water: 53 parts of a mixture;
preparing a polycarboxylic acid water reducing agent for concrete:
adding 32 parts of deionized water into a reaction bottle, putting the reaction bottle filled with 32 parts of deionized water into a low-temperature constant-temperature reaction bath, and adjusting the temperature of the low-temperature constant-temperature reaction bath to control the temperature of the low-temperature constant-temperature reaction bath to be 0 ℃;
adding 31 parts of 2+4 type vinyl polyglycol ether into a reaction bottle, simultaneously dropwise adding the first mixed solution, the second mixed solution and the third mixed solution, and keeping the temperature for 1 hour;
adding 3 parts of potassium hydroxide and 0.2 part of ethanolamine into a reaction bottle to obtain a polycarboxylic acid water reducing agent for concrete;
wherein the first mixed solution is obtained by mixing 6 parts of methacrylic acid and 12 parts of maleic anhydride glyceride in a beaker, and the dropping time of the first mixed solution is 2 hours;
the second mixed solution is obtained by mixing 0.25 part of tert-butyl hydroperoxide and 8 parts of deionized water in a beaker, and the dripping time of the second mixed solution is 2.5 hours;
the third mixed solution was obtained by mixing 0.1 part of sulfonated thioglycolic acid and 13 parts of deionized water in a beaker, and the second mixed solution was added dropwise for 2.5 hours.
Example 5
2+4 type vinyl polyglycol ether: 32 parts of (1);
acrylic acid: 7 parts;
methyl amide phosphate ester: 13 parts;
peroxyacetic acid: 0.25 part;
sulfonated thioglycolic acid: 0.15 part;
sodium hydroxide: 2 parts of (1);
n-methyldiethanolamine: 0.3 part;
deionized water: 55 parts of (1);
preparing a polycarboxylic acid water reducing agent for concrete:
adding 33 parts of deionized water into a reaction bottle, placing the reaction bottle filled with 33 parts of deionized water into a low-temperature constant-temperature reaction bath, and adjusting the temperature of the low-temperature constant-temperature reaction bath to control the temperature of the low-temperature constant-temperature reaction bath to be 10 ℃;
adding 32 parts of 2+4 type vinyl polyglycol ether into a reaction bottle, simultaneously dropwise adding the first mixed solution, the second mixed solution and the third mixed solution, and keeping the temperature for 1 hour;
adding 2 parts of sodium hydroxide and 0.3 part of N-methyldiethanolamine into a reaction bottle, and reacting for 0.5h to obtain a polycarboxylic acid water reducer for concrete;
wherein the first mixed solution is obtained by mixing 7 parts of acrylic acid and 13 parts of methyl amide phosphate in a beaker, and the dripping time of the first mixed solution is 2.5 hours;
the second mixed solution is obtained by mixing 0.25 part of peroxyacetic acid and 9 parts of deionized water in a beaker, and the dripping time of the second mixed solution is 3 hours;
the third mixed solution was obtained by mixing 0.15 part of sulfonated thioglycolic acid and 13 parts of deionized water in a beaker, and the third mixed solution was added dropwise for 3 hours.
Performance evaluation
Further, the effect of the polycarboxylic acid water reducing agent for concrete of the present invention was evaluated by using a commercially available conventional polycarboxylic acid water reducing agent (PE) as comparative example 1 in combination with examples 1 to 5 of the present invention.
(1) Experimental raw materials
Cement: sea snail cement P.O42.5;
sand: the machine-made sand has a fineness modulus of 2.8 and a mud content of 3.8 percent;
stone: the grain diameter is 5 mm-10 mm, the mud content is 0.7 percent, and the crushing value is 13.2 percent;
accelerator: the solid content is 50 percent;
commercially available conventional polycarboxylic acid water reducing agent (PE): the solid content is 10 percent;
(2) concrete mixing proportion
The formulation of the concrete, in addition to the amount of water and the accelerator, is shown in table 1:
TABLE 1 concrete mix proportion (unit: kg/m)3)
| Raw material | Cement | Sand | Stone | Water reducing agent |
| Dosage of | 480 | 875 | 835 | 4.8 |
The polycarboxylic acid water reducing agents for concrete obtained in examples 1 to 5 were compounded into samples having a solid content of 10%, the samples obtained in examples 1 to 5 and comparative example 1 were prepared in the mixing ratio shown in table 1, the amount of deionized water was adjusted so that the slump of concrete was controlled to 160mm, and further, each group of concrete for spraying was evaluated, and the evaluation results are shown in table 2.
TABLE 2 evaluation results of polycarboxylic acid water reducing agent Properties
As is clear from Table 2, the concrete without the water reducing agent required the water consumption of the concrete reached 280kg/m in the shotcreting work3(ii) a When the concrete added with the traditional polycarboxylic acid water reducing agent sold in the market is subjected to spray construction, 220kg/m of the polycarboxylic acid water reducing agent needs to be added3The amount of water used; compared with the concrete without the water reducing agent, the water consumption is reduced during the construction; when the concrete added with the polycarboxylic acid water reducing agent for concrete in the embodiments 1 to 5 of the invention is constructed, the maximum water consumption of the concrete is 205kg/m3The minimum can be reduced to 190kg/m3Compared with the concrete added with the conventional polycarboxylic acid water reducing agent sold in the market, the water consumption of the concrete added with the polycarboxylic acid water reducing agent for the concrete in the embodiments 1 to 5 of the invention is reduced, so that the water-cement ratio in the concrete is reduced, the rebound resilience of the concrete is reduced, and the construction performance of the concrete in the jet construction is improved.
Secondly, when the concrete without the water reducing agent is subjected to spray construction, the required dosage of the accelerator reaches 43kg/m3When the concrete added with the traditional polycarboxylic acid water reducing agent sold in the market is subjected to spray construction, the required consumption of the accelerator is 36kg/m3Concrete without adding water reducing agent and concrete added with conventional polycarboxylic acid water reducing agent sold in the marketCompared with soil, the dosage of the accelerator is reduced; when the concrete added with the polycarboxylic acid water reducing agent for concrete in the embodiments 1 to 5 of the invention is subjected to spray construction, the maximum amount of the accelerator required is 31kg/m3The minimum amount can be reduced to 28.5kg/m3Compared with the concrete added with the conventional polycarboxylic acid water reducing agent sold in the market, the concrete added with the polycarboxylic acid water reducing agent for concrete in the embodiments 1 to 5 of the invention has the advantages that the consumption of the accelerator is reduced, and the consumption cost of the accelerator is reduced.
According to experimental data of setting time, rebound rate and compressive strength, when the concrete without the water reducing agent is constructed, the initial setting time of the concrete is 4 minutes and 55 seconds, the final setting time of the concrete is 11 minutes and 50 seconds, the setting time is longer, the rebound rate of the concrete is higher, and the compressive strength of the concrete is lower, so that the data of the rebound rate and the compressive strength of the concrete can be obtained when the concrete without the water reducing agent is subjected to spray construction; further, as is clear from table 2, even when the concrete to which the conventional polycarboxylic acid water reducing agent on the market was added was subjected to the shotcreting work, the initial setting time of the concrete was 4 minutes 5 seconds, the final setting time was 10 minutes 25 seconds, and the rebound resilience was 15%, which was lower than the setting time and the rebound resilience of the concrete to which the water reducing agent was not added, but the setting time and the rebound resilience were not so reduced; however, when the concrete added with the polycarboxylic acid water reducer for concrete in embodiments 1-5 of the invention is subjected to spray construction, the initial setting time of the concrete is less than 3min, and the shortest time can reach 2 min to 30 sec; the final setting time is 8 minutes and 5 seconds at most and can reach 6 minutes and 50 seconds at least; the rebound rate of the concrete is less than 5%, wherein the rebound rate can be reduced to 2% at least, the rebound rate of the concrete added with the polycarboxylic acid water reducing agent for the concrete in the embodiments 1-5 of the invention is far less than that of the concrete added with the traditional polycarboxylic acid water reducing agent sold on the market, so that the compressive strength of the concrete is greatly enhanced, the compressive strength reaches 8.2-8.8 MPa, and is both 5MPa greater than that of the concrete added with the traditional polycarboxylic acid water reducing agent sold on the market and 7MPa greater than that of the concrete not added with the water reducing agent; the compressive strength ratios of the concrete to which the polycarboxylic acid water reducing agent for concrete of examples 1 to 5 of the present invention was added in 28 days (d) and 90 days (d) were also larger than those of the concrete to which the conventional polycarboxylic acid water reducing agent was added in the market in 28 days (d) and 90 days (d), and those of the concrete to which no water reducing agent was added in 28 days (d) and 90 days (d).
In addition, compared with the concrete added with the commercially available traditional polycarboxylic acid water reducing agent and the concrete not added with the water reducing agent, the concrete added with the polycarboxylic acid water reducing agent for the concrete in the embodiments 1 to 5 of the invention has the advantages that the water consumption of the concrete is reduced, but the slump of the concrete finally used for the spray construction is consistent, namely the workability of the concrete finally used for the spray construction is consistent; from the above, it is found that when the workability of the concrete finally used for the shotcrete is uniform, that is, the fluidity of the concrete finally used for the shotcrete is uniform, the smaller the amount of water used for the concrete is, the better the workability of the concrete before the amount of water used for the concrete is not adjusted, that is, the better the fluidity of the concrete before the amount of water used for the concrete is not adjusted, and therefore, the fluidity of the concrete to which the polycarboxylic acid water reducing agent for concrete in examples 1 to 5 of the present invention is added is better than that of the concrete to which the commercially available conventional polycarboxylic acid water reducing agent is added and that to which the water reducing agent is not added.
In conclusion, the polycarboxylic acid water reducing agent for concrete can increase the fluidity of concrete, reduce the water consumption and the consumption of the accelerating agent required by concrete construction, shorten the setting time of the concrete, reduce the rebound rate, improve the strength of the concrete and ensure the construction performance of the concrete.
To further prove that the polycarboxylic acid water-reducing agent for concrete of the present invention can increase the fluidity of concrete, the fluidity of the polycarboxylic acid water-reducing agent for concrete of the present invention was evaluated by using a commercially available conventional polycarboxylic acid water-reducing agent (PE) as comparative example 1 in combination with examples 1 to 5 of the present invention.
The formulation of concrete for evaluating the fluidity of the polycarboxylic acid water reducing agent for concrete is shown in table 3:
TABLE 3 concrete mix proportion (unit: kg/m)3)
| Raw material | Water (W) | Cement | Sand | Stone | Water reducing agent |
| Dosage of | 200 | 480 | 875 | 835 | 5.4 |
The concrete polycarboxylic acid water reducing agent obtained in the examples 1 to 5 is compounded into a sample with a solid content of 10%, then the sample obtained in the examples 1 to 5 and the comparative example 1 are prepared according to the mixing ratio in the table 1, and the slump and the expansion of the prepared concrete are evaluated, and the results are shown in the table 4:
TABLE 4 evaluation results of concrete slump/extension
As can be seen from Table 4, the concrete without the water-reducing agent added had an initial slump/expansion of 180mm/450mm and no fluidity after 1 hour, and the concrete with the commercially available conventional polycarboxylic acid water-reducing agent added had an initial slump/expansion of 200mm/530mm, a slump/expansion of 160mm/410mm after 1 hour, a slump/expansion loss of 40mm/120mm and a slump/expansion loss of a large magnitude, whereas the concrete with the polycarboxylic acid water-reducing agent of examples 1 to 5 of the present invention had an initial slump/expansion of more than 210mm/570mm, a slump/expansion of more than 180mm/495mm after 1 hour, and particularly the concrete with the polycarboxylic acid water-reducing agent of example 3 added had a slump/expansion of 225mm/590mm and a slump/expansion of 210mm/550mm after 1 hour, the slump/expansion loss was small, and the slump/expansion loss in example 3 was 15mm/40mm, which indicates that the slump retaining property of the concrete was the best, and it can be seen that the concrete to which the polycarboxylic acid water-reducing agent for concrete in examples 1 to 5 of the present invention was added had better fluidity than the concrete to which no water-reducing agent was added and the concrete to which a commercially available conventional polycarboxylic acid water-reducing agent was added.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. The polycarboxylic acid water reducing agent for concrete is characterized by comprising the following components in parts by weight:
polyether macromonomer: 30-50 parts of a solvent;
unsaturated acid: 4-8 parts;
small monomers: 8-15 parts;
initiator: 0.15-0.3 part;
sulfonated chain transfer agent: 0.1-0.3 part;
water: 48-72 parts.
2. The polycarboxylic acid water reducer for concrete according to claim 1, further comprising one or more of 1 to 3 parts of a neutralizing agent and 0.2 to 0.8 part of a strength modifier.
3. The polycarboxylic acid water reducer for concrete according to claim 1, wherein the polyether macromonomer comprises one or more of 2+2 type vinyl polyglycol ether and 2+4 type vinyl polyglycol ether.
4. The polycarboxylic acid water reducing agent for concrete according to claim 3, wherein the 2+2 type vinyl polyglycol ether has the following structure:
wherein n is an integer of 45 to 105.
5. The polycarboxylic acid water reducing agent for concrete according to claim 3, wherein the 2+4 type vinyl polyglycol ether has the following structure:
wherein n is an integer of 45 to 105.
6. The polycarboxylic acid water reducer for concrete according to claim 1, wherein the unsaturated acid comprises one or more of acrylic acid, methacrylic acid and fumaric acid.
7. The polycarboxylic acid water reducer for concrete according to claim 1, wherein the small monomer comprises one or more of maleic anhydride glyceride, maleic anhydride monomethyl ether polyethylene glycol ester and methylene amide phosphate ester.
8. The polycarboxylic acid water reducer for concrete according to claim 1, wherein the initiator comprises one or more of cumene hydroperoxide, peracetic acid and tert-butyl hydroperoxide.
9. The polycarboxylic acid water reducer for concrete according to claim 1, wherein the sulfonated chain transfer agent comprises one or more of sulfonated thioglycolic acid and sulfonated thioglycolic alcohol.
10. The preparation method of the polycarboxylic acid water reducing agent for concrete is characterized by comprising the following steps of:
adding 30-45 parts of water into a reactor, putting the reactor filled with 30-45 parts of water into a low-temperature constant-temperature reaction bath, and adjusting the temperature of the low-temperature constant-temperature reaction bath to control the temperature of the low-temperature constant-temperature reaction bath to be-20-15 ℃;
adding 30-50 parts of polyether macromonomer, the first mixed solution, the second mixed solution and the third mixed solution into the reactor, and preserving the temperature for 1-2 hours to obtain the polycarboxylic acid water reducer;
wherein the first mixed solution is a mixture of 4-8 parts of unsaturated acid and 8-15 parts of small monomer;
the second mixed solution is a mixture of 0.15-0.3 part of initiator and 8-12 parts of water;
the third mixed solution is a mixture of 0.1-0.3 part of sulfonated chain transfer agent and 10-15 parts of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110032912.7A CN112851879B (en) | 2021-01-11 | 2021-01-11 | Polycarboxylate superplasticizer for concrete and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110032912.7A CN112851879B (en) | 2021-01-11 | 2021-01-11 | Polycarboxylate superplasticizer for concrete and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112851879A true CN112851879A (en) | 2021-05-28 |
| CN112851879B CN112851879B (en) | 2022-09-13 |
Family
ID=76002580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110032912.7A Active CN112851879B (en) | 2021-01-11 | 2021-01-11 | Polycarboxylate superplasticizer for concrete and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112851879B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114085334A (en) * | 2021-11-17 | 2022-02-25 | 科之杰新材料集团有限公司 | Slump-retaining type polycarboxylate superplasticizer with vinyl ether ester mixed structure and preparation method thereof |
| CN114163580A (en) * | 2021-12-22 | 2022-03-11 | 贵州乾鑫丰建材有限公司 | Thixotropic early-strength water reducing agent and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775089A (en) * | 2012-08-21 | 2012-11-14 | 南京瑞迪高新技术有限公司 | Star polycarboxylic-acid high-performance water reducing agent and preparation method thereof |
| CN103588969A (en) * | 2013-10-24 | 2014-02-19 | 中科院广州化学有限公司 | Polyethylene glycol methyl ether maleate, and preparation method and application thereof |
| CN103588412A (en) * | 2013-10-24 | 2014-02-19 | 中科院广州化学有限公司 | Polyether mixed concrete water reducer, and preparation method and application thereof |
| CN106279557A (en) * | 2015-06-02 | 2017-01-04 | 石家庄市海森化工有限公司 | A kind of energy saving and environment friendly polycarboxylate water-reducer and preparation method thereof |
| CN106349473A (en) * | 2015-12-17 | 2017-01-25 | 邯郸学院 | Method for preparing dipolyethylene glycol maleate by using ionic liquid |
| CN106366254A (en) * | 2016-08-29 | 2017-02-01 | 青神鑫统领建材有限公司 | Ethylene glycol vinyl ether polyethenoxy ether based acrylic acid copolymer, and preparation method and application thereof |
| CN110128603A (en) * | 2019-06-11 | 2019-08-16 | 云南建投高分子材料有限公司 | Stablize the method for synthesis polycarboxylate water-reducer under cryogenic conditions |
| CN111019061A (en) * | 2019-12-13 | 2020-04-17 | 上海东大化学有限公司 | Polycarboxylate superplasticizer, high-stone-powder concrete and preparation method thereof |
| CN111019056A (en) * | 2019-12-05 | 2020-04-17 | 上海东大化学有限公司 | Water-reducing bulk polymerization solid polycarboxylate superplasticizer and preparation method, use method and application thereof |
-
2021
- 2021-01-11 CN CN202110032912.7A patent/CN112851879B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775089A (en) * | 2012-08-21 | 2012-11-14 | 南京瑞迪高新技术有限公司 | Star polycarboxylic-acid high-performance water reducing agent and preparation method thereof |
| CN103588969A (en) * | 2013-10-24 | 2014-02-19 | 中科院广州化学有限公司 | Polyethylene glycol methyl ether maleate, and preparation method and application thereof |
| CN103588412A (en) * | 2013-10-24 | 2014-02-19 | 中科院广州化学有限公司 | Polyether mixed concrete water reducer, and preparation method and application thereof |
| CN106279557A (en) * | 2015-06-02 | 2017-01-04 | 石家庄市海森化工有限公司 | A kind of energy saving and environment friendly polycarboxylate water-reducer and preparation method thereof |
| CN106349473A (en) * | 2015-12-17 | 2017-01-25 | 邯郸学院 | Method for preparing dipolyethylene glycol maleate by using ionic liquid |
| CN106366254A (en) * | 2016-08-29 | 2017-02-01 | 青神鑫统领建材有限公司 | Ethylene glycol vinyl ether polyethenoxy ether based acrylic acid copolymer, and preparation method and application thereof |
| CN110128603A (en) * | 2019-06-11 | 2019-08-16 | 云南建投高分子材料有限公司 | Stablize the method for synthesis polycarboxylate water-reducer under cryogenic conditions |
| CN111019056A (en) * | 2019-12-05 | 2020-04-17 | 上海东大化学有限公司 | Water-reducing bulk polymerization solid polycarboxylate superplasticizer and preparation method, use method and application thereof |
| CN111019061A (en) * | 2019-12-13 | 2020-04-17 | 上海东大化学有限公司 | Polycarboxylate superplasticizer, high-stone-powder concrete and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| PETR JANSA,等: "A conversion of aromatic thiocyanates into sulfothioates: new synthetic route to aromatic Bunte salts", 《RSC ADVANCES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114085334A (en) * | 2021-11-17 | 2022-02-25 | 科之杰新材料集团有限公司 | Slump-retaining type polycarboxylate superplasticizer with vinyl ether ester mixed structure and preparation method thereof |
| CN114085334B (en) * | 2021-11-17 | 2023-08-25 | 科之杰新材料集团有限公司 | Slump-retaining polycarboxylate water reducer with vinyl ether ester mixed structure and preparation method thereof |
| CN114163580A (en) * | 2021-12-22 | 2022-03-11 | 贵州乾鑫丰建材有限公司 | Thixotropic early-strength water reducing agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112851879B (en) | 2022-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112851879B (en) | Polycarboxylate superplasticizer for concrete and preparation method thereof | |
| CN105884979B (en) | The normal temperature preparation method of sustained-release polycarboxylic slump retaining agent | |
| WO2021217762A1 (en) | Unsaturated polyether monomer, and polycarboxylate superplasticizer and preparation method therefor | |
| NZ566940A (en) | Slump retention in cementitious compositions | |
| CN109053972B (en) | Preparation method of blocking intercalation anti-mud type polycarboxylate superplasticizer | |
| CN110759663A (en) | Preparation method and application of anti-mud polycarboxylate superplasticizer | |
| JP4883859B2 (en) | High initial strength cement and additive and method for producing the same | |
| CN106749983A (en) | A kind of ultra early-strength polycarboxylate water-reducer and preparation method thereof | |
| CN101585900B (en) | Method for synthesizing polycarboxylic acid concrete high-performance water reducing agent | |
| CN109790261B (en) | Preparation method of block slow-release concrete admixture | |
| CN109369860A (en) | It is sustained controllable type polycarboxylate superplasticizer mother liquor and preparation method thereof | |
| CN106397683A (en) | Polycarboxylate superplasticizer for reducing viscosity of high-grade concrete and preparation method thereof | |
| CN109438629B (en) | Super early strength polycarboxylate superplasticizer and preparation method thereof | |
| CN107698715A (en) | A kind of anti-mud polycarboxylate water-reducer | |
| US6358310B1 (en) | Air entraining admixture compositions | |
| CN107698717A (en) | A kind of preparation method of anti-mud polycarboxylate water-reducer | |
| CN109704619B (en) | Sulfamate high-efficiency water reducing agent and preparation process thereof | |
| CN109111146B (en) | Multifunctional ester polycarboxylate superplasticizer and preparation method thereof | |
| CN109627394A (en) | A kind of polycarboxylate concrete dehydragent and preparation method thereof being adapted to Machine-made Sand | |
| CN116177918A (en) | Additive for wet-mixed mortar and preparation method thereof | |
| CN109021179B (en) | Phosphonic acid-based polymer, preparation method thereof and phosphate mother liquor | |
| CN114685085B (en) | Wet-mixed mortar additive and preparation method thereof | |
| CN109336447B (en) | Stable slump retaining agent and preparation and use methods thereof | |
| CN108084358B (en) | Preparation method of collapse-proof polycarboxylate superplasticizer | |
| CN106632890A (en) | Slump loss resistant type polycarboxylate superplasticizer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |