CN108147700B - Preparation method of shrinkage-reducing viscosity-reducing polycarboxylic acid plasticizer - Google Patents
Preparation method of shrinkage-reducing viscosity-reducing polycarboxylic acid plasticizer Download PDFInfo
- Publication number
- CN108147700B CN108147700B CN201711468756.9A CN201711468756A CN108147700B CN 108147700 B CN108147700 B CN 108147700B CN 201711468756 A CN201711468756 A CN 201711468756A CN 108147700 B CN108147700 B CN 108147700B
- Authority
- CN
- China
- Prior art keywords
- amino
- unsaturated carboxylic
- acid
- phosphorus
- methyl
- 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.)
- Active
Links
Classifications
-
- 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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention discloses a preparation method of a shrinkage-reducing viscosity-reducing polycarboxylic acid plasticizer, which comprises the following steps: (1) carrying out copolymerization reaction; (2) and (4) neutralizing. The preparation method is characterized in that the polycarboxylic acid plasticizer is prepared by copolymerizing 4-hydroxybutyl vinyl polyoxyethylene ether, a compound A, an unsaturated silicon-containing small monomer, unsaturated carboxylic ester and unsaturated carboxylic acid or unsaturated carboxylic anhydride small monomer. Carboxyl, phosphate group, amino, siloxy, ester group, hydroxyl and other groups are introduced into the molecular structure of the polycarboxylic acid plasticizer, and under the synergistic action of various groups, the polycarboxylic acid plasticizer disclosed by the invention has the advantages of higher water reducing rate, better shrinkage, high slump resistance and low sensitivity.
Description
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to a preparation method of a shrinkage-reducing viscosity-reducing polycarboxylic acid plasticizer.
Background
The polycarboxylic acid water reducing agent has the advantages of low mixing amount, high water reducing rate, good slump retaining property, strong molecular structure adjustability, environmental protection and the like, and becomes the most important product in the current concrete admixture market. With the development of society and the progress of science and technology, human beings continuously widen the living space of the human beings. People are constantly developing towards high altitude, ground and ocean, and the trend that modern buildings tend to be higher-rise, light-weighted and large-span is formed. These require a continuous increase in the level of concrete technology and production technology. Compared with the common concrete, the high-strength concrete has the advantages that the durability of the concrete is effectively improved; the energy consumption and the building cost are reduced. But also has the disadvantages of higher viscosity and great pumping difficulty.
The concrete viscosity is influenced by a plurality of factors, such as water cement ratio, the type and dosage of admixture, sand rate, the type (shape) and gradation of sand, the shape and gradation of stone, the mud content and powder content of sand and stone, the type and dosage of additive and the like. The viscosity reduction method is mainly achieved by improving the mixing amount of a water reducing agent, a high-quality mineral admixture and optimizing the grain composition. However, the construction cost is increased, and segregation and bleeding and aggregate separation are easily caused in the later period of the concrete, so that the durability of the concrete is influenced, and even the concrete shrinks. The shrinkage of concrete has always been an important factor affecting the quality of concrete works. The shrinkage causes cracks in the concrete, so that the strength of the concrete is reduced, the degradation process of the concrete is accelerated, channels for other harmful substances to enter the concrete are increased, and the concrete is easy to have the problems of durability such as steel bar corrosion, alkali aggregate reaction and the like. If the shrinkage of concrete can be reduced, the occurrence of internal defects in the concrete can be effectively controlled and the risk of cracking can be reduced. Therefore, the research and development of the viscosity-reducing polycarboxylic acid plasticizer with the shrinkage reducing function have great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a shrinkage-reducing viscosity-reducing polycarboxylic acid plasticizer.
The technical scheme of the invention is as follows:
a preparation method of a shrinkage-reducing viscosity-reducing polycarboxylic acid plasticizer comprises the following steps:
(1) and (3) copolymerization reaction: adding 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 400-6000 and water into a reaction kettle, stirring uniformly to dissolve, then respectively dropwise adding an initiator, a molecular weight regulator, a compound A, an unsaturated silicon-containing small monomer, unsaturated carboxylic ester, unsaturated carboxylic acid or unsaturated carboxylic anhydride aqueous solution into the reaction kettle to react, wherein the reaction temperature is 0-25 ℃, the dropwise adding time is 0.5-6.5 h, and after the dropwise adding is finished, keeping the temperature for 0-3.5 h to obtain a copolymerization product; wherein the mass ratio of the 4-hydroxybutyl vinyl polyoxyethylene ether to the unsaturated carboxylic acid or unsaturated carboxylic anhydride to the unsaturated carboxylic ester to the compound A to the unsaturated silicon-containing small monomer is 200: 10-30: 2-20: 1-20: 0.5-5, the mass of the initiator accounts for 0.5-2.5% of that of the 4-hydroxybutyl vinyl polyoxyethylene ether, and the mass of the molecular weight regulator accounts for 0.3-2.5% of that of the 4-hydroxybutyl vinyl polyoxyethylene ether; the compound A is ethyl 2-amino-4-methyl-5-phosphorus-3-pentenoate, propyl 2-amino-4-methyl-5-phosphorus-3-pentenoate, ethyl 2-amino-4-propyl-5-phosphorus-3-pentenoate, propyl 2-amino-4-propyl-5-phosphorus-3-pentenoate, ethyl 2-amino-4-ethyl-5-phosphorus-3-pentenoate, propyl 2-amino-4-ethyl-5-phosphorus-3-pentenoate, 2-amino-4-methyl-5-phosphorus-3-pentenoate, methyl 2-amino-4-methyl-5-phosphorus-3-pentenoate, 2-amino-4-propyl-5-phosphorus-3-pentenoic acid, 2-amino-4-ethyl-5-phosphorus-3-pentenoic acid, 2-amino-5-phosphono-3-enoic acid, 1-amino-3-phosphono-2-cyclopentene-1-carboxylic acid and 1-amino-3-phosphono-3-cyclopentene-1-carboxylic acid, wherein the unsaturated silicon-containing small monomer is at least one of methyl 3-trimethylsiloxy-2-butenoate, allyloxy trimethylsilane, 1-methoxy-1-trimethylsiloxypropylene and methyl 3- (trimethylsiloxy) crotonate, the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is at least one of maleic anhydride, acrylic acid, methacrylic acid, fumaric acid and itaconic acid;
(2) and (3) neutralization reaction: and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain the shrinkage-reducing and viscosity-reducing polycarboxylic acid plasticizer with the solid content of 20-80%.
In a preferred embodiment of the present invention, the step (1) is: adding 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 400-6000 and water into a reaction kettle, stirring uniformly to dissolve, then respectively dropwise adding an initiator, a molecular weight regulator, a compound A, an unsaturated silicon-containing small monomer, unsaturated carboxylic ester, unsaturated carboxylic acid or unsaturated carboxylic anhydride aqueous solution into the reaction kettle to react, wherein the reaction temperature is 10-20 ℃, the dropwise adding time is 0.5-6.0 h, and after the dropwise adding is finished, keeping the temperature for 0-3.0 h to obtain a copolymerization product; wherein the mass ratio of the 4-hydroxybutyl vinyl polyoxyethylene ether to the unsaturated carboxylic acid or unsaturated carboxylic anhydride to the unsaturated carboxylic ester to the compound A to the unsaturated silicon-containing small monomer is 200: 12-30: 2-18: 1-18: 0.5-5, the mass of the initiator accounts for 0.5-2.0% of that of the 4-hydroxybutyl vinyl polyoxyethylene ether, and the mass of the molecular weight regulator accounts for 0.3-2.0% of that of the 4-hydroxybutyl vinyl polyoxyethylene ether.
Further preferably, the unsaturated carboxylic acid ester is at least one of methyl methacrylate, methyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, isooctyl acrylate and isooctyl methacrylate.
Further preferably, the initiator is a water-soluble redox initiation system or a water-soluble azo initiator.
Further preferably, the molecular weight regulator is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, trisodium phosphate, sodium formate, sodium acetate, and dodecanethiol.
The invention has the beneficial effects that:
1. the preparation method is characterized in that the polycarboxylic acid plasticizer is prepared by copolymerizing 4-hydroxybutyl vinyl polyoxyethylene ether, a compound A, an unsaturated silicon-containing small monomer, unsaturated carboxylic ester and unsaturated carboxylic acid or unsaturated carboxylic anhydride small monomer. Carboxyl, phosphate group, amino, siloxy, ester group, hydroxyl and other groups are introduced into the molecular structure of the polycarboxylic acid plasticizer, and under the synergistic action of various groups, the polycarboxylic acid plasticizer disclosed by the invention has the advantages of higher water reducing rate, better shrinkage, high slump resistance and low sensitivity.
2. According to the preparation method, phosphate groups are introduced into a molecular structure, so that the molecular structure of the polymer generates proper crosslinking, and the polymer can effectively reduce the viscosity of concrete and improve the workability of the concrete under the mutual synergistic action of the phosphate groups, the silicon-oxygen groups and the carboxyl groups, and is soft in material and high in flow rate; meanwhile, the shrinkage of concrete can be effectively reduced, and concrete cracks can be reduced; the interaction between amino groups and phosphate groups in the molecular chain can effectively improve the early strength of the concrete.
3. When the shrinkage-reducing viscosity-reducing polycarboxylic acid plasticizer prepared by the invention is applied to concrete, the water in the concrete can be locked, the volatilization of the water can be delayed, the ester hydrolysis speed can be effectively controlled, and the slump retaining performance is good and the fluidity is stable; meanwhile, the concrete is insensitive to the change of materials, environmental temperature, mixing amount and single water consumption, so that the stable control of the concrete quality can be realized.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1
(1) And (3) copolymerization reaction: 200.00g of 4-hydroxybutyl vinyl polyoxyethylene ether with molecular weight of 2000 and 100.00g of water are added into a reaction kettle for stirring, after the mixture is uniformly stirred and dissolved and the reaction temperature is 10 ℃, sodium persulfate aqueous solution (1.00 g of sodium persulfate and 20.00g of water), sodium formaldehyde sulfoxylate aqueous solution (1.00 g of sodium formaldehyde sulfoxylate and 20.00g of water), mercaptoethanol aqueous solution (0.80 g of mercaptoethanol and 20.00g of water), ethyl 2-amino-4-methyl-5-phosphorus-3-pentenoate, methyl 3-trimethylsiloxy-2-butenoate, methyl methacrylate and acrylic acid aqueous solution (8.00 g of ethyl 2-amino-4-methyl-5-phosphorus-3-pentenoate, 2.00g of methyl 3-trimethylsiloxy-2-butenoate), 10.00g of methyl methacrylate, 26.00g of acrylic acid and 40.00g of water) for reaction, the dripping time is 2.0h, and the temperature is kept for 3.0h after the dripping is finished, so as to obtain a copolymerization product;
(2) and (3) neutralization reaction: and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain the shrinkage-reducing and viscosity-reducing polycarboxylic acid plasticizer PCE-1.
Example 2
(1) And (3) copolymerization reaction: 200.00g of 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 2400 and 120.00g of water are added into a reaction kettle for stirring, after the mixture is uniformly stirred and dissolved and the reaction temperature is 12 ℃, sodium persulfate aqueous solution (1.60 g of sodium persulfate and 20.00g of water), sodium bisulfite aqueous solution (1.00 g of sodium bisulfite and 20.00g of water), trisodium phosphate aqueous solution (0.90 g of trisodium phosphate and 20.00g of water), 2-amino-4-methyl-5-phosphorus-3-pentenoic acid propyl ester, 1-methoxy-1-trimethylsiloxypropene, isooctyl methacrylate and methacrylic acid aqueous solution (10.00 g of 2-amino-4-methyl-5-phosphorus-3-pentenoic acid propyl ester, 3.00g of 1-methoxy-1-trimethylsiloxypropene), sodium hydrogen sulfite aqueous solution, sodium hydrogen sulfite aqueous, 13.00g of isooctyl methacrylate, 28.00g of methacrylic acid and 40.00g of water) for reaction, the dripping time is 1.5h, and the temperature is kept for 2.0h after the dripping is finished, thus obtaining a copolymerization product;
(2) and (3) neutralization reaction: and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain the shrinkage-reducing and viscosity-reducing polycarboxylic acid plasticizer PCE-2.
Example 3
(1) And (3) copolymerization reaction: 200.00g of 4-hydroxybutyl vinyl polyoxyethylene ether with molecular weight of 2800 and 180.00g of water are added into a reaction kettle for stirring, after the mixture is uniformly stirred and dissolved and the reaction temperature is 15 ℃, azobiscyanovaleric acid (3.00 g of azobiscyanovaleric acid, 20.00g of water), an aqueous solution of mercaptopropionic acid (1.20 g of mercaptopropionic acid, 20.00g of water), ethyl 2-amino-4-propyl-5-phosphorus-3-pentenoate, allyloxytrimethylsilane, hydroxypropyl methacrylate and an aqueous solution of maleic anhydride (11.00 g of ethyl 2-amino-4-propyl-5-phosphorus-3-pentenoate, 4.00g of allyloxytrimethylsilane, 15.00g of hydroxypropyl methacrylate, 24.00g of maleic anhydride and 40.00g of water) are respectively added into the reaction kettle for reaction, the adding time is 1.0h, after the dropwise addition, the temperature is kept for 3.0h to obtain a copolymerization product;
(2) and (3) neutralization reaction: and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain the shrinkage-reducing and viscosity-reducing polycarboxylic acid plasticizer PCE-3.
Example 4
(1) And (3) copolymerization reaction: 200.00g of 4-hydroxybutyl vinyl polyoxyethylene ether having a molecular weight of 3000 and 200.00g of water were added to a reaction vessel and stirred, and after uniformly dissolving with stirring and the reaction temperature was 16 ℃, azobisisobutylamidine hydrochloride (1.80 g of azobisisobutylamidine hydrochloride, 20.00g of water), mercaptopropionic acid and an aqueous isopropanol solution (1.00 g of mercaptopropionic acid, 2.00g of isopropanol, 20.00g of water), 2-amino-4-propyl-5-phosphorus-3-pentenoic acid, methyl 3- (trimethylsiloxy) crotonate, hydroxypropyl acrylate and an aqueous methacrylic acid solution (12.00 g of 2-amino-4-propyl-5-phosphorus-3-pentenoic acid, 5.00g of methyl 3- (trimethylsiloxy) crotonate, 8.00g of hydroxypropyl acrylate), were added dropwise to the reaction vessel and stirred, respectively, 25.00g of methacrylic acid and 60.00g of water) are reacted, the dripping time is 1.0h, and the temperature is kept for 2.0h after the dripping is finished, so as to obtain a copolymerization product;
(2) and (3) neutralization reaction: and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain the shrinkage-reducing and viscosity-reducing polycarboxylic acid plasticizer PCE-4.
Example 5
(1) And (3) copolymerization reaction: 200.00g of 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 4000 and 240.00g of water are added into a reaction kettle for stirring, after the mixture is uniformly stirred and dissolved and the reaction temperature is 18 ℃, a hydrogen peroxide aqueous solution (3.00 g of hydrogen peroxide and 20.00g of water), an ascorbic acid aqueous solution (1.00 g of ascorbic acid and 20.00g of water), a trisodium phosphate aqueous solution (4.00 g of trisodium phosphate and 20.00g of water), 2-amino-4-propyl-5-phosphorus-3-pentenoic acid, 3-trimethylsiloxy-2-butenoic acid methyl ester, hydroxyethyl acrylate and an acrylic acid aqueous solution (10.00 g of 2-amino-4-ethyl-5-phosphorus-3-pentenoic acid ethyl ester, 4.00g of 3-trimethylsiloxy-2-butenoic acid methyl ester, sodium hydrogen carbonate) are respectively added into the reaction kettle in a dropwise manner, 7.00g of hydroxyethyl acrylate, 20.00g of methacrylic acid and 40.00g of water) for reaction, the dripping time is 1.5h, and the temperature is kept for 2.0h after the dripping is finished, so as to obtain a copolymerization product;
(2) and (3) neutralization reaction: and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain the shrinkage-reducing and viscosity-reducing polycarboxylic acid plasticizer PCE-5.
Example 6
(1) And (3) copolymerization reaction: 200.00g of 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 5000 and 270.00g of water are added into a reaction kettle for stirring, after the mixture is uniformly stirred and dissolved and the reaction temperature is 10 ℃, sodium persulfate aqueous solution (1.80 g of sodium persulfate and 20.00g of water), sodium hypophosphite aqueous solution (1.00 g of sodium hypophosphite and 20.00g of water), trisodium phosphate aqueous solution (1.80 g of trisodium phosphate and 20.00g of water), 2-amino-4-ethyl-5-phosphorus-3-pentenoic acid propyl ester, 3-trimethylsiloxy-2-butenoic acid methyl ester, methyl methacrylate and fumaric acid aqueous solution (16.00 g of 2-amino-4-ethyl-5-phosphorus-3-pentenoic acid propyl ester, 3-trimethylsiloxy-2-butenoic acid methyl ester, 3.00g of sodium hypophosphite, sodium hypophosphite aqueous solution, sodium hypophosphite, 6.00g of methyl methacrylate, 18.00g of fumaric acid and 40.00g of water) for reaction, the dripping time is 1.0h, and the temperature is kept for 2.0h after the dripping is finished, so as to obtain a copolymerization product;
(2) and (3) neutralization reaction: and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain the shrinkage-reducing and viscosity-reducing polycarboxylic acid plasticizer PCE-6.
Adopting Huarun P.O 42.5.5 ordinary portland cement, the concrete mix proportion is: 330kg/m cement380kg/m of fly ash390kg/m of mineral powder3700kg/m of sand31040kg/m of pebbles3160kg/m of water3The concrete performance test was performed on the shrinkage-reducing and viscosity-reducing polycarboxylic acid plasticizers obtained in examples 1 to 6 and the commercially available viscosity-reducing polycarboxylic acid water reducing agent (PCE) at a bending content of 0.12%, and the results are shown in table 1.
TABLE 1 concrete Performance test results for different admixtures
As shown in Table 1, compared with a commercially available viscosity reduction type polycarboxylate superplasticizer (PCE), the shrinkage reduction and viscosity reduction type polycarboxylate plasticizer prepared by the invention has the advantages of better slump retaining property, better workability, soft material, low viscosity and the like, and the shrinkage percentage of 28d is obviously reduced, so that the shrinkage reduction and viscosity reduction type polycarboxylate plasticizer prepared by the invention can effectively reduce the viscosity of concrete and has better shrinkage reduction effect and better slump retaining effect.
It will be understood by those skilled in the art that the raw materials and parameters used in the present invention can still obtain the same or similar technical effects as the above examples when they are changed within the following ranges, and still fall into the protection scope of the present invention:
a preparation method of a shrinkage-reducing viscosity-reducing polycarboxylic acid plasticizer comprises the following steps:
(1) and (3) copolymerization reaction: adding 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 400-6000 and water into a reaction kettle, stirring uniformly to dissolve, then respectively dropwise adding an initiator, a molecular weight regulator, a compound A, an unsaturated silicon-containing small monomer, unsaturated carboxylic ester, unsaturated carboxylic acid or unsaturated carboxylic anhydride aqueous solution into the reaction kettle to react, wherein the reaction temperature is 0-25 ℃, the dropwise adding time is 0.5-6.5 h, and after the dropwise adding is finished, keeping the temperature for 0-3.5 h to obtain a copolymerization product; wherein the mass ratio of the 4-hydroxybutyl vinyl polyoxyethylene ether to the unsaturated carboxylic acid or unsaturated carboxylic anhydride to the unsaturated carboxylic ester to the compound A to the unsaturated silicon-containing small monomer is 200: 10-30: 2-20: 1-20: 0.5-5, the mass of the initiator accounts for 0.5-2.5% of that of the 4-hydroxybutyl vinyl polyoxyethylene ether, and the mass of the molecular weight regulator accounts for 0.3-2.5% of that of the 4-hydroxybutyl vinyl polyoxyethylene ether; the compound A is ethyl 2-amino-4-methyl-5-phosphorus-3-pentenoate, propyl 2-amino-4-methyl-5-phosphorus-3-pentenoate, ethyl 2-amino-4-propyl-5-phosphorus-3-pentenoate, propyl 2-amino-4-propyl-5-phosphorus-3-pentenoate, ethyl 2-amino-4-ethyl-5-phosphorus-3-pentenoate, propyl 2-amino-4-ethyl-5-phosphorus-3-pentenoate, 2-amino-4-methyl-5-phosphorus-3-pentenoate, methyl 2-amino-4-methyl-5-phosphorus-3-pentenoate, 2-amino-4-propyl-5-phosphorus-3-pentenoic acid, 2-amino-4-ethyl-5-phosphorus-3-pentenoic acid, 2-amino-5-phosphono-3-enoic acid, 1-amino-3-phosphono-2-cyclopentene-1-carboxylic acid and 1-amino-3-phosphono-3-cyclopentene-1-carboxylic acid, wherein the unsaturated silicon-containing small monomer is at least one of methyl 3-trimethylsiloxy-2-butenoate, allyloxy trimethylsilane, 1-methoxy-1-trimethylsiloxypropylene and methyl 3- (trimethylsiloxy) crotonate, the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is at least one of maleic anhydride, acrylic acid, methacrylic acid, fumaric acid and itaconic acid;
(2) and (3) neutralization reaction: and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain the shrinkage-reducing and viscosity-reducing polycarboxylic acid plasticizer with the solid content of 20-80%.
The unsaturated carboxylic ester is at least one of methyl methacrylate, methyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, isooctyl acrylate and isooctyl methacrylate. The initiator is a water-soluble redox initiation system or a water-soluble azo initiator. The molecular weight regulator is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, trisodium phosphate, sodium formate, sodium acetate and dodecanethiol.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (4)
1. A preparation method of a shrinkage-reducing viscosity-reducing polycarboxylic acid plasticizer is characterized by comprising the following steps: the method comprises the following steps:
(1) and (3) copolymerization reaction: adding 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 400-6000 and water into a reaction kettle, stirring uniformly to dissolve, then respectively dropwise adding an initiator, a molecular weight regulator, a compound A, an unsaturated silicon-containing small monomer, unsaturated carboxylic ester, unsaturated carboxylic acid or unsaturated carboxylic anhydride aqueous solution into the reaction kettle to react, wherein the reaction temperature is 0-25 ℃, the dropwise adding time is 0.5-6.5 h, and after the dropwise adding is finished, keeping the temperature for 0-3.5 h to obtain a copolymerization product; wherein the mass ratio of the 4-hydroxybutyl vinyl polyoxyethylene ether to the unsaturated carboxylic acid or unsaturated carboxylic anhydride to the unsaturated carboxylic ester to the compound A to the unsaturated silicon-containing small monomer is 200: 10-30: 2-20: 1-20: 0.5-5, the initiator accounts for 0.5-2.5% of the mass of the 4-hydroxybutyl vinyl polyoxyethylene ether, and the molecular weight regulator accounts for 0.3-2.5% of the mass of the 4-hydroxybutyl vinyl polyoxyethylene ether; the compound A is ethyl 2-amino-4-methyl-5-phosphorus-3-pentenoate, propyl 2-amino-4-methyl-5-phosphorus-3-pentenoate, ethyl 2-amino-4-propyl-5-phosphorus-3-pentenoate, propyl 2-amino-4-propyl-5-phosphorus-3-pentenoate, ethyl 2-amino-4-ethyl-5-phosphorus-3-pentenoate, propyl 2-amino-4-ethyl-5-phosphorus-3-pentenoate, 2-amino-4-methyl-5-phosphorus-3-pentenoate, methyl 2-amino-4-methyl-5-phosphorus-3-pentenoate, 2-amino-4-propyl-5-phosphorus-3-pentenoic acid, 2-amino-4-ethyl-5-phosphorus-3-pentenoic acid, 2-amino-5-phosphono-3-enoic acid, 1-amino-3-phosphono-2-cyclopentene-1-carboxylic acid and 1-amino-3-phosphono-3-cyclopentene-1-carboxylic acid, wherein the unsaturated silicon-containing small monomer is at least one of methyl 3-trimethylsiloxy-2-butenoate, allyloxy trimethylsilane, 1-methoxy-1-trimethylsiloxypropylene and methyl 3- (trimethylsiloxy) crotonate, the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is at least one of maleic anhydride, acrylic acid, methacrylic acid, fumaric acid and itaconic acid; the unsaturated carboxylic ester is at least one of methyl methacrylate, methyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, isooctyl acrylate and isooctyl methacrylate;
(2) and (3) neutralization reaction: and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain the shrinkage-reducing and viscosity-reducing polycarboxylic acid plasticizer with the solid content of 20-80%.
2. The method of claim 1, wherein: the step (1) is as follows: adding 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 400-6000 and water into a reaction kettle, stirring uniformly to dissolve, then respectively dropwise adding an initiator, a molecular weight regulator, a compound A, an unsaturated silicon-containing small monomer, unsaturated carboxylic ester, unsaturated carboxylic acid or unsaturated carboxylic anhydride aqueous solution into the reaction kettle to react, wherein the reaction temperature is 10-20 ℃, the dropwise adding time is 0.5-6.0 h, and after the dropwise adding is finished, keeping the temperature for 0-3.0 h to obtain a copolymerization product; wherein the mass ratio of the 4-hydroxybutyl vinyl polyoxyethylene ether to the unsaturated carboxylic acid or unsaturated carboxylic anhydride to the unsaturated carboxylic ester to the compound A to the unsaturated silicon-containing small monomer is 200: 12-30: 2-18: 1-18: 0.5-5, the initiator accounts for 0.5-2.0% of the mass of the 4-hydroxybutyl vinyl polyoxyethylene ether, and the molecular weight regulator accounts for 0.3-2.0% of the mass of the 4-hydroxybutyl vinyl polyoxyethylene ether.
3. The method of claim 1 or 2, wherein: the initiator is a water-soluble redox initiation system or a water-soluble azo initiator.
4. The method of claim 1 or 2, wherein: the molecular weight regulator is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, trisodium phosphate, sodium formate, sodium acetate and dodecanethiol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711468756.9A CN108147700B (en) | 2017-12-28 | 2017-12-28 | Preparation method of shrinkage-reducing viscosity-reducing polycarboxylic acid plasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711468756.9A CN108147700B (en) | 2017-12-28 | 2017-12-28 | Preparation method of shrinkage-reducing viscosity-reducing polycarboxylic acid plasticizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108147700A CN108147700A (en) | 2018-06-12 |
| CN108147700B true CN108147700B (en) | 2020-12-29 |
Family
ID=62462370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711468756.9A Active CN108147700B (en) | 2017-12-28 | 2017-12-28 | Preparation method of shrinkage-reducing viscosity-reducing polycarboxylic acid plasticizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108147700B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311752A (en) * | 2014-10-10 | 2015-01-28 | 科之杰新材料集团有限公司 | Polycarboxylic acid water reducer and preparation method thereof |
| CN106380551A (en) * | 2016-09-13 | 2017-02-08 | 科之杰新材料集团有限公司 | Low-sensitivity anti-mud polycarboxylic acid water reducing agent and preparation method thereof |
| CN106496444A (en) * | 2016-10-31 | 2017-03-15 | 科之杰新材料集团有限公司 | A kind of preparation method of ethers polycarboxylic acid slump retaining agent |
-
2017
- 2017-12-28 CN CN201711468756.9A patent/CN108147700B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311752A (en) * | 2014-10-10 | 2015-01-28 | 科之杰新材料集团有限公司 | Polycarboxylic acid water reducer and preparation method thereof |
| CN106380551A (en) * | 2016-09-13 | 2017-02-08 | 科之杰新材料集团有限公司 | Low-sensitivity anti-mud polycarboxylic acid water reducing agent and preparation method thereof |
| CN106496444A (en) * | 2016-10-31 | 2017-03-15 | 科之杰新材料集团有限公司 | A kind of preparation method of ethers polycarboxylic acid slump retaining agent |
Non-Patent Citations (1)
| Title |
|---|
| 聚羧酸系超塑化剂的功能化;逢建军;《混凝土世界》;20170430;第91页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108147700A (en) | 2018-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108047393B (en) | Preparation method of viscosity-reduction-enhanced polycarboxylic acid plasticizer | |
| CN108659177A (en) | A kind of overlength sustained release slump retaining agent of high-adaptability and its normal low temperature preparation method | |
| CN112694574B (en) | Polycarboxylate superplasticizer with high mud resistance and high slump loss resistance and preparation method thereof | |
| CN108864374B (en) | Preparation method of ether high-water-retention polycarboxylate superplasticizer | |
| CN109970921B (en) | High-water-reduction low-sensitivity polycarboxylate superplasticizer and preparation method thereof | |
| CN109608594A (en) | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof | |
| CN104231188B (en) | A kind of esters polycarboxylic acid slump retaining agent and preparation method thereof | |
| CN108047396B (en) | Multi-cation mud-resistant polycarboxylate superplasticizer and preparation method thereof | |
| CN109790261B (en) | Preparation method of block slow-release concrete admixture | |
| CN109734353A (en) | A kind of high-slump-retentionpolycarboxylate polycarboxylate water reducer | |
| CN109369859B (en) | Concrete tackifying type viscosity regulator and preparation method thereof | |
| CN110358026B (en) | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN110642994A (en) | Preparation method of stone powder adaptive polycarboxylate superplasticizer | |
| CN110606922B (en) | Preparation method of polycarboxylate superplasticizer with hydration heat regulation and control function | |
| CN109369860A (en) | It is sustained controllable type polycarboxylate superplasticizer mother liquor and preparation method thereof | |
| CN111592272A (en) | Polycarboxylate superplasticizer for machine-made sand concrete prestressed component and preparation method thereof | |
| CN104496253B (en) | Special early-strength polycarboxylate superplasticizer for prefabricated parts and preparation method of special early-strength polycarboxylate superplasticizer | |
| CN110713573A (en) | Method for synthesizing polycarboxylate superplasticizer slump-retaining mother liquor | |
| CN112745464A (en) | Phosphate-containing high-adaptability early-strength polycarboxylate superplasticizer and preparation method and application thereof | |
| CN109180876B (en) | Preparation method of viscosity-reducing polycarboxylate superplasticizer | |
| CN108530587B (en) | Preparation method of ester water retention thixotropic polycarboxylate superplasticizer | |
| CN108218282B (en) | Preparation method of anti-mud viscosity-reducing polycarboxylic acid plasticizer | |
| CN109721271B (en) | Polycarboxylate water reducing agent composition for self-compacting high-workability concrete | |
| CN108147700B (en) | Preparation method of shrinkage-reducing viscosity-reducing polycarboxylic acid plasticizer | |
| CN114195953B (en) | Low-sensitivity high-water-retention 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 |