CN108516866B - Preparation method of modified super absorbent resin internal curing agent - Google Patents
Preparation method of modified super absorbent resin internal curing agent Download PDFInfo
- Publication number
- CN108516866B CN108516866B CN201810361370.6A CN201810361370A CN108516866B CN 108516866 B CN108516866 B CN 108516866B CN 201810361370 A CN201810361370 A CN 201810361370A CN 108516866 B CN108516866 B CN 108516866B
- Authority
- CN
- China
- Prior art keywords
- absorbent resin
- super absorbent
- modified
- curing agent
- primary amine
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/04—Preventing evaporation of the mixing water
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of a modified super absorbent resin internal curing agent, which comprises the following steps: firstly, modifying fatty primary amine in an organic solvent by adopting polyunsaturated fatty acid to obtain an unsaturated fatty primary amine monomer; and then carrying out free radical polymerization reaction on unsaturated fatty primary amine monomers, unsaturated ester monomers and unsaturated polyoxyethylene ether macromonomers under the action of an initiator and a reducing agent, and adding a modified sodium silicate solution and a dispersing agent after the reaction is finished to obtain the modified super absorbent resin internal curing agent. The modified super absorbent resin internal curing agent prepared by the method can effectively control the water absorption rate of the water absorbent resin for curing concrete, reduce the early shrinkage of the concrete and improve the working performance and compressive strength of the concrete.
Description
Technical Field
The invention relates to the technical field of modified super absorbent resin internal curing agents, in particular to a preparation method of a modified super absorbent resin internal curing agent.
Background
The concrete is one of the most used building materials in the current building engineering, the comprehensive performance of the concrete depends on the composition and proportion of raw materials and is closely related to the later-stage good maintenance, and the maintenance is a means for keeping the concrete in a saturated or nearly saturated state so that a cement hydration product can continuously fill a free water space in fresh concrete. If the concrete is not cured in time after construction, the water in the concrete is evaporated to the outside through the capillary pores of the system, so that the hydration in the cementing material is insufficient, the hydration products are reduced, and the performance of the concrete is reduced.
The traditional curing modes mainly comprise: water curing, steam curing, embedding curing and plastic film curing. But also has the problems of large water consumption, time and labor waste, incomplete curing, incapability of ensuring the uniformity of concrete, high curing cost and the like. Compared with the traditional curing mode, the curing agent is a novel efficient concrete curing mode which is specifically divided into internal curing and external curing, wherein the external curing is to spray or paint a layer of chemical substance with film-forming property and permeability on the surface layer of the concrete after the concrete is constructed, and the substance forms a layer of uniform and continuous compact film in a short time, so that the evaporation of water in the concrete is inhibited, and the cementing material is promoted to be fully hydrated; the internal curing is that a water-absorbing substance with a porous medium or hydrophilic groups is added in the preparation process of the concrete, the substance is uniformly dispersed in a concrete system to play an internal water storage role, and when the concrete is in a low water-gel ratio or dry environment, the substance releases the stored water to provide enough power for the complete hydration of the cementing material. Therefore, the innovative curing agent curing technology has very important significance for improving the performance of the cement concrete.
The types of external curing agents currently mainly include four main types: water glass, emulsion, organic solvent and organic-inorganic composite. However, the curing agent is easy to volatilize, is unfavorable to environmental ecology, has low water retention rate and poor film water solubility, and is easy to have the phenomena of peeling, falling off, cracking, emulsion breaking, flocculation and the like after being influenced by temperature. The internal curing is originated from the last 90 years, the curing process occurs inside concrete, the internal curing materials are divided into water-saturated Lightweight Aggregate (LAW) and Super Absorbent Polymer (SAP), and the internal curing materials have good water absorption, water release and moisture retention functions and can improve the problems of concrete shrinkage and cracking. However, LAW has high internal porosity and large pore size, which leads to poor workability of concrete and affected mechanical properties. SAP is a high water-absorbing polymer with a linear chain, branched chain and cross-linked coexistent network structure, and hydrophilic groups such as-COOH, -OH and the like in the structure are easy to form hydrogen bonds with free water; meanwhile, free water is fixed in the network structure of the SAP through swelling, and under the high-alkalinity environment (pH is 12-13) of cement hydration, the water absorption multiplying power of the super absorbent resin is reduced, and the pre-absorbed water can be released, so that the internal humidity is ensured, the cement hydration is maintained, and the durability of concrete such as cracking resistance, shrinkage resistance, freezing resistance and the like can be obviously improved. The control of the crosslinking of the super absorbent resin is an important aspect for controlling the state of the spatial structure, and the density of the crosslinking points directly influences the water absorption and water retention capacity of the super absorbent resin. The surface crosslinking of the super absorbent resin affects the volume expansion at the time of liquid absorption, and therefore adversely affects the liquid absorption capacity, and generally lowers the liquid absorption capacity of the super absorbent resin.
Patent CN105330334A reports a preparation method of a silane modified concrete internal curing agent, in which inorganic clay is completely dispersed in deionized water, then neutralized acrylic acid solution, a cross-linking agent and an initiator are added and mixed uniformly to obtain super absorbent resin gel, and the super absorbent resin is obtained after granulation, drying, crushing, screening and surface cross-linking, so that the influence of the super absorbent resin on the workability of concrete can be reduced, the early self-shrinkage reducing effect of concrete is improved, and the problem of early cracking of concrete is solved. Patent CN102558574A reports a surface modification method for carboxyl-containing super absorbent resin, which uses a monofunctional compound as a modifier to perform surface modification treatment on carboxyl-containing super absorbent resin, so that part of the hydrophilic structure on the surface layer of the super absorbent resin is changed into a hydrophobic structure, and further the moisture diffusion channel is reduced, thereby effectively reducing the imbibition rate of the super absorbent resin, and the influence on the imbibition rate is small, the early stage can absorb water slowly, the influence on the working performance of concrete is reduced, but the above reports do not significantly improve the working performance and mechanical performance of concrete.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a modified super absorbent resin internal curing agent, which is used for improving the continuous working performance, mechanical property and durability of concrete.
The technical scheme of the invention adopts the following specific steps:
(1) preparing modified super absorbent resin: firstly, dissolving fatty primary amine in organic ether, and then adding polyunsaturated fatty acid to obtain an unsaturated fatty primary amine monomer; then preparing an aqueous solution from an unsaturated polyoxyethylene ether macromonomer, an unsaturated fatty primary amine monomer and an unsaturated ester monomer, and carrying out free radical polymerization reaction under the action of an initiator and a reducing agent to obtain the modified super absorbent resin; wherein the molar ratio of the polyunsaturated fatty acid to the primary aliphatic amine to the organic ether is 1 (1.5-2.0) to 1.5-2.8; wherein the mass component ratio of the unsaturated polyoxyethylene ether macromonomer, the unsaturated fatty primary amine monomer and the unsaturated ester monomer between the initiator and the reducing agent is 1: (0.8-1.2): (0.5-0.8): (0.01-0.02): (0.05-0.08);
(2) preparing a modified sodium silicate solution: dissolving sodium silicate in the aluminum modified silica sol dispersion liquid, adding 2-methacrylic acid chromium tetrachloride under a high shear condition, and stirring for 5-10 h to obtain modified sodium silicate; wherein the mass component ratio of the sodium silicate to the aluminum modified silica sol to the 2-methacrylic acid chromium tetrachloride is 1: (1-1.5): (0.01: 0.06);
(3) preparing the modified super absorbent resin internal curing agent: adding the modified sodium silicate obtained in the step (2) into the modified super absorbent resin obtained in the step (1), and adding a dispersant for dispersing; finally, dehydrating, separating and drying the product to obtain the modified super absorbent resin internal curing agent; wherein the mass component ratio of the modified super absorbent resin, the modified sodium silicate and the dispersant is 1: (0.03-0.07): (0.001-0.007).
Further, in the step (1), adding polyunsaturated fatty acid, and stirring at 45-63 ℃ for 1-2 h to obtain unsaturated fatty primary amine monomers; then, preparing 20-26% aqueous solution of unsaturated polyoxyethylene ether macromonomer, unsaturated fatty primary amine monomer and unsaturated ester monomer, carrying out free radical polymerization reaction under the action of an initiator and a reducing agent, and stirring for 1-5 h at 30-50 ℃ to obtain the modified super absorbent resin;
in the step (2), the particle size of the aluminum modified silica sol is 5 nm-10 nm;
in the step (3), after the dispersing agent is added, ultrasonic dispersion is carried out for 1-5 h at the temperature of 10-45 ℃.
The fatty primary amine is at least one of dodecyl primary amine, tetradecyl primary amine, hexadecyl primary amine or octadecyl primary amine;
the organic ether is at least one of diethylene glycol monobutyl ether, diethylene glycol dipropylene glycol monobutyl ether, dipropylene glycol diethylene glycol monobutyl ether or tetraethylene glycol monobutyl ether;
the polyunsaturated fatty acid is at least one of octadecatrienoic acid, docosahexaenoic acid or eicosapentaenoic acid;
the unsaturated polyoxyethylene ether macromonomer is methyl allyl alcohol polyoxyethylene ether, isobutylene alcohol polyoxyethylene ether or prenol polyoxyethylene ether, and the molecular weight is 800-8000;
the unsaturated ester monomer macromonomer is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate;
the initiator is at least one of hydrogen peroxide, ammonium persulfate, sodium persulfate or potassium persulfate;
the reducing agent is at least one of sodium formaldehyde sulfoxylate, ascorbic acid, sodium sulfite or sodium hypophosphite;
the dispersant is at least one of stearic acid monoglyceride, diethanolamine and sepiolite magnesium silicate;
the preparation method of the modified super absorbent resin internal curing agent has the advantages that:
1. the preparation method of the modified super absorbent resin internal curing agent provided by the invention is characterized in that the free radical solution polymerization reaction is adopted, the process is simple, the preparation is carried out at low temperature, and the preparation method is green and environment-friendly; can freely control the water absorption and has obvious shrinkage reducing effect.
2. According to the invention, primary aliphatic amine is pretreated by polyunsaturated fatty acid to form a spherical surrounding unsaturated primary aliphatic amine monomer, the monomer is copolymerized with a slow-release unsaturated ester monomer, the degree of grafting and the crosslinking point are improved by unsaturated polyoxyethylene ether, and the obtained modified super absorbent resin has a net structure with curling flexibility, can form a curling winding shape in concrete, has the effect that the crosslinking density and the space are similar to those of a sponge, locks water molecules in the net structure, and plays a vital role in controlling the water absorption and shrinkage of the concrete.
3. The curing agent obtained by modifying sodium silicate with the aluminum modified silica sol and reacting with the modified super absorbent resin under the action of the dispersing agent is applied to concrete, can fill air holes in time when water in the concrete is evaporated, has stronger dispersion permeability, improves the water retention rate and strength of the concrete, and does not influence the working performance of the concrete.
Detailed Description
The technical solution of the present invention is further described in detail by examples below.
Example 1
(1) Firstly, dissolving 1.5mol of dodecyl primary amine in 2.8mol of diethylene glycol dipropylene glycol monobutyl ether, then adding 1mol of octadecatrienoic acid, and stirring for 1 hour at 45 ℃ to obtain an unsaturated fatty primary amine monomer; then dissolving 100 parts of methallyl alcohol polyoxyethylene ether (molecular weight 800), 80 parts of unsaturated fatty primary amine monomer and 80 parts of hydroxyethyl acrylate in 740 parts of water, carrying out free radical polymerization reaction under the action of 1 part of hydrogen peroxide and 5 parts of ascorbic acid, and stirring for 5 hours at 30 ℃ to obtain the modified super absorbent resin;
(2) dissolving 100 parts of sodium silicate in 100 parts of aluminum modified silica sol (10nm) dispersion liquid, adding 1 part of 2-methacrylic acid chromium tetrachloride under a high shear condition, and stirring for 5 hours to obtain the modified sodium silicate.
(3) Adding 3 parts of modified sodium silicate into 100 parts of modified super absorbent resin, adding 0.1 part of glycerol monostearate, and performing ultrasonic dispersion for 1 hour at 10 ℃. And finally, dehydrating, separating and drying the product to obtain the modified super absorbent resin internal curing agent.
Example 2
(1) Firstly, dissolving 2mol of tetradecyl primary amine in 1.5mol of diethylene glycol monobutyl ether, then adding 1mol of docosahexaenoic acid, and stirring at 63 ℃ for 1.5h to obtain an unsaturated fatty primary amine monomer; then dissolving 100 parts of isobutylene polyoxyethylene ether (molecular weight 8000), 100 parts of unsaturated fatty primary amine monomer, 50 parts of hydroxypropyl acrylate in 1000 parts of water, carrying out free radical polymerization reaction under the action of 1.5 parts of ammonium persulfate and 8 parts of sodium formaldehyde sulfoxylate, and stirring for 1h at 50 ℃ to obtain the modified super absorbent resin;
(2) dissolving 100 parts of sodium silicate in 150 parts of aluminum modified silica sol (5nm) dispersion liquid, adding 5 parts of 2-methacrylic acid chromium tetrachloride under a high shear condition, and stirring for 8 hours to obtain modified sodium silicate;
(3) adding 7 parts of modified sodium silicate into 100 parts of modified super absorbent resin, adding 0.7 part of diethanol amine, and performing ultrasonic dispersion for 5 hours at the temperature of 45 ℃. And finally, dehydrating, separating and drying the product to obtain the modified super absorbent resin internal curing agent.
Example 3
(1) Firstly, dissolving 1.6mol of hexadecyl primary amine in 2mol of dipropylene glycol diethylene glycol monobutyl ether, adding 1mol of eicosapentaenoic acid, and stirring for 1h at 50 ℃ to obtain an unsaturated fatty primary amine monomer; then dissolving 100 parts of prenyl alcohol polyoxyethylene ether (with the molecular weight of 5000), 120 parts of unsaturated aliphatic primary amine monomer and 60 parts of hydroxyethyl methacrylate in 840 parts of water, carrying out free radical polymerization under the action of 2 parts of sodium persulfate and 6 parts of sodium sulfite, and stirring for 3 hours at 40 ℃ to obtain the modified super absorbent resin;
(2) dissolving 100 parts of sodium silicate in 120 parts of aluminum modified silica sol (10nm) dispersion liquid, adding 6 parts of 2-methacrylic acid chromium tetrachloride under a high shear condition, and stirring for 10 hours to obtain modified sodium silicate;
(3) adding 5 parts of modified sodium silicate into 100 parts of modified super absorbent resin, adding 0.3 part of sepiolite magnesium silicate, and performing ultrasonic dispersion for 3 hours at the temperature of 20 ℃. And finally, dehydrating, separating and drying the product to obtain the modified super absorbent resin internal curing agent.
Example 4
(1) Firstly, dissolving 1.8mol of octadecyl primary amine in 2.6mol of tetraethyleneglycol monobutyl ether, then adding 1mol of octadecatrienoic acid, and stirring for 2 hours at 55 ℃ to obtain unsaturated fatty primary amine monomers; then 100 parts of methallyl alcohol polyoxyethylene ether (molecular weight 1400), 80 parts of unsaturated fatty primary amine monomer and 70 parts of hydroxypropyl methacrylate are dissolved in 835 parts of water, and the mixture is stirred for 4 hours at 40 ℃ under the action of 2 parts of potassium persulfate and 7 parts of sodium hypophosphite to obtain modified super absorbent resin;
(2) dissolving 100 parts of sodium silicate in 110 parts of aluminum modified silica sol (5nm) dispersion liquid, adding 3 parts of 2-methacrylic acid chromium tetrachloride under a high shear condition, and stirring for 3 hours to obtain modified sodium silicate;
(3) adding 6 parts of modified sodium silicate into 100 parts of modified super absorbent resin, adding 0.5 part of diethanol amine, and performing ultrasonic dispersion for 2 hours at 40 ℃. And finally, dehydrating, separating and drying the product to obtain the modified super absorbent resin internal curing agent.
Example 5
(1) Firstly, dissolving 2mol of dodecyl primary amine in 1.5mol of tetraethylene glycol monobutyl ether, then adding 1mol of eicosapentaenoic acid, and stirring for 2 hours at 60 ℃ to obtain unsaturated fatty primary amine monomers; then dissolving 100 parts of isobutylene polyoxyethylene ether (molecular weight is 3000), 90 parts of unsaturated aliphatic primary amine monomer and 80 parts of hydroxypropyl acrylate in 1080 parts of water, carrying out free radical polymerization reaction under the action of 1.8 parts of ammonium persulfate and 7.5 parts of ascorbic acid, and stirring for 3 hours at 50 ℃ to obtain the modified super absorbent resin;
(2) dissolving 100 parts of sodium silicate in 150 parts of aluminum modified silica sol (5nm) dispersion liquid, adding 4 parts of 2-methacrylic acid chromium tetrachloride under a high shear condition, and stirring for 10 hours to obtain modified sodium silicate;
(3) adding 4 parts of modified sodium silicate into 100 parts of modified super absorbent resin, adding 0.4 part of glycerol monostearate, and performing ultrasonic dispersion for 5 hours at 35 ℃. And finally, dehydrating, separating and drying the product to obtain the modified super absorbent resin internal curing agent.
Example 6
(1) Firstly, dissolving 1.5mol of tetradecyl primary amine in 1.5mol of dipropylene glycol diethylene glycol monobutyl ether, then adding 1mol of docosahexaenoic acid, and stirring at 50 ℃ for 2h to obtain unsaturated fatty primary amine monomers; then dissolving 100 parts of prenyl alcohol polyoxyethylene ether (molecular weight 1400), 115 parts of unsaturated fatty primary amine monomer and 50 parts of hydroxyethyl acrylate in 1060 parts of water, carrying out free radical polymerization reaction under the action of 1 part of hydrogen peroxide and 7 parts of ascorbic acid, and stirring for 5 hours at 50 ℃ to obtain the modified super absorbent resin;
(2) dissolving 100 parts of sodium silicate in 140 parts of aluminum modified silica sol (10nm) dispersion liquid, adding 3 parts of 2-methacrylic acid chromium tetrachloride under a high shear condition, and stirring for 6 hours to obtain modified sodium silicate;
(3) adding 6 parts of modified sodium silicate into 100 parts of modified super absorbent resin, adding 0.7 part of diethanol amine, and performing ultrasonic dispersion for 5 hours at 10 ℃. And finally, dehydrating, separating and drying the product to obtain the modified super absorbent resin internal curing agent.
Comparative example 1
(1) Firstly, dissolving 2mol of dodecyl primary amine in 2.3mol of diethylene glycol dipropylene glycol monobutyl ether, then adding 1mol of octadecatrienoic acid, and stirring for 2 hours at 45 ℃ to obtain an unsaturated fatty primary amine monomer; then dissolving 100 parts of methallyl alcohol polyoxyethylene ether (with the molecular weight of 5000), 80 parts of unsaturated aliphatic primary amine monomer and 80 parts of hydroxyethyl methacrylate in 740 parts of water, carrying out free radical polymerization reaction under the action of 1 part of ammonium persulfate and 5 parts of sodium hypophosphite, and stirring for 5 hours at 30 ℃ to obtain the modified super absorbent resin;
(2) adding 3 parts of sodium silicate into 100 parts of modified super absorbent resin, adding 0.1 part of glycerol monostearate, and performing ultrasonic dispersion for 1 hour at 10 ℃. And finally, dehydrating, separating and drying the product to obtain the modified super absorbent resin internal curing agent.
Comparative example 2
(1) Dissolving 100 parts of isobutylene alcohol polyoxyethylene ether (molecular weight is 3000), 100 parts of acrylamide monomer and 80 parts of hydroxypropyl acrylate in 940 parts of water, carrying out free radical polymerization under the action of 1 part of hydrogen peroxide and 5 parts of sodium formaldehyde sulfoxylate, and stirring for 5 hours at 40 ℃ to obtain the super absorbent resin;
(2) dissolving 100 parts of sodium silicate in 100 parts of aluminum modified silica sol (5nm) dispersion liquid, adding 1 part of 2-methacrylic acid chromium tetrachloride under a high shear condition, and stirring for 5 hours to obtain modified sodium silicate;
(3) adding 6 parts of modified sodium silicate into 100 parts of modified super absorbent resin, adding 0.1 part of sepiolite magnesium silicate, and performing ultrasonic dispersion for 3 hours at 40 ℃. And finally, dehydrating, separating and drying the product to obtain the modified super absorbent resin internal curing agent.
Comparative example 3
(1) Dissolving 100 parts of prenyl alcohol polyoxyethylene ether (molecular weight of 2400) and 80 parts of acrylamide in 600 parts of water, carrying out free radical polymerization under the action of 1 part of sodium persulfate and 5 parts of sodium hypophosphite, and stirring for 5 hours at 30 ℃ to obtain super absorbent resin;
(2) 5 parts of sodium silicate is added into 100 parts of super absorbent resin, 0.5 part of diethanolamine is added, and ultrasonic dispersion is carried out for 2 hours at 30 ℃. And finally, dehydrating, separating and drying the product to obtain the super absorbent resin internal curing agent.
Effects of the implementation
The test refers to GB8077-2012 test method for homogeneity of concrete admixture, W/C is 0.29, and the net slurry fluidity of each example and the control example in the reference cement is tested under the same mixing amount. Referring to GB/T50082-2009 test method for long-term performance and durability of common concrete, the size of a prepared concrete shrinkage test piece is 100mm multiplied by 515 mm; referring to GB/T50081-2002 ordinary concrete mechanical property test method, the size of a prepared concrete strength test piece is 100mm multiplied by 100 mm. The test was carried out using a reference cement. A commercially available internal curing agent was selected as comparative example 4. The test results are shown in Table 1.
TABLE 1 results of performance testing of examples and comparative examples
As can be seen from Table 1, the modified super absorbent resin internal curing agent in the examples has a remarkable effect in comparison with the super absorbent resin internal curing agent in the comparative examples in terms of liquid absorption rate, mortar shrinkage ratio, fluidity and compressive strength. The concrete has obvious improvement effect on the compressive strength and the continuous working performance of the concrete.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical solution according to the technical idea of the present invention falls within the protection scope of the present invention.
Claims (10)
1. A preparation method of a modified super absorbent resin internal curing agent is characterized by comprising the following steps:
step 1, preparation of modified super absorbent resin: firstly, dissolving fatty primary amine in organic ether, and then adding polyunsaturated fatty acid to obtain an unsaturated fatty primary amine monomer; then preparing an aqueous solution from an unsaturated polyoxyethylene ether macromonomer, an unsaturated fatty primary amine monomer and an unsaturated ester monomer, and carrying out free radical polymerization reaction under the action of an initiator and a reducing agent to obtain the modified super absorbent resin; wherein the molar ratio of the polyunsaturated fatty acid to the primary fatty amine to the organic ether is 1 (1.5-2.0) to 1.5-2.8; wherein the mass component ratio of the unsaturated polyoxyethylene ether macromonomer, the unsaturated fatty primary amine monomer and the unsaturated ester monomer between the initiator and the reducing agent is 1: (0.8-1.2): (0.5-0.8): (0.01-0.02): (0.05-0.08);
step 2, preparing a modified sodium silicate solution: dissolving sodium silicate in the aluminum modified silica sol dispersion liquid, adding 2-methacrylic acid chromium tetrachloride under a high shear condition, and stirring for 5-10 h to obtain modified sodium silicate; wherein the mass component ratio of the sodium silicate to the aluminum modified silica sol to the 2-methacrylic acid chromium tetrachloride is 1: (1-1.5): (0.01: 0.06);
step 3, preparing the modified super absorbent resin internal curing agent: adding the modified sodium silicate obtained in the step 2 into the modified super absorbent resin obtained in the step 1, and adding a dispersant for dispersing; finally, dehydrating, separating and drying the product to obtain the modified super absorbent resin internal curing agent; wherein the mass component ratio of the modified super absorbent resin, the modified sodium silicate and the dispersant is 1: (0.03-0.07): (0.001-0.007).
2. The method for preparing the modified super absorbent resin internal curing agent as claimed in claim 1, wherein:
in the step 1, adding polyunsaturated fatty acid, and stirring at 45-63 ℃ for 1-2 h to obtain unsaturated fatty primary amine monomers; then, preparing 20-26% aqueous solution of unsaturated polyoxyethylene ether macromonomer, unsaturated fatty primary amine monomer and unsaturated ester monomer, carrying out free radical polymerization reaction under the action of an initiator and a reducing agent, and stirring for 1-5 h at 30-50 ℃ to obtain the modified super absorbent resin;
in the step 2, the particle size of the aluminum modified silica sol is 5 nm-10 nm;
in the step 3, after the dispersing agent is added, ultrasonic dispersion is carried out for 1-5 h at the temperature of 10-45 ℃.
3. The method for preparing the modified super absorbent resin internal curing agent as claimed in claim 1 or 2, wherein: the fatty primary amine in the step 1 is at least one of dodecyl primary amine, tetradecyl primary amine, hexadecyl primary amine or octadecyl primary amine.
4. The method for preparing the modified super absorbent resin internal curing agent as claimed in claim 1 or 2, wherein: the organic ether in the step 1 is at least one of diethylene glycol monobutyl ether, diethylene glycol dipropylene glycol monobutyl ether, dipropylene glycol diethylene glycol monobutyl ether or tetraethylene glycol monobutyl ether.
5. The method for preparing the modified super absorbent resin internal curing agent as claimed in claim 1 or 2, wherein: the polyunsaturated fatty acid in the step 1 is at least one of octadecatrienoic acid, docosahexaenoic acid or eicosapentaenoic acid.
6. The method for preparing the modified super absorbent resin internal curing agent as claimed in claim 1 or 2, wherein: the unsaturated polyoxyethylene ether macromonomer in the step 1 is methyl allyl alcohol polyoxyethylene ether, isobutylene alcohol polyoxyethylene ether and isoamylol polyoxyethylene ether, and the molecular weight is 800-8000.
7. The method for preparing the modified super absorbent resin internal curing agent as claimed in claim 1 or 2, wherein: the unsaturated ester monomer in the step 1 is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
8. The method for preparing the modified super absorbent resin internal curing agent as claimed in claim 1 or 2, wherein: the initiator in the step 1 is at least one of hydrogen peroxide, ammonium persulfate, sodium persulfate or potassium persulfate.
9. The method for preparing the modified super absorbent resin internal curing agent as claimed in claim 1 or 2, wherein: the reducing agent in the step 1 is at least one of sodium formaldehyde sulfoxylate, ascorbic acid, sodium sulfite or sodium hypophosphite.
10. The method for preparing the modified super absorbent resin internal curing agent as claimed in claim 1 or 2, wherein: the dispersant in the step 3 is at least one of stearic acid monoglyceride, diethanolamine and sepiolite magnesium silicate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810361370.6A CN108516866B (en) | 2018-04-20 | 2018-04-20 | Preparation method of modified super absorbent resin internal curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810361370.6A CN108516866B (en) | 2018-04-20 | 2018-04-20 | Preparation method of modified super absorbent resin internal curing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108516866A CN108516866A (en) | 2018-09-11 |
| CN108516866B true CN108516866B (en) | 2020-09-18 |
Family
ID=63428922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810361370.6A Active CN108516866B (en) | 2018-04-20 | 2018-04-20 | Preparation method of modified super absorbent resin internal curing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108516866B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133699A (en) * | 2018-09-17 | 2019-01-04 | 佛山朝鸿新材料科技有限公司 | A kind of preparation method of durable high-strength composite expansive agents for concrete material |
| CN112094074B (en) * | 2020-09-24 | 2022-05-20 | 鹤壁宝来化工科技有限公司 | Preparation method of water-soluble super absorbent resin internal curing agent |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2477888T3 (en) * | 2010-01-20 | 2014-07-18 | W.R. Grace & Co.-Conn. | Setting retardant applied to a surface that induces high healing |
| CN105330334B (en) * | 2015-11-18 | 2018-02-23 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of silane-modified concrete inner curing agent |
| CN105347724B (en) * | 2015-11-26 | 2018-04-10 | 桂林理工大学 | The preparation method of conserving material in a kind of inierpeneirating network structure concrete |
| CN105646767B (en) * | 2015-12-31 | 2018-02-09 | 交通运输部公路科学研究所 | A kind of concrete super absorbent resin epoxy-type Self-curing material and preparation method |
| CN106749959A (en) * | 2016-11-11 | 2017-05-31 | 中建商品混凝土眉山新材料有限公司 | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof |
-
2018
- 2018-04-20 CN CN201810361370.6A patent/CN108516866B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108516866A (en) | 2018-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112724329A (en) | Viscosity-reducing polycarboxylic acid concrete water reducer and preparation method thereof | |
| CN103864340B (en) | A kind of mortar concrete waterproofing agent | |
| CN103693883B (en) | A kind of collapse protective poly-carboxylic acid water reducing agent and preparation method thereof | |
| CN109369860B (en) | Slow-release controllable polycarboxylate superplasticizer mother liquor and preparation method thereof | |
| CN111925489B (en) | High-water-reduction slump-retaining type polycarboxylate superplasticizer and preparation method and application thereof | |
| CN105110687A (en) | Mud resisting and slump retaining type polycarboxylic acids water reducer and preparation method thereof | |
| CN109516714B (en) | Ceramsite carrier concrete internal curing agent and preparation method thereof | |
| CN110938176A (en) | Super-long slump loss resistant cement-based polycarboxylate superplasticizer mother liquor and application thereof | |
| CN110734243A (en) | SAPs microcapsule and cement-based self-repairing material | |
| CN108516866B (en) | Preparation method of modified super absorbent resin internal curing agent | |
| CN109665745B (en) | Multifunctional polycarboxylic acid water reducing agent and preparation method thereof | |
| CN103613308A (en) | Water-reducing polycarboxylic concrete slump retaining agent and preparation method thereof | |
| CN110642995A (en) | Preparation method of polycarboxylic acid water reducer for low-slump concrete | |
| CN113105578B (en) | Saline-alkali resistant slow-release water-absorbent resin and application thereof | |
| CN104628972A (en) | Preparation method of anti-crack shrinkage reducing polycarboxylate based superplasticizer | |
| CN112723788A (en) | Efficient water-saving maintenance material | |
| CN115784651A (en) | Steel slag-based anti-freezing geopolymer and preparation method thereof | |
| CN106496439A (en) | Star-like slow release slump retaining polycarboxylate water reducer of a kind of Y words and preparation method thereof | |
| CN109232830B (en) | Preparation method of concrete slump-retaining reinforcing agent | |
| US20220212995A1 (en) | Cement additive, cement admixture, cement composition, molded body, and method for improving strength of molded body | |
| CN112279973B (en) | Polycarboxylate superplasticizer for pipe pile and preparation method and application thereof | |
| CN112897929B (en) | Slow-release polycarboxylate superplasticizer microsphere and preparation method thereof | |
| CN116040980B (en) | Wet-mixed mortar additive, preparation method thereof and wet-mixed mortar | |
| CN115260534A (en) | Cement-based material self-repairing microsphere and preparation method and application thereof | |
| CN108586672A (en) | A kind of cross-linking type polycarboxylic acid super-plasticizer and its preparation method and application |
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 |