CN113717335B - Organic-inorganic composite modified water-absorbent resin type curing material, preparation method thereof and machine-made sand concrete containing same in alpine region - Google Patents

Organic-inorganic composite modified water-absorbent resin type curing material, preparation method thereof and machine-made sand concrete containing same in alpine region Download PDF

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CN113717335B
CN113717335B CN202110996098.0A CN202110996098A CN113717335B CN 113717335 B CN113717335 B CN 113717335B CN 202110996098 A CN202110996098 A CN 202110996098A CN 113717335 B CN113717335 B CN 113717335B
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absorbent resin
water
aluminosilicate
curing material
organic
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CN113717335A (en
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李志�
刘方华
马富山
高增
王兆平
徐艳
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CCCC First Highway Engineering Co Ltd
Third Engineering Co Ltd of Highway Engineering Bureau of CCCC
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CCCC First Highway Engineering Co Ltd
Third Engineering Co Ltd of Highway Engineering Bureau of CCCC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • 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
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F283/002—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers modified by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • 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
    • C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/76—Use at unusual temperatures, e.g. sub-zero
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Polymers & Plastics (AREA)
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Abstract

The invention relates to the technical field of building materials, and discloses an organic-inorganic composite modified water-absorbent resin type curing material, a preparation method thereof and high and cold area machine-made sand concrete containing the same, wherein the curing material is prepared by forming a coordination intermediate by aluminosilicate loaded with transition metal ions and polyphosphazene, and carrying out free radical polymerization reaction on the coordination intermediate and raw material components of the water-absorbent resin; the mass ratio of the aluminosilicate loaded with the transition metal ions to the polyphosphazene to the water-absorbent resin is 20-50:5-20:100. According to the curing material, the water-absorbent resin is grafted into the aluminosilicate through the polyphosphazene, so that the tolerance of the water-absorbent resin can be improved, and meanwhile, the water absorbency and the water retention capacity of the curing material can be improved.

Description

Organic-inorganic composite modified water-absorbent resin type curing material, preparation method thereof and machine-made sand concrete containing same in alpine region
Technical Field
The invention relates to the technical field of building materials, in particular to an organic-inorganic composite modified water-absorbent resin curing material, a preparation method thereof and machine-made sand concrete containing the same in alpine regions.
Background
Concrete has been widely used since its advent, which has been an irreplaceable role in construction engineering. In the development of concrete, the durability of concrete is often neglected due to the excessive pursuit of high strength. In the alpine region, many buildings and bridge and culvert structures have concrete damage conditions such as cracking, peeling, exposed corrosion of reinforcing steel bars and the like on the surface of the foundation part, especially the concrete near a water level line, in a very short time of construction, so that the safety of the structure is seriously affected. For alpine regions, the durability of concrete is mainly represented by the ability of concrete to resist freeze-thaw damage. In the severe cold region, the climate is severe and the temperature difference changes greatly. The temperature is repeatedly changed from positive temperature to negative temperature, and the change of dry and wet is frequent due to the seasonal influence, so that the concrete is easily damaged by freeze thawing under the condition, and the larger the temperature difference change is, the more severe the damage caused by freeze thawing is. In order to solve the problem, the frost resistance of the concrete can be improved mainly from the aspects of reducing the water-cement ratio, improving the pore structure, increasing the hydration product, reasonably using the admixture and the like.
As is currently done, the durability of concrete is improved by adding air entraining agents to the concrete to form air entrained concrete. However, the bubbles introduced by the air entraining agent are all life-long, and the bubbles of the freshly mixed concrete are inevitably broken in the processes of stirring, transporting, pouring and the like, so that the loss of air content is caused. Meanwhile, in China, the dependency of concrete on the fly ash is higher, the content of the fly ash in normal concrete is up to more than 30%, unburned carbon particles in fly ash particles have higher adsorption capacity on polar substances such as air entraining agents, and the air bubble formation and stability are further seriously affected, so that the loss of air content is caused. The problem of air content loss generated by the air entraining agent makes the control and design of the real air content of the hardened concrete difficult, the air entraining agent doping amount is often increased to achieve the air entraining purpose, and most importantly, if the real air content of the hardened concrete is too high, the concrete strength is rapidly reduced; the air content is too low, and the high freezing resistance is difficult to ensure.
In high-cold high-altitude areas, concrete needs to achieve double guarantees of high strength and high freezing resistance, and the method of adopting the air entraining agent is difficult to control the freezing resistance of the concrete, and meanwhile, the strength is possibly weakened at the cost. Super absorbent resins (SAPs) are polymeric materials having a three-dimensional network structure with a low degree of cross-linking, which begin to swell upon contact with water or aqueous solutions, forming hydrogels. Conventionally, a super absorbent resin has been used as an internal curing material capable of effectively preventing or reducing deformation of concrete itself. As SAP can release water when the relative humidity in the concrete changes, the air-containing micropores formed in the hardened concrete after the water release play the roles of freezing resistance and being beneficial to secondary hydration of the initial setting concrete. The SAP alone has problems of small water absorption and poor water retention, and for this purpose, it is currently used to improve the water absorption and water retention by adding an inorganic filler having a high specific surface area to the SAP. As in the patent publication nos. CN104310845A and CN103058566a, the water-absorbent resin is prepared by blending with an inorganic filler, and although the water absorption and water retention are partially improved, the water-absorbent resin is difficult to uniformly disperse and easy to agglomerate, and when silicate cement is added to carry out cement hydration, a large amount of alkali-exciting agent forms an alkaline environment, and the alkali resistance of the water-absorbent resin is poor, thereby causing the stability of the water-absorbent resin to be reduced.
Disclosure of Invention
< technical problem to be solved by the invention >
The current water-absorbent resin has poor tolerance in alkaline concrete and has a problem of poor water storage capacity.
< technical scheme adopted by the invention >
Aiming at the technical problems, the invention aims to provide an organic-inorganic composite modified water-absorbent resin type curing material, a preparation method thereof and high-cold area machine-made sand concrete containing the same.
The specific contents are as follows:
firstly, the invention provides an organic-inorganic composite modified water-absorbent resin curing material, which is obtained by forming a coordination intermediate by aluminosilicate loaded with transition metal ions and polyphosphazene, and carrying out free radical polymerization reaction on the coordination intermediate and raw material components of the water-absorbent resin; the mass ratio of the aluminosilicate loaded with the transition metal ions to the polyphosphazene to the water-absorbent resin is 20-50:5-20:100.
The invention provides a preparation method of an organic-inorganic composite modified water-absorbent resin curing material, which comprises the following steps:
s1, dispersing aluminosilicate loaded with transition metal ions in acetonitrile solution, adding the aluminosilicate into acetonitrile solution containing polyphosphazene and triethylamine to obtain mixed solution, and placing the mixed solution into a high-pressure reaction kettle to react to obtain a coordination intermediate;
and S2, carrying out free radical polymerization reaction on the coordination intermediate and raw material components of the water-absorbent resin to obtain a finished product.
Thirdly, the invention provides machine-made sand concrete in alpine regions, which comprises the organic-inorganic composite modified water-absorbent resin type curing material.
< beneficial effects achieved by the invention >
(1) The aluminosilicate is a porous material with a three-dimensional structure, and the aluminosilicate and the water-absorbent resin are subjected to grafting treatment, so that the water absorption capacity and the water-retaining capacity of the maintenance material can be improved, the stability of the water-absorbent resin is improved, and the tolerance of the maintenance material is further improved;
(2) Polyphosphazene is an organic-inorganic hybrid polymer with main chains of phosphorus and nitrogen atoms alternately arranged, and has high reactivity and high stability. Polyphosphazenes contain a large number of phosphorus and nitrogen electron rich groups and are capable of coordinating with aluminosilicates loaded with transition metal ions to form organometallic ligands. The organic metal ligand is grafted with the water absorbent resin, so that the connection strength of aluminosilicate and the water absorbent resin can be improved, and the organic metal ligand is grafted in a free radical polymerization mode, so that the organic metal ligand is uniformly dispersed in the water absorbent resin. Because aluminosilicate is grafted and compounded with the water-absorbent resin, the tolerance of the water-absorbent resin can be improved, and the degradation of the water-absorbent resin in the cement hydration process can be avoided, so that a stable environment is provided for the water-absorbent resin; in addition, the polyphosphazene is easy to hydrolyze in water, and the organic metal ligand is copolymerized with the monomer of the water absorbent resin, so that the water resistance of the polyphosphazene can be improved, and the connection stability of the maintenance material is improved.
(3) When the curing material is dispersed in concrete, the basic structural units of aluminosilicate and zeolite molecular sieve are identical to SiO 4 ] 4- And [ AlO ] 4 ] 5- Tetrahedra, having similar chemical composition and structure, are incorporated into concrete, and when the concrete is hydrated, the amorphous aluminosilicate can be partially converted into zeolite molecular sieves of ordered nanocrystalline structure by the alkaline substances in the concrete. Specifically: in the first aspect, the damage of alkaline substances in the concrete to the water-absorbent resin can be effectively reduced; in the second aspect, the formed zeolite molecular sieve has large specific surface area and high specific pore area, can further improve the water absorption capacity and keep high water holding capacity, is beneficial to the secondary hydration process of the concrete in the curing process, and further improves the durability of the concrete; in a third aspect, the zeolite molecular sieve formed is capable of enhancing the strength of concrete, further enhancing durability.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Firstly, the invention provides an organic-inorganic composite modified water-absorbent resin curing material, which is obtained by forming a coordination intermediate by aluminosilicate loaded with transition metal ions and polyphosphazene, and carrying out free radical polymerization reaction on the coordination intermediate and raw material components of the water-absorbent resin; the mass ratio of the aluminosilicate loaded with the transition metal ions to the polyphosphazene to the water-absorbent resin is 20-50:5-20:100.
In the present inventionThe transition metal ion includes Fe 3+ 、Fe 2+ 、Ti 4+ 、Ni 2+ 、Cu 2+ 、Cr 3+ Or Zn 2+ At least one of them.
In the present invention, the aluminosilicate comprises at least one of metakaolin, low-calcium/no-calcium fly ash, low-calcium/no-calcium silica fume, blast furnace slag, volcanic ash, red mud, halloysite, coal gangue, or alkaline tailings.
The preparation method of the aluminosilicate loaded with the transition metal ions comprises the steps of immersing the aluminosilicate in a salt solution containing the transition metal ions, carrying out isovolumetric immersion adsorption for 1-3 h, and obtaining the aluminosilicate loaded with the transition metal ions through draining, drying and calcining.
In the present invention, the transition metal ions constitute 0.5 to 3wt.% of the total weight of the aluminosilicate.
In the invention, the drying condition is 75-110 ℃ and the drying time is 10-20 hours.
In the invention, the calcination condition is that the temperature is raised by 380-500 ℃ at a temperature raising rate of 5 ℃/min, and the calcination is carried out for 1.5-4 hours.
In the present invention, the aluminosilicate is ground and dried to a constant weight.
In the present invention, the salt solution containing the filtered metal ions may be sulfate, hydrochloride, nitrate, carbonate, or the like. Further, the salt solution is configured as a supersaturated solution.
In the invention, the raw material components of the water-absorbent resin comprise acrylic acid monomer, acrylamide monomer, cross-linking agent and initiator.
The invention provides a preparation method of an organic-inorganic composite modified water-absorbent resin curing material, which comprises the following steps:
s1, dispersing aluminosilicate loaded with transition metal ions in acetonitrile solution, adding the aluminosilicate into acetonitrile solution containing polyphosphazene and triethylamine to obtain mixed solution, and placing the mixed solution into a high-pressure reaction kettle to react to obtain a coordination intermediate;
the S2 coordination intermediate and each raw material component of the water-absorbent resin are obtained through free radical polymerization reaction.
In the invention, the mass ratio of polyphosphazene to triethylamine is 1:5-10.
In the invention, the temperature of the high-pressure reaction kettle is 120-150 ℃ and the reaction time is 45-100 min.
In the invention, in S1, after the reaction is finished, cooling to room temperature, filtering, washing by ethanol, drying and crushing to obtain the coordination intermediate.
In the present invention, the polyphosphazene includes at least one of hexachlorocyclotriphosphazene, hexaphenoxycyclotriphosphazene, or ethoxy (pentafluoro) cyclotriphosphazene.
In the invention, in S2, adding a coordination intermediate, an acrylic acid monomer, an acrylamide monomer, a cross-linking agent and an initiator into deionized water to react, and drying and grinding after the reaction is finished.
Preparing a sodium hydroxide aqueous solution with the mass fraction of 20%, sequentially dripping acrylic monomers and acrylamide monomers into the sodium hydroxide aqueous solution, and blending to obtain a monomer solution; and (3) dropwise adding a cross-linking agent into the monomer solution, adding a coordination intermediate for blending treatment, dropwise adding an initiator, heating for reaction, and then cooling, crushing and drying. The mass ratio of the acrylic acid monomer to the acrylamide monomer to the initiator to the cross-linking agent is 70-90:10-20:0.5-1:0.1-0.5.
In the present invention, the acrylic monomer includes acrylic acid and/or a derivative of acrylic acid, and further, acrylic acid, methacrylic acid or ethacrylic acid is specifically mentioned.
In the present invention, the acrylamide monomer is acrylamide.
Third, the invention provides machine-made sand concrete in alpine regions, which comprises the organic-inorganic composite modified water-absorbent resin type curing material.
The curing material obtained by the invention is doped into concrete in a dry doping or pre-water absorbing mode, is firstly mixed with the cementing material, and then is mixed with the sand aggregate and water for stirring and molding.
< example >
Example 1
An organic-inorganic composite modified water-absorbent resin curing material comprises aluminosilicate loaded with transition metal ions, polyphosphazene and water-absorbent resin with a mass ratio of 30:10:100. The preparation method comprises the following steps:
s1 preparation of transition metal ion-supported aluminosilicate
Metakaolin is selected as aluminosilicate, and transition metal ion is Cu 2+ 。
Grinding metakaolin, drying to constant weight, immersing metakaolin in saturated CuSO 4 Soaking and adsorbing in the solution for 2 hr, draining, drying at 100deg.C for 15 hr, heating to 420 deg.C at a heating rate of 5deg.C/min, and calcining for 2 hr to obtain Cu-loaded material 2+ Metakaolin of (2), wherein, cu 2+ 2wt.% of the total weight of metakaolin.
Preparation of S2 coordination intermediate
Loaded with Cu 2+ The metakaolin is dispersed in acetonitrile solution, then added into acetonitrile solution containing hexachlorocyclotriphosphazene and triethylamine to obtain mixed solution, and the mixed solution is placed into a high-pressure reaction kettle for reaction, wherein the temperature of the high-pressure reaction kettle is 135 ℃, and the reaction time is 60min. Cooling to room temperature after the reaction is finished, filtering, washing by ethanol, drying and crushing to obtain the coordination intermediate. The mass ratio of hexachlorocyclotriphosphazene to triethylamine is 1:8.
S3 preparation of maintenance material
Preparing a sodium hydroxide aqueous solution with the mass fraction of 20%, sequentially dripping 90 parts of acrylic acid and 10 parts of acrylamide into the sodium hydroxide aqueous solution, and blending to obtain a monomer solution; dropwise adding 0.3 part of N-N' -methylene bisacrylamide into the monomer solution, adding a coordination intermediate for blending treatment, dropwise adding 0.8 part of potassium persulfate, heating to 80 ℃, carrying out heat preservation treatment for 5 hours, cooling to room temperature, crushing and drying to obtain the maintenance material. The curing material was ball milled into 100 μm spherical particles using a ball mill.
Example 2
The difference between this example and example 1 is that the mass ratio of aluminosilicate loaded with transition metal ions, polyphosphazene, water absorbent resin is 40:15:100.
Example 3
The difference between this example and example 1 is that the mass ratio of aluminosilicate loaded with transition metal ions, polyphosphazene, water absorbent resin is 25:5:100.
Example 4
The difference between this example and example 1 is that the aluminosilicate is fly ash and the transition metal ion is Fe 2+ The salt solution is FeSO 4 。
Example 5
The difference between this example and example 1 is that metakaolin is used as aluminosilicate and Zn is used as transition metal ion 2+ The salt solution is Zn (NO) 3 ) 2 。
Example 6
An organic-inorganic composite modified water-absorbent resin curing material comprises aluminosilicate loaded with transition metal ions, polyphosphazene and water-absorbent resin with a mass ratio of 30:10:100. The preparation method comprises the following steps:
s1 preparation of transition metal ion-supported aluminosilicate
The aluminosilicate is calcium-free fly ash, and the transition metal ion is Ti 4+ 。
Grinding calcium-free fly ash, drying to constant weight, immersing the calcium-free fly ash in saturated TiCl 4 Soaking and adsorbing in the solution for 1.5 hr, draining, drying at 85deg.C for 12 hr, heating to 400deg.C at a heating rate of 5deg.C/min, and calcining for 1.5 hr to obtain Ti-loaded material 4+ Calcium-free fly ash of (1), wherein Ti 4+ 1.6wt.% of the total weight of the calcium-free fly ash.
Preparation of S2 coordination intermediate
Load of Ti 4+ Dispersing calcium-free fly ash in acetonitrile solution, adding the mixture into acetonitrile solution containing hexaphenoxy cyclotriphosphazene and triethylamine to obtain mixed solution, placing the mixed solution into a high-pressure reaction kettle for reaction,the temperature of the high-pressure reaction kettle is 140 ℃, and the reaction time is 45min. Cooling to room temperature after the reaction is finished, filtering, washing by ethanol, drying and crushing to obtain the coordination intermediate. The mass ratio of hexaphenoxy cyclotriphosphazene to triethylamine is 1:7.
S3 preparation of maintenance material
Preparing a sodium hydroxide aqueous solution with the mass fraction of 20%, sequentially dripping 90 parts of methacrylic acid and 10 parts of acrylamide into the sodium hydroxide aqueous solution, and blending to obtain a monomer solution; dropwise adding 0.3 part of N-N' -methylene bisacrylamide into the monomer solution, adding a coordination intermediate for blending treatment, dropwise adding 0.8 part of potassium persulfate, heating to 80 ℃, carrying out heat preservation treatment for 5 hours, cooling to room temperature, crushing and drying to obtain the maintenance material. The curing material was ball milled into 100 μm spherical particles using a ball mill.
Example 7
An organic-inorganic composite modified water-absorbent resin curing material comprises aluminosilicate loaded with transition metal ions, polyphosphazene and water-absorbent resin with a mass ratio of 30:10:100. The preparation method comprises the following steps:
s1 preparation of transition metal ion-supported aluminosilicate
The aluminosilicate is blast furnace slag, and the transition metal ion is Cu 2+ 。
The blast furnace slag is ground and dried to constant weight, and the blast furnace slag is immersed into saturated CuCl 2 Soaking and adsorbing in the solution for 1 hr, draining, drying at 80deg.C for 18 hr, heating to 1500deg.C at a heating rate of 5deg.C/min, and calcining for 2 hr to obtain Cu-loaded material 2+ In (2) a blast furnace slag in which Cu 2+ 1.2wt.% of the total weight of blast furnace slag.
Preparation of S2 coordination intermediate
Loaded with Cu 2+ The blast furnace slag is dispersed in acetonitrile solution, then added into acetonitrile solution containing ethoxy (pentafluoro) cyclotriphosphazene and triethylamine to obtain mixed solution, and the mixed solution is placed into a high-pressure reaction kettle for reaction, wherein the temperature of the high-pressure reaction kettle is 120 ℃, and the reaction time is 70min. Reverse-rotationCooling to room temperature after finishing, filtering, washing with ethanol, drying, and pulverizing to obtain coordination intermediate. The mass ratio of hexaphenoxy cyclotriphosphazene to triethylamine is 1:10.
S3 preparation of maintenance material
Preparing a sodium hydroxide aqueous solution with the mass fraction of 20%, sequentially dripping 90 parts of ethacrylic acid and 10 parts of acrylamide into the sodium hydroxide aqueous solution, and blending to obtain a monomer solution; dropwise adding 0.3 part of N-N' -methylene bisacrylamide into the monomer solution, adding a coordination intermediate for blending treatment, dropwise adding 0.8 part of potassium persulfate, heating to 80 ℃, carrying out heat preservation treatment for 5 hours, cooling to room temperature, crushing and drying to obtain the maintenance material. The curing material was ball milled into 100 μm spherical particles using a ball mill.
Example 8
An organic-inorganic composite modified water-absorbent resin curing material comprises aluminosilicate loaded with transition metal ions, polyphosphazene and water-absorbent resin with a mass ratio of 30:10:100. The preparation method comprises the following steps:
s1 preparation of transition metal ion-supported aluminosilicate
The aluminosilicate is halloysite, and the transition metal ion is Cu 2+ 。
Grinding halloysite, drying to constant weight, and soaking halloysite in saturated Cu (NO 3 ) 2 Soaking and adsorbing in the solution for 2 hr, draining, drying at 110deg.C for 12 hr, heating to 470 deg.C at a heating rate of 5deg.C/min, and calcining for 1 hr to obtain Cu-loaded material 2+ Halloysite of (a), wherein, cu 2+ 2wt.% of the total weight of halloysite.
Preparation of S2 coordination intermediate
Loaded with Cu 2+ Dispersing halloysite in acetonitrile solution, adding the halloysite into acetonitrile solution containing ethoxy (pentafluoro) cyclotriphosphazene and triethylamine to obtain mixed solution, and placing the mixed solution into a high-pressure reaction kettle for reaction at the temperature of 140 ℃ for 55min. Cooling to room temperature after the reaction is finished, filtering, washing with ethanol, and dryingAnd crushing to obtain a coordination intermediate. The mass ratio of hexaphenoxy cyclotriphosphazene to triethylamine is 1:10.
S3 preparation of maintenance material
Preparing a sodium hydroxide aqueous solution with the mass fraction of 20%, sequentially dripping 90 parts of acrylic acid monomer and 10 parts of acrylamide monomer into the sodium hydroxide aqueous solution, and blending to obtain a monomer solution; dropwise adding 0.3 part of N-N' -methylene bisacrylamide into the monomer solution, adding a coordination intermediate for blending treatment, dropwise adding 0.8 part of potassium persulfate, heating to 80 ℃, carrying out heat preservation treatment for 5 hours, cooling to room temperature, crushing and drying to obtain the maintenance material. The curing material was ball milled into 100 μm spherical particles using a ball mill.
Comparative example
Comparative example 1
The difference between this comparative example and example 1 is that in the organic-inorganic composite modified water absorbent resin type curing material, the mass ratio of metakaolin to water absorbent resin is 30:100; metakaolin is added to the monomer solution.
The method specifically comprises the following steps: and S3, dropwise adding N-N' methylene bisacrylamide into the monomer solution, adding metakaolin, blending, dropwise adding potassium persulfate, heating to 80 ℃, carrying out heat preservation for 5 hours, cooling to room temperature, crushing, and drying to obtain the maintenance material.
Comparative example 2
The difference between this comparative example and example 1 is that in the organic-inorganic composite modified water absorbent resin type curing material, the mass ratio of hexachlorocyclotriphosphazene to water absorbent resin is 10:100; hexachlorocyclotriphosphazene is added to the monomer solution.
The method specifically comprises the following steps: and S3, dropwise adding N-N' -methylene bisacrylamide into the monomer solution, adding hexachlorocyclotriphosphazene, blending, dropwise adding potassium persulfate, heating to 80 ℃, carrying out heat preservation for 5 hours, cooling to room temperature, crushing and drying to obtain the maintenance material.
Comparative example 3
The difference between the comparative example and the example 1 is that in the organic-inorganic composite modified water-absorbent resin curing material, the mass ratio of metakaolin, hexachlorocyclotriphosphazene and water-absorbent resin is 30:10:100; metakaolin and hexachlorocyclotriphosphazene are added to the monomer solution.
The method specifically comprises the following steps: and S3, dropwise adding N-N' methylene bisacrylamide into the monomer solution, adding metakaolin and hexachlorocyclotriphosphazene, blending, dropwise adding potassium persulfate, heating to react, heating to 80 ℃, preserving heat for 5 hours, cooling to room temperature, crushing and drying to obtain the maintenance material.
Comparative example 4
This comparative example differs from example 1 in that metakaolin was immersed in saturated CuSO 4 In the solution, the equal volume immersion adsorption is carried out for 0.5h, and Cu is measured 2+ 0.3wt.% of the total weight of metakaolin.
< test example >
Experiments were performed using examples 1 to 5 and comparative examples 1 to 4 as samples.
Sequentially adding the weighed machine-made sand, aggregate and cement into a stirrer for stirring until the materials are uniformly mixed, adding the water reducer and the mixing water for stirring, finally adding the curing material, uniformly blending the materials in the concrete to obtain the concrete, and casting and molding. The formulation of the concrete is shown in Table 1.
TABLE 1 concrete formulation (unit: kg/m) 3 )
Component (A) Cement and its preparation method Mineral powder Fly ash Machine-made sand Broken stone Water and its preparation method Water reducing agent Curing agent
Addition amount of 270 65 50 750 800 180 5.6 7.0
Performance test
(1) Compressive and flexural strength:
detecting the mechanical properties of the concrete by referring to GB/T50081-2002 standard of a common method for testing the mechanical properties of the concrete;
(2) Freeze thawing resistance: the freezing resistance of concrete is tested by adopting a rapid freezing tester according to JTGE30-2005 Highway engineering Cement and Cement concrete test procedure, the time for one freezing and thawing cycle is 2-5 hours, the freezing and thawing temperature is-18 ℃, and the size of a sample is 100mm multiplied by 500mm.
The test results are shown in Table 2.
Figure BDA0003233860730000131
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. The organic-inorganic composite modified water-absorbent resin type curing material is characterized in that the curing material is obtained by forming a coordination intermediate by aluminosilicate loaded with transition metal ions and polyphosphazene, and carrying out free radical polymerization reaction on the coordination intermediate and raw material components of the water-absorbent resin; the mass ratio of the aluminosilicate loaded with the transition metal ions to the polyphosphazene to the water-absorbent resin is 20-50:5-20:100;
the polyphosphazene is at least one of hexachlorocyclotriphosphazene, hexaphenoxy cyclotriphosphazene or ethoxy pentafluoroetriphosphazene;
the raw material components of the water-absorbent resin are acrylic acid monomer, acrylamide monomer, cross-linking agent and initiator.
2. The organic-inorganic composite modified water absorbent resin curing material according to claim 1, wherein the transition metal ion comprises Fe 3+ 、Fe 2+ 、Ti 4+ 、Ni 2+ 、Cu 2+ 、Cr 3+ Or Zn 2+ At least one of them.
3. The organic-inorganic composite modified water absorbent resin curing material according to claim 1, wherein the aluminosilicate comprises at least one of metakaolin, low-calcium/no-calcium fly ash, low-calcium/no-calcium silica fume, blast furnace slag, volcanic ash, red mud, halloysite, coal gangue, or alkaline tailings.
4. The organic-inorganic composite modified water-absorbent resin curing material according to claim 1, wherein the preparation method of the aluminosilicate loaded with the transition metal ions comprises the steps of immersing the aluminosilicate in a salt solution containing the transition metal ions, carrying out isovolumetric impregnation and adsorption for 1-3 hours, and obtaining the aluminosilicate loaded with the transition metal ions through draining, drying and calcining.
5. The organic-inorganic composite modified water-absorbent resin curing material according to claim 4, wherein the drying condition is 75-110 ℃ and the drying time is 10-20 hours; and the calcination condition is that the temperature is raised to 380-500 ℃ at a temperature rising rate of 5 ℃/min, and the calcination is carried out for 1.5-4 hours.
6. The organic-inorganic composite modified water absorbent resin curing material according to claim 2, wherein the transition metal ions account for 0.5 to 3wt.% of the total weight of the aluminosilicate in the aluminosilicate loaded with the filter metal ions.
7. A method for producing the organic-inorganic composite modified water absorbent resin curing material as claimed in any one of claims 1 to 6, comprising the steps of:
s1, dispersing aluminosilicate loaded with transition metal ions in acetonitrile solution, adding the aluminosilicate into acetonitrile solution containing polyphosphazene and triethylamine to obtain mixed solution, placing the mixed solution into a high-pressure reaction kettle for reaction, washing and drying after the reaction to obtain a coordination intermediate;
and S2, carrying out free radical polymerization reaction on the coordination intermediate and raw material components of the water-absorbent resin to obtain a finished product.
8. The machine-made sand concrete for alpine regions, which is characterized by comprising the organic-inorganic composite modified water-absorbent resin type curing material as claimed in claim 1.
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