CN113999680B - Organic polymer saline soil modifier and preparation method thereof - Google Patents
Organic polymer saline soil modifier and preparation method thereof Download PDFInfo
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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Abstract
The invention provides an organic polymer saline soil modifier and a preparation method thereof. The saline soil modifier consists of an organic polymer, an alkaline auxiliary agent, an acid regulator, a cross-linking agent and a stabilizer; the organic polymer is at least one of carboxymethyl cellulose, polyethylene glycol, polyacrylic acid, polyacrylamide, polyvinyl alcohol and polyethylene oxide, and accounts for 0.1-3% of the total mass of the modifier. The organic polymer salinized soil improver is mainly applied to improvement of salinized soil foundations of highway engineering in northwest arid and semi-arid regions, is combined with soil particles through hydrogen bonds and winding effects, has the characteristics of high strength and stable property, takes water as a solvent, and has the characteristics of low engineering cost, simple construction method, energy conservation and no pollution.
Description
Technical Field
The invention relates to an organic polymer saline soil improving agent and a preparation method thereof, belonging to the technical field of saline soil improvement.
Background
The climate in the northwest region of China belongs to the arid climate of continents in warm temperature zones, and the underground water level is buried deeply. The surface soil along the highway is mainly composed of degraded surface silt and silt. The saline soil mainly takes chlorine, sulfurous acid and sulfate saline soil as main materials, the saline soil forms the defects of swelling and cracking of a roadbed and a road surface, aggravation of roadbed frost heaving and slurry turning, settlement deformation during water immersion and the like, and the saline soil can cause corrosion of concrete structures, metals and other road facilities, thereby causing serious influence on highway engineering. CN109054855A discloses an improver suitable for low-salinity chlorine saline soil, which mainly comprises ionic rare earth slag powder, marble stone powder, cement, quicklime and calcium stearate. CN106495615A discloses a method for solidifying saline soil by in-situ polymerization of organic matters, which mainly takes acrylamide as a main component, and after soil improvement, the acrylamide and the soil are subjected to in-situ polymerization reaction through an initiator. The inorganic modifier in the method has the characteristics of large dosage and high mixing difficulty with the saline soil, while the organic in-situ polymerization method needs to be mixed with the saline soil for the second time and has harsh in-situ polymerization conditions, and the characteristics limit the large-scale improvement application of the saline soil.
Disclosure of Invention
The invention provides a saline soil modifier taking water-soluble organic polymer macromolecular composite material as a main component and a preparation method thereof, aiming at the problems of damage of saline soil to highway subgrade and improvement of the saline soil in northwest China.
The organic polymer saline soil modifier consists of an organic polymer, an alkaline assistant, an acid regulator, a cross-linking agent and a stabilizer; the organic polymer is at least one of carboxymethyl cellulose, polyethylene glycol, polyacrylic acid, polyacrylamide, polyvinyl alcohol and polyethylene oxide, and accounts for 0.1-3% of the total mass of the modifier.
The alkaline auxiliary agent is at least one of N, N-dimethylformamide, formamide, acrylamide and ethanolamine, and accounts for 0.1-3% of the total mass of the modifier.
The acid regulator is at least one of lactic acid, acetic acid, oxalic acid, citric acid, acrylic acid and maleic anhydride, and accounts for 0.1-3% of the total mass of the modifier.
The cross-linking agent is at least one of N, N methylene bisacrylamide, divinylbenzene and diisocyanate and accounts for 0.01-1% of the total mass of the modifier.
The stabilizer is glycerol and accounts for 0.1-3% of the total mass of the modifier.
The organic polymer saline soil modifier is mainly applied to improvement of saline soil subgrade of highway engineering in northwest arid and semi-arid areas, and the addition amount of the organic polymer saline soil modifier in saline soil is 0.5-10%. When the addition amount of the organic polymer saline soil modifier is 2.85 percent of the saline soil, the freeze-thaw cycle quality loss rate, the dry-wet cycle strength loss rate, the unconfined compressive strength, the compressive resilience modulus, the California bearing ratio and other performances of the modified saline soil are the best, the indexes are far better than those of the plain saline soil, and the road requirements of the saline soil base filler are completely met.
The preparation method of the organic polymer saline soil modifier comprises the following steps:
(1) Adding an alkaline assistant into water, fully stirring and dissolving at the stirring temperature of 25-50 ℃ to obtain an alkaline assistant solution, wherein the alkaline assistant mainly has the function of assisting in dissolving the organic polymer and simultaneously has a crosslinking function on the organic polymer;
(2) Adding an organic polymer into water, and fully stirring and dissolving at the temperature of 35-95 ℃ to obtain transparent sol, wherein chain-shaped macromolecules in the organic polymer can stabilize soil particles and salt;
(3) Adding the organic polymer sol obtained in the step (2) into the alkaline assistant solution obtained in the step (1), uniformly stirring to obtain a transparent mixed solution, adding a glycerol stabilizer into the mixed solution, stirring for dissolving to prepare a pre-modified solution, wherein the stirring temperature is 25-50 ℃;
(4) Adding an acid regulator into the mixed solution obtained in the step (3), fully stirring and dissolving to obtain a transparent viscous fluid, wherein the stirring temperature is 25-50 ℃;
(5) And (4) adding the cross-linking agent into the transparent viscous fluid obtained in the step (4), and stirring at 25-50 ℃ until the cross-linking agent is completely dissolved to obtain the organic polymer modifier.
Organic polymers in the organic polymer are crosslinked by reacting with an alkaline assistant, a stabilizer, an acid regulator and a crosslinking agent, so that a large number of polymer chains and primary network structures are formed in the salinized soil improver, active groups contained in the chain polymers and the primary network structures have high polarity and high reaction activity, and are easily combined with clay minerals containing-OH groups through hydrogen bonds to generate strong adsorption action, so that clay particles are connected together, a stable network structure bridged by the polymer chains is formed among the soil particles, the cementation action among the particles is enhanced, the soil particles form a whole body, the dispersion and migration of the clay particles are inhibited, and meanwhile, the polymer chain network structures can anchor and solidify salt segregants in the salinized soil through adsorption, wrapping and chelation actions, so that the salinized soil is stabilized for a long time, and the strength and the stability of the salinized soil improver are improved.
The invention has the beneficial effects that:
(1) The saline soil modifier provided by the invention is prepared by dissolving and compounding the organic polymer and other components which are hydrophilic organic matters with water, is simple in preparation method, and can be used for modifying saline soil by directly spraying the modifier on the saline soil, so that the saline soil modifier has the characteristics of simple construction method, energy conservation and no pollution.
(2) The saline soil modifier is combined with soil particles through hydrogen bonds and winding action to form a stable cross-linked network structure with semi-rigid combination, has the characteristics of high strength and stable property, and can reduce the road engineering cost in saline soil areas to a great extent due to higher strength and smaller using amount.
(3) The saline soil modifier has a good effect on modifying saline soil roadbed filling in road construction, and can also be used in the fields of modification of soil building materials in saline soil areas and protection of ancient cultural relics in soil ruins.
The specific implementation mode is as follows:
the organic polymer saline soil improver of the present invention and the preparation and properties thereof are further illustrated by the following specific examples.
Example 1
Firstly, adding 285 g of N, N dimethylformamide into 1100 g water, fully stirring for dissolving, wherein the stirring temperature is 25 ℃; adding 214 g organic polymer polyacrylamide into 1000 g water, fully stirring and dissolving the mixture at 35 ℃ to obtain transparent viscous sol, and adding the transparent viscous sol into an N, N dimethylformamide aqueous solution to obtain a transparent mixed solution; then adding 114 g glycerol stabilizer into the mixed solution, stirring and dissolving to prepare a pre-modified solution, wherein the stirring temperature is 35 ℃; and finally, adding 371 g acetic acid into the pre-modified solution, fully stirring for dissolving, adding 4 g divinylbenzene, and continuously stirring for about 1h at the temperature of 35 ℃ to obtain the organic polymer saline soil modifying agent. And adding the obtained modifier aqueous solution into the saline soil, wherein the modifier of the organic polymer saline soil accounts for 2.0 percent of the saline soil. The strength and stability of the improved saline soil are detected through tests such as unconfined compressive strength, freeze-thaw cycle, dry-wet cycle, compressive resilience modulus and the like, and specific results are shown in table 1.
Example 2
Firstly, 399 g acrylamide is added into 1250 g water, and the mixture is fully stirred and dissolved, wherein the stirring temperature is 25 ℃; adding 210 g organic polymer carboxymethyl cellulose into 800 g water, fully stirring and dissolving the mixture at 35 ℃ to obtain transparent viscous sol, and adding the transparent viscous sol into an acrylamide aqueous solution to obtain a transparent mixed solution; then adding 350 g glycerol stabilizer into the mixed solution, stirring and dissolving to prepare a pre-modified solution, wherein the stirring temperature is 35 ℃; and finally, adding 250 g citric acid into the pre-modified solution, fully stirring and dissolving, adding 2 g of N, N methylene bisacrylamide, and continuously stirring at 35 ℃ for about 1h to obtain the organic polymer modifier. And adding the obtained modifier aqueous solution into saline soil, wherein the organic polymer saline soil modifier accounts for 5.5% of the saline soil. The strength and stability of the improved saline soil are detected through tests such as unconfined compressive strength, freeze-thaw cycle, dry-wet cycle, compression resilience modulus and the like, and specific results are shown in table 1.
Example 3
Firstly, adding 335 g ethanolamine into 930 g water, fully stirring and dissolving, wherein the stirring temperature is 35 ℃; adding 105 g organic polymer polyvinyl alcohol into 1170 g water, fully stirring and dissolving the mixture at 95 ℃ to obtain transparent viscous sol, and adding the transparent viscous sol into an ethanolamine water solution to obtain a transparent mixed solution; then adding 230 g glycerol stabilizer into the mixed solution, stirring and dissolving to prepare a pre-modified solution, wherein the stirring temperature is 35 ℃; and finally adding 180 g oxalic acid into the pre-modified solution, fully stirring and dissolving, adding 2 g diisocyanate, and continuously stirring at 35 ℃ for about 1h to obtain the organic polymer modifier. And adding the obtained modifier aqueous solution into the saline soil, wherein the modifier of the organic polymer saline soil accounts for 0.8 percent of the saline soil. The strength and stability of the improved saline soil are detected through tests such as unconfined compressive strength, freeze-thaw cycle, dry-wet cycle, compressive resilience modulus and the like, and specific results are shown in table 1.
Example 4
Firstly, adding 405 g formamide into 1100 g water, and fully stirring for dissolving, wherein the stirring temperature is 35 ℃; adding 58 g organic polymer polyethylene oxide into 900 g water, fully stirring and dissolving the mixture at 55 ℃ to obtain transparent viscous sol, and adding the transparent viscous sol into formamide aqueous solution to obtain transparent mixed solution; adding 390 g glycerol stabilizer into the mixed solution, stirring and dissolving to prepare a pre-modified solution, wherein the stirring temperature is 35 ℃; and finally, adding 510 g acrylic acid into the pre-modified solution, fully stirring and dissolving, adding 5 g divinylbenzene, and continuously stirring at 35 ℃ for about 1h to obtain the organic polymer modifier. And adding the obtained modifier aqueous solution into saline soil, wherein the organic polymer saline soil modifier accounts for 7.5% of the saline soil. The strength and stability of the improved saline soil are detected through tests such as unconfined compressive strength, freeze-thaw cycle, dry-wet cycle, compression resilience modulus and the like, and specific results are shown in table 1.
Example 5
Firstly, 160 g acrylamide and 200 g formamide are added into 900 g water, fully stirred and dissolved, and the stirring temperature is 45 ℃; adding 295 g carboxymethyl cellulose and 120 g polyacrylic acid into 1200 g water, fully stirring and dissolving at 45 ℃ to obtain transparent viscous sol, and adding the transparent viscous sol into an aqueous solution of acrylamide and formamide to obtain a transparent mixed solution; adding 185 g glycerol stabilizer into the mixed solution, stirring and dissolving to prepare a pre-modified solution, wherein the stirring temperature is 45 ℃; finally, 210 g lactic acid is added into the pre-modified solution, 14 g of N, N methylene bisacrylamide is added after the lactic acid is fully stirred and dissolved, and the stirring is continued at the temperature of 45 ℃ for about 1 hour, so that the organic polymer modifier is obtained. And adding the obtained modifier aqueous solution into the saline soil, wherein the modifier of the organic polymer saline soil accounts for 1.2 percent of the saline soil. The strength and stability of the improved saline soil are detected through tests such as unconfined compressive strength, freeze-thaw cycle, dry-wet cycle, compression resilience modulus and the like, and specific results are shown in table 1.
Example 6
Firstly, 265 g of N, N-dimethylformamide and 150 g ethanolamine are added into 900 g water, and are fully stirred and dissolved, wherein the stirring temperature is 45 ℃; adding 180 g polyvinyl alcohol into 1300 g water, fully stirring and dissolving at 55 ℃ to obtain transparent viscous sol, then adding 200 g polyethylene glycol, stirring and mixing uniformly, and adding the mixture into N, N dimethylformamide and ethanolamine aqueous solution to obtain transparent mixed solution; then adding 100 g glycerol stabilizer into the mixed solution, stirring and dissolving to prepare a pre-modified solution, wherein the stirring temperature is 45 ℃; finally, 100 g acetic acid and 150 g crylic acid are added into the pre-modified solution, 20 g diisocyanate is added after the full stirring and dissolution, and the stirring is continued for about 1h at the temperature of 45 ℃, so that the organic polymer modifier is obtained. And adding the obtained modifier aqueous solution into the saline soil, wherein the modifier of the organic polymer saline soil accounts for 3.3% of the saline soil. The strength and stability of the improved saline soil are detected through tests such as unconfined compressive strength, freeze-thaw cycle, dry-wet cycle, compression resilience modulus and the like, and specific results are shown in table 1.
Example 7
Firstly, 265 g of N, N-dimethylformamide and 150 g acrylamide are added into 1000 g water, and fully stirred and dissolved, wherein the stirring temperature is 45 ℃; adding 320 g polyacrylamide and 100 g carboxymethyl cellulose into 1000 g water, fully stirring and dissolving at 65 ℃ to obtain transparent viscous sol, and adding the transparent viscous sol into N, N dimethylformamide and acrylamide aqueous solution to obtain transparent mixed solution; then adding 80 g glycerol stabilizer into the mixed solution, stirring and dissolving to prepare a pre-modified solution, wherein the stirring temperature is 45 ℃; finally, 110 g acetic acid, 60 g maleic anhydride and 210 g lactic acid are added into the pre-modified solution, after the mixture is fully stirred and dissolved, 5.7 g diisocyanate is added, and the mixture is continuously stirred at 45 ℃ for about 1h, so that the organic polymer modifier is obtained. And adding the obtained modifier aqueous solution into the saline soil, wherein the modifier of the organic polymer saline soil accounts for 6.4% of the saline soil. The strength and stability of the improved saline soil are detected through tests such as unconfined compressive strength, freeze-thaw cycle, dry-wet cycle, compression resilience modulus and the like, and specific results are shown in table 1.
Example 8
Firstly, adding 365 g ethanolamine into 800 g water, fully stirring for dissolving, wherein the stirring temperature is 45 ℃; adding 120 g polyvinyl alcohol into 1000 g water, fully stirring and dissolving at 45 ℃, then adding 100 g polyacrylamide into the polyvinyl alcohol solution, fully stirring and dissolving to obtain transparent viscous sol, and adding the transparent viscous sol into the ethanolamine aqueous solution to obtain a transparent mixed solution; then adding 280 g glycerol stabilizer into the mixed solution, stirring and dissolving to prepare a pre-modified solution, wherein the stirring temperature is 45 ℃; finally, 260 g citric acid is added into the pre-modified solution, 5.7 g diisocyanate is added after the full stirring and dissolution, and the mixture is continuously stirred for about 1h at the temperature of 45 ℃, so that the organic polymer modifier is obtained. And adding the obtained modifier aqueous solution into the saline soil, wherein the modifier of the organic polymer saline soil accounts for 8.6 percent of the saline soil. The strength and stability of the improved saline soil are detected through tests such as unconfined compressive strength, freeze-thaw cycle, dry-wet cycle, compressive resilience modulus and the like, and specific results are shown in table 1.
Example 9
Firstly, 150 g ethanolamine, 200 g acrylamide and 150 g formamide are added into 900 g water and are fully stirred and dissolved, and the stirring temperature is 45 ℃; adding 120 g polyethylene oxide and 220 g polyvinyl alcohol into 900 g water, fully stirring and dissolving at 55 ℃ to obtain transparent viscous sol, and adding the transparent viscous sol into an aqueous solution of ethanolamine, acrylamide and formamide to obtain a transparent mixed solution; then adding 450 g glycerol stabilizer into the mixed solution, stirring and dissolving to prepare a pre-modified solution, wherein the stirring temperature is 55 ℃; finally, 460 g maleic anhydride is added into the pre-modified solution, 13 g divinylbenzene is added after full stirring and dissolution, and the organic polymer modifier is obtained after stirring for about 1h at 50 ℃. And adding the obtained modifier aqueous solution into saline soil, wherein the organic polymer saline soil modifier accounts for 9.2% of the saline soil. The strength and stability of the improved saline soil are detected through tests such as unconfined compressive strength, freeze-thaw cycle, dry-wet cycle, compressive resilience modulus and the like, and specific results are shown in table 1.
Example 10
Firstly, 200 g of N, N-dimethylformamide, 200 g ethanolamine, 200 g acrylamide and 100 g formamide are added into 800 g water and are fully stirred and dissolved, and the stirring temperature is 45 ℃; adding 100 g polyacrylic acid and 210 g polyethylene glycol into 1200 g water, fully stirring and dissolving at 75 ℃ to obtain transparent viscous sol, and adding the transparent viscous sol into an aqueous solution of N, N dimethylformamide, ethanolamine and acrylamide to obtain a transparent mixed solution; then adding 360 g glycerol stabilizer into the mixed solution, stirring and dissolving to prepare a pre-modified solution, wherein the stirring temperature is 55 ℃; finally, adding 100 g acetic acid, 100 g citric acid and 100 g maleic anhydride into the pre-modified solution, fully stirring and dissolving, adding 13 g divinylbenzene, and continuously stirring at 50 ℃ for about 1h to obtain the organic polymer modifier. And adding the obtained modifier aqueous solution into the saline soil, wherein the modifier of the organic polymer saline soil accounts for 4.2 percent of the saline soil. The strength and stability of the improved saline soil are detected through tests such as unconfined compressive strength, freeze-thaw cycle, dry-wet cycle, compression resilience modulus and the like, and specific results are shown in table 1.
The above-mentioned embodiment is only one of the preferred proportions made according to the technical scheme of the invention, and does not limit the protection scope of the invention, therefore, the equivalent changes made according to the main components, preparation method, state, saline soil improvement scheme and principle of the improver of the invention all belong to the protection scope of the invention.
Claims (2)
1. An organic polymer saline soil modifier is characterized in that: the modifier consists of an organic polymer, an alkaline assistant, an acid regulator, a cross-linking agent and a stabilizer;
the organic polymer is at least one of carboxymethyl cellulose, polyethylene glycol, polyacrylic acid, polyacrylamide, polyvinyl alcohol and polyethylene oxide, and accounts for 0.1-3% of the total mass of the modifier;
the alkaline auxiliary agent is at least one of N, N-dimethylformamide, formamide, acrylamide and ethanolamine, and accounts for 0.1-3% of the total mass of the modifier;
the acid regulator is at least one of lactic acid, acetic acid, oxalic acid, citric acid, acrylic acid and maleic anhydride, and accounts for 0.1-3% of the total mass of the modifier;
the cross-linking agent is at least one of N, N methylene bisacrylamide, divinylbenzene and diisocyanate and accounts for 0.01-1% of the total mass of the modifier;
the stabilizer is glycerol and accounts for 0.1-3% of the total mass of the modifier.
2. A method of preparing the organic polymer saline soil improver of claim 1, comprising the steps of:
(1) Adding an alkaline auxiliary agent into water, fully stirring and dissolving, wherein the stirring temperature is 25-50 ℃, and obtaining an alkaline auxiliary agent solution;
(2) Adding an organic polymer into water, and fully stirring and dissolving at the temperature of 35-95 ℃ to obtain transparent sol;
(3) Adding the organic polymer sol obtained in the step (2) into the alkaline assistant solution obtained in the step (1), uniformly stirring to obtain a transparent mixed solution, adding a glycerol stabilizer into the mixed solution, stirring for dissolving to prepare a pre-modified solution, wherein the stirring temperature is 25-50 ℃;
(4) Adding an acid regulator into the mixed solution obtained in the step (3), fully stirring and dissolving to obtain transparent viscous fluid, wherein the stirring temperature is 25-50 ℃;
(5) And (4) adding the cross-linking agent into the transparent viscous fluid obtained in the step (4), and stirring at 25-50 ℃ until the cross-linking agent is completely dissolved to obtain the organic polymer saline soil modifier.
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| CN1331983C (en) * | 2004-06-15 | 2007-08-15 | 西北大学 | Water absorbing and preserving polymer soil protecting net film spray agent and its preparation |
| CN102516476B (en) * | 2011-12-05 | 2015-11-25 | 北京希涛技术开发有限公司 | The synthesis of two property ion Polymer soil amendment |
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