JP6103838B2 - Soil erosion prevention method using ionic polymer fine particles - Google Patents

Description

The present invention relates to a soil erosion prevention method for preventing soil scattering and preventing soil erosion due to rainfall or inundation.

The soil may be temporarily contaminated due to the leakage of hazardous substances after waste disposal sites and factories and after the fact. When soil is contaminated with contaminants such as heavy metals and harmful organic substances, it is necessary to immediately decontaminate the soil. However, the soil left until this decontamination work has a problem that granular particles such as earth and sand are scattered by the wind from the surface portion, and pollutants are scattered with the soil in the neighboring area. . In addition, in the case of bare ground or slopes where grass and trees do not grow, the soil is easily eroded by rainfall or water inundation, and there is a high risk of diffusing harmful substances.

With regard to such contaminated soil, it is necessary to prevent soil erosion due to wind, etc., and soil erosion due to rain and inundation until the decontamination work is completed. If the contamination range is narrow, a simple method such as covering with a blue sheet can be used.However, in an environment where the range is large and dangerous and cannot be worked for a long time, the method of fixing soil is effective. is there. Therefore, a method is known in which an aqueous emulsion or the like is sprayed on the soil surface and solidified to prevent the soil from scattering (Patent Document 1). Although this method can firmly solidify the soil surface after spraying, it has the effect of preventing soil scattering, but the polymer component is washed away little by little by rain or inundation, and long-term soil fixation can be achieved. It was difficult. When a large amount of time is required for decontamination work, it is necessary to fix the soil for a long period of time. Therefore, there is a strong demand for a chemical agent that has a function of preventing soil scattering and can prevent soil erosion due to rainfall or inundation.
Non-Patent Document 1 discloses a method in which a polyion complex having a positive charge, a negative charge and a polyion complex dissolved in an aqueous solution having an appropriate salt concentration is applied to the soil. A satisfactory result is not obtained, and there is a problem that it takes time to prepare the polyion complex solution and the working efficiency is lowered.
JP 2004-8897 A "Removal of radioactive cesium from soil surface using polyion complex as a fixing agent", Japanese Atomic Energy Society, Japanese Journal, Vol. 10, no. 4, p. 227-234 (2011)

This invention is made | formed in view of the said situation, The objective provides the soil erosion prevention method which can prevent scattering of soil over a long period of time and can prevent the erosion of the soil by rain or inundation. There is.

As a result of intensive studies, the present inventors have obtained a dispersion of ionic polymer particles containing a polysaccharide and produced by dispersion polymerization, and a mixed dispersion solution containing a cationic polymer or a polycondensation polymer and an inorganic salt. It was found that the problem can be achieved by spraying on the soil surface, and the present invention has been achieved.

According to the soil erosion prevention method of the present invention, soil can be stably fixed for a long period of time, so that scattering due to wind can be prevented and soil erosion due to rainfall or flooding can be prevented.

Hereinafter, the present invention will be described in detail. The mixed aqueous dispersion used in the soil erosion prevention method of the present invention is a combination of a ionic polymer fine particle dispersion containing a polysaccharide and produced by dispersion polymerization and a cationic polymer or a polycondensation polymer, both The above polymer is mixed with an aqueous solution containing inorganic salts, and the mixed dispersed aqueous solution is sprayed on the soil surface.

The ionic polymer fine particle dispersion of the present invention prepares an aqueous solution of a polyvalent anion salt such as ammonium sulfate, in which a polysaccharide and a water-soluble anionic monomer, and if necessary, a water-soluble nonionic monomer It is possible to synthesize a body by dispersing a polymer dispersing agent soluble in the aqueous salt solution as a dispersing agent, and dispersing and polymerizing with stirring.

As the polysaccharide used in the present invention, various known ones can be used, for example, corn, potato, tapioca, wheat, rice, sago palm, various starches obtained from waxy maize, celluloses, cationization Starch derivatives such as starch, oxidized starch, phosphoric acid-modified starch, carboxymethylated starch, hydroxyethylated starch, carbamylethylated starch, dialdehyde-modified starch, acetic acid-modified starch, etc. Chitosan etc. are mentioned.

The addition ratio of the polysaccharide used in the present invention to the monomer (mixture) is 1 to 50% by mass, preferably 5 to 25% by mass.

The ionic polymer fine particle used in the present invention contains 2 to 100 mol% of the anionic monomer represented by the general formula (1) and 0 to 98 mol% of the copolymerizable nonionic monomer. A copolymer obtained by polymerizing a monomer or a monomer mixture.
General formula (1)
R ₁ is hydrogen, methyl group or carboxymethyl group, A is SO ₃ , C ₆ H ₄ SO ₃ , CONHC (CH ₃ ) ₂ CH ₂ SO ₃ , C ₆ H ₄ COO or COO, R ₂ is hydrogen or COOY ₂ , Y ₁ or Y ₂ represents hydrogen or a cation, respectively.

The anionic monomer represented by the general formula (1) may be a sulfonic acid group-containing monomer, but is preferably a single monomer mainly composed of a carboxyl group-containing monomer or a carboxyl group-containing monomer. A body mixture is suitable. Examples of the carboxyl group-containing monomer are methacrylic acid, acrylic acid, itaconic acid, maleic acid or p-carboxystyrene. Further, the anionic polymer may be a copolymer with another nonionic monomer. For example, (meth) acrylamide, N, N-dimethylacrylamide, vinyl acetate, acrylonitrile, methyl acrylate, 2-hydroxyethyl (meth) acrylate, diacetone acrylamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide And acryloylmorpholine, which is a copolymer of one or more selected from these water-soluble anionic monomers and one or more selected from nonionic monomers. The most preferred combination is acrylic acid and acrylamide.

The copolymerization molar ratio of an anionic monomer is 2-100 mol%, Preferably it is 5-80 mol%. Furthermore, the copolymerization mol% of the water-soluble nonionic monomer that can be copolymerized is 0 to 98 mol%, preferably 20 to 95 mol%. A cationic monomer may be contained to such an extent that the effect of the ionic polymer fine particles is not inhibited, and the copolymerization molar ratio is in the range of 0 to 20 mol%. Examples of cationic monomers include tertiary amino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide and salts thereof. A cationic monomer is mentioned. Also, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminopropyldimethylbenzylammonium chloride, (meth) acryloyloxy-2 -Quaternary ammonium base-containing cationic monomers such as hydroxypropyltrimethylammonium chloride.

The anionic group of the ionic polymer fine particle dispersion of the present invention may be neutralized with an alkaline substance such as sodium hydroxide, but is preferably not neutralized.

The product form of the ionic polymer fine particle dispersion of the present invention is a dispersion in salt water. The salt water dispersion type is a dispersion of ionic polymer fine particles obtained by coexisting a soluble polymer dispersant in an aqueous solution containing inorganic salts and performing dispersion polymerization under stirring. The salt water dispersion type is characterized by being insoluble in water in the acidic to neutral range.

Inorganic salts used to form an aqueous salt solution include salts of alkali metal ions such as sodium and potassium, ammonium ions, halide ions, sulfate ions, nitrate ions, phosphate ions, etc. And the salt is more preferable. Particularly preferred are divalent anion salts such as ammonium sulfate, sodium sulfate and aluminum sulfate. The salt concentration of these salts can be used from 7% by mass to saturation concentration.

As the polymer dispersant soluble in the aqueous salt solution, either a nonionic or ionic polymer can be used, but an ionic polymer is more preferable.

Examples of anionic polymers used as polymer dispersants include anionic monomers such as (meth) acrylic acid, maleic acid, itaconic acid, acrylamide 2-methylpropanesulfonic acid styrenesulfonic acid, and salts thereof. (Co) polymer. Further non-ionic monomers such as acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N, N-dimethylacrylamide, acrylonitrile, diacetone acrylamide, 2-hydroxyethyl (meth) acrylate, etc. Copolymers with can also be used. Other examples include anion-modified polyvinyl alcohol, styrene / maleic anhydride copolymer, butene / maleic anhydride copolymer, or partially amidated products thereof. The most preferred ionic polymer is 2-acrylamido-2-methylpropanesulfonic acid polymer.

Cationic polymers used as polymer dispersants include (meth) acrylic cationic monomers such as inorganic acids and organic acids such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylamide. Or a copolymer of quaternary ammonium salt and acrylamide with methyl chloride or benzyl chloride. For example, as the cationic monomer, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxy 2-hydroxypropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxy Ethyldimethylbenzylammonium chloride, (meth) acryloyloxy 2-hydroxypropyldimethylbenzylammonium chloride, (meth) acryloylaminopropyldimethylbenzylammonium chloride, and the like. These monomer polymers or copolymers, or A copolymer with a nonionic monomer may be used. Also, diallylamine-based (co) polymers such as dimethyldiallylammonium chloride polymer can be used.

The molecular weight of the ionic polymer used as the polymer dispersant is 5,000 to 3,000,000, preferably 50,000 to 1,500,000. The molecular weight of the nonionic polymer is 1,000 to 1,000,000, preferably 1,000 to 500,000. The amount of these polymer dispersants added to the monomer is 1/100 to 30/100, preferably 5/100 to 20/100.

In the present invention, a monomer having a plurality of vinyl groups can coexist as appropriate to form a crosslinked or branched polymer. Examples of such polyfunctional monomers having a plurality of vinyl groups include methylene bisacrylamide, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and the like. Thermally crosslinkable monomers such as N, N-dimethylacrylamide or N, N-diethylacrylamide can also be used.

The temperature at the time of superposition | polymerization is 5-75 degreeC, Preferably it is 15-45 degreeC. When the temperature is higher than 75 ° C., it is difficult to control the polymerization, and a rapid temperature rise or agglomeration of the polymerization solution occurs, so that a stable dispersion is not generated.

For the initiation of polymerization, a radical polymerization initiator is used. These initiators may be either oil-soluble or water-soluble, and can be polymerized by any of azo, peroxide, and redox systems. Examples of oil-soluble azo initiators are 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2-methylpropionate), 4,4-azobis (4-methoxy-2,4dimethyl) valeronitrile and the like are mentioned and dissolved in a water-miscible solvent and added.

Examples of water-soluble azo initiators include 2,2′-azobis (amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] And dihydrochloride, 4,4′-azobis (4-cyanovaleric acid), and the like. Examples of redox systems include combinations of ammonium peroxodisulfate with sodium sulfite, sodium hydrogen sulfite, trimethylamine, tetramethylethylenediamine, and the like. Further examples of peroxides include ammonium or potassium peroxodisulfate, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, and t-butylperoxy 2-ethylhexanoate. I can give you. Most preferred among these initiators are 2,2′-azobis (amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazoline), which is a water-soluble azo initiator. -2-yl) propane] dihydrochloride.

The weight average molecular weight of the ionic polymer fine particles is in the range of 500,000 to 5,000,000, preferably 1,000,000 to 3,000,000.

The cationic polymer used in the present invention is a polymer containing the monomer represented by the general formula (2) or (3) as an essential component.
General formula (2)
R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are alkyl or hydroxyalkyl groups having 1 to 3 carbon atoms, R ₄ is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 7 to 20 carbon atoms or aryl a group, may be the same or different, a is oxygen or NH, B represents an alkylene group or an alkoxylene group having 2 to 4 carbon atoms, X ₁ ^- represents respectively an anion.

General formula (3)
R ₅ represents hydrogen or a methyl group, R ₆ and R ₇ represent an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and X ₂ ⁻ represents an anion.

Examples of the tertiary amino group-containing cationic monomer among the cationic monomers represented by the general formula (2) or (3) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, Examples thereof include dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, and salts thereof. Examples of quaternary ammonium base-containing cationic monomers include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyl. Examples include aminopropyldimethylbenzylammonium chloride and (meth) acryloyloxy 2-hydroxypropyltrimethylammonium chloride. Examples thereof include allylamine, diallylmethylamine and salts thereof, diallyldimethylammonium chloride and the like. It is also possible to use a combination of a plurality of these cationic water-soluble monomers. The copolymerization molar ratio of the cationic monomer is 10 to 100 mol%, preferably 30 to 100 mol%, and more preferably 50 to 100 mol%. The range of the weight average molecular weight of the cationic polymer is 10,000 to 2,000,000, preferably 100,000 to 1,000,000.

Polycondensation polymers may be used in place of the above cationic polymers, such as monomethylamine, dimethylamine, monoethylamine, diethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine. Etc. and epichlorohydrin condensate, or those obtained by further condensing the above aliphatic amine / epichlorohydrin condensate with ethylenediamine, diethylenetriamine, triethylenetetramine or hexamethylenediamine. Further, as other cationic polymers, polyethyleneimine, polyvinylamine, polyamidine and the like may be used. The weight average molecular weight of the polycondensation polymer is in the range of 1,000 to 100,000, preferably 1,000 to 10,000. The weight average molecular weight of polyethyleneimine is in the range of 500 to 150,000, preferably 1000 to 100,000. The weight average molecular weight of polyvinylamine is in the range of 1 million to 10 million, preferably 3 million to 7 million. The weight average molecular weight of polyamidine is in the range of 1 million to 10 million, preferably 2 million to 6 million.

In the present invention, it is necessary to mix the ionic polymer fine particle dispersion and the cationic polymer in an aqueous solution containing inorganic salts for the purpose of spreading to the soil. Examples of the inorganic salts used here include ammonium sulfate, sodium sulfate, sodium chloride, potassium chloride, and the like, and ammonium sulfate is particularly preferable.

The total content of the ionic polymer fine particle dispersion and the cationic polymer contained in the mixed dispersion is 0.1 to 10% by mass, preferably 0.5 to 6% by mass, more preferably 1 to 4% by mass. If the content is too large, the viscosity of the solution is large and the permeability to the soil is poor, and if the content is too small, the strength of soil fixation becomes small. The pure mass ratio of the ionic polymer fine particles to the cationic polymer is 1: 4 to 4: 1. Further, the content of the inorganic salts in the mixed dispersion is 0.1 to 5% by mass, preferably 0.5 to 3% by mass.

The viscosity of the mixed dispersion is desirably in the range of 1 to 100 mPa · s (measured at 25 ° C. with a B-type viscometer), more preferably in the range of 1 to 30 mPa · s. If the viscosity is too large, the penetration into the soil will worsen and the strength of soil fixation will be reduced.

The method for spraying the mixed dispersion of the present invention on the soil is not particularly limited, and it can be sprayed by a conventionally known method using a shower nozzle, a sprayer, a sprinkler, or the like. In consideration of workability at the time of spraying, spraying efficiency, and the like, it may be further diluted with water as necessary.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Synthesis Example 1 Deionized water: 109.2 g, 60% acrylic acid: 22.7 g, 50% acrylamide: 80 in a four-necked 500 ml separable flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube 0.7 g, ammonium sulfate 64.0 g, phosphated starch powder: 5.4 g (10% by weight of monomer) and 15% by weight aqueous solution of acrylamide 2-methylpropanesulfonic acid sodium salt polymer (molecular weight: 300,000) 18 0.0 g (5% by mass of monomer) was added. Thereafter, nitrogen is introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature is adjusted to 30 ° C. using a constant temperature water bath. Thirty minutes after the introduction of nitrogen, 0.275% by weight of an aqueous solution of 0.2% by weight ammonium peroxodisulfate and 0.2% by weight aqueous solution of ammonium hydrogensulfite was added in this order, respectively, to initiate polymerization. 2 hours after the addition of the initiator, the viscosity of the reaction liquid slightly increased but did not increase any more. After 6 hours from the start of polymerization, the same amount of the initiator was added, and the polymerization was continued for another 15 hours. finished. This prototype is designated as prototype 1. The molar ratio of acrylic acid / acrylamide in trial production 1 was 25/75, and the viscosity was 470 mPa · s.

(Synthesis example 2) It carried out by the method similar to the synthesis example 1 except not having added phosphate esterified starch powder. This prototype is designated as prototype 2.

(Samples 1 to 3)
Using Sample 1 obtained in Synthesis Example 1 as an ionic polymer fine particle dispersion, mixed dispersion samples 1 to 3 in which a cationic polymer and inorganic salts are mixed are prepared and shown in Table 1. Content represents each mass% in the aqueous solution sample. The following items were evaluated using the mixed dispersion samples 1-3.

(Table 1)

(Comparative samples 1 to 3)
Mixed dispersion comparison samples 1 to 3 shown in Table 2 were prepared. The content represents each mass% in the mixed dispersion sample. The following items were evaluated using the mixed dispersion comparative samples 1 to 3.

(Table 2)

550 g of sand containing about 4% water was spread in a polypropylene container having a radius of 7 cm and a height of 3 cm, and the mixed dispersion samples 1 to 3 shown in Table 1 were evenly sprayed on the sand surface. Then, it was dried with a dryer at 50 ° C. for 24 hours, and the solidified sand was taken out of the container and used as a mixed dispersion sample. The mixed dispersion sample was evaluated in each of four stages according to the method described below. The results are shown in Table 3.

(Evaluation of solidification of fixed soil)
The state of solidification of the mixed dispersion sample when taken out from the container was evaluated in four stages.
1: It was solidified almost without collapse 2: There was a part that collapsed a little, but most was solidified 3: Half was broken 4: Most was broken

(Evaluation of water resistance of fixed soil)
The state when the mixed dispersion sample was immersed in water was evaluated in four stages.
1: Almost no cracks occurred 2: Slightly cracked, partially collapsed 3: Cracked, about half collapsed 4: Cracks occurred, most collapsed

(Comparative example)
550 g of sand containing about 4% of water was spread in a polypropylene container having a radius of 7 cm and a height of 3 cm, and the mixed dispersion samples 1 to 3 shown in Table 2 were evenly sprayed on the sand surface. Then, it was dried with a dryer at 50 ° C. for 24 hours, and the solidified sand was taken out of the container and used as a mixed dispersion sample. The mixed dispersion sample was evaluated in each of four stages in the same manner as in Example 1. The results are shown in Table 3.

(Table 3)

From the results of Example 1 and Comparative Example, by using a mixed dispersion of an ionic polymer fine particle dispersion and a cationic polymer produced by dispersion polymerization containing a polysaccharide, the fixing strength and water resistance are improved. An excellent method for preventing soil erosion can be provided.

Claims (5)

The soil erosion prevention method characterized by spraying the mixed dispersion liquid containing following (A), (B), (C) on the soil surface.
(A) Disperse at least one polysaccharide in an aqueous salt solution, 2 to 100 mol% of an anionic monomer represented by the following general formula (1), a nonionic monomer 0 to copolymerizable 0 An ionic polymer fine particle dispersion obtained by subjecting a monomer or monomer mixture containing 98 mol% to dispersion polymerization under stirring in the presence of a soluble polymer dispersant in the aqueous salt solution.
(B) the following general formula (2) or the monomer mixture polymerized cationic high content child containing monomer as an essential represented by (3).
(C) Inorganic salts.
General formula (1)
Where R ₁ is hydrogen, methyl group or carboxymethyl group, A is SO ₃ , C ₆ H ₄ SO ₃ , CONHC (CH ₃ ) ₂ CH ₂ SO ₃ , C ₆ H ₄ COO or COO, R ₂ is hydrogen or COOY ₂ , Y ₁ or Y ₂ represents hydrogen or a cation, respectively
General formula (2)
R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are alkyl or hydroxyalkyl groups having 1 to 3 carbon atoms, R ₄ is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 7 to 20 carbon atoms or aryl a group, may be the same or different, a is oxygen or NH, B represents an alkylene group or an alkoxylene group having 2 to 4 carbon atoms, X ₁ ^- represents respectively an anion.
General formula (3)
R ₅ represents hydrogen or a methyl group, R ₆ and R ₇ represent an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and X ₂ ⁻ represents an anion. The anionic monomer of the general formula (1) is one or more selected from (meth) acrylic acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, or a salt thereof. Item 2. A method for preventing soil erosion according to Item 1. Formula (2) or the cationic high content child of (3) is, polydiallyldimethyl ammonium chloride, acrylamide - diallyldimethylammonium chloride copolymer, poly (meth) acryloyloxyethyl trimethyl ammonium chloride, acrylamide - (meth) acryloyloxyethyl trimethylammonium chloride copolymer, poly (meth) acryloyloxyethyl dimethyl benzyl ammonium chloride, acrylamide - a (meth) acryloyloxyethyl dimethyl benzyl ammonium chloride copolymer, is at least one selected additive al The method for preventing soil erosion according to claim 1. The method for preventing soil erosion according to claim 1, wherein the inorganic salt according to claim 1 is at least one selected from ammonium sulfate, sodium sulfate, and sodium chloride. The method of preventing soil erosion according to claim 1, wherein the polysaccharide according to claim 1 is starch.