JPH0816221B2 - Method for producing waterproofing agent - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a waterproofing agent.

More specifically, the present invention relates to an improvement in a method for producing a waterproofing agent, which is a combination of a water-soluble polymerizable monomer (hereinafter referred to as a monomer), a redox catalyst and an alkaline hydraulic cement in the presence of an aqueous medium.

The waterproofing agent composition obtained by the method of the present invention forms a water-insoluble elastic gel body, stabilizes the ground, and is used for general civil engineering and construction work such as prevention of spring and leakage of water in the ground, and a cable. It is preferably used for preventing infiltration of water or leakage in pipe facilities such as pipes and sewer pipes.

[Prior Art] As a ground stabilization or water-stopping agent chemical using a water-soluble monomer, acrylamide type, methylol acrylamide type, (meth) acrylate type, etc. have been conventionally known. Various compositions based on (di) (meth) acrylic acid esters have been proposed. (JP-B-57-15631, JP-A-61-231)
081, JP-A-62-22882, US Pat. No. 4,295,762, etc.). Further, JP-A-62-34977 proposes to use hydraulic cement together.

As a catalyst for polymerizing these water-soluble monomers and gelling, a redox-based catalyst in which a reducing agent and an oxidizing agent are combined is used.

[Problems to be solved by the invention]

However, the base polyethylene glycol (di)
A liquid obtained by mixing (meth) acrylic acid esters, a reducing agent component of a redox catalyst and an alkaline hydraulic cement and a liquid B containing an oxidizing agent component of a redox catalyst are mixed to obtain a water blocking agent. The method has the following problems.

1) Mixing solution A with alkaline hydraulic cement,
If the elapsed time from the addition of cement to the mixing with solution B exceeds 15 minutes, the drug solution will not gel.

2) A chemical solution containing a water-soluble monomer and an alkaline hydraulic cement has little effect immediately after the cement is added, but
The gelation time of the drug solution tends to be delayed with time.

3) From the above, stable gelation time cannot be obtained. 4) When preparing and injecting a large amount of drug solution, there is a difference in gelation time between the early and late stages of injection. It will be difficult to carry out reliable construction.

The present inventors have found a method for producing a waterproofing agent capable of forming a high-strength gel body, which does not cause gelation, even when an alkaline hydraulic cement is used, to obtain a constant gelling time. Various studies were conducted to provide the information, and it was found that the object can be achieved by the method shown below, and the present invention was completed.

[Means for solving problems]

That is, the present invention "in the production of a waterproofing agent comprising a combination of a water-soluble polymerizable monomer, a redox catalyst and an alkaline hydraulic cement in the presence of an aqueous medium, the water-soluble polymerizable monomer Of at least one of polyethylene glycol di (meth) acrylic acid ester (hereinafter referred to as component-A) represented by the following formula (1) or a monomer component copolymerizable with component-A and component-A A mixture, a chemical solution-A containing a reducing agent component of a redox-based catalyst and an alkaline hydraulic cement, and a chemical solution-B containing an oxidizing agent component of a redox-based catalyst were separately prepared, and the resulting chemical solutions were obtained. A method for producing a waterproofing agent, which comprises mixing -A with a drug solution -B within 15 minutes after preparation.

Equation _{(1): CH 2 = C} (R 1) -CO-O - (- CH 2 -CH 2 -
O-) m-CO-C ( R 2) = CH 2, ( formula (1), R ¹ and R ² is a hydrogen atom or a methyl group, also, m is an integer of 2 to 50.) " Is the gist.

 The present invention will be described below.

The (di) (meth) acrylic acid ester of polyethylene glycol (hereinafter referred to as PEG) is used as the water-soluble monomer as the base of the water blocking agent in the present invention.

PEG di (meth) acrylic acid esters (hereinafter referred to as component-
A) is a diacrylate or dimethacrylate of PEG and is hereinafter referred to as PEG di (meth) acrylate. Component -A has the formula _{(1): CH 2 = C} (R 1) -CO-O - (- CH 2 -CH 2 -O-) m-CO-C (R 2) = CH 2, ( formula ( 1), R ¹ and R ^{2 each} represent a hydrogen atom or a methyl group, and m represents an integer of 2 to 50), and specific examples thereof include diethylene glycol di (meth) acrylate and triethylene glycol di. (Meth) acrylate, tetraethylene glycol di (meth) acrylate, PEG # 350 di (meth) acrylate, (# is
Means (-CH ₂ -CH ₂ -O-) average molecular weight of m-. The same shall apply hereinafter), PEG # 600 di (meth) acrylate, PEG # 100
Examples include 0 di (meth) acrylate and PG # 2000 di (meth) acrylate.

In the present invention, the component-A having an average addition mole number of ethylene oxide in the range of 2 to 50 is used. When the number of added moles is less than 2, the strength of the gel obtained is reduced, which is not preferable. On the other hand, when it exceeds 50, the gelled product is not sufficiently crosslinked, which is not preferable.

The PEG mono (meth) acrylic acid esters (hereinafter referred to as component-B) used in the present invention is a monoacrylate or monomethacrylate of PEG, and is hereinafter referred to as PEG mono (meth) acrylate. Ingredient-
Of B, equation _{(2): CH 2 = C} (R 3) -CO-O - (- CH 2 -CH 2 -O-) n-H,
(In the formula (2), R ³ represents a hydrogen atom or a methyl group,
n represents an integer of 2 or more), and specific examples thereof include diethylene glycol mono (meth).
Acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, PEG # 350 mono (meth) acrylate, PEG # 6
00 Mono (meth) acrylate, PEG # 1000 Mono (meth) acrylate, PEG # 2000 Mono (meth) acrylate, PEG #
6000 mono (meth) acrylate etc. can be mentioned.

In the present invention, as the component-B, those having an ethylene oxide addition mole number of 2 or more may be used within a range in which water solubility is not lost. Further, polypropylene glycol monoacrylate, methoxy polyethylene glycol monomethacrylate, ethyldiethylene glycol acrylate, methyltriethylene glycol acrylate, etc. may be added as long as the water solubility is not lost.

The base of the waterproofing agent in the present invention is component-A alone or a mixture of component-A and component-B (mixing ratio ... component-A: 100-0.1 parts by weight relative to component-B: 0- 99.9 parts by weight)
As the component-A or the component-B, a single compound or a mixture of the compounds represented by the formula (1) or the formula (2) can be used.

These bases are preferably used as an aqueous solution having a concentration of 3 to 60% by weight.

Further, as long as the characteristics of the present invention are not lost, the component-
As the monomer component copolymerizable with A, anionic or cationic monomers and water-soluble monovinyl or divinyl compounds may be added alone or as a mixture.

Examples of the anionic monomer include (meth) acrylic acid and salts thereof, 2-acrylamido-2-methylpropanesulfonic acid and salts thereof, and the like. As the salt, alkali metal salts such as sodium and potassium,
An ammonium salt, a salt with a cationic monomer, or a salt thereof can be used as a complex salt.

Examples of the cationic monomer include dimethylaminoethyl (meth) acrylate, a salt thereof and a quaternary compound thereof,
Diethylaminoethyl (meth) acrylate, its salts and their quaternary compounds, dimethylaminopropyl (meth)
Examples thereof include acrylamide, a salt thereof and a quaternary product thereof, diethylaminopropyl (meth) acrylamide, a salt thereof, a quaternary product thereof and the like.

The salt is a salt of an inorganic acid such as hydrochloric acid or sulfuric acid, or a salt with an anionic monomer, and the quaternary compound is a quaternary compound such as methyl chloride or dimethyl sulfate.
Alternatively, it can be used as a complex salt thereof.

Water-soluble monovinyl compounds include (meth) acrylamide and methylol (meth) acrylamide, and divinyl compounds include methylenebisacrylamide, ethyleneureabisacrylamide, 1,3-di (acrylamidomethyl) -2-imidazolidone, Hexahydro-1,3,5-triacryloyl-S-triazine, glycerol diacrylate and the like can be mentioned.

As the reducing agent component of the redox catalyst used in the present invention, ferrous sulfate, potassium hydrogen sulfite, sodium hydrogen sulfite, ammonium hydrogen sulfite, lithium sulfite, potassium sulfite, sodium sulfite, ammonium sulfite, sodium thiosulfate, Rongalit, Chelating agents that form stable complexes with ferrous sulfate in the presence of tertiary amines or alkaline substances-for example, oxyacids such as tartaric acid, citric acid, malic acid, lactic acid or their alkali metal salts, succinic acid, nitrilo. Combinations of triacetic acid and the like, and various amines such as dimethylaminopropionitrile, dimethylaminoethanol, dimethylaminopropanol, triethanolamine, nitrilotrispropionamide, triethylamine, trimethylamine, N, N, N , Tertiary amines such as N'-tetramethylethylenediamine, secondary amines such as diethanolamine, morpholine and piperazine, polyethylenepolyamines such as triethylenetetramine and tetraethylenepentamine, polyethyleneimine, dimethylaminoethylated polyacrylamide, Examples thereof include polymeric amines such as polydimethylaminoethyl methacrylate, and triethanolamine, ferrous sulfate, and combinations of ferrous sulfate and a chelating agent are preferably used. These reducing agent components may be used alone or in combination of two or more.

Examples of the oxidant component of the redox catalyst include ammonium persulfate, sodium persulfate, potassium persulfate, ammonium perchlorate, sodium perchlorate, potassium perchlorate, hydrogen peroxide, and the like. It is preferably used.

The amount of the redox-based catalyst may be appropriately determined according to the desired gelling time, but the amount of the redox-based catalyst in the present invention is used after the chemical liquids A and B are mixed.
The amount is preferably such that it can gel within 15 minutes.For example, in order to obtain a gelling time within a few seconds to 15 minutes at a temperature of 20 to 25 ° C., usually 100 parts by weight of the water-soluble monomer,
Amounts of catalyst ranging from 0.1 to 100 parts by weight may be used.

When the amount of catalyst is such that the gelling time exceeds 15 minutes, when the drug solution-B containing the cement and the drug solution-A containing the water-soluble monomer are mixed, gelation does not occur depending on the amount of the alkaline hydraulic cement.

Examples of the alkaline hydraulic cement used in the present invention include ordinary Portland cement, early strength Portland cement, super early strength Portland cement, moderate heat Portland cement, high-oxidation iron type Portland cement, white Portland cement and other Portland cements, blast furnace cement.・ Mixed cement such as silica cement, fly ash cement, masonry cement,
Special cements such as alumina cement, ultra rapid hardening cement (jet cement), colloidal cement, expansive cement, oil well cement, grout cement, sludge solidifying agent, cement for hazardous substance solidification treatment, high sulfate slag cement, etc. These can be used alone or in admixture of two or more. Considering the dispersibility of the particles and the prevention of the clogging trouble of the injection device at the time of construction, the average particle size of these particles is preferably 100 μm or less.

The amount of alkaline hydraulic cement used in the present invention is the total amount of water used in the chemical liquid-A and the chemical liquid-B 10
The amount is 10 to 200 parts by weight, preferably 50 to 150 parts by weight, relative to 0 parts by weight.

If it is less than 10 parts by weight, the effect of increasing the strength of the gel body is small, while if it exceeds 200 parts by weight, the strength of the gel body increases, but the fluidity of the chemical liquid deteriorates and it becomes difficult to handle with a pump. Not preferable.

The viscosity of chemical liquid-B is 10 as the value measured by a B-type viscometer.
00cps or less, preferably 800cps or less, more preferably 400
It should be adjusted to cps or less. If the viscosity exceeds 1000 cps, handling with a pump is difficult and the chemicals are not sufficiently mixed, so that a non-uniform gel body is formed, which is not preferable.

In the present invention, the chemical liquid-cement 150k per B100
When g or more is added, it is preferable to add a water reducing agent for the purpose of preventing the viscosity of the drug solution-B from increasing and making it difficult to handle with a pump.

Examples of the water reducing agent used in the present invention include polyalkylallyl sulfonate, lignin sulfonate, polycarboxylate, melamine formalin resin sulfonate,
Examples thereof include a polyol complex, an oxycarboxylic acid salt, and a creosote oil sulfonic acid condensate. These can be used alone or in combination of two or more.

The amount of water reducing agent used is 0.1 to 100 parts by weight of cement.
It is in the range of 10 parts by weight, preferably 0.1 to 2 parts by weight. 0.1
If it is less than 10 parts by weight, the effect of decreasing the viscosity of the slurry is small, while if it is used in excess of 10 parts by weight, the effect of decreasing the viscosity does not increase so much, which is not economical.

In the present invention, one or more kinds of water-soluble polymer substance and polymer latex can be used as other additives.

Examples of water-soluble polymer substances include starch, gelatin,
Natural polymers such as glue, tragacanth gum, agar and gum arabic, methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, or their modified natural polymers such as alkali metal salts and alginates, polyvinyl alcohol, polyvinylpyrrolidone, acrylic acid or methacrylic acid Polymers of the above, alkali metal salts thereof, polyacrylamide, polyethylene oxide and the like.

As the polymer latex, natural rubber latex;
Styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), chloroprene, synthetic rubber latex such as methyl methacrylate-butadiene rubber; acrylic ester type, vinyl acetate type, ethylene-vinyl acetate copolymer type, vinylidene chloride- Examples thereof include various aqueous polymer dispersions such as synthetic resin emulsions such as vinyl chloride copolymer system.

These are used for keeping the chemical solution at an appropriate viscosity and dispersing the cement particles to prevent sedimentation. In addition,
When A and -B are mixed, the viscosity of the mixed solution is lowered, and when the gelation time is short, the sedimentation of the cement particles is small and there is no problem. Since a uniform gel body is formed, if it is added to the drug solution-A in order to prevent this, the waterproof / waterproof performance and the adhesiveness can be further improved.

The amount of the water-soluble polymer substance used is 0.05 to 5 parts by weight, preferably 0.1 to 100 parts by weight of the alkaline hydraulic cement.
The range of 1 to 1 part by weight is preferable.

If it is less than 0.05 parts by weight, the viscosity is low and the dispersibility of cement particles is poor, and the gel body becomes non-uniform and stable strength cannot be obtained. If it exceeds 5 parts by weight, the dispersibility of the cement particles will be improved, but the viscosity becomes too high and injection becomes difficult, which is not preferable.

The amount of the polymer latex used is in the range of 1 to 30 parts by weight, preferably 5 to 20 parts by weight as a solid content, relative to 100 parts by weight of the alkaline hydraulic cement. If it is less than 1 part by weight, the effect of improving the adhesion to the underground buried object is small, while if it is used in excess of 30 parts by weight, the effect is not improved so much, which is uneconomical.

A metal rust preventive and a rust preventive for reinforced concrete can be added to the chemical solution of the present invention.

A metal rust preventive and a rust preventive for reinforced concrete can be added to the chemical solution of the present invention.

The method for preparing a chemical solution in the present invention is to prepare various raw materials in a predetermined amount ratio of a mixing / stirring device, add water and stir the mixture.
Mix and knead.

The above-mentioned materials may be in the form of powder or liquid, or those which have been mixed or dissolved in advance may be used, and these may be added in any order.

In the preparation of the drug solution in the present invention, an apparatus suitable for handling the raw materials to be used may be selected, and either a batch system or a continuous system may be adopted, and there is no limitation.

In any case, the time during which the water-soluble monomer is in contact with the alkaline hydraulic cement before the water-soluble monomer contained in the liquid-A is mixed with the liquid-B and the water-soluble monomer contained in the liquid-A is polymerized into a gel by the redox catalyst. Does not exceed 15 minutes.

When a large amount of chemical solution is required, it is preferable to use the continuous method. As an embodiment thereof, the prepared drug solution-A
So as not to exceed the retention time of 15 minutes, the raw material supply and the prepared drug solution-A withdrawing while balancing the feed amount of the drug solution-A with the device for preparing the drug solution-A and the withdrawal amount of the prepared drug solution-A. Parallel.

As a cement supply device, a device known as a powder quantitative supply device may be used.

As a device for mixing the chemical liquid-A and the chemical liquid-B, a device used in a normal chemical liquid injection method such as a stirring tank, a Y-tube, a pipe mixer or an injection pipe provided with a mixing device at the tip is used. be able to.

The drug solution-B may be prepared by a conventional method. In addition, the liquid chemical-A has type I and type I which show acidity or weak alkalinity.
Various anhydrous gypsum such as I type, III type, α type, β type hemihydrate gypsum,
Hydraulic cement that does not exhibit strong alkalinity, such as blast furnace slag, fly ash, and fumed silica, may be added.

[Effect of the present invention]

According to the method of the present invention, the gelling time of the drug solution can be stabilized and a gel body having high strength can be formed.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

. Example -1～12, Comparative Example-1 to 4 1) Preparation of drug solution: · A ₁ liquid ... water-soluble monomer (component -A, component -B, etc.) and the respective tables of the reducing agent of the redox catalyst - The mixture was mixed at the ratio shown in 1 and water was added to make 600.

· Chemical -A ... stirring mixing bath equipped with a raw material supply port and withdrawal of the drug solution (capacity: 5) to, the A ₁ solution at 10 / min, also using a screw type quantitative feeder 10 kg / Alkaline hydraulic cement was simultaneously supplied in parallel at a rate of minutes to prepare a slurry-like drug solution-A.

Chemical liquid-B ... 12 kg of potassium persulfate as an oxidizing agent for the redox catalyst was added with water to make 600, and cement was added to each in an amount ratio shown in Table 1 to prepare a slurry chemical liquid-B.

2) Mixing of chemicals and evaluation items: The chemicals-A and the chemicals-B obtained by preparing them separately were withdrawn from their respective mixing tanks at a temperature of 20 to 25 ° C by using a plunger pump, and the tip portions thereof were extracted. A pipe mixer (diameter: 12 mm, length: 1200 mm; 32 fluid mixing elements were internally installed) was installed in a double-tube injection pipe for mixing.

The gelling time of the drug solution obtained by mixing and the compressive strength of the gel body (1 day after gelling) were measured, and the results are shown in Table 1.

<Elapsed extraction time> in Table 1 indicates the elapsed time from the preparation of the A ₁ liquid to the mixing of the alkaline hydraulic cement and the start of the preparation of the drug liquid-A.

In the "gelation time" column in Table-1, "X" indicates that gelation did not occur even after 180 minutes or more after mixing the chemicals,
Moreover, in the column of "compressive strength of gel body", it is shown that the strength was not obtained.

Was fed at a rate of time each said A ₁ solution and cement blending tank of Example -1～12. Chemical -A. Table after starting supply of raw materials
During the signal shown in the "residence time" column in 1, the chemical solution-A is not withdrawn, and only the raw material is supplied. When the "residence time" has elapsed, the chemical solution-A is withdrawn. Starting, and thereafter, the extracted chemical liquid-A was mixed with the chemical liquid-B while the supply of the raw material and the extraction of the chemical liquid-A were performed in parallel by the above method.

The results are as shown in Table-1 until the preparation of the drug solution-A by mixing the alkaline hydraulic cement.
Even if the elapsed time in the state of A ₁ solution reaches 60 minutes, if the elapsed time from the preparation of the drug solution-A to the mixing with the drug solution-B is within 15 minutes, in any case, The gelling time of the drug solution and the compressive strength of the gel body showed stable values.

Examples-13 to 14 and Comparative Examples- _{1 to 2.} Liquid A ₁ and ordinary Portland cement were simultaneously supplied to the mixing tank of the drug solution-A at the above-mentioned speed for 25 seconds respectively, and the resulting drug solution-A was added to the tank. The solution was retained for 5 to 60 minutes, and then extracted by the above method and mixed with the chemical solution-B.

The results show that, as shown in Table-1, if the retention time of the drug solution-A is within 15 minutes, the gel time of the drug solution and the compressive strength of the formed gel body should be values that can be used as a water blocking agent. Indicated.

On the other hand, when the retention time of the drug solution-A exceeds 15 minutes, gelation is significantly delayed, and when the retention time exceeds 30 minutes, gelation does not occur even 180 minutes after mixing both solutions. ,
No strength was obtained even after 1 day had passed (Comparative Examples-1 to 1).
2).

Claims (1)

[Claims] 1. When producing a waterproofing agent comprising a combination of a water-soluble polymerizable monomer, a redox catalyst and an alkaline hydraulic cement in the presence of an aqueous medium, the water-soluble polymerizable monomer is used as the water-soluble polymerizable monomer. At least one kind of polyethylene glycol di (meth) acrylic acid ester represented by the following formula (1) (hereinafter referred to as component-A) or component-
A mixture of a monomer component copolymerizable with A and component-A, a chemical liquid-A containing a reducing agent component of a redox-based catalyst and an alkaline hydraulic cement, and an oxidizing agent component of the redox-based catalyst. A method for producing a waterproofing agent, which comprises separately preparing the drug solution-B and mixing the obtained drug solution-A with the drug solution-B within 15 minutes after the preparation. Formula (1): CH ₂ = C (R ¹ ) -CO-O-(-CH ₂ -CH ₂ -O) m-CO-C (R
² ) = CH ₂ , (in the formula (1), R ¹ and R ² represent a hydrogen atom or a methyl group, and m represents an integer of 2 to 50.)