KR100938027B1 - An admixture for concrete, prepared using byproduct of petrochemical industry, and a method for preparation of the same - Google Patents

Abstract

The present invention relates to a concrete admixture prepared from by-products of the petrochemical industry, and more particularly, to a graft copolymerization using a by-product of the petrochemical industry as a monomer, as well as having excellent dispersibility and stability. The present invention relates to a method for producing a concrete admixture capable of imparting flow characteristics of cement and concrete system even in a small amount, and to a concrete admixture manufactured using the same.

Concrete admixture prepared according to the method of the present invention is easy to change the structure of the molecule, has a variety of properties depending on the molecular weight and molecular structure, not only has excellent dispersibility and stability, but also in a small amount flow characteristics of cement and concrete system It can be applied to various functional admixtures such as high performance-high flow-high strength as well as general AE water reducing agent. In addition, in the manufacturing process, the production cost of the manufacturing process due to incineration, which is a main treatment method of waste, and the secondary environmental pollution problem can be overcome.

Concrete, admixture, dispersant, industrial by-product, industrial waste, copolymerization

Description

Admixture for concrete, prepared using by product of petrochemical industry, and a method for preparation of the same}

The present invention relates to a concrete admixture prepared from by-products of the petrochemical industry, and more particularly, to a graft copolymerization using a by-product of the petrochemical industry as a monomer, as well as having excellent dispersibility and stability. The present invention relates to a method for producing a concrete admixture capable of imparting flow characteristics of cement and concrete system even in a small amount, and to a concrete admixture manufactured using the same.

In the petrochemical industry, industrial by-products have been generated in recent years with the increase in the amount of use and the range of use of polymer materials. Examples of such industrial by-products include industrial by-products generated from a methylmethacrylic acid (MMA) manufacturing process, a trinitrotoluene (TNT) manufacturing process, and a terephthalic acid (TPA) manufacturing process.

Since these industrial by-products are mainly sent to incinerators for incineration, there is a problem of waste treatment along with production of polymer materials. Moreover, incineration of these industrial by-products causes a large amount of water to incompletely burn and release greenhouse gases such as carbon dioxide, which causes another secondary environmental pollution problem.

In addition to incineration, various methods for the effective treatment or reuse of the industrial by-products have been studied, but not only new facility investment is required, but also problems such as the recovery rate of the produced material, the purity of the recovered material, and the recycling method thereof are difficult to put to practical use. .

Meanwhile, the admixture for concrete is a compound belonging to a chemical chemical as a fourth component following cement, water, and aggregate, and is widely used for improving the quality and workability of concrete. The properties of concrete are governed by fluidity and controlled by the dispersion of cement particles. In order to have a higher fluidity can be obtained by the addition of a superplasticizer, the role of the high fluidizing agent according to the increase in size and height of the building structure is becoming increasingly important. Chemical admixtures, such as AE and AE reducing agents, which have been used to improve the workability and durability of concrete since the 1940s, have problems such as poor water-reducing effect and poor hardening of cement depending on the amount added. In order to compensate for this, a high-performance water reducing agent, which is a kind of a new polymer surfactant, has been developed, and they are able to realize high fluidity and high strength of concrete because they are adsorbed on cement particles and exhibit high dispersibility.

The surfactant is used for various purposes, for example, it can be used for applications such as fiber salt, inorganic dispersant, dispersant for concrete, fluidizing agent and water reducing agent. The method for preparing the surfactant is hydrophilicity such as sulfonation, hydroxylation or esterification in order to prepare a non-aqueous alkylbenzene, naphthalene, etc. into a water-soluble salt having a dispersibility, that is, to introduce a hydrophilic group into the lipophilic material. The introduction process of the functional groups must be carried out essentially. The preparation of the above water-soluble salts as surfactants has a relatively severe reaction condition of 120 ° C. or more, and has to undergo a sulfonation process in which a large amount of toxic sulfuric acid gas is generated during the reaction process. There are many difficulties in the handling and operation of the process, which must be removed, resulting in waste.

In addition, according to Japanese Patent Application No. 58-38380, Japanese Patent Application No. 59-18338, Japanese Patent Application No. 5-11057, US Patent No. 4962173, US Patent No. 5290869 and US Patent No. 5362829, Cement admixtures prepared using copolymers have a lower slump loss but have a lower coagulation delay than the case of using naphthalene sulfonic acid formalin condensate salt or melamine sulfonic acid formalin high condensate salt. There is a problem.

Patent documents related to the manufacturing method of the admixture for concrete using conventional industrial by-products include Korean Patent No. 754610, Korean Patent No. 834589, Korean Patent Publication No. 10-2007-0103692. The methods disclosed in the above patent documents simply convert the methyl (-CH ₃ ) or hydroxyl (-OH) groups substituted by benzene, which is a major component of the industrial by-product, to convert into carboxyl groups (-COOH) and give hydrophilicity to concrete admixtures. How to use them. However, concrete admixtures prepared by the industrial by-products and oxidation reactions can be used only as a substitute for general water-reducing products, which are gradually decreasing in use, by simply converting a lipophilic group or a weak hydrophilic substituent to a high hydrophilic toothbrush. The disadvantage is that it is possible.

Therefore, to overcome the disadvantages of the method of simply converting the substituent to a hydrophilic substituent, such as a method for producing a concrete admixture using the industrial by-products, to prepare a concrete admixture having a multi-function, such as high strength-high flow-high durability In order to do this, it is necessary to carry out various structural changes of the surfactant.

Therefore, the present inventors have studied to overcome the disadvantages of the prior art as described above, the method using the conventional oxidation reaction by performing a graft copolymer (graft copolymer) method using the by-products generated in various petrochemical industry as a monomer Compared to the other, it is easy to change the structure of the molecule, has various characteristics according to the molecular weight and molecular structure, and has a good dispersibility and stability, and also a concrete admixture that can impart the flow characteristics of cement and concrete system in a small amount The present invention completed the present invention.

It is an object of the present invention to perform graft copolymerization using a by-product of the petrochemical industry as a monomer, thereby easily modifying the structure of the molecule, having various characteristics depending on the molecular weight and molecular structure agent, as well as having excellent dispersibility and stability. Another object of the present invention is to provide a method for preparing a concrete admixture capable of imparting flow characteristics of cement and concrete.

Another object of the present invention is to provide a admixture for concrete produced by the above production method.

In one embodiment, the present invention provides a method for producing a concrete admixture by performing graft copolymerization using by-products of the petrochemical industry as monomers.

As used herein, the term "by-product of the petrochemical industry" includes a compound having a carbonyl group (C = O), a compound having a sulfuric acid group (-SOx) by sulfation, or a compound having a nitric acid group (-NOx) by nitrification. Etc., but is not limited thereto. More specifically, the by-products of the petrochemical industry include benzoic acid, para-toluic acid, styrene oxide, 1,2-epoxy-phenoxypropane, glycidyl-2-methylphenyl ether, (2,3-epoxypropyl) benzene, 1-phenylpropylene oxide, stilbene oxide, 2- (or 3- or 4-) halo (eg chloro, fluorine, bromo, or iodo) stilbene oxide, benzyl glycidyl ether, C1-10 Straight or branched chain alkyl (e.g. methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, etc.) phenyl glycidyl ether, 4-halo (e.g. chloro , Fluoro, bromo, or iodo) phenyl glycidyl ethers and the like.

By-products of the petrochemical industry are by-products from the process of producing petrochemical products. Specifically, by-products generated during terephthalic acid production, phthalic acid production, isophthalic acid production, 2,6-naphthalene dicarboxylic acid production, trimellitic acid production, methacrylic acid production or nitrotoluene production Say

In a specific embodiment of the present invention, by-products generated during the process of preparing terephthalic acid (TPA), the process of preparing methacrylic acid (MMA), and the process of preparing nitrotoluenes were used.

The by-products of the present invention may be in the form of sludge or residue, and the like, but are not limited thereto.

As a preferred embodiment of the present invention, the by-product may use 5 to 95% by weight, preferably 30 to 80% by weight, more preferably 50 to 70% by weight of the total weight of the admixture for concrete produced.

As a preferred embodiment of the present invention, the method for preparing admixtures for concrete using by-products of the petrochemical industry may include the following steps:

Preparing a mixture in a neutral to alkaline pH range by adding a pH adjusting agent to a by-product of the petrochemical industry including an aromatic oxide;

Injecting a co-monomer into the pH-adjusted mixture; And

Adding a polymerization initiator to the mixture into which the co-monomer is added and copolymerizing it.

As a preferred embodiment of the present invention, the pH adjuster used may be any solution as long as it has basic properties, such as sodium hydroxide (caustic soda), potassium hydroxide, calcium hydroxide, or a combination thereof.

In a preferred embodiment of the present invention, adjusting the by-products in a neutral to alkaline state may include adding a pH adjuster such that the material in the suspension solution state in which the fine particles are dispersed becomes a pH until the fine particles are in solution. This can be done by. The pH range is pH 5.0 to 14.0, preferably pH 6.0 to 12.0, more preferably pH 8.0 to 11.0, most preferably pH 10.0.

In a preferred embodiment of the present invention, the method for producing a concrete admixture is 5 to 5 while maintaining the pH adjusted mixture at a temperature of 20 ~ 100 ℃ before the step of adding a co-monomer (co-monomer) to the pH adjusted mixture Stirring for 60 minutes may be further included.

In the present invention, as a co-monomer used for graft copolymerization

Monocarboxylic acid monomers such as acrylic acid, methacrylic acid, C1-C6 alkylmethacrylic acid and crotonic acid, anhydrides and salts thereof;

Dicarboxylic acid monomers such as maleic acid, itaconic acid and fumaric acid, anhydrides and salts thereof;

Sulfonic acid monomers such as metharyl sulfonic acid and p-methacryloxybenzene sulfonic acid, anhydrides and salts thereof;

Methoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol polypropylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol polypropylene Glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, n-propoxy polyethylene glycol (meth) acrylate, n-propoxy polyethylene glycol polypropylene glycol (meth) acrylate, isopropoxy polyethylene glycol C1-C6 alkoxypolyC2-C6 alkylene glycol (meth) acrylates, such as mono (meth) acrylate and isopropoxy polyethylene glycol polypropylene glycol (meth) acrylate;

PolyC2-C6 alkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, and polypropylene glycol (meth) acrylate; And

Methoxypolyethoxyethyl (meth) acrylate, ethoxypolyethoxyethyl (meth) acrylate, n-propoxypolyethoxyethyl (meth) acrylate, isopropoxypolyethoxyethyl (meth) acrylate C1-C6 alkoxypolyethoxyethyl (meth) acrylates, such as these, can be used.

In this case, the salt may be an alkali metal salt, an alkaline earth metal salt, a trivalent metal salt, an ammonium salt, or an organic amine salt.

In addition, these co-monomers may be used alone or in combination of two or more.

In the present invention, a general initiator may be used as the polymerization initiator, and is not limited. Examples of such a polymerization initiator include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate; Hydrogen peroxide; Azo compounds, such as azobis-2 methyl propionamidine hydrochloric acid and azoisobutylonitrile; Peroxides, such as a benzoyl peroxide, lauroyl peroxide, and cuman hydroperoxide, etc. can be mentioned, One or two or more of these can be used.

Further, in the present invention, as an accelerator together with a polymerization initiator, reducing agents such as sodium hydrogen sulfite, sodium sulfite, mohr's salt, sodium pyro sulfite, sodium formaldehyde sulfoxylate and ascorbic acid; One kind or two or more kinds of amine compounds such as ethylenediamine, sodium ethylenediamine tetraacetate, and glycine may be used in combination.

In the present invention, a chain transfer agent during copolymerization may be used as necessary. As a chain transfer agent, a general thing can be used and it does not specifically limit, For example, a mercap propionic acid, a mercap propionic acid 2-ethylhexyl ester, a oxic acid 2-mel cap ethyl ester, a 1,8- dimalcap-3,6- Dioxaoctane, decanthriolol, dodecyl multicaptan, nucleodecanethiol, decanthiol, carbon tetrachloride, 4-brocarbon, α-methylstyrene dimer, talpinorene and the like, and one or two or more of these may be used. .

In the present invention, the temperature of the copolymerization reaction can be adjusted differently depending on the active temperature of the co-monomer used, specifically, about 50 to 120 ℃ is not limited thereto.

In this invention, there is no big restriction | limiting in the time of dripping (adding) a polymerization initiator, and it is not a big problem if dripping time is between 30 minutes and 5 hours.

In one preferred embodiment, the present invention comprises the steps of adjusting the pH to a neutral or alkaline state by adding a pH regulator to the by-products of the petrochemical industry; Injecting a co-monomer into the pH-adjusted mixture; Copolymerizing by adding a polymerization initiator to the mixture into which the co-monomer is added; And further mixing any one or more additives selected from the group consisting of an air entrainer, a slump holding agent, an antifoaming agent, a fastening agent, a retardant, a bleeding inhibitor, a water reducing agent, an air freshener, and a fireproofing agent. Can provide.

The air entraining agent, the slump holding agent, the antifoaming agent, the fastening agent, the retardant, the bleeding inhibitor, the water reducing agent, the fragrance or the refractory agent may be selected and used suitably for the use of the concrete admixture to be produced. For example, an air entrainer is added to the concrete admixture prepared by the present invention to impart an air entraining effect, a slump retainer to impart slump retention performance, and an antifoaming agent to impart defoaming action, It is to add a fastener to induce quenching, a retarder to induce condensation retardation of concrete, a bleeding inhibitor to suppress bleeding of large concrete, and a water reducing agent to increase the susceptibility. The air entraining agent, the slump holding agent, the antifoaming agent, the fastening agent, the retardant, the bleeding inhibitor, the water reducing agent, the fragrance and the refractory agent may use a commercially available product.

In a preferred embodiment of the present invention, the additive is included in a proportion of 0.5 to 95% by weight, preferably 5 to 50% by weight, based on the total weight of the admixture for concrete.

As another aspect, the present invention provides a admixture for concrete produced by the above production method.

The concrete admixture prepared by the above method of the present invention is easy to change the structure of the molecule, has various properties depending on the molecular weight and molecular structure, and has excellent dispersibility and stability as well as flow properties of cement and concrete system in a small amount Can be given.

The present invention is easy to modify the structure of the molecule by graft copolymerization by using the by-product of the petrochemical industry as a monomer, has a variety of properties depending on the molecular weight and molecular structure, not only excellent dispersibility and stability but also in a small amount The concrete admixture that can impart the flow characteristics of cement and concrete system can be prepared, so that it is applicable to various functional admixtures such as high performance-high flow-high strength as well as general AE water reducing agent. In addition, in the manufacturing process, the production cost of the manufacturing process due to incineration, which is a main treatment method of waste, and the secondary environmental pollution problem can be overcome.

Hereinafter, the present invention will be described in detail through production examples and examples. The following Preparation Examples and Examples are merely intended to describe the present invention in more detail, and are not intended to limit the present invention thereto.

Production Example  One

Prepare a device equipped with a thermometer, a stirrer, a nitrogen injector, a reflux cooler in a four-necked flask and inject 100 g of the substance in the form of sludge or suspension solution generated during the production process of terephthalic acid having the components shown in Table 1 above. An amount of caustic soda (NaOH, 50%) was added dropwise to prepare the material in neutral or alkaline state. An appropriate amount of caustic soda was sufficient to add a pH such that the substance in the suspension solution state in which the fine particles of Table 1 were dispersed became a solution in which the fine particles were not seen. The mixture was then warmed to 75 ° C. and stirred for 20 minutes in a nitrogen atmosphere while maintaining the temperature. Thereafter, 0.6 g of acrylic acid (AA, 99%) was slowly added dropwise to the mixture with a co-monomer, followed by stirring for 10 minutes. Potassium persulfate (K ₂ S ₂ O ₈ , 99%) 0.2g and 2.0 g of hydrogen peroxide (H ₂ O ₂ , 35%) were slowly added dropwise for 1 hour, and then reacted for 1 hour at 75 ° C. to obtain a final product.

Process residues generated during the production of terephthalic acid ingredient content % water 20.0 to 80.0 Benzoic acid 10.0-40.0 Terephthalic acid 5.0-20.0 Isophthalic acid 3.0 to 15.0 Para-toluic acid 0.5 to 7.5 Catalysts (cobalt, manganese), etc. 0.1 to 5.0

Production Example  2

Preparation Example 2 was carried out under the same conditions as in Preparation Example 1, but the final product was obtained using the same molar ratio of Ethyl acrylate (CH ₂ = CHCOOC ₂ H ₅ , 99%) instead of Acrylic acid.

Production Example  3

Preparation Example 3 was carried out under the same conditions as in Preparation Example 1, but the final product was obtained using the same molar ratio of Methyl methacylate (CH ₂ = C (CH ₃ ) COOCH ₃ , 99%) instead of Acrylic acid.

Production Example  4

Preparation Example 4 was carried out under the same conditions as in Preparation Example 1, but a final product was obtained using 2.4 g of acrylic acid (CH ₂ = CHCOOH, 99%) as a co-monomer instead of 0.6 g.

Production Example  5

Preparation Example 5 was carried out under the same conditions as in Preparation Example 1, but one of the polymerization initiators, Potassium persulfate (K ₂ S ₂ O ₈ , 99%) was used instead of 0.2g to obtain the final product.

Production Example  6

Preparation Example 6 was carried out under the same conditions as in Preparation Example 1, except that 10.0 g of hydrogen peroxide (H ₂ O ₂ , 35%), which is one of the polymerization initiators, was used instead of 2.0 g to obtain a final product.

Production Example  7

Preparation Example 7 was carried out under the same conditions as in Preparation Example 1, but one of the polymerization initiators, Potassium persulfate (K ₂ S ₂ O ₈ , The final product was obtained using the same molar ratio of Ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ , 98%) instead.

Production Example  8

Preparation Example 8 is carried out under the same conditions as in Preparation Example 1, but instead of the sludge generated during the process of preparing terephthalic acid or a suspension solution, the meta methacrylate having a component as shown in Table 2 The final product was obtained using 100 g of material in sludge or suspension solution.

Process residues that occur during the production of methacrylate ingredient content % water 20.0 to 80.0 Methmethylcrylic acid 10.0-40.0 Terephthalic acid 5.0-40.0 Other monomer 5.0 to 30.0 Other oligomer 5.0 to 30.0 Catalyst residue (diatomaceous earth), etc. 5.0-20.0

Production Example  9

Preparation Example 9 was carried out under the same conditions as in Preparation Example 1, but the sludge generated during the production process of nitrotoluenes having the components shown in Table 3 in place of the sludge generated during the production process of the terephthalic acid or the suspension solution. B. The final product was obtained by using 100 g of the material in suspension.

Process residues generated during nitrotoluene manufacturing process ingredient content % water 5.0 to 80.0 Dinitrocresol 5.0 to 50.0 Dinitrotoluene 5.0 to 80.0 Mononitrotoluene 5.0 to 60.0 Other salts 5.0-20.0

Production Example  10-19

By using the preparations prepared in Preparation Examples 1 to 9 (Preparation Examples 11-19) and naphthalene sulfonic acid formaldehyde condensates (PNS, Preparation Example 10), which are used as high-performance dispersants in the existing market, as shown in Table 4 below. The admixtures for concrete of Preparation Examples 10 to 19 were prepared, respectively, and their physical properties were compared.

Admixture Composition for Concrete (Manufacturing Example 10-19), Unit: g PNS Ca-Lig Na-Lig SG AE Admixture derived from industrial by-product water G Preparation Example 10 250 200 400 50 20 - 80 1,000 Preparation Example 11 - 200 400 50 20 Preparation Example 1: 250 80 1,000 Preparation Example 12 - 200 400 50 20 Preparation Example 2: 250 80 1,000 Preparation Example 13 - 200 400 50 20 Preparation Example 3: 250 80 1,000 Preparation Example 14 - 200 400 50 20 Preparation Example 4 250 80 1,000 Preparation Example 15 - 200 400 50 20 Preparation Example 5 250 80 1,000 Preparation Example 16 - 200 400 50 20 Preparation Example 6: 250 80 1,000 Preparation Example 17 - 200 400 50 20 Preparation Example 7 250 80 1,000 Preparation Example 18 - 200 400 50 20 Preparation Example 8: 250 80 1,000 Preparation Example 19 - 200 400 50 20 Preparation Example 9: 250 80 1,000 [Note] PNS: Naphthalene sulfonic acid formaldehyde condensate-based admixture Ca-Lig: Calcium Lignisulfonate-based admixture Na-Lig: Sodium Lignisulfonate-based admixture SG: Sodium Glyconate-based admixture

Example  1-10: Comparison of Properties of Inventive Admixtures in Concrete

Exemplary materials and the concrete mixture used in Example 1-10 was used as Ssangyong Cement normal portland cement 365kg / m ^3, water, sand is 175kg / m ^3, including the instructor 891kg / m ^3, coarse aggregate 934kg / m ³ and AE water-reducing agent . The amount of each product added from Preparation Examples 10 to 19 used in the concrete system of Example 1-10 was 0.6% by weight based on the cement solids.

Table 5 below shows the results of measuring physical properties of the concrete and the hard concrete of Example 1-10. The slump and air volume test was performed immediately after the concrete mixing due to the physical properties of the concrete that did not harden. As the physical properties of the hard concrete, the curing temperature is shown in Table 5 by measuring the compressive strength of 3 days, 7 days, 28 days of age at 20 ℃.

additive Slump (cm) Air volume (%) Compressive strength according to age (kgf / cm ² ) Immediately After 40 minutes Immediately After 40 minutes 3 days 7 days 28 days Example 1 Preparation Example 10 14.0 10.0 4.5 3.5 108.1 170.5 258.3 Example 2 Preparation Example 11 15.0 12.0 4.2 4.1 115.2 175.2 274.2 Example 3 Preparation Example 12 15.0 14.5 4.3 4.1 120.1 180.3 286.9 Example 4 Preparation Example 13 15.5 12.5 4.5 4.3 117.5 172.1 261.0 Example 5 Preparation Example 14 16.5 14.0 4.3 4.1 128.0 189.6 291.5 Example 6 Preparation Example 15 16.0 13.5 4.0 4.2 125.5 198.5 292.1 Example 7 Preparation Example 16 16.0 13.0 4.2 4.0 123.3 179.2 285.6 Example 8 Preparation Example 17 15.5 12.5 4.3 4.0 118.2 180.0 263.2 Example 9 Preparation Example 18 15.0 12.0 4.0 4.1 112.3 171.8 264.1 Example 10 Preparation Example 19 14.5 12.0 4.3 4.0 110.2 169.2 267.5

As can be seen from Table 5 showing the measurement results of the slump, the air volume and the slump and the air volume over time, which are physical properties of the concrete, the high-performance dispersant used in the existing market (Production Example 10, Example 1). The slump of the concrete mixing system using the concrete admixture prepared by the invention was excellent, and the change over time was also small (Examples 2-10). In the results according to the co-monomer morphology (Examples 2-4), there was no significant difference in the initial slump value, but when Ethyl acrylate was used as the co-monomer, the retention performance was excellent with little change over time. In both the results according to the amount of co-monomer added (Examples 2 and 5) and the results according to the amount of polymerization initiator added (Examples 2, 6 and 7), the initial slump and retention performance were better as the amount added. Confirmed. The results according to the type of polymerization initiator (Examples 2 and 8) showed similar results regardless of the type of polymerization initiator.

On the other hand, even in the compressive strength results according to the age of the physical properties of the hard concrete concrete results of the concrete admixtures (Examples 2-10) of the present invention more excellent than the high performance dispersant (Example 1) used in the existing market It was confirmed that the copolymerization method using the monomer was effective in increasing the strength. And as the amount of the added co-monomer and polymerization initiator increases, it was confirmed that the excellent strength was expressed (Examples 2-7).

In addition to the by-products of terephthalic acid (TPA) manufacturing in the petrochemical industry, by-products of manufacturing of methyl methacrylate (MMA) (preparation examples 18 and 9) and byproducts of nitro toluene (TNT) manufacturing (preparation 19, When Example 10) is used, the results of the characteristics of the hardened concrete and the hardened concrete showed similar results with the TPA manufacturing process by-products, and the results of the TPA manufacturing process by-products as well as the MMA manufacturing process by-products and the TNT manufacturing process by-products were similar. It was confirmed that high performance functional admixture processing is possible.

Through the above results, it was found that the admixture of the present invention can be applied to various functional admixtures such as high performance-high flow-high strength as well as general AE water reducing agent.

Claims (14)

Preparing a mixture in a neutral to alkaline pH range by adding a pH adjusting agent to the by-product of the petrochemical industry; Injecting a co-monomer into the pH-adjusted mixture; And Method of producing a concrete admixture comprising the step of copolymerizing by adding a polymerization initiator to the mixture in which the co-monomer is added. According to claim 1, wherein the by-product of the petrochemical industry is a compound having a carbonyl group (C = O), a compound having a sulfuric acid group (-SOx) by sulfation, and a compound having a nitric acid group (-NOx) by nitrification Method for producing a concrete admixture, characterized in that selected from the group consisting of. According to claim 1, The by-products of the petrochemical industry is terephthalic acid production process, phthalic acid production process, isophthalic acid production process, 2,6-naphthalene dicarboxylic acid production process, trimellitic acid production process, methacrylic acid production process And nitrotoluenes, and by-products generated in any one or more manufacturing processes selected from the group consisting of manufacturing processes. The method of claim 1, wherein the by-product is used in the concrete admixture, characterized in that 5 to 95% by weight of the total weight of the admixture for concrete produced. The method according to claim 1, wherein the pH adjusting agent is sodium hydroxide, potassium hydroxide, calcium hydroxide, or a combination thereof. The method of claim 1, wherein the pH range of the adjusted concrete admixture, characterized in that pH 5.0 to 14.0. The method of claim 1, wherein the co-monomer is selected from the group consisting of acrylic acid, methacrylic acid, C1-C6 alkylmethacrylic acid, crotonic acid, anhydrides and salts thereof; Maleic acid, itaconic acid, fumaric acid, anhydrides and salts thereof; Metharylsulfonic acid, p-metharyloxybenzenesulfonic acid, anhydrides and salts thereof; C1-C6 alkoxypolyC2-C6 alkylene glycol (meth) acrylates; PolyC2-C6 alkylene glycol mono (meth) acrylates; And A method for producing a concrete admixture, characterized in that at least one member selected from the group consisting of C1-C6 alkoxypolyethoxyethyl (meth) acrylates. The said C1-C6 alkoxypoly C2-C6 alkylene glycol (meth) acrylate is methoxy polyethyleneglycol (meth) acrylate, methoxy polyethyleneglycol polypropylene glycol (meth) acrylate, and methoxy Polypropylene glycol (meth) acrylate, Ethoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, n-propoxy polyethylene glycol (meth) acrylate, n-propoxy At least one member selected from the group consisting of polyethylene glycol polypropylene glycol (meth) acrylate, isopropoxy polyethylene glycol mono (meth) acrylate, and isopropoxy polyethylene glycol polypropylene glycol (meth) acrylate Method for preparing concrete admixtures. The method of claim 7, wherein the poly C2-C6 alkylene glycol mono (meth) acrylates are polyethylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, and polypropylene glycol (meth) Concrete admixture manufacturing method characterized in that at least one selected from the group consisting of acrylates. The said C1-C6 alkoxypolyethoxyethyl (meth) acrylate is a methoxy polyethoxyethyl (meth) acrylate, an ethoxy polyethoxyethyl (meth) acrylate, n-propoxy. A method for producing a concrete admixture, characterized in that at least one member selected from the group consisting of polyethoxyethyl (meth) acrylate and isopropoxypolyethoxyethyl (meth) acrylate. The method of claim 1, wherein the polymerization initiator is ammonium persulfate, sodium persulfate, calcium persulfate, hydrogen peroxide, azobis-2methylpropionamidine hydrochloride, azoisobutylonitrile, benzoyl peroxide, lauroyl fur Oxide, and the concrete admixture manufacturing method characterized in that at least one member selected from the group consisting of cuman hydroperoxide. The method of claim 1, further comprising, after the step, further mixing any one or more additives selected from the group consisting of an air entrainer, a slump maintainer, an antifoaming agent, a fastener, a retardant, a bleeding inhibitor, a water reducing agent, an air freshener, and a fireproofing agent. Concrete admixture manufacturing method comprising a. 13. The method of claim 12, wherein the additive is included in a proportion of 0.5 to 95% by weight based on the total weight of the concrete admixture. delete