KR20060007610A - A manufacture method of highly efficient cement didpersion agant with antifoamer force and rised skill to drainage - Google Patents

Abstract

In the method for polymerizing and preparing polyalkylene glycol mono and (meth) acrylic acid ester monomers obtained by transesterification of polyalkylene glycol mono and (meth) acrylic acid, the optimum conditions for the selection and use of catalysts for the ester reaction It is to make inventions with improved functions that secure economic feasibility.

Inorganic acid salt in the mixture obtained by polymerizing polyalkylene glycol mono (meth) acrylic acid ester monomer by controlling the reaction time and removing the inorganic acid salt simultaneously with alkali neutralization after ester reaction by using the catalyst of ester reactant As the ratio of the alcohol and the hyalcohol is closer to the weight percent in the polyalkylene glycol mono (meth) acrylic acid, it is an invention to prepare a dispersant which can be used as a cement dispersant and economically and can obtain a blend containing waterproof and antifoaming power.

Parcel, waterproof, cement, dispersant, manufacturing method

Description

{A manufacture method of highly efficient cement didpersion agant with antifoamer force and rised skill to drainage}

The present invention relates to a high performance cement dispersion production method improved defoaming power and waterproof function.

In recent years, the safety and aggregate performance of concrete structures are reduced due to earthquakes. In order to solve various problems such as quality control of concrete and maintaining high dispersion and fluidity of concrete due to time delay of transportation process caused by traffic congestion in the city, ultra high performance dispersant High performance cement dispersant with improved anti-foaming and waterproofing ability to obtain a beautiful and safe structure by controlling high air continuity due to deterioration of concrete and aggregate degradation due to deterioration of aggregate and characteristics of polycarboxylic acid-based dispersant. It relates to a manufacturing method.

In addition, cement dispersing materials are largely divided into lignin, naphthalene, melanin, polycarboxylic acid, etc., and the susceptibility is 20% or more classified as a high-performance dispersant, and two or more carboxylic acid groups are given within thousands to tens of thousands of molecules. As a method of producing water-based polycarboxylic acid dispersions and admixtures that provide antifoaming and waterproofing functions, polyalkylene obtained by transesterification of methyl methacrylate by polymerization of hydrophilic polyalkylene glycol mono and (meth) acrylic acid A polycarboxylic acid cement dispersant consisting of a dispersant imparting a defoaming power and a waterproofing function, a cement, and water comprising a polymer obtained by polymerizing a monomer component comprising a lene glycol mono (meth) acrylic acid ester monomer.

In the prior art shown in the prior application No. 10-155071, polyalkylene glycol mono is prepared by polymerizing ester monomers of methyl methacrylate and poly alkylene glycol mono.

During this process, a large amount of methyl methacrylate is refluxed and inorganic salts and hyalcohols are used as catalysts.

This production method can control the reaction time according to the reaction substitution and disadvantageously remove the methanol in methyl methacrylate and remove the unreacted methyl methacrylate present in the reaction product, but the base and the hyalcohol used as a catalyst Is removed by substitution filtering.

A method for preparing polyalkylene glycol mono (meth) acrylate by the ester monomer method is disclosed in Patent 10-0247527, and a method of preparing methacrylate by transesterification of polyalkylene glycol mono and acrylic acid is known. The inventors remove the generated water generated by using an acid catalyst such as sulfuric acid, which is used as a catalyst, with solvent cyclohexane, but the weight ratio of unreacted polyalkylene glycol mono (meth) acrylate during the reaction due to excessive use of this solvent. It is described that the method is less than 5%, and the reaction time is not economical manufacturing method with more than 22 hours.

In addition, solvent cyclohexane and the like should also be removed after the reaction, and the method of inhibiting the product of the unreacted polyalkylene glycol mono (meth) acrylate shown in the conventional manufacturing method has not been specifically described.

There arises a problem that the content of such unreacted poly alkylene glycol mono acrylate determines the performance exhibiting cement dispersion performance.

According to the present invention, the polyalkylene glycol mono acrylate transesterification reaction is performed by copolymerizing an unsaturated carboxylic acid high alcohol and the like, and then adding and neutralizing a certain amount of a high molecular compound, thereby making it more functional than a conventional polycarboxylic acid-based dispersant. It is to provide a product with excellent cement dispersion and excellent antifoam resistance.

In the present invention, in the preparation of polyethylene glycol mono methacrylate, which is an ester monomer, ultra-high performance poly carbon having a constant antifoaming and water resistance while controlling the complete substitution reaction and reaction rate of unreacted polyalkylene glycol mono methacrylate. To prepare an acidic dispersant.

Formula 1

R ₁ O (R ₂ + O) n H

Wherein R ₁ represents a carbonyl group having 1-22 carbon atoms, R ₂ + O represents one or two or more mixtures of oxyalkylene groups having 2-4 carbon atoms, and n represents an average added mole number of the oxyalkylene group. Polyalkylene glycol mono acrylate represented by the numbers 1-100

(Formula 2)

R ₂

           │

CH₃-C- COOR ₄

In the above formula, R2 represents a hydrogen atom or a methyl group, and is transesterified by unreacted polyalkylene glycol mono and acrylate represented by an alkyl group having 1 to 22 carbon atoms.

(Formula 3)

           R₃

           │

CH₃ = C-COO (R ₂ O) nR ₄

In the above formula, R 1, R ₂ O.R 4, n are as described above, and represent an average added mole number.

When the amount of the inorganic salt catalyst such as sulfuric acid that uses the polyalkylene glycol mono (meth) acrylate represented as described above is small, the transesterification reaction rate is significantly slowed and the economic efficiency of the manufacturing process is lowered, thereby catalyzing a certain amount of hyalcohol. When used as, the polyalkylene glycol mono acrylate as a main raw material in the production of a polycarbonate-based cement dispersant affects the copolymerization reaction it can be seen that shortening the reaction time, maintaining the dispersibility, and the defoaming power and waterproofing effect.

As such, the present invention uses an inorganic acid catalyst and a hyalcohol through a transesterification reaction of an unsaturated carboxylic acid group (Chemical Formula 1) with unreacted polyalkylene glycol mono and acrylate (Chemical Formula 2), and uses a polyalkylene glycol mono (meth) acrylic compound. Copolymerization of the rate and an unsaturated carboxylic acid, to prepare an ultra high performance cement dispersant imparting antifoaming and waterproofing.

In the present invention, in the transesterification reaction for synthesizing poly alkylene glycol mono (meth) acrylate, the molar ratio of unsaturated carboxylic acid and alkylene glycol mono alkyl racer in the reaction raw material is preferably 1: 1-5: 1, preferably 1 1: 1: 1 is suitable.

In order to remove the generated water generated during the reaction, cyclohexane can be used which has azeotropes with the produced water. Examples include aromatic hydrocarbons such as benzene and toluene, alicyclic compounds such as cyclohexane, and aliphatic hydrocarbons such as n-hexane. .

Suitable catalysts for the transesterification reaction include sulfuric acid, paratoluene sulfonic acid, methane sulfonic acid, nitric acid, phosphoric acid, and the like, and 1-10% by weight of the amount of polyalkylene glycol monoalkyl racer administered in the reaction is more preferable. 2-8% by weight is suitable.

In addition, if the amount of the catalyst is too small, the reaction rate is remarkably lowered, which causes problems in economical efficiency. If the amount is too large, the polymerization reaction of the unsaturated carboxylic acid occurs.

In order to prevent the polymerization of the unsaturated carboxylic acid during the reaction, a polymerization inhibitor is used, and a known polymerization inhibitor such as hydroquinone and phenocyazine can be used.

As reaction temperature, 60-150 degreeC is suitable at normal pressure.

After the transesterification reaction was completed, the polymer compound was added and then depressurized after a certain time to remove cyclohexane and solvent, and water was added to the reaction product to prepare an aqueous solution such that the weight of the reaction product was 60-92% by weight. The acid catalyst present in the solution is neutralized to form a salt and then removed.

There are several ways to remove, and as an example, when a large amount of aqueous sodium hydroxide solution, such as an acid catalyst, is used, sodium sulfate is formed when sulfuric acid is a catalyst, and when left for a certain time, sodium sulfate is separated by layers and can be easily removed.

Another method is to add a solid salt such as Mgo, CaO to the aqueous solution of the reaction product to neutralize and precipitate the acid catalyst, and to remove the salt of the acid catalyst efficiently by filtering.

As described above, the reaction product from which the acid catalyst is removed is copolymerized with a polyalkylene glycol mono (meth) acrylate (Formula 3) and a methacrylate monomer to synthesize a final product of a cement dispersant.

Since the polyalkylene glycol mono methacrylate and methacrylic acid monomer are present at the same time in the reaction product prepared as described above, the reaction product can be copolymerized as it is, and other copolymerizable monomers can be added to perform the copolymerization reaction.

Examples of monomers that can be copolymerized include maleic acid, fumaric acid, polyethylene glycols, and allyl isomers. The molecular weight of the copolymer after copolymerization is preferably 5,000-50,000 when analyzed by gel permeation chromatography (GPC). .

More preferably, 8,000-28,000 are suitable.

In addition, the high alcohol having antifoaming power and the high molecular compound exhibiting waterproofing performance are high molecular compounds obtained by esterifying fatty acids with allyl alcohol.

As long as the polymerization initiator is water-soluble, general persulfates such as ammonium persulfate, sodium persulfate and potassium sulfate are suitable.

A chain transfer agent may be used as necessary for molecular weight control, and a known compound such as merceto propionic acid, merceto acetic acid, merceto propionic acid 2, and ethyl hexyl ester may be used as the chain transfer agent.

Co-polymerization reaction temperature is suitable 60-150 ℃, but 60-120 ℃ is preferred.

After the completion of the copolymerization reaction, neutralize with a basic substance such as alkali metal hydroxide, alkali earth metal hydroxide or amine so that the pH of the product is 5-7.5.

The cement dispersant containing the copolymer obtained as described above as a main component improves the dispersibility of the cement and the waterproofing effect of delayed hydration reaction when the cement composition is composed of cement and water.

At this time, when the 0-1,2% by weight of the weight of the polyethylene glycol mono methacrylate as described above, the dispersion capacity and the maintenance ability of the antifoam waterproofing of the cement dispersant is significantly improved.

Based on the above matters will be described in detail the present invention.

Example 1

Into a 3-liter glass reactor equipped with a stirrer, thermometer, cooling reflux, and reaction water separator, 750.5 g of polyethylene glycol mono having an average molecular weight of 500 was added first, 13 g of sulfuric acid, a reaction catalyst, and hydroquinone was added as a polymerization inhibitor. g is added to dissolve the hydroquinone completely.

Thereafter, 202 g of methacrylic acid was quantified and introduced into the reactor, 320 g of cyclohexane and 60.8 g of high alcohol were injected, and then the temperature was raised to directly start an ester reaction.

After confirming that a small amount of water generated, cyclohexane was removed from the reactor under reduced pressure and water was added to the reaction product to prepare a 92% aqueous solution.

20.6 g of 50 wt% caustic soda (NaOH) was added to the reaction product with water and stirred at room temperature to completely neutralize sulfuric acid used as a catalyst.

After neutralization is completed, the stirring is stopped for a while and the whole solution is injected into the separating funnel.

While the solution is held for a while, the sodium sulfate produced by neutralization is separated from the solution and liquid-separated at the bottom of the solution to form a layer of sodium sulfate.

After the phase separation is completed, the bottom sodium sulfate layer is removed from the separating funnel.

As described above, 28.2 g of acrylic acid and 24.4 g of methacrylic acid were added to 311 g of the ester reaction product from which the salt of the inorganic acid catalyst was completely removed, and 3.1 g of mercetoacetic acid was mixed with a chain transfer agent to prepare a co-polymerization mixture.

180 g of water was added to a glass reactor equipped with a stirrer, replaced with nitrogen, and the reaction temperature was maintained at 98 ° C.

After completing the above mixture in the reactor, 61.2 g of the polymer compound was added dropwise thereto, followed by further reaction for 1 hour and 20 minutes to terminate the copolymerization reaction.

After completion of the reaction, the product was neutralized with ca.

The salt of the residual inorganic acid catalyst after the completion of the copolymerization reaction was 0.8% by weight of the polyethylene glycol monomethacrylate weight.

The average molecular weight of the copolymer weight obtained at this time was 23,000.

Example 2

When neutralizing sulfuric acid, the inorganic acid catalyst of the ester reaction, Mgo powder, which is a solid salt instead of 50% caustic soda, may be used, and the method is the same as in Example 1.

6.8 g of Mgo powder was added to the aqueous 92% ester reaction product, followed by stirring. After confirming that the product was neutralized, the salts of Mgo and sulfuric acid were filtered and then copolymerized.

The weight average molecular weight of the cement dispersant prepared after the co-polymerization reaction was 25,000, and the salt of sulfuric acid, a catalyst which is an inorganic acid catalyst, was 0.13 g wt% of the weight of polyethylene glycol mono methacrylate.

Example 3

788 g of polyethylene glycol mono having a molecular weight of 1000 was added to the same reactor used in Example 1, and maintained at 98 ° C., followed by 16 g of sulfuric acid as a reaction catalyst.

Hydroquinone 1.58g was added as a polymerization inhibitor to dissolve it, 198g of methacrylic acid was added thereto, 385g of cyclohexane, 72.2g of high alcohol, and the resulting extraction solvent were injected and heated to start the reaction.

After generating a small amount of water, cyclohexane was removed under reduced pressure and water was mixed to prepare 92% aqueous solution.

At room temperature, 50% caustic soda weight 30.7% was added to the aqueous solution and stirred to terminate the neutralization reaction, and the mixture was transferred to a separatory funnel for purification.

Inorganic acid catalyst salts were separated from the mixture and separated completely under the separating funnel.

16.8 g of acrylic acid and 15.8 g of methacrylic acid were mixed with 311 g of the above-described salt-free aqueous solution, and 3.3 g of mercetoacetic acid was mixed with a chain transfer agent to prepare a co-polymerization mixture. 180 g of water was added to a 3 liter glass reactor equipped with a stirrer. After reaction substitution with nitrogen, the reaction temperature was maintained at 98 ° C.

After the copolymerization mixture was added dropwise to the copolymerization mixture and 68 g of the polymer compound for 4 hours, the reaction was completed after maintaining the reaction mixture at 98 ° C. for 1 hour 40 minutes.

After completion of the co-polymerization reaction, 33% caustic soda was neutralized to give a pH of 5-7.5.

It was 0.42 weight% of the weight average molecular weight of the cement dispersant thus prepared.

[Cement Concrete Test]

The cement used ordinary Portland cement, and general water sand and hard sandstone crushed stone.

The cement dispersants prepared in Examples 1, 2 and 3 were used, respectively. The concrete mix design is 300 kg of cement, 165 kg of water, 835 kg of sand and 979 kg of gravel.

Under the above conditions, the change of bar slump (floor) over time according to the KS F2560 condition was measured, and the role of the concrete dispersant and the defoaming waterproofing force were measured, respectively.

 Inventive dispersant  Design strength  Amount added (cx%)     Slump (cm)   Compressive strength (Mpa / m) Air volume  Waterproof ability Remarks  Early  30 minutes  60 minutes  3 days  7 days  28 days  Early Existing Dispersant Example Example 1 210 0.25 19.5 19 18.5 150 210 227 0.2 100 87.7 Example 2 270 0.30 19.5 19 18 175 238 298 0.2 100 89.1 Example 3 300 0.35 19 18.5 18 194 269 330 0.2 100 90.3

As shown in Table 1), it can be seen that the performance of the cement dispersant using the hyalcohol and the polymer compound after the copolymerization reaction is excellent.

It is possible to reduce unreacted polyalkylene glycol methacrylate in controlling the reaction rate when preparing a cement dispersant prepared by polymerizing monomer components including high alcohols and polymer compounds in the transesterification reaction of polyalkylene glycol mono methacrylate. Economical safety was obtained by giving the safety and additional functions of the reaction, and it was possible to produce concrete cement with excellent dispersion capacity of cement dispersant and waterproofing of slump holding parcel.

Claims (4)

In the method of polymerizing and manufacturing the polyalkylene glycol mono and (meth) acrylic acid ester monomer obtained by the transesterification reaction of polyalkylene glycol mono and (meth) acrylic acid, Injecting nitrogen into a 2L reactor equipped with a stirrer, a thermometer, a pressure reducing device, and a cooling reflux, 1-38% by weight of OLEYL ALCOHOL3, 13.6-17.2% by weight of CETYL ALCOHOL, 4.9-5.6% by weight of STEARYL ALCOHCL, and OLEYL ACID 45.5-57.7 % And adding 0.8-1.2% by weight of Paraffin Toluene Sulfonic Acid or H ₂ SO ₄ as a catalyst to start the ester reaction; A second step of raising the temperature to 150 ° C.-170 ° C., raising the pressure of 200 mm / Hg for 20 hours, and maintaining a dehydration reaction of 3.2-3.9 wt% of the produced by-product water;   After the temperature was maintained, the acid value was measured, and when the measured value reached 0.1-3, the reaction was terminated and Triethanolamine was added as 0.12-2% by weight as a terminator. Method of manufacturing cement dispersant. The antifoaming and waterproofing properties according to claim 1, wherein the cement dispersant obtained by copolymerization of an unsaturated polycarbon monomer with a polyalkylene glycol monomethacrylic acid monomer line segment and a hyalcohol in a transesterification reaction suppresses air entrainment. High performance cement dispersant with improved function. 3. The antifoaming and waterproofing function of claim 2, wherein the cement dispersant obtained by the transesterification reaction including the polymer compound in the polyalkylene glycol monomethacrylic acid ester copolymerization has waterproof performance to the concrete composition composed of cement and water. This improved high performance cement dispersant manufacturing method. The cement dispersant according to claim 2, wherein the cement dispersant comprises a copolymer obtained by copolymerizing monomer components containing a polyalkylene glycol methacrylate ester monomer in a direct ester reaction of a polyalkylene glycol mono alkyl racer with an unsaturated carboxylic acid. Cement dispersant, characterized in that the salt of the inorganic acid catalyst for ester reaction remaining in the final cement dispersant is from 0 to 0.5% by weight of polyalkylene glycol methacrylate. Manufacturing method.