CN103965416A - Early-strength polycarboxylate water reducing agent for component and preparation method for early-strength polycarboxylate water reducing agent - Google Patents

Abstract

The invention discloses an early-strength polycarboxylate water reducer for components and a preparation method thereof, belonging to the field of water reducer preparation. The water reducer is polymerized from the following components in terms of weight percentage, and each component includes: 80-85% of methene butyl polyoxyethylene polyoxypropylene monomer with molecular weight above 2400; unsaturated monovalent carboxylic acid Acid and its derivatives monomer 10-15%; unsaturated ethylenic sulfonic acid and its sodium salt 0.5-5%. The preparation method is as follows: each component is polymerized in an aqueous solution by using a redox initiation system at a temperature of 20 to 40 ° C, and after the polymerization, it is neutralized by a neutralizing agent to obtain a low air-entraining amount and good dispersibility. For good polymers, the early-strength performance of polycarboxylate-based superplasticizers increases with the increase in the molecular weight of macromonomers, which can meet the requirements for early-strength or super-early-strength components.

Description

Early-strength polycarboxylate water reducer for components and preparation method thereof

technical field

The invention relates to the field of preparation of concrete water reducers, in particular to an early-strength polycarboxylate water reducer for prefabricated components and a preparation method thereof.

Background technique

Precast concrete technology has the advantages of good product quality, fast construction, and clean site, and is suitable for elevated long-span prestressed U-shaped bridges and prestressed high-strength concrete pipe piles. With the development of the construction industry, resource conservation and environmental friendliness are constantly advocated in the 21st century. C40-C100 precast concrete is often mixed with a large amount of mineral admixtures, and it is more and more widely used and developed faster in the field of municipal and construction engineering. . Generally, early-strength concrete uses traditional admixture products such as naphthalene-based water-reducers, aliphatic water-reducers, sulfamic acid-based water-reducers, and melamine-based water-reducers. There are many problems in the production of high-performance precast concrete, among which The most important thing is that there are different degrees of retardation and poor adaptability. For example, under normal temperature, the compressive strength can only reach about 20% of the design strength in 1 day, and can reach 40-50% in 3 days. Concrete with a large amount of mineral admixture has lower early strength, and the strength can reach about 50% in 7 days, and the early strength of concrete may be lower when the temperature is lower than 5°C.

The early-strength type or super-early-strength polycarboxylate water-reducer technology with ultra-high water-reducing rate can increase the amount of mineral fine powder admixture, reduce ordinary Portland cement, and achieve ultra-low concrete water-binder ratio. It can make the concrete obtain high strength in the early stage, and the strength grows steadily in the later stage. The C60~C80 super early strength concrete that can be prepared under normal temperature conditions can reach about 50% of the design strength grade in one day, even at a low temperature of about 0°C. And under the premise of ensuring that the concrete has good working performance, it can also shorten the static stop and curing time of the components. The setting time can meet the requirements of rapid demoulding. The concrete components will not appear honeycomb and pitting, which can fully meet the quality requirements. Therefore, there is an urgent need for a special early-strength water-reducer that can meet the requirements of concrete slump retention, fast setting, early-strength and rapid demoulding. The super-early-strength polycarboxylate water-reducer for component concrete is the key to precast concrete technology. Technology is also the development direction of concrete admixtures for components.

As we all know, polycarboxylate water reducing agent has high water reducing rate, good workability of concrete, small slump loss, low chloride ion and alkali content, small shrinkage of concrete, and the production and application process is environmentally friendly and harmless to human body. , but the current early-strength or super-early-strength polycarboxylate-based superplasticizer component admixtures are rare in the domestic market. In China, inorganic salt or organic early strength agent is usually combined with polycarboxylate water reducer to improve the effect of concrete, but the strength in 28 days often increases little or even shrinks, and the strength within 1 day is super early strength. Basically nonexistent. Chinese invention patent CN102786248A discloses a "synthesis method of polycarboxylate high-efficiency water reducer for high-performance prefabricated components", which uses methallyl polyoxyethylene polyoxypropylene macromonomer and acrylic acid, 2-acrylamide Small monomers such as base-2-methylpropanesulfonic acid are synthesized at a medium temperature of 60-65°C aqueous solution system, and the early-strength effect of the product is not obvious; CN101205128A discloses "a formula and manufacturing "Method" uses allyl polyoxyethylene macromonomers with a degree of polymerization of 37 and 54 and small monomers such as acrylic acid, acrylamide, and sodium methacrylate sulfonate to be synthesized at a temperature above 55°C. The polymerization degree of the macromonomer is low and slow Severe coagulation, no super early strength effect; CN101085701A discloses a preparation method of super early strength polycarboxylate water reducer, due to the use of acrylic acid and methoxypolyethylene glycol 4000 esterification to obtain large molecular weight esters body, the esterification reaction temperature is high (above 120 ° C), the molecular weight is too large to cause many by-products, the esterification rate is low to reduce the active ingredient, the second step synthesis reaction temperature is 60 ~ 100 ° C, the temperature is too high and high quality is not easy to control; CN101066853A published "A polyether super early strength concrete superplasticizer" also uses methallyl polyoxyethylene polyoxypropylene macromonomer with a molecular weight of more than 4000, and acrylic acid and maleic anhydride polyoxyethylene polyoxyethylene Acrylic ester and others have synthesized a polycarboxylate water reducer with low foam, high water reduction and super early strength. The synthesis process of maleic anhydride polyoxyethylene polyoxypropylene ester itself is complicated, and the addition of this substance leads to a decrease in water reducing rate. , although the product has a super early strength effect, but because the water reducing rate is too low, the dosage needs to be increased.

Contents of the invention

The technical problem to be solved by the present invention is to provide an early-strength polycarboxylate water-reducer for components and its preparation method. The concrete components required by the early strength of the day are environmentally friendly and harmless to the human body, thereby solving the problems of the existing polycarboxylate-based water-reducing agents with poor early strength and poor reducing properties.

In order to solve the above-mentioned technical problems, the present invention provides an early-strength polycarboxylate water-reducer for components, which is polymerized from the following components by weight percentage, and each component includes:

80% to 85% of methyl butyl polyoxyethylene polyoxypropylene monomer with a molecular weight of not less than 2400;

Unsaturated monocarboxylic acid and its derivatives monomer 10-15%;

Unsaturated alkenyl sulfonic acid and its sodium salt 0.5-5%.

The embodiment of the present invention also provides a method for preparing an early-strength polycarboxylate water reducer for components, including:

Get each component by formula of the present invention;

Under the temperature condition of 20-40℃, each component is polymerized in an aqueous solution by using a redox initiation system. After the polymerization reaction, the polymer obtained after being neutralized by a neutralizing agent is the early-strength type for building blocks. Or super early strength polycarboxylate superplasticizer.

The beneficial effect of the present invention is: by combining the methene butyl polyoxyethylene polyoxypropylene monomer with molecular weight not less than 2400, unsaturated monocarboxylic acid and its derivative monomer and unsaturated ethylenic sulfonic acid and its sodium salt Polymerize under the redox initiation system to form an early-strength or super-early-strength polycarboxylate water-reducer, the water-reducer molecule has dense polyoxyalkylene long side chains, which is beneficial to cement The dispersion of particles increases the hydration rate of cement in concrete, and the structure with 10-15% carboxylic acid group, amide group and sulfonic acid group stabilizes the adsorption of cement and admixture in the early stage of cement hydration, and can To control the initial concrete slump loss, when the cement begins to set, the cement hydration rate is enhanced. The early strength performance of the water reducer is enhanced with the increase of the molecular weight of butyl polyoxyethylene polyoxypropylene, and the use of butyl polyoxyethylene polyoxypropylene monomer with a molecular weight of 2400 makes the concrete have 1-3 days Early strength effect, and the use of methene butyl polyoxyethylene polyoxypropylene monomer with a molecular weight of more than 4000 makes the concrete have a super early strength effect within 1 day. Well, it has the advantage of being harmless to the human body.

Detailed ways

The following clearly and completely describes the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

An embodiment of the present invention provides an early-strength polycarboxylate water-reducer for components. The water-reducer is polymerized from the following components by weight percentage, and each component includes:

80% to 85% of methyl butyl polyoxyethylene polyoxypropylene monomer with a molecular weight of not less than 2400;

Unsaturated monocarboxylic acid and its derivatives monomer 10-15%;

Unsaturated alkenyl sulfonic acid and its sodium salt 0.5-5%.

Among the above water reducers, the methene butyl polyoxyethylene polyoxypropylene monomer with a molecular weight of not less than 2400 is represented by the following general formula 1:

Formula 1

In the general formula 1, m is the average number of added moles of oxyethylene groups, m is any number from 50 to 200; n is the average number of added moles of oxypropylene groups, and n is 1 to 5 any number.

Preferably, as the methene butyl polyoxyethylene polyoxypropylene monomer, a methene butyl polyoxyethylene polyoxypropylene monomer with a molecular weight of 2,400 to 4,000 can be used to obtain an early-strength polycarboxylate water reducer.

If the methene butyl polyoxyethylene polyoxypropylene monomer with a molecular weight of 4000-9000 is used as the methene butyl polyoxyethylene polyoxypropylene monomer, a super early strength polycarboxylate water reducer can be obtained.

In practice, different molecular weights of methylene butyl polyoxyethylene polyoxypropylene monomers can be used according to needs, so as to obtain early-strength or super-early-strength polycarboxylate water reducers.

Among the above water reducers, unsaturated monocarboxylic acid and its derivative monomers are represented by general formula 2:

Formula 2

In the general formula 2, R ₂ represents hydrogen and methyl; R ₃ represents OM ₁ , wherein M ₁ represents hydrogen, monovalent metal, divalent metal, ammonium or organic amine; in the copolymer, unsaturated monocarboxylic acid and One of its derivative monomers can be used alone or in combination.

The above-mentioned water reducing agent also includes: unsaturated ethylenic sulfonic acid and its sodium salt, and its dosage is 0.5-5% by mass percentage.

Among the above water reducers, the unsaturated sulfonic acid or its sodium salt is selected from: allylsulfonic acid or its salt, methallylsulfonic acid or its salt, styrenesulfonic acid or its salt, 2-methylpropene Any one or two of amido-3-propenesulfonic acid or its salts.

The embodiment of the present invention also provides a method for preparing an early-strength polycarboxylate water reducer for components, including:

Get each component by the formula of the embodiment of the invention;

Under the temperature condition of 20-40℃, each component is polymerized in an aqueous solution by using a redox initiation system. After the polymerization reaction, the polymer obtained after being neutralized by a neutralizing agent is the early-strength type for building blocks. Polycarboxylate water reducer.

In the above preparation method, the oxidizing agent in the redox initiation system used is one of hydroperoxide, persulfate or their mixture, and the amount of said oxidizing agent is 0.2% to 0.2% of the total monomer weight in each component. 2.0%;

The reducing agent in the redox initiation system used is one of the low-valent compounds of sulfur, L-ascorbic acid or their mixture, and the amount of the reducing agent is 0.1-1.0% of the total weight of all monomers in the raw material components .

In the above preparation method, the polymerization reaction speed is controlled in the following way, the oxidizing agent in the redox initiation system used is formulated into a solution, or the reducing agent is formulated into a solution, or the oxidizing agent and the reducing agent are formulated into a solution separately, instead of being formulated into The other component of the solution can be directly added to the reaction kettle, and the prepared solution is added dropwise to the reaction system to control the polymerization reaction speed, and the dropping time is controlled within 1 to 5 hours.

In the above preparation method, after the polymerization reaction, any one of sodium hydroxide, triethanolamine, ethylenediamine, diethylenetriamine, etc. can be used for neutralization to obtain the said member with a mass concentration of 40-60%. Early-strength polycarboxylate superplasticizer.

The above-mentioned early-strength polycarboxylate superplasticizer can be used as a mother liquor. When used, it is generally necessary to add water to the mother liquor to make 10-20% of the admixture, and then use it according to the actual optimal dosage.

The present invention adopts a simple production process at normal temperature, when selecting methacrylic acid, acrylamide, sodium methacryl sulfonate or amide and sulfonate with a molecular weight of more than 4000 When the acid-based small monomer 2-acrylamide-2-methylpropanesulfonic acid and other raw materials are used, the ultra-early-strength polycarboxylate water-reducing agent for component concrete can be synthesized, which has low air-entraining amount and good dispersibility. , It has super early strength effect within 1 day, is environmentally friendly and harmless to human body.

The water reducer of the present invention will be further described in conjunction with specific examples below.

An embodiment of the present invention provides an early-strength or super-early-strength polycarboxylate water-reducer for components. The water-reducer is polymerized from the following components by weight percentage, and each component includes:

80% to 85% of methyl butyl polyoxyethylene polyoxypropylene monomer with a molecular weight of not less than 2400;

Unsaturated monocarboxylic acid and its derivatives monomer 10-15%;

Unsaturated alkenyl sulfonic acid and its sodium salt 0.5-5%.

Further, the methylene butyl polyoxyethylene polyoxypropylene monomer in the above water reducer is represented by the following general formula 1:

Formula 1

In the above general formula 1, m is the average addition mole number of oxyethylene groups, and m is any number from 50 to 200; n is the average addition mole number of oxypropylene groups, and n is any number from 1 to 5. a number.

Among the above water reducers, unsaturated monocarboxylic acid and its derivative monomers are represented by general formula three:

Formula 2

In general formula 2, R ₂ represents hydrogen and methyl; R ₃ represents OM ₁ , wherein M ₁ represents hydrogen, monovalent metal, divalent metal, ammonium or organic amine; in copolymers, unsaturated monocarboxylic acid and its derivatives One of the monomers can be used alone or in combination.

The unsaturated sulfonic acid or its salt in the above water reducer is selected from: allylsulfonic acid or its salt, methallylsulfonic acid or its salt, styrenesulfonic acid or its salt, 2-methacrylamide - any one of 3-propenesulfonic acid or its salts or a mixture of any two.

The embodiment of the present invention also provides a method for preparing the early-strength polycarboxylate water-reducer for the above components, including:

According to the above formula, each component is taken, and each component is polymerized in an aqueous solution at a temperature of 20-40°C using a redox initiation system. After the polymerization, it is neutralized by a neutralizing agent to obtain a concentration of 40 ~60% of the polymer is the early-strength polycarboxylate water reducer mother liquor for the component.

In the above method, the oxidant in the redox initiation system used is one of hydroperoxide, persulfate or their mixture, and the amount of the oxidant is 0.2% to 0.2% of the total weight of the monomers in each component. 2.0%;

The reducing agent in the redox initiation system used is one of low-valent compounds of sulfur, L-ascorbic acid or a mixture thereof, and the amount of the reducing agent is 0.1 to 0.1% of the total weight of all monomers in the raw material components. 1.0%.

Further, in the above method, the speed of the polymerization reaction is controlled in the following manner, the oxidizing agent in the redox initiation system used is formulated into a solution, or the reducing agent is formulated into a solution, or the oxidizing agent and the reducing agent are separately formulated into a solution, and the Method Add the prepared solution dropwise to the reaction system to control the polymerization reaction speed, and the dropping time is controlled within 1 to 5 hours.

This example provides an early-strength polycarboxylate water reducer for components. The actual raw materials used for each component are as follows:

The molecular weight of methene butyl polyethylene glycol polypropylene glycol ether is 2400-9000;

Unsaturated monocarboxylic acid and its derivative monomers can be: (meth)acrylic acid, (meth)acrylamide, (meth)acrylic acid methyl (or ethyl, or propyl, or butyl) ester, (meth)acrylic acid Hydroxyethyl ester, hydroxypropyl (meth)acrylate, etc.;

Alkenylsulfonic acid and its sodium salt monomers are: (meth)allylsulfonic acid or its salt, styrenesulfonic acid or its salt, 2-methacrylamide-3-propenesulfonic acid or its salt, etc.

The water reducer adopts a redox initiation system to polymerize each component in an aqueous solution. In the redox initiation system used, the oxidizing agent includes: ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, etc.;

The reducing agent includes: sodium thiosulfate, sodium bisulfite, sodium sulfite, sodium hydroxymethyl bisulfite, stannous sulfate, ferrous sulfate, L-ascorbic acid, etc.

The molecular weight regulator that adopts can be: mercaptoacetic acid, mercaptopropionic acid.

The neutralizing agent may be one or more of sodium hydroxide, ethylenediamine, diethylenetriamine, triethylenetetramine, triethanolamine and the like.

In the preparation process, all the macromonomers are added before the reaction starts, and other monomers can be added partly before the reaction, or can be added in batches or continuously after the reaction starts, or these adding methods can be used in combination.

During preparation, the conductivity of deionized water used is 1-20 us/cm (preferably 5-10 us/cm); in the redox initiation system, the amount of oxidizing agent is 0.2%-2.0% of the total weight of monomers used, and the amount of reducing agent 0.1-1.0% of the total weight of the monomers used, the amount of the molecular weight regulator is 0.1-2.0% of the total weight of the monomers used, the mass concentration of the polymerized monomer mixed solution is 50-60%, and the reaction time is controlled at 1-5 Hour. Alkali or alkaline organic amine is used for neutralization, the amount used is 0.5-2.0% of the total weight of monomers in each component. The prepared early-strength polycarboxylate water reducer for components is a light brown transparent liquid, and the final mass concentration of the mother liquor diluted with water is 40% to 60%.

The present invention is further described below in conjunction with embodiment.

Embodiment one

This example provides an early-strength polycarboxylate water-reducer for components. The preparation method is as follows: the addition amount of each component used in the water-reducer is by weight. Add 450 parts by weight of methylbutenyl polyethylene glycol propylene glycol ether (m=55, n=1) with a weight average molecular weight of 2500, 400 parts by weight of the four-necked glass flask of the device, reflux condenser and nitrogen protection device Ionized water and 4.0 parts by weight of hydrogen peroxide with a mass concentration of 27% were stirred and the temperature was controlled at 25±3°C, and 37.5 parts by weight of acrylic acid, 7.5 parts by weight of acrylic acid and 7.5 parts by weight of Parts of acrylamide, 2.5 parts by weight of sodium methacryl sulfonate and 100 parts by weight of deionized water monomer solution, dropwise mixed with 2.5 parts by weight of mercaptopropionic acid and 60 parts by weight of the mass concentration of 2% The reaction accelerator solution of L-ascorbic acid, after the dropwise addition is completed, the reaction ends, and the temperature is controlled below 50°C for 60 minutes to continue the heat preservation, so that the polymerization reaction is completed. The sodium oxide solution was neutralized, and water was added to adjust the mass concentration to 45%, so as to obtain the early-strength polycarboxylate-based water reducer for components in this example. The superplasticizer was named PE-ER1 in the follow-up comparative experiment.

Embodiment two

This example provides an early-strength polycarboxylate water-reducer for components. The preparation method is as follows: the addition amount of each component used in the water-reducer is by weight, and it is equipped with a stirrer, a thermometer, and a dropping device. 450 parts by weight of methylbutenyl polyethylene glycol dipropylene glycol ether (m=87, n=2) with a weight average molecular weight of 4000, 400 parts by weight of Ionized water and 4.0 parts by weight of hydrogen peroxide with a mass concentration of 27% were stirred and the temperature was controlled at 25±3°C, and 40.0 parts by weight of acrylic acid, 7.5 parts by weight of The monomer solution of 2-methacrylamide-3-propenesulfonic acid and 100 parts by weight of deionized water was added dropwise and mixed with 2.5 parts by weight of mercaptopropionic acid and 60 parts by weight of L- The reaction accelerator solution of ascorbic acid, after the dropwise addition, the reaction ends, the temperature is controlled below 50°C and the insulation is continued for 60 minutes, so that the polymerization reaction is completed, and after the insulation is completed, 20 parts by weight of ethylenediamine with a mass concentration of 30% are added Neutralize, and add water to adjust to a mass concentration of 45%, to obtain the early-strength polycarboxylate water reducer for components in this example. The superplasticizer was named PE-ER2 in the follow-up comparative experiment.

Embodiment Three

This example provides an early-strength polycarboxylate water-reducer for components. The preparation method is as follows: the addition amount of each component used in the water-reducer is by weight. Add 450 parts by weight of methylbutenyl polyethylene glycol tripropylene glycol ether (m=132, n=3) with a weight average molecular weight of 6000, and 400 parts by weight of Ionized water and 4.0 parts by weight of hydrogen peroxide with a mass concentration of 27% were stirred and the temperature was controlled at 25±3°C, and 35 parts of acrylic acid and 10.5 parts by weight of A monomer solution of 2-methacrylamide-3-propene sulfonic acid and 100 parts by weight of deionized water was added dropwise and mixed with 2.5 parts by weight of mercaptopropionic acid and 60 parts by weight of L-ascorbic acid with a mass concentration of 2%. The reaction accelerator solution, after the dropwise addition, the reaction ends, the temperature is controlled below 50°C and the insulation is continued for 60 minutes, so that the polymerization reaction is completed, and after the insulation is completed, 10 parts by weight of triethanolamine with a mass concentration of 85% is added to neutralize , and add water to adjust the mass concentration to 45%, to obtain the early-strength polycarboxylate water reducer for components of this embodiment. The superplasticizer was named PE-ER3 in the follow-up comparative experiment.

Comparative example 1

This comparative example provides a commonly used standard polycarboxylate water-reducer, the preparation method of which is as follows: the amount of each component used in the water-reducer is by weight, and it is equipped with a stirrer, a thermometer, dropwise Add 450 parts by weight of molecular weight to the methallyl polyethylene glycol of 2400, the deionized water of 400 parts by weight and the mass concentration of 4.0 parts by weight in the four-necked glass flask of device, reflux condenser, and nitrogen protection device to be 27.5% After the hydrogen peroxide is heated to 60°C, within 1 to 3 hours, the reaction accelerator solution of 50.5 parts by weight of acrylic acid and 49.5 parts by weight of deionized water and 2.0 parts by weight of mercaptopropionic acid is added dropwise to the reaction vessel at the same time. , the reaction temperature is controlled at 50-65°C. After the dropwise addition, continue to keep warm at 65°C for 60 minutes to complete the polymerization reaction. and, and adding water to adjust the mass concentration to 40%, to obtain the standard polycarboxylate water reducer of this comparative example, which was named PE-C1 in the subsequent comparative experiments.

In the performance comparison experiment of the water reducer prepared in the embodiment of the present invention, the early strength type water reducer and the comparative sample admixture for components include PE-ER1, PE-ER2, PE-ER3, PE-C1 water reducer samples All are formulated into 15% mass concentration for use, which will be further elaborated below.

Application example 1 (clean cement paste inspection):

BBMG P.O.42.5 cement was selected, and the water consumption of standard consistency and coagulation test were carried out in accordance with the standard "Cement Standard Consistency Water Consumption, Setting Time, and Stability Test Method" (GB/T1346-2001). The amount of water reducing agent was 2%. The results are shown in Table 1

Table 1 Water Consumption and Setting Time of Standard Consistency of Cement Paste

Application example (cement mortar test) 2:

Refer to the cement mortar strength test method (ISO), increase the amount of cement by 50g, take 500g, standard sand 1350g, blank sample water-binder ratio 0.5, water-reducing agent concentration 15%, water-binder ratio is the same, take 0.22, control the degree of mortar expansion at 130±20mm, the results are shown in Table 2.

Table 2 Cement mortar compressive strength

Application example (concrete test) 3:

Concrete application performance test is carried out in accordance with "GB50081-2002 Ordinary Concrete Mechanical Properties Test Method". The slump of high-performance concrete for prefabricated components is controlled at 180-200 mm. Admixtures are mixed according to solid effective components, and water is deducted from the total water consumption. , the amount of single concrete material is shown in Table 3. (1) Detect the average compressive strength of concrete with different strength grades in 1 day, 2 days, 3 days, and 28 days under standard curing conditions; Steam curing at 55-60°C after stopping, demoulding after natural cooling, test the compressive strength of the test block and compare the average compressive strength of the later standard curing to 28 days with the compressive strength of the non-steaming test block; (3) for C80 super For high-strength concrete, test the average compressive strength of the test block under the condition of 0-5°C in winter and 30-35°C in summer for 1 day and 3 days of natural curing and later standard curing up to 28 days. The results are shown in Table 4, Table 5, and Table 6.

Table 3 Consumption of high-performance concrete single-party material for prefabricated components (kg)

Table 4 Compressive strength of precast concrete at different ages under standard maintenance conditions

Table 5 Strength of C50 strength grade precast concrete under different curing conditions

Table 6 Compressive strength of precast concrete at different ages under moisturizing and curing conditions at the highest temperature of 10°C

From the results of Table 4, Table 5, and Table 6, it can be seen that the super early strength polycarboxylate water reducer PE-ER1, PE-ER2, and PE-ER3 obtained by the embodiment of the present invention have water reducing ratios divided by PE-ER1 Except for the comparison sample PE-C1, the molecular weight of the macromonomer decreases significantly, PE-ER1 has obvious early strength effect, PE-ER2 and PE-ER3 have super early strength effect, early strength polycarboxylate water reducing No matter what kind of curing method is used, the early strength of 1-3 days is significantly higher than that of the common comparison sample PE-C1, especially the concrete of PE-ER2 and PE-ER within 31 days The early strength effect is more obvious. Under winter temperature conditions, the 1-day strength of C80 concrete can reach more than 30% of the design strength, and the average compressive strength at 28 days is basically the same.

The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person familiar with the technical field can easily conceive of changes or changes within the technical scope disclosed in the present invention. Replacement should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.

Claims (9)

1. a member high-early strength type polycarboxylic acids dehydragent, is characterized in that, this water reducer is polymerized by following each component by weight percentage, and each component comprises:

Molecular weight is not less than 2400 methyl alkene butyl polyoxyethylene polyoxypropylene monomer 80～85%;

Unsaturated monocarboxylic acid and derivatives monomer 10～15% thereof;

Unsaturated thiazolinyl sulfonic acid and sodium salt 0.5～5% thereof.

2. water reducer as claimed in claim 1, is characterized in that, described molecular weight is not less than 2400 methyl alkene butyl polyoxyethylene polyoxypropylene monomer by following general formula one expression:

General formula one

The average addition mole number of group that in described general formula one, m is oxyethylene group, arbitrary number that m is 50～200; N is the average addition mole number of the group of oxypropylene group, arbitrary number that n is 1～5.

3. water reducer as claimed in claim 1 or 2, is characterized in that, described methyl alkene butyl polyoxyethylene polyoxypropylene monomer adopts the methyl alkene butyl polyoxyethylene polyoxypropylene monomer that molecular weight is 4000～9000.

4. water reducer as claimed in claim 1, is characterized in that, described unsaturated monocarboxylic acid and derivatives monomer thereof are represented by general formula two:

General formula two

R in described general formula two ₂represent hydrogen, methyl; R ₃represent OM ₁, wherein M ₁represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine; In multipolymer, unsaturated monocarboxylic acid and derivatives monomer thereof are for wherein a kind of use separately or multiple mixing are used.

5. the water reducer as described in claim 1,2 or 4, it is characterized in that, described unsaturated sulfonic acid or its sodium salt are selected from: any in allyl sulphonic acid or its salt, methallylsulfonic acid or its salt, styrene sulfonic acid or its salt, 2-Methacrylamide-3-propene sulfonic acid or its salt or any two kinds.

6. a preparation method for high-early strength type polycarboxylic acids dehydragent for member, is characterized in that, comprising:

Get each component by formula described in claim 1 to 5 any one;

Under 20～40 DEG C of temperature condition, adopt redox initiation system to make each component in the aqueous solution, carry out polyreaction each component, after polyreaction through in neutralizing agent and after the polymkeric substance that obtains be member high-early strength type polycarboxylic acids dehydragent.

7. method as claimed in claim 6, it is characterized in that, oxygenant in the redox initiation system of described employing is a kind of in hydroperoxide, persulphate or their mixture, the consumption of described oxygenant be in each component total monomer weight 0.2%～2.0%;

Reductive agent in the redox initiation system of described employing is a kind of in the sub-compound, L-AA of sulphur or their mixture, and the consumption of described reductive agent is in feed composition all 0.1～1.0% of total monomer weights.

8. method as claimed in claim 7, it is characterized in that, in described method, control in the following manner polymerization rate, oxygenant in the redox initiation system of employing is mixed with to solution, or reductive agent is mixed with to solution, or oxygenant and reductive agent are mixed with respectively solution, can directly add in reactor and do not need to be mixed with another component of solution, by dropping mode by the solution of preparation to dripping and control polymerization rate in reaction system, time for adding is controlled at 1～5 hour.

9. method as claimed in claim 6, it is characterized in that, in described method, after polyreaction, after neutralizing with any in sodium hydroxide, trolamine, quadrol, diethylenetriamine, obtain mass concentration and be 40～60% member high-early strength type polycarboxylic acids dehydragent.