CN104692699A - Early strength type ether polycarboxylate superplasticizer and preparation method thereof - Google Patents

Abstract

The invention discloses a polycarboxylate water reducer with early strength function and a preparation method thereof, and relates to the technical field of building materials. The water reducer is made of the following raw materials in parts by weight: 20-30 parts of prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 27, and prenyl alcohol polyethylene glycol monomethyl ether with a degree of polymerization of 113. 50-60 parts of ethylene glycol monomethyl ether macromonomer, 6.5-8.6 parts of acrylic acid or its derivative monomer, 0.3-1.5 parts of chain transfer agent, 0.4-0.6 parts of initiator, 2-acrylamido-2-methyl Base-1-propanesulfonic acid 2.5-3.5 parts, deionized water 125-135 parts. The beneficial effects produced by the present invention are: small dosage, remarkable early strength effect, high water reducing rate, small slump loss, environmental protection, small molecular weight distribution and high free radical polymerization conversion rate. The early strength of the concrete prepared by the synthetic sample of the invention is better than that of the concrete using the ordinary water reducer.

Description

A kind of early-strength ether polycarboxylate water reducer and preparation method thereof

Technical field:

The invention relates to the technical field of building materials, in particular to a polycarboxylate water reducer with early strength function and a preparation method thereof.

Background technique:

In recent years, with the rapid development of high-performance concrete, the research on concrete admixtures has been unprecedentedly active. Ordinary polycarboxylate superplasticizers will delay cement hydration, especially under low temperature conditions, and the early strength development is slow, which limits the use of ordinary polycarboxylate superplasticizers. In prefabricated components and emergency repair projects, etc., in order to increase production efficiency and speed up construction progress, polycarboxylate superplasticizers are not only required to have a good water-reducing and dispersing effect, but also to be able to improve the early strength of concrete.

At present, the commonly used method of early-strength polycarboxylate superplasticizer is to compound traditional organic (triethanolamine, calcium acetate, etc.) and inorganic (calcium chloride, calcium nitrate, sodium nitrite, etc.) early-strength components. The polycarboxylate superplasticizer obtained by the method can improve the early strength to a certain extent when used in concrete, but the improvement range is not large.

In recent years, there has been a lot of research on the synthesis of polycarboxylate water reducer with early strength function. Patent CN101205128B discloses an early strength polycarboxylate water reducer and its manufacturing method. The degree of polymerization of ethylene oxide is 37 and 54. Allyl polyethylene glycol, acrylic acid, acrylamide, and sodium methacrylsulfonate are obtained by five-member copolymerization in aqueous solution. However, the patent did not point out that due to the low polymerization activity of allyl polyethylene glycol and the low conversion rate of the product, a large amount of allyl polyethylene glycol remaining in the synthesized polycarboxylate water reducer caused the water reducer to reduce Low water rate will significantly prolong the setting time of concrete and affect the use of the product.

Patent CN 103450412A discloses a preparation method of ester early-strength polycarboxylate water reducer. The early-strength water reducer is obtained through amidation reaction to prepare amide small monomer, esterification reaction to prepare esterified macromonomer, and then free radical copolymerization with other unsaturated monomers. In actual production, ester monomers can only be produced through high-temperature esterification. At the same time, water-carrying agents must be used, water separation devices and reflux devices, and vacuum distillation to remove solvents. This requires high equipment requirements and high processing costs. Moreover, the water-carrying agent itself has considerable toxicity, which is not conducive to environmental protection. The esterification reaction is complicated to operate and the reaction process is difficult to control. This makes the entire production process time-consuming, and the polymerization inhibitor added in the esterification reaction has a certain impact on the later copolymerization reaction.

In view of the above problems, the present invention develops a green concrete admixture with small dosage, remarkable early strength effect, high water reducing rate, small slump loss, and environmental friendliness from the perspective of molecular design.

Contents of the invention

The technical problem to be solved by the present invention is to provide a green concrete admixture with small dosage, remarkable early strength effect, high water reducing rate, small slump loss and environmental friendliness.

In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:

An early-strength ether polycarboxylate water reducer, characterized in that: the water reducer is made of the following raw materials in parts by weight: isopentenol polyethylene glycol monomethyl ether with a polymerization degree of 27 20-30 parts of macromonomer, 50-60 parts of isopentenol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 113, 6.5-8.6 parts of acrylic acid, 0.3-1.5 parts of chain transfer agent, and 0.4-0 parts of initiator 0.6 parts, 2.5-3.5 parts of 2-acrylamido-2-methyl-1-propanesulfonic acid, 125-135 parts of deionized water.

A further technical solution is: the water reducer is made of the following raw materials in parts by weight: 20-30 parts of prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 27, and a macromonomer with a degree of polymerization of 113 50-60 parts of isopentenol polyethylene glycol monomethyl ether macromonomer, 6.5-8.6 parts of acrylic acid or its derivative monomer, 0.3-1.5 parts of chain transfer agent, 0.4-0.6 parts of initiator, 2-acryloyl 2.5-3.5 parts of amino-2-methyl-1-propanesulfonic acid, 125-135 parts of deionized water.

The further technical solution is: the water reducer is made of the following raw materials in parts by weight: 20 parts of isopentenol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 27, isopentyl alcohol with a degree of polymerization of 113 50 parts of enol polyethylene glycol monomethyl ether macromer, 6.5 parts of acrylic acid or its derivative monomer, 0.3 part of chain transfer agent, 0.4 part of initiator, 2-acrylamido-2-methyl-1-propane 2.5 parts of sulfonic acid, 125 parts of deionized water.

A further technical solution is: the water reducer is made of the following raw materials in parts by weight: 30 parts of isopentenol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 27, isopentyl alcohol with a degree of polymerization of 113 60 parts of enol polyethylene glycol monomethyl ether macromonomer, 8.6 parts of acrylic acid or its derivative monomer, 1.5 parts of chain transfer agent, 0.6 parts of initiator, 2-acrylamido-2-methyl-1-propane 3.5 parts of sulfonic acid, 135 parts of deionized water.

A further technical solution is: the water reducer is made of the following raw materials in parts by weight: 25 parts of isopentenol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 27, isopentyl alcohol with a degree of polymerization of 113 55 parts of enol polyethylene glycol monomethyl ether macromonomer, 7.55 parts of acrylic acid or its derivative monomer, 0.9 part of chain transfer agent, 0.5 part of initiator, 2-acrylamido-2-methyl-1-propane 3 parts of sulfonic acid, 130 parts of deionized water.

A further technical solution is: the chain transfer agent is one or a combination of mercaptoacetic acid, mercaptopropionic acid and sodium methallylsulfonate.

A further technical solution is: the initiator is one or a combination of hydrogen peroxide, vitamin C, and ammonium persulfate.

A further technical solution is: the preparation method of the early-strength ether polycarboxylate water reducer is characterized in that it comprises the following steps:

(1) By parts by weight, the prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a polymerization degree of 27, the prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a polymerization degree of 113, 2- Add acrylamido-2-methyl-1-propanesulfonic acid and deionized water into the three-necked flask, heat and start the stirrer to dissolve;

(2) Chain transfer agent and initiator are dissolved in 40 parts of deionized water in parts by weight;

(3) Acrylic acid is added into 35 parts of deionized water to dissolve in parts by weight;

(4) After the temperature of the reactor rises to 38-42°C and the isopentenol polyethylene glycol monomethyl ether macromonomer is dissolved, a constant flow pump is used to drop the mixed solution of chain transfer agent and initiator 2-3 Hour;

(5) After 3 minutes, start to use a constant flow pump to drop the reactant monomer solution for 1.5-2.5 hours;

(6) After the dropwise addition, continue to insulate and react at 40°C for 1.0-2.0 hours, and cool naturally to below 45°C;

(7) The pH value of the obtained product is adjusted to 6.5-7.0 with a concentrated alkali solution to obtain a polycarboxylate superplasticizer product with early strength function.

A further technical solution is: the preparation method of the early-strength ether polycarboxylate water reducer is characterized in that it comprises the following steps:

(1) By parts by weight, the prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a polymerization degree of 27, the prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a polymerization degree of 113, 2- Add acrylamido-2-methyl-1-propanesulfonic acid and deionized water into the three-necked flask, heat and start the stirrer to dissolve;

(2) Chain transfer agent and initiator are dissolved in 40 parts of deionized water in parts by weight;

(3) adding the acrylic acid derivative monomer into 35 parts of deionized water to dissolve in parts by weight;

(4) After the temperature of the reactor rises to 38-42°C and the isopentenol polyethylene glycol monomethyl ether macromonomer is dissolved, a constant flow pump is used to drop the mixed solution of chain transfer agent and initiator 2-3 Hour;

(5) After 3 minutes, start to use a constant flow pump to drop the reactant monomer solution for 1.5-2.5 hours;

(8) After the dropwise addition, continue to insulate and react at 40°C for 1.0-2.0 hours, and cool naturally to below 45°C;

(9) The pH value of the obtained product is adjusted to 6.5-7.0 with a concentrated alkali solution to obtain a polycarboxylate superplasticizer product with early strength function.

The beneficial effects produced by adopting the above-mentioned technical scheme are:

Small dosage, remarkable early strength effect, high water reducing rate and small slump loss, environmental protection, small molecular weight distribution and high free radical polymerization conversion rate, the early strength of concrete prepared by using the synthetic sample of the present invention It has better early strength than concrete using ordinary water reducer.

Description of drawings

The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.

Fig. 1 is the GPC curve of the early-strength polycarboxylate superplasticizer sample synthesized in Example 1 of the present invention;

Fig. 2 is the GPC curve of the early-strength polycarboxylate superplasticizer sample synthesized in Example 2 of the present invention;

Fig. 3 is the GPC curve of the early-strength polycarboxylate superplasticizer sample synthesized in Example 3 of the present invention;

Fig. 4 is the GPC curve of the common water reducer sample of the present invention.

Among them: 1- After the sample of the early-strength polycarboxylate superplasticizer synthesized in Example 1 of the present invention is separated by GPC, the curve light scattering detector test curve can characterize the absolute molecular weight of each component of the sample;

2- After the sample of the early-strength polycarboxylate superplasticizer synthesized in Example 1 of the present invention is separated by GPC, the curve differential refractive index detector test curve can characterize the concentration (that is, the proportion) of each component of the sample;

3- After the sample of the early-strength polycarboxylate superplasticizer synthesized in Example 2 of the present invention is separated by GPC, the curve light scattering detector test curve can characterize the absolute molecular weight of each component of the sample;

4- After the sample of the early-strength polycarboxylate superplasticizer synthesized in Example 2 of the present invention is separated by GPC, the curve differential refractive index detector test curve can characterize the concentration (that is, the proportion) of each component of the sample;

5- After the sample of the early-strength polycarboxylate superplasticizer synthesized in Example 3 of the present invention is separated by GPC, the curve light scattering detector test curve can characterize the absolute molecular weight of each component of the sample;

6- After the sample of the early-strength polycarboxylate superplasticizer synthesized in Example 3 of the present invention is separated by GPC, the curve differential refractive index detector test curve can characterize the concentration (that is, the proportion) of each component of the sample;

7- After the ordinary water reducer sample of the present invention is separated by GPC, the curve light scattering detector test curve can characterize the absolute molecular weight of each component of the sample;

8- After the ordinary water reducer sample of the present invention is separated by GPC, the curve differential refractive index detector test curve can characterize the concentration (that is, the proportion) of each component of the sample.

Detailed ways

The technical solutions in the embodiments of the present invention are clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, 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.

In the following description, a lot of specific details are set forth in order to fully understand the present invention, but the present invention can also be implemented in other ways different from those described here, and those skilled in the art can do it without departing from the meaning of the present invention. By analogy, the present invention is therefore not limited to the specific examples disclosed below.

According to the theoretical design, the present invention synthesizes a water-reducing agent containing side chains of different lengths, which will not affect the water-reducing performance while effectively improving the early strength of concrete, and has good slump-preserving performance.

The water reducer is made of the following raw materials in parts by weight: 20-30 parts of prenyl alcohol polyethylene glycol monomethyl ether macromer with a degree of polymerization of 27, and prenyl alcohol polyethylene glycol monomethyl ether with a degree of polymerization of 113. 50-60 parts of glycol monomethyl ether macromonomer, 6.5-8.6 parts of acrylic acid, 0.3-1.5 parts of chain transfer agent, 0.4-0.6 parts of initiator, 2-acrylamido-2-methyl-1-propanesulfonic acid 2.5-3.5 parts, 125-135 parts of deionized water.

A further technical solution is: the water reducer is made of the following raw materials in parts by weight: 20-30 parts of prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 27, and a macromonomer with a degree of polymerization of 113 50-60 parts of isopentenol polyethylene glycol monomethyl ether macromonomer, 6.5-8.6 parts of acrylic acid or its derivative monomer, 0.3-1.5 parts of chain transfer agent, 0.4-0.6 parts of initiator, 2-acryloyl 2.5-3.5 parts of amino-2-methyl-1-propanesulfonic acid, 125-135 parts of deionized water.

The further technical solution is: the water reducer is made of the following raw materials in parts by weight: 20 parts of isopentenol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 27, isoprenyl alcohol with a degree of polymerization of 113 50 parts of pentenol polyethylene glycol monomethyl ether macromer, 6.5 parts of acrylic acid or its derivative monomer, 0.3 part of chain transfer agent, 0.4 part of initiator, 2-acrylamido-2-methyl-1- 2.5 parts of propanesulfonic acid, 125 parts of deionized water.

The further technical solution is: the water reducer is made of the following raw materials in parts by weight: 30 parts of isopentenol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 27, isoprenyl alcohol with a degree of polymerization of 113 60 parts of pentenol polyethylene glycol monomethyl ether macromonomer, 8.6 parts of acrylic acid or its derivative monomer, 1.5 parts of chain transfer agent, 0.6 parts of initiator, 2-acrylamido-2-methyl-1- 3.5 parts of propanesulfonic acid, 135 parts of deionized water.

The further technical solution is: the water reducer is made of the following raw materials in parts by weight: 25 parts of isopentenol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 27, isoprenyl alcohol with a degree of polymerization of 113 55 parts of pentenol polyethylene glycol monomethyl ether macromonomer, 7.55 parts of acrylic acid or its derivative monomer, 0.9 part of chain transfer agent, 0.5 part of initiator, 2-acrylamido-2-methyl-1- 3 parts of propanesulfonic acid, 130 parts of deionized water.

The chain transfer agent is one or a combination of mercaptoacetic acid, mercaptopropionic acid and sodium methallyl sulfonate. The initiator is one or a combination of hydrogen peroxide, vitamin C and ammonium persulfate.

The preparation method of early-strength ether polycarboxylate water reducer is characterized in that it comprises the following steps:

(1) By parts by weight, the prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a polymerization degree of 27, the prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a polymerization degree of 113, 2- Add acrylamido-2-methyl-1-propanesulfonic acid and deionized water into the three-necked flask, heat and start the stirrer to dissolve;

(2) Chain transfer agent and initiator are dissolved in 40 parts of deionized water in parts by weight;

(3) Acrylic acid is added into 35 parts of deionized water to dissolve in parts by weight;

(4) After the temperature of the reactor rises to 38-42°C and the isopentenol polyethylene glycol monomethyl ether macromonomer is dissolved, a constant flow pump is used to drop the mixed solution of chain transfer agent and initiator 2-3 Hour;

(5) After 3 minutes, start to use a constant flow pump to drop the reactant monomer solution for 1.5-2.5 hours;

(6) After the dropwise addition, continue to insulate and react at 40°C for 1.0-2.0 hours, and cool naturally to below 45°C;

(7) The pH value of the obtained product is adjusted to 6.5-7.0 with a concentrated alkali solution to obtain a polycarboxylate superplasticizer product with early strength function.

A further technical solution is: the preparation method of the early-strength ether polycarboxylate water reducer is characterized in that it comprises the following steps:

(1) By parts by weight, the prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a polymerization degree of 27, the prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a polymerization degree of 113, 2- Add acrylamido-2-methyl-1-propanesulfonic acid and deionized water into the three-necked flask, heat and start the stirrer to dissolve;

(2) Chain transfer agent and initiator are dissolved in 40 parts of deionized water in parts by weight;

(3) adding the acrylic acid derivative monomer into 35 parts of deionized water to dissolve in parts by weight;

(4) After the temperature of the reactor rises to 38-42°C and the isopentenol polyethylene glycol monomethyl ether macromonomer is dissolved, a constant flow pump is used to drop the mixed solution of chain transfer agent and initiator 2-3 Hour;

(5) After 3 minutes, start to use a constant flow pump to drop the reactant monomer solution for 1.5-2.5 hours;

(6) After the dropwise addition, continue to insulate and react at 40°C for 1.0-2.0 hours, and cool naturally to below 45°C;

(7) The pH value of the obtained product is adjusted to 6.5-7.0 with a concentrated alkali solution to obtain a polycarboxylate superplasticizer product with early strength function.

Example 1:

As shown in Figure 1, the polycarboxylate water reducer with early strength function can be preferably made of the following raw materials in parts by weight:

24 parts of prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 27, 50 parts of prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 113, 6.5 parts of acrylic acid, chain transfer 0.3 parts of agent, 0.58 parts of initiator, 2.8 parts of 2-acrylamido-2-methyl-1-propanesulfonic acid, and 125 parts of deionized water. Wherein, the chain transfer agent is mercaptopropionic acid; the initiator is a combination of hydrogen peroxide and vitamin C, and in 0.49 parts of the initiator, hydrogen peroxide accounts for 0.4 part, and vitamin C accounts for 0.09 part.

The deionized water includes deionized water X, deionized water Y and deionized water Z. The parts by weight of deionized water X used to dissolve polyoxyethylene ether macromonomers and 2-acrylamido-2-methyl-1-propanesulfonic acid are 50 parts for dissolving initiators and chain transfer The parts by weight of the deionized water Y used as the agent is 40 parts, and the parts by weight of the deionized water Z used to dissolve acrylic acid or its derivative monomers is 35 parts.

The preparation method of the polycarboxylate water reducer with early strength function comprises the following process steps:

①According to the above weight ratio, 24 parts of prenyl alcohol polyethylene glycol monomethyl ether macromonomers with a polymerization degree of 27 (polyoxyethylene ether macromonomers), and prenyl alcohol polyethylene glycol monomethyl ether macromonomers with a polymerization degree of 113 50 parts of glycol monomethyl ether macromonomer, 2.8 parts of 2-acrylamido-2-methyl-1-propanesulfonic acid and deionized water X were poured into a three-necked flask, stirred in a water bath and heated to 42°C, and then heated in a three-necked flask Adding 0.4 parts by weight in the flask is 30% hydrogen peroxide; in a container (beaker), vitamin C and mercaptopropionic acid are dissolved in deionized water Y to make solution A; in another container (another beaker) Dissolve acrylic acid in deionized water Z to prepare solution B; ② After all the solids in the three-necked flask are dissolved, add solution A and solution B to the three-necked flask respectively at a temperature of 42°C using a constant-flow pump. B began to add dropwise 3 minutes after solution A was added dropwise. The dropwise addition time of solution B was controlled at 1.5 hours, and the dropwise addition time of solution A was controlled at 2.0 hours. Hours, after natural cooling to a certain temperature (can be 45 ° C), the resulting product is adjusted to a pH value of 7.0 with 30 wt% sodium hydroxide solution to obtain a polycarboxylate superplasticizer product with early strength function.

Example 2:

As shown in Figure 2, the polycarboxylate water reducer with early strength function can also be preferably made of the following raw materials in parts by weight:

20 parts of prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 27, 60 parts of prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 113, 7.6 parts of acrylic acid, chain transfer 1.2 parts of agent, 0.48 parts of initiator, 2.5 parts of 2-acrylamido-2-methyl-1-propanesulfonic acid, and 135 parts of deionized water. Wherein, the chain transfer agent is sodium methallylsulfonate; the initiator is ammonium persulfate.

The deionized water includes deionized water X, deionized water Y and deionized water Z. The parts by weight of deionized water X used to dissolve polyoxyethylene ether macromonomers and 2-acrylamido-2-methyl-1-propanesulfonic acid are 60 parts for dissolving initiators and chain transfer The parts by weight of the deionized water Y used as the agent is 40 parts, and the parts by weight of the deionized water Z used to dissolve acrylic acid or its derivative monomers is 35 parts.

The preparation method of the polycarboxylate water reducer with early strength function comprises the following process steps:

①According to the above weight ratio, 20 parts of prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a polymerization degree of 27 (polyoxyethylene ether macromonomer), and prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a polymerization degree of 113 60 parts of glycol monomethyl ether macromonomer, 2.5 parts of 2-acrylamido-2-methyl-1-propanesulfonic acid and deionized water X were poured into a 500ml three-necked flask, stirred in a water bath and heated to 40°C; Dissolve sodium methallylsulfonate and initiator ammonium persulfate in deionized water Y to prepare solution A; in another container (another beaker), dissolve acrylic acid in deionized water Z to prepare Obtain solution B; ② After all the solids in the three-necked flask are dissolved, use a constant-flow pump to add solution A and solution B to the three-necked flask respectively at a temperature of 40°C, where solution B starts 3 minutes after solution A is added dropwise. Add dropwise, the dripping time of solution B is controlled at 2.0 hours, the dripping time of solution A is controlled at 2.5 hours, continue to insulate (the temperature is still 40 ℃) reaction 1.5 hours after dropping, after naturally cooling to a certain temperature, the obtained The pH value of the product is adjusted to 6.8 with 30 wt% sodium hydroxide solution to obtain a polycarboxylate water reducer product with early strength function.

Example 3:

As shown in Figure 3, the polycarboxylate water reducer with early strength function can also be preferably made of the following raw materials in parts by weight:

22 parts of prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 27, 55 parts of prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a degree of polymerization of 113, 8.6 parts of acrylic acid, chain transfer 0.35 parts of agent, 0.55 parts of initiator, 3.5 parts of 2-acrylamido-2-methyl-1-propanesulfonic acid, and 132 parts of deionized water. Wherein, the chain transfer agent is a combination of thioglycolic acid and mercaptopropionic acid, in 0.35 parts of the chain transfer agent, thioglycolic acid accounts for 0.11 parts, and mercaptopropionic acid accounts for 0.24 parts; the initiator is hydrogen peroxide and vitamin C. The combination of species, in 0.55 parts of initiator, hydrogen peroxide accounts for 0.45 parts, and vitamin C accounts for 0.10 parts.

The deionized water includes deionized water X, deionized water Y and deionized water Z. The parts by weight of the deionized water X used for dissolving polyoxyethylene ether macromonomer, 2-acrylamido-2-methyl-1-propanesulfonic acid is 57 parts, used for dissolving initiator and chain transfer The parts by weight of the deionized water Y used as the agent is 40 parts, and the parts by weight of the deionized water Z used to dissolve acrylic acid or its derivative monomers is 35 parts.

The preparation method of the polycarboxylate water reducer with early strength function comprises the following process steps:

①According to the above weight ratio, 22 parts of prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a polymerization degree of 27 (polyoxyethylene ether macromonomer), and prenyl alcohol polyethylene glycol monomethyl ether macromonomer with a polymerization degree of 113 55 parts of glycol monomethyl ether macromonomer, 3.5 parts of 2-acrylamido-2-methyl-1-propanesulfonic acid and deionized water X were poured into a 500ml three-necked flask, heated to 38°C with stirring in a water bath, and then Adding 0.45 parts by weight fraction in the there-necked flask is 30% hydrogen peroxide; Vitamin C and thioglycolic acid mercaptopropionic acid are dissolved in the deionized water Y in the container (beaker) simultaneously, make solution A; In another container (another Dissolve acrylic acid in deionized water Z in a beaker) to prepare solution B; ②After all the solids in the three-necked flask are dissolved, at 38°C, use a constant-flow pump to add solution A and solution respectively in the three-necked flask B, where solution B began to drop in 3 minutes after solution A was added dropwise, the dropwise time of solution B was controlled at 2.5 hours, and the dropwise time of solution A was controlled at 3.0 hours, and continued to insulate after dropwise (the temperature was still 38 ℃) reacted for 1.0 hour, and naturally cooled to a certain temperature (can be 45 ℃), the resulting product was adjusted to a pH value of 6.5 with 30wt% sodium hydroxide solution to obtain a polycarboxylate superplasticizer product with early strength function.

The polycarboxylate water-reducer obtained in each embodiment of the present invention not only obtains high-performance water-reducing effect, but also has early-strength function. Refer to the following experimental data charts, Figures 1-3 are the GPC curves of the samples synthesized in Examples 1-3 determined by gel permeation chromatography, and Figure 4 is the GPC curve of a common water reducer. Table 1 shows the molecular weight distribution of the samples synthesized in Examples 1-3 and common water reducers, as well as the conversion rate of free radical polymerization determined by gel permeation chromatography. Table 2 shows the fluidity of the net slurry tested with benchmark cement. According to GB/T80772012 "Test Method for Homogeneity of Concrete Admixtures", the water-binder ratio is 0.29, and the dosage is converted into effective solid dosage, which is 0.08% by weight of cement. Table 3(1) is the mix ratio of the concrete experiment, and Table 3(2) is the concrete experiment data. Esheng cement is used, the dosage is 0.18% by cement weight (converted into solid content), and the slump is controlled at 180±10mm. GB 8076-2008 "Concrete Admixtures", measure its slump and strength of concrete at different ages. Wherein the comparative sample is common polycarboxylate water reducer.

Table 1,

Table 2,

Table 3(1)

Table 3(2)

The present invention has small dosage, remarkable early strength effect, high water reducing rate, small slump loss, environmental protection, small molecular weight distribution and high radical polymerization conversion rate, and the concrete prepared by using the synthetic sample of the present invention The early strength is better than the early strength of concrete using ordinary water reducer.

Claims (9)

1. an early-strength type ethers polycarboxylic acid water reducing agent, it is characterized in that: this water reducer is made up of the raw material of following portions by weight: the polymerization degree is prenol poly glycol monomethyl ether polymeric monomer 20-30 part of 27, the polymerization degree is prenol poly glycol monomethyl ether polymeric monomer 50-60 part of 113, vinylformic acid 6.5-8.6 part, chain-transfer agent 0.3-1.5 part, initiator 0.4-0.6 part, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid 2.5-3.5 part, deionized water 125-135 part.

2. a kind of early-strength type ethers polycarboxylic acid water reducing agent according to claim 1, it is characterized in that: this water reducer is made up of the raw material of following portions by weight: the polymerization degree is prenol poly glycol monomethyl ether polymeric monomer 20-30 part of 27, the polymerization degree is prenol poly glycol monomethyl ether polymeric monomer 50-60 part of 113, vinylformic acid or its derivatives monomer 6.5-8.6 part, chain-transfer agent 0.3-1.5 part, initiator 0.4-0.6 part, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid 2.5-3.5 part, deionized water 125-135 part.

3. a kind of early-strength type ethers polycarboxylic acid water reducing agent according to claim 1 and 2, it is characterized in that: this water reducer is made up of the raw material of following portions by weight: the polymerization degree is the prenol poly glycol monomethyl ether polymeric monomer 20 parts of 27, the polymerization degree is the prenol poly glycol monomethyl ether polymeric monomer 50 parts of 113, vinylformic acid or its derivatives monomer 6.5 parts, chain-transfer agent 0.3 part, initiator 0.4 part, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid 2.5 parts, deionized water 125 parts.

4. a kind of early-strength type ethers polycarboxylic acid water reducing agent according to claim 1 and 2, it is characterized in that: this water reducer is made up of the raw material of following portions by weight: the polymerization degree is the prenol poly glycol monomethyl ether polymeric monomer 30 parts of 27, the polymerization degree is the prenol poly glycol monomethyl ether polymeric monomer 60 parts of 113, vinylformic acid or its derivatives monomer 8.6 parts, chain-transfer agent 1.5 parts, initiator 0.6 part, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid 3.5 parts, deionized water 135 parts.

5. a kind of early-strength type ethers polycarboxylic acid water reducing agent according to claim 1 and 2, it is characterized in that: this water reducer is made up of the raw material of following portions by weight: the polymerization degree is the prenol poly glycol monomethyl ether polymeric monomer 25 parts of 27, the polymerization degree is the prenol poly glycol monomethyl ether polymeric monomer 55 parts of 113, vinylformic acid or its derivatives monomer 7.55 parts, chain-transfer agent 0.9 part, initiator 0.5 part, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid 3 parts, deionized water 130 parts.

6. a kind of early-strength type ethers polycarboxylic acid water reducing agent of any one according to claim 1-5, is characterized in that: described chain-transfer agent is the combination of one or several components in Thiovanic acid, thiohydracrylic acid, methallylsulfonic acid sodium.

7. a kind of early-strength type ethers polycarboxylic acid water reducing agent of any one according to claim 1-5, is characterized in that: described initiator is one or several the combination in hydrogen peroxide, vitamins C, ammonium persulphate.

8. the preparation method of a kind of early-strength type ethers polycarboxylic acid water reducing agent of any one described in claim 1-5, is characterized in that, comprise the following steps:

(1) by the polymerization degree be by weight 27 prenol poly glycol monomethyl ether polymeric monomer, the polymerization degree be 113 prenol poly glycol monomethyl ether polymeric monomer, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid and deionized water join in there-necked flask, heat and start agitator and dissolve;

(2) by weight chain-transfer agent and initiator are dissolved in 40 parts of deionized waters;

(3) vinylformic acid is added in 35 parts of deionized waters by weight and dissolve;

(4) question response still temperature rises to 38-42 DEG C, starts to adopt constant flow pump to drip the mixing solutions 2-3 hour of chain-transfer agent and initiator after prenol poly glycol monomethyl ether polymeric monomer all dissolves;

Within (5) 3 minutes, start to adopt constant flow pump dropwise reaction thing monomer solution, 1.5-2.5 hour later;

(6) drip rear continuation at 40 DEG C of insulation reaction 1.0-2.0 hour, naturally cool to less than 45 DEG C;

(7) products therefrom is by concentrated alkali solution adjust ph to 6.5-7.0, namely obtains having early powerful polycarboxylate water-reducer product.

9. the preparation method of a kind of early-strength type ethers polycarboxylic acid water reducing agent of any one described in claim 1-5, is characterized in that, comprise the following steps:

(1) by the polymerization degree be by weight 27 prenol poly glycol monomethyl ether polymeric monomer, the polymerization degree be 113 prenol poly glycol monomethyl ether polymeric monomer, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid and deionized water join in there-necked flask, heat and start agitator and dissolve;

(2) by weight chain-transfer agent and initiator are dissolved in 40 parts of deionized waters;

(3) acrylic acid derivative monomer is added in 35 parts of deionized waters by weight and dissolve;

(4) question response still temperature rises to 38-42 DEG C, starts to adopt constant flow pump to drip the mixing solutions 2-3 hour of chain-transfer agent and initiator after prenol poly glycol monomethyl ether polymeric monomer all dissolves;

Within (5) 3 minutes, start to adopt constant flow pump dropwise reaction thing monomer solution, 1.5-2.5 hour later;

(8) drip rear continuation at 40 DEG C of insulation reaction 1.0-2.0 hour, naturally cool to less than 45 DEG C;

(9) products therefrom is by concentrated alkali solution adjust ph to 6.5-7.0, namely obtains having early powerful polycarboxylate water-reducer product.