CN103483504B - The method of polycarboxylate water-reducer is prepared in the polyether macromonomer combination of two kinds of structures - Google Patents

Abstract

The invention discloses a method for preparing a polycarboxylate water reducer by combining polyether macromonomers with two structures, which is characterized in that: macromonomer A (methallyl polyoxyethylene ether), macromonomer C ( Prenyl alcohol polyoxyethylene ether), water into the reactor, stirring at 40°C to 60°C to mix and dissolve, then add small monomers (acrylic acid, etc.), add mercaptoacetic acid, and heat up to 75°C to 85°C , add ammonium persulfate aqueous solution dropwise within 70-90 minutes, then keep warm at 75°C-85°C for 2-3 hours to carry out polymerization reaction, then cool the reacted material to room temperature, and use 30% sodium hydroxide The aqueous solution is neutralized to pH = 6.8-7.2 to obtain a polycarboxylate water reducer. The present invention uses macromonomers to carry out combined copolymerization to synthesize a high-performance polycarboxylate water reducer, which is beneficial to the balance between water reduction and slump retention and performance adjustment of existing polycarboxylate water reducer products.

Description

Method for preparing polycarboxylate water reducer by combining polyether macromonomers with two structures

technical field

The invention belongs to the preparation of polymer compounds used in concrete or similar building materials, and relates to a method for preparing polycarboxylate water reducers by combining polyether macromonomers with two structures. The prepared polycarboxylate water reducer is suitable for use as a constituent material of concrete and the like to construct concrete structures such as (long-span) bridges and (high-rise) buildings.

Background technique

Concrete is the most widely used building material in the world today. The development of concrete admixtures has a significant effect on modern concrete and is the key force to promote the progress of concrete technology. At present, concrete has entered the era of "green" and "high performance". Correspondingly, higher requirements are put forward for the raw materials, workability, durability, energy saving and environmental protection of concrete, and economy. Polycarboxylate superplasticizer has the characteristics of low dosage, high water reducing rate, low chlorine, low alkali, low slump loss, clean and environmentally friendly, and good cement adaptability. Application hotspots. Unlike naphthalene-based, melamine-based, sulfamic acid-based and aliphatic-based high-efficiency water reducers that are synthesized by formaldehyde condensation, polycarboxylate water reducers are synthesized by free radical polymerization. Large adjustment space. The polycarboxylate superplasticizer has a comb-shaped structure, the main chain is generally a fatty segment, and contains long side chains and various functional groups (such as hydroxyl, carboxyl, sulfonic acid, ester, ether, nitrile, amide, etc.) group, imide group, and siloxy group, etc.), thus endowing it with a variety of performance changes; the type and quantity of functional groups, the structure and molecular weight of long side chains, the density of long side groups in the superplasticizer molecule, The molecular weight and molecular weight distribution of the superplasticizer will greatly affect the performance of the polycarboxylate superplasticizer. my country is currently in the peak period of infrastructure construction, and the amount of cement and concrete is huge, which is close to 60% of the world's total. Therefore, the demand for concrete admixtures, especially the polycarboxylate superplasticizer with excellent performance, is very huge .

As far as the overall development level of polycarboxylate superplasticizers is concerned, there is still a big gap between my country and developed countries, especially in terms of variety, functionality, difference, and molecular structure design of superplasticizers. The key raw materials of polycarboxylate superplasticizers have fewer varieties of active macromonomers and single functional groups of macromonomers, which lead to the homogeneity of domestic polycarboxylate superplasticizer products. Therefore, it is very necessary to study the use of existing commercially available reactive macromonomers, to study the combination of different types and varieties of reactive macromonomers, and to synthesize new polycarboxylate superplasticizers.

In the prior art, polycarboxylate superplasticizers are mostly synthesized by copolymerization of ether macromonomers with small monomers such as acrylic acid and maleic anhydride, and the ether macromonomers used are all single macromonomers of the same type. Therefore, the performance of the synthesized water reducer has certain limitations, and it is difficult to meet the actual needs.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing a polycarboxylate water reducer by combining polyether macromonomers with two structures. The present invention adopts the mixed copolymerization of different kinds of ether macromonomers, that is to say, two kinds of macromonomers with different activities, methallyl polyoxyethylene ether and isopentenol polyoxyethylene ether, are mixed and copolymerized, and the chain structures complement each other. Therefore, a method for preparing the polycarboxylate water reducer by combining polyether macromonomers with two structures that can effectively improve the comprehensive performance of the polycarboxylate water reducer and have excellent performance is provided.

The content of the present invention is: a method for preparing a polycarboxylate water reducer by combining polyether macromonomers with two structures, which is characterized in that it includes the following steps: macromonomer A5-30 mass parts, macromonomer C6.8- Add 46.6 parts by mass and 40-65 parts by mass of water into the reactor, stir, mix and dissolve at a temperature of 40°C-60°C (preferably 40°C-50°C), then add small monomers, add mercapto Acetic acid (as a chain transfer agent) 0.2-1.2 parts by mass, heat up to 75°C-85°C, add dropwise an aqueous solution of ammonium persulfate (as an initiator) with a mass percentage concentration of 2.4-3.0% for 15-15 minutes within 70-90 minutes 30 parts by mass, and then kept at a temperature of 75°C to 85°C for 2 to 3 hours to carry out polymerization reaction, then cooled the reacted material to room temperature, and neutralized it to pH=6.8~ 7.2, that is, the polycarboxylate water reducer is prepared;

The macromonomer A is methallyl polyoxyethylene ether (HPEG for short, 4C), and the chemical structural formula of the macromonomer A is as follows:

In the formula: n=32～44, the average molecular weight range of the macromonomer A is 1500～2000; preferably n=39, the molecular weight is 1788;

The macromonomer C is isopentenol polyoxyethylene ether (abbreviated as TPEG, 5C), and the chemical structural formula of the macromonomer C is as follows:

In the formula: m=52～62, the average molecular weight range of the macromonomer C is 2400～2814; preferably m=62, the molecular weight is 2814;

The small monomer is 3.5-20 parts by mass of acrylic acid (preferably 4-20 parts by mass).

In the content of the present invention: 5-30 parts by mass of macromonomer A and 6.8-46.6 parts by mass of macromonomer C can be replaced by 6.0-35.2 parts by mass of macromonomer A and 9.2-54.8 parts by mass of macromonomer B share;

The macromonomer B is isopentenol polyoxyethylene ether (TPEG, 5C for short), and the chemical structural formula of the macromonomer B is as follows:

In the formula, m=32-44, and the average molecular weight of the macromonomer B is in the range of 1500-2000; preferably m=36 and the molecular weight is 1670.

In the content of the present invention: the small monomer is 3.5-12 parts by mass of acrylic acid, which can be replaced by 3.5-12 parts by mass of acrylic acid and 0.05-2 parts by mass of sodium propylene sulfonate.

In the content of the present invention: the small monomer is 3.5-12 parts by mass of acrylic acid, and it can also be replaced by the small monomer being 3.5-12 parts by mass of acrylic acid, 0.05-2 parts by mass of sodium propylene sulfonate and 0.05-1.00 parts by mass of acrylonitrile parts by mass.

In the above content: the chemical structural formula of the macromonomer A is preferably n=39 and the molecular weight is 1788; the chemical structural formula of the macromonomer C is preferably m=62 and the molecular weight is 2814.

In the above content: the chemical structural formula of the macromonomer B is preferably m=36 and the molecular weight is 1670.

The synthesis reaction principle of the present invention is as follows: each monomer undergoes free radical polymerization in aqueous solution under the condition of an initiator through the proportioning mode of ternary, quaternary and pentadic.

The reaction formula of ternary polymerization is as follows:

The reaction formula of quaternary polymerization is as follows:

The reaction formula of five-membered polymerization is as follows:

In the above reaction formula: the ternary polymerization is the ternary copolymerization of the macromonomers A and B or A and C, and the small monomer acrylic acid; the tetrapolymerization is the macromonomers A and C Quaternary copolymerization of two macromonomers B or A and C, and two small monomers of acrylic acid and sodium propylene sulfonate; the pentapolymerization is that the macromonomer is A and B or two macromonomers A and C , and five-membered copolymerization of three small monomers of acrylic acid, sodium propylene sulfonate and acrylonitrile.

Characterization and physical property test of the prepared polycarboxylate water reducer: structural characterization of the prepared polycarboxylate water reducer by infrared analysis (FT-IR) and gel permeation chromatography (GPC); cement slurry test and concrete Test for performance evaluation.

In the content of the present invention: the molecular structure of the active macromonomer is characterized by ¹ H-NMR; the molecular weight is obtained from the calculation result of ¹ H-NMR and the measurement result of GPC. Characterized by ¹ H-NMR, it can be determined that macromonomer A is methallyl polyoxyethylene ether (HPEG, 4C), and macromonomers B and C are prenol polyoxyethylene ether (TPEG, 5C).

In the content of the present invention: characterized by infrared spectroscopy and gel permeation chromatography (infrared and GPC analysis data, see the description of the drawings), the synthesized polymer, that is, the prepared polycarboxylate water reducer, has a characteristic functional group, The weight-average molecular weight of the obtained polycarboxylate water reducer polymer is between 40,000 and 100,000, and the polycarboxylate water reducer molecules have a relatively high dispersibility within this range.

In the content of the present invention: in the performance test of the prepared polycarboxylate superplasticizer, the fluidity test of the cement paste is tested according to the national standard GB/T8077-2000 "Concrete Admixture Homogeneity Test Method"; the concrete test is carried out according to the national standard GB/T50080-2002 "Standard for Performance Test of Ordinary Concrete Mixture"; GB/T50081-2002 "Standard for Test Method of Mechanical Properties of Ordinary Concrete" to conduct relevant tests.

Compared with the prior art, the present invention has the following characteristics and beneficial effects:

(1) The present invention adopts the method of combining macromonomers with different molecular structures to synthesize polycarboxylate superplasticizer (referred to as PC) through polypolymerization, combining the advantages of two polyether macromonomers with different structures (structure, molecular weight), The synthetic molecular structure is reasonable and the molecular weight is moderate, which can effectively improve the comprehensive performance of polycarboxylate superplasticizer, and the performance is good;

(2) Using the present invention, the synthesized polycarboxylate water-reducer has an initial fluidity of 270-320mm when the solid-folding amount is 0.10%; When it is 0.15%, the slump of the concrete mixture can reach 200mm±20mm, the slump loss within 1h is within 10mm, the water reducing rate can reach more than 25%, and the compressive strength ratios of 3d, 7d, and 28d are 125%~ 135%, 140%～155%, 130%～150%; through the combined use of active macromonomers of two structures, compared with the prior art products, the present invention affects the reduction of polycarboxylic acid through the structural difference of active macromonomers. The structure of the water agent (such as the flexibility of the chain, and the inert barrier and steric hindrance of the side group, etc.) Dispersion retention ability, etc.), to better balance the relationship between the water reducing rate of polycarboxylate superplasticizer and slump retention performance, etc.; Under certain conditions, it has a high water-reducing rate, and has both excellent dispersion retention and an increase in the compressive strength of concrete at all ages;

(3) The present invention uses macromonomers to carry out combined copolymerization to synthesize high-performance polycarboxylate superplasticizers, which is beneficial to the balance and performance adjustment between water reduction and slump retention of existing polycarboxylate superplasticizer products; The preparation process is simple, the process is simple and convenient, the reaction conditions are easy to control, the operation is easy, and the practicability is strong.

Description of drawings

Figure 1 is the infrared spectrogram (FT-IR) of the polycarboxylate superplasticizer prepared by ternary copolymerization prepared in the example of the present invention. In Figure 1, the abscissa is the wave number (cm ^-1 ), and the ordinate is the transmission rate (%); in the infrared spectrum, 1730.9cm ^-1 is the contraction vibration peak of carboxylic acid carbonyl C=O; 529.3cm ^-1 is the in-plane bending vibration peak of carboxylic acid CC=O; 1114.1cm ^-1 is the large single The stretching vibration peak of COC in bulk ether; the above characteristic peaks can indicate that acrylic acid and two types of polyether macromonomers are copolymerized in solution to form a polycarboxylate water reducer;

Figure 2 is the gel permeation chromatogram (GPC) of the tetrapolymeric polycarboxylate water reducer prepared in the example of the present invention; from the final measurement results, Mw=4.46×10 ⁴ , Mn=4.13×10 ⁴ , Mw/ Mn=1.08, the average molecular weight is moderate, and the molecular weight distribution is narrow; the moderate molecular weight indicates that the copolymer chain length is reasonable, which is more beneficial to the water reducing rate; the narrow molecular weight distribution indicates that the structure of the water reducing agent is more uniform.

detailed description

The embodiment given below intends to further illustrate the present invention, but can not be interpreted as the restriction to protection scope of the present invention, those skilled in the art make some non-essential improvements and adjustments to the present invention according to the above-mentioned content of the present invention, still Belong to the protection scope of the present invention.

Example 1:

The method for preparing a polycarboxylate water reducer by combining polyether macromonomers with two structures is to add 11.0g of macromonomer A, 17.1g of macromonomer C and 55g of water into a flask at 50°C, and place the flask Put it into the oil bath of a magnetic stirrer, heat and stir at 40°C to 50°C, after fully dissolving, add 4g of acrylic acid and 0.4g of mercaptoacetic acid, stir evenly and then heat up to 80°C. 15 g of ammonium persulfate solution with a mass concentration of 2.6% was dripped into the flask through a dropping funnel. After the dropwise addition, keep the temperature at this temperature for 2 hours, then lower the temperature to 30°C, and then add NaOH solution with a mass concentration of 30% to adjust the pH of the resulting solution to 7.0 to obtain a polycarboxylate superplasticizer.

Example 2:

The method for preparing a polycarboxylate water reducer by combining polyether macromonomers with two structures is to add 11.0g of macromonomer A, 17.1g of macromonomer C and 55g of water into a flask at 50°C, and place the flask Put it into the oil bath of a magnetic stirrer, heat and stir at 40°C to 50°C, and after fully dissolving, add 4g of acrylic acid, 0.08g of sodium propylene sulfonate and 0.4g of mercaptoacetic acid, stir evenly and heat up to 78°C. 15 g of ammonium persulfate solution with a mass concentration of 3.0% was dropped into the flask through a dropping funnel. After the dropwise addition, keep the temperature at this temperature for 2 hours, then lower the temperature to 30°C, and then add NaOH solution with a mass concentration of 30% to adjust the pH of the resulting solution to 7.2 to obtain a polycarboxylate superplasticizer.

Example 3:

The method of preparing polycarboxylate water reducer by combining polyether macromonomers with two structures is to add 8.82g of macromonomer A, 13.72g of macromonomer B and 55g of water into the flask at 50°C, and place the flask Put it into the oil bath of a magnetic stirrer, heat and stir under the condition of 40℃～50℃, after fully dissolving, add 3.98g acrylic acid, 0.1g sodium propylene sulfonate, 0.06g acrylonitrile and 0.4g mercaptoacetic acid, and stir evenly The temperature was raised to 85°C. 15 g of ammonium persulfate solution with a mass concentration of 2.6% was dripped into the flask through a dropping funnel. After the dropwise addition, keep the temperature at this temperature for 2 hours, then lower the temperature to 30°C, and then add NaOH solution with a mass concentration of 30% to adjust the pH of the resulting solution to 6.8 to obtain a polycarboxylate superplasticizer.

Embodiment 4:

The method of preparing polycarboxylate water reducer by combining polyether macromonomers with two structures is to add 11.0g of macromonomer A, 20.7g of macromonomer B and 55g of water into the flask at 50°C, and place the flask Put it into the oil bath of a magnetic stirrer, heat and stir at 40°C to 50°C, after fully dissolving, add 4g of acrylic acid and 0.4g of mercaptoacetic acid, stir evenly and then heat up to 75°C. 15 g of ammonium persulfate solution with a mass concentration of 2.6% was dripped into the flask through a dropping funnel. After the dropwise addition, keep the temperature at this temperature for 2 hours, then lower the temperature to 30°C, and then add NaOH solution with a mass concentration of 30% to adjust the pH of the resulting solution to 7.2 to obtain a polycarboxylate superplasticizer.

Example 5:

The method of preparing polycarboxylate water reducer by combining polyether macromonomers with two structures is to add 11.0g of macromonomer A, 20.7g of macromonomer C and 55g of water into the flask at 50°C, and place the flask Put it into the oil bath of a magnetic stirrer, heat and stir at 40°C to 50°C, and after fully dissolving, add 4g of acrylic acid, 0.08g of sodium propylene sulfonate and 0.4g of mercaptoacetic acid, stir evenly and heat up to 75°C. 15 g of ammonium persulfate solution with a mass concentration of 2.6% was dripped into the flask through a dropping funnel. After the dropwise addition, keep the temperature at this temperature for 2 hours, then lower the temperature to 30°C, and then add NaOH solution with a mass concentration of 30% to adjust the pH of the resulting solution to 7.0 to obtain a polycarboxylate superplasticizer.

Application example:

The cement paste test and concrete test were carried out on the synthesized polycarboxylate superplasticizer. The performance index of polycarboxylate superplasticizer is in accordance with the industry standard JG/T223-2007 "polycarboxylate high-performance water reducer"; the fluidity test of cement slurry is in accordance with the national standard GB/T8077-2000 "concrete admixture homogeneity test Method" to carry out the test, the water-reducing agent is 0.1%, and the test results are shown in Table 1; the concrete test is in accordance with the national standard GB/T50080-2002 "General Concrete Mixture Performance Test Standard", and the water-reducing agent is mixed. 0.15%; GB-T50081-2002 "Standards for Test Methods of Mechanical Properties of Ordinary Concrete" to carry out relevant tests.

Table 1: Application performance test results:

Description: Polycarboxylate superplasticizer with a reduced solid content of 0.10%, Zhonglian P.O42.5R cement (produced by China United Cement Group Beichuan Zhonglian Cement Co., Ltd.).

Table 2: C ₃₀ Concrete Test Results:

Note: The test polycarboxylate superplasticizer has a reduced solid content of 0.15%, using Jingong P.O42.5R cement (produced by Sichuan Jingong Cement Co., Ltd.), medium sand (machine-made sand), 5-25 continuous particle size gravel, cement The amount of each side is 360kg, and the sand rate is 45%.

Embodiment 6:

A method for preparing a polycarboxylate water reducer by combining polyether macromonomers with two structures, comprising the following steps: adding 5 to 30 parts by mass of macromonomer A, 6.8 to 46.6 parts by mass of macromonomer C, and 40 to 65 parts by mass of water Add parts by mass into the reactor, stir, mix and dissolve at a temperature of 40°C~60°C (preferably 40°C~50°C), then add small monomers, add thioglycolic acid (as a chain transfer agent) 0.2~ 1.2 parts by mass, heat up to 75°C-85°C, add 15-30 parts by mass of ammonium persulfate (as an initiator) aqueous solution with a mass percentage concentration of 2.4-3.0% dropwise within 70min-90min, and then Insulate at 85°C for 2 to 3 hours to carry out polymerization reaction, then cool the reacted material to room temperature, and neutralize with 30% sodium hydroxide aqueous solution to pH = 6.8 to 7.2 to obtain polycarboxylic acid liquid;

The macromonomer A is methallyl polyoxyethylene ether (HPEG for short, 4C), and the chemical structural formula of the macromonomer A is as follows:

In the formula: n=32～44, the average molecular weight range of the macromonomer A is 1500～2000; preferably n=39, the molecular weight is 1788;

The macromonomer C is isopentenol polyoxyethylene ether (abbreviated as TPEG, 5C), and the chemical structural formula of the macromonomer C is as follows:

In the formula: m=52～62, the average molecular weight range of the macromonomer C is 2400～2814; preferably m=62, the molecular weight is 2814;

The small monomer is 3.5-20 parts by mass of acrylic acid (preferably 4-20 parts by mass).

Embodiment 7:

The method for preparing a polycarboxylate water reducer by combining polyether macromonomers of two structures comprises the following steps: adding 5 parts by mass of macromonomer A, 6.8 parts by mass of macromonomer C, and 40 parts by mass of water into the reactor After stirring, mixing and dissolving at a temperature of 40°C to 60°C (preferably 40°C to 50°C), add small monomers, add 0.2 parts by mass of thioglycolic acid (as a chain transfer agent), and heat up to 75°C ~85°C, dropwise add 15 parts by mass of ammonium persulfate (as an initiator) aqueous solution with a mass percentage concentration of 2.4% within 70 minutes, and then keep it at a temperature of 75°C to 85°C for 2 hours to carry out polymerization reaction, and then react After the material is cooled to room temperature, it is neutralized to pH = 6.8 to 7.2 with an aqueous sodium hydroxide solution with a mass percentage concentration of 30% to obtain a polycarboxylate water reducer; the small monomer is 3.5 parts by mass of acrylic acid; other same Embodiment 6, omitted.

Embodiment 8:

The method for preparing a polycarboxylate water reducer by combining polyether macromonomers with two structures comprises the following steps: adding 30 parts by mass of macromonomer A, 46.6 parts by mass of macromonomer C, and 65 parts by mass of water into the reactor After stirring, mixing and dissolving at a temperature of 40°C to 60°C (preferably 40°C to 50°C), add small monomers, add 1.2 parts by mass of thioglycolic acid (as a chain transfer agent), and heat up to 75°C ~85°C, add dropwise 30 parts by mass of ammonium persulfate (as an initiator) aqueous solution with a concentration of 3.0% by mass within 90 minutes, and then keep warm at a temperature of 75°C to 85°C for 3 hours to carry out polymerization reaction, and then react After the material is cooled to room temperature, it is neutralized to pH=6.8-7.2 with an aqueous solution of sodium hydroxide with a mass percentage concentration of 30% to obtain a polycarboxylate water reducer; the small monomer is 20 parts by mass of acrylic acid; other same Embodiment 6, omitted.

Embodiment 9:

The method for preparing a polycarboxylate water reducer by combining polyether macromonomers of two structures comprises the following steps: adding 18 mass parts of macromonomer A, 26 mass parts of macromonomer C, and 52 mass parts of water into the reactor, Stir, mix and dissolve at a temperature of 40°C to 60°C (preferably 40°C to 50°C), then add small monomers, add 0.7 parts by mass of thioglycolic acid (as a chain transfer agent), and heat up to 75°C to 85°C. ℃, 22 mass parts of ammonium persulfate (as an initiator) aqueous solution with a mass percentage concentration of 2.7% was added dropwise within 80 minutes, and then kept at a temperature of 75 ℃ to 85 ℃ for 2.5 hours to carry out polymerization reaction, and then the reaction The material is cooled to room temperature, and neutralized with an aqueous solution of sodium hydroxide with a mass percentage concentration of 30% to pH = 6.8-7.2 to obtain a polycarboxylate water-reducer; the small monomer is 12 parts by mass of acrylic acid; other implementations are the same Example 6, omitted.

Embodiment 10～16:

A method for preparing a polycarboxylate water reducer by combining polyether macromonomers with two structures, comprising the following steps: adding 5 to 30 parts by mass of macromonomer A, 6.8 to 46.6 parts by mass of macromonomer C, and 40 to 65 parts by mass of water Add parts by mass into the reactor, stir, mix and dissolve at a temperature of 40°C~60°C (preferably 40°C~50°C), then add small monomers, add thioglycolic acid (as a chain transfer agent) 0.2~ 1.2 parts by mass, heat up to 75°C-85°C, add dropwise 15-30 parts by mass of ammonium persulfate (as an initiator) aqueous solution with a mass percentage concentration of 2.6% within 70min-90min, and then Polymerization reaction was carried out at a temperature of 2.5 hours, and then the reacted material was cooled to room temperature, and neutralized with a 30% sodium hydroxide aqueous solution to pH = 6.8 to 7.2 to obtain a polycarboxylate water reducer; The small monomer is 3.5-20 parts by mass of acrylic acid; others are the same as in Example 6, omitted;

The specific mass parts consumption of each raw material component is shown in the following table 3 in each embodiment:

table 3:

Embodiment 17～23:

A method for preparing a polycarboxylate water reducer by combining polyether macromonomers with two structures, replacing 5-30 parts by mass of macromonomer A and 6.8-46.6 parts by mass of macromonomer C described in Example 6 with macromonomers Body A6.0～35.2 parts by mass, macromonomer B9.2～54.8 parts by mass;

The specific mass parts consumption of each raw material component in each embodiment can be seen in the following table 4:

Table 4:

The macromonomer B is isopentenol polyoxyethylene ether (TPEG, 5C for short), and the chemical structural formula of the macromonomer B is as follows:

In the formula, m=32～44, the average molecular weight range of the macromonomer B is 1500～2000; preferably m=36, the molecular weight is 1670;

Others are the same as any one of Embodiments 6 to 16, and are omitted.

Example 24:

The method for preparing a polycarboxylate water reducer by combining polyether macromonomers of two structures comprises the following steps: adding 6.0 parts by mass of macromonomer A, 9.2 parts by mass of macromonomer B, and 40 parts by mass of water to In the reactor, stir, mix and dissolve at a temperature of 40°C to 60°C (preferably 40°C to 50°C), then add small monomers, add 0.2 parts by mass of thioglycolic acid (as a chain transfer agent), and heat up to At 75°C, 15 parts by mass of ammonium persulfate (as an initiator) aqueous solution with a mass percentage concentration of 2.4% was added dropwise within 70 minutes, and then kept at 75°C for 3 hours to carry out polymerization reaction, and then the reacted material was cooled to At room temperature, use 30% sodium hydroxide aqueous solution to neutralize to pH = 6.8-7.2 to obtain polycarboxylate water reducer;

The macromonomer A is methallyl polyoxyethylene ether (HPEG for short, 4C), and the chemical structural formula of the macromonomer A is as follows:

In the formula: n=32～44, the average molecular weight range of the macromonomer A is 1500～2000; preferably n=39, the molecular weight is 1788;

The macromonomer B is isopentenol polyoxyethylene ether (TPEG, 5C for short), and the chemical structural formula of the macromonomer B is as follows:

In the formula, m=32～44, the average molecular weight range of the macromonomer B is 1500～2000; preferably m=36, the molecular weight is 1670;

The small monomer is 3.5 parts by mass of acrylic acid.

Example 25:

The method for preparing a polycarboxylate water reducer by combining polyether macromonomers of two structures comprises the following steps: adding 35.2 mass parts of macromonomer A, 54.8 mass parts of macromonomer B, and 65 mass parts of water to In the reactor, stir, mix and dissolve at a temperature of 40°C to 60°C (preferably 40°C to 50°C), then add small monomers, add 1.2 parts by mass of thioglycolic acid (as a chain transfer agent), and heat up to 85°C, dropwise add 30 parts by mass of ammonium persulfate (as an initiator) aqueous solution with a mass percentage concentration of 3.0% within 90 minutes, and then keep warm at 85°C for 2 hours to carry out polymerization reaction, and then cool the reacted material to At room temperature, use 30% sodium hydroxide aqueous solution to neutralize to pH = 6.8-7.2 to obtain polycarboxylate water reducer;

The macromonomer A is methallyl polyoxyethylene ether (HPEG for short, 4C), and the chemical structural formula of the macromonomer A is as follows:

In the formula: n=32～44, the average molecular weight range of the macromonomer A is 1500～2000; preferably n=39, the molecular weight is 1788;

The macromonomer B is isopentenol polyoxyethylene ether (TPEG, 5C for short), and the chemical structural formula of the macromonomer B is as follows:

In the formula, m=32～44, the average molecular weight range of the macromonomer B is 1500～2000; preferably m=36, the molecular weight is 1670;

The small monomer is 20 parts by mass of acrylic acid.

Example 26:

The method for preparing a polycarboxylate water reducer by combining polyether macromonomers of two structures comprises the following steps: adding 20 mass parts of macromonomer A, 32 mass parts of macromonomer B, and 53 mass parts of water into the reactor, Stir, mix and dissolve at a temperature of 40°C-60°C (preferably 40°C-50°C), then add small monomers, add 0.6 parts by mass of thioglycolic acid (as a chain transfer agent), heat up to 80°C, and 20 mass parts of ammonium persulfate (as an initiator) aqueous solution with a mass percentage concentration of 2.8% was added dropwise within 80 minutes, and then kept at a temperature of 80°C for 2.5 hours to carry out polymerization reaction, and then the reacted material was cooled to room temperature, and used Aqueous sodium hydroxide solution with a concentration of 30% by mass is neutralized to pH = 6.8-7.2 to obtain a polycarboxylate water reducer;

The macromonomer A is methallyl polyoxyethylene ether (HPEG for short, 4C), and the chemical structural formula of the macromonomer A is as follows:

In the formula: n=32～44, the average molecular weight range of the macromonomer A is 1500～2000; preferably n=39, the molecular weight is 1788;

The macromonomer B is isopentenol polyoxyethylene ether (TPEG, 5C for short), and the chemical structural formula of the macromonomer B is as follows:

In the formula, m=32～44, the average molecular weight range of the macromonomer B is 1500～2000; preferably m=36, the molecular weight is 1670;

The small monomer is 12 parts by mass of acrylic acid.

Embodiment 27～33:

A method for preparing a polycarboxylate water reducer by combining polyether macromonomers with two structures, replacing the small monomer described in the above examples with acrylic acid and its parts by mass with the small monomer being 3.5-12 parts by mass of acrylic acid and 0.05 to 2 parts by mass of sodium propylene sulfonate;

The specific mass parts consumption of each raw material component in each embodiment can be seen in the following table 5:

table 5:

Others are the same as any one of Embodiments 6 to 26, and are omitted.

Embodiment 34～40:

The method for preparing a polycarboxylate water reducer by combining polyether macromonomers with two structures is characterized in that: the small monomer described in the above examples is acrylic acid and its mass parts are replaced by the small monomer being acrylic acid 3.5 ～12 parts by mass, 0.05～2 parts by mass of sodium propylene sulfonate and 0.05～1.00 parts by mass of acrylonitrile;

The specific mass parts consumption of each raw material component in each embodiment can be seen in the following table 6:

Table 6:

Others are the same as any one of Embodiments 6 to 26, and are omitted.

In the above embodiment: the chemical structural formula of the macromonomer A is preferably n=39 and the molecular weight is 1788; the chemical structural formula of the macromonomer C is preferably m=62 and the molecular weight is 2814.

In the above embodiment: the chemical structural formula of the macromonomer B is preferably m=36 and the molecular weight is 1670.

In above-mentioned embodiment: each raw material that adopts is commercially available product.

In the above-mentioned examples: among the percentages used, those not specified are all percentages by mass (weight) or percentages known to those skilled in the art; the parts by mass (weight) can all be grams or kilograms.

Among the above-mentioned embodiments: the process parameters (temperature, time, concentration, etc.) in each step and the numerical values of the amounts of each component are within the range, and any point is applicable.

The content of the present invention and the technical content not specifically described in the above embodiments are the same as the prior art.

The present invention is not limited to the above-mentioned embodiments, and all of the contents of the present invention can be implemented and have the above-mentioned good effects.

Claims (4)

1. The method for preparing a polycarboxylate water-reducer by combining polyether macromonomers of two structures is characterized in that it comprises the following steps: macromonomer A5～30 mass parts, macromonomer C6.8～46.6 mass parts, and 40-65 parts by mass of water are added into the reactor, stirred, mixed and dissolved at a temperature of 40°C-60°C, then small monomers are added, 0.2-1.2 parts by mass of thioglycolic acid are added, and the temperature is raised to 75°C-85°C, Add 15 to 30 parts by mass of ammonium persulfate aqueous solution with a mass percentage concentration of 2.4 to 3.0% dropwise within 70 minutes to 90 minutes, and then incubate at a temperature of 75°C to 85°C for 2 to 3 hours to carry out the polymerization reaction, and then the reaction The material is cooled to room temperature, and neutralized with an aqueous solution of sodium hydroxide with a mass percentage concentration of 30% to pH = 6.8-7.2 to obtain a polycarboxylate water reducer; Described macromonomer A is methallyl polyoxyethylene ether, and the chemical structural formula of this macromonomer A is as follows: In the formula: n=32～44, the average molecular weight range of macromonomer A is 1500～2000; The macromonomer C is isopentenol polyoxyethylene ether, and the chemical structural formula of the macromonomer C is as follows: In the formula: m=52～62, the average molecular weight range of macromonomer C is 2400～2814; The small monomers are 3.5-12 parts by mass of acrylic acid, 0.05-2 parts by mass of sodium propylene sulfonate and 0.05-1.00 parts by mass of acrylonitrile. 2. The method for preparing a polycarboxylate water reducer by combining polyether macromonomers of two structures according to claim 1, is characterized in that: said macromonomer A5～30 parts by mass, macromonomer C6.8～ 46.6 parts by mass are replaced by 6.0 to 35.2 parts by mass of macromonomer A and 9.2 to 54.8 parts by mass of macromonomer B; The macromonomer B is isopentenol polyoxyethylene ether, and the chemical structural formula of the macromonomer B is as follows: In the formula, m=32-44, and the average molecular weight range of the macromonomer B is 1500-2000. 3. the method for preparing polycarboxylate water-reducer by the polyether macromonomer combination of two kinds of structures described in claim 1 is characterized in that: in the chemical structural formula of described macromonomer A, n=39, molecular weight are 1788; In the chemical structural formula of the macromonomer C, m=62 and the molecular weight is 2814. 4. the method for preparing polycarboxylate water-reducer by the polyether macromonomer combination of two kinds of structures described in claim 2 is characterized in that: m=36, molecular weight are 1670 in the chemical structural formula of described macromonomer B.