CN113372508A

CN113372508A - Method for synthesizing polycarboxylate superplasticizer through manganese oxide heterogeneous catalysis quaternary copolymerization of 6C polyether macromonomer

Info

Publication number: CN113372508A
Application number: CN202110641707.0A
Authority: CN
Inventors: 刘才林; 张恒通; 王浚; 任先艳; 杨海君; 舒豆豆; 舒学军; 何年; 罗率
Original assignee: Sichuan Tongzhou Chemical Technology Co ltd; Southwest University of Science and Technology
Current assignee: Sichuan Tongzhou Chemical Technology Co ltd; Southwest University of Science and Technology
Priority date: 2021-06-09
Filing date: 2021-06-09
Publication date: 2021-09-10

Abstract

The invention discloses a method for synthesizing a polycarboxylic acid water reducing agent by manganese oxide heterogeneous catalysis quaternary copolymerization of a 6C polyether macromonomer, which is characterized by comprising the following steps: taking raw materials including a macromonomer, a small monomer A, a small monomer B, a small monomer C, a chain transfer agent, a reducing agent, an oxidant, a catalyst and water, mixing the small monomer A, the small monomer B and the small monomer C with the water to prepare solution A, mixing the reducing agent, the chain transfer agent and the water to prepare solution B, wherein the small monomer A is acrylic acid, the small monomer B is acrylamide, and the small monomer C is sodium allylsulfonate; adding a macromonomer and water into a reactor, controlling the temperature to be 5-20 ℃, adding a catalyst and an oxidant, simultaneously dropwise adding the solution A and the solution B at a constant speed, carrying out heat preservation reaction, and standing the reacted materials to room temperature to obtain the catalyst. The polycarboxylic acid water reducing agent prepared by the method is low in synthesis temperature and short in synthesis time, is suitable for concrete preparation, and has good cement dispersing performance, slump retaining performance over time, compressive strength and durability, and strong practicability.

Description

Method for synthesizing polycarboxylate superplasticizer through manganese oxide heterogeneous catalysis quaternary copolymerization of 6C polyether macromonomer

Technical Field

The invention belongs to the preparation of a concrete admixture-water reducing agent in the building industry, and relates to a method for synthesizing a polycarboxylic acid water reducing agent by manganese oxide heterogeneous catalysis quaternary copolymerization of a 6C polyether macromonomer (namely diethylene glycol monovinyl ether). The polycarboxylic acid water reducer synthesized by manganese oxide heterogeneous catalysis quaternary copolymerization of the 6C polyether macromonomer is suitable for preparation of concrete.

Background

The development of the concrete admixture technology has a decisive effect on the development of the concrete technology. The concrete admixture is an essential important component in modern concrete except cement, sand, stone, water and admixture, especially the third generation polycarboxylic acid series high performance admixture accounts for about 80 percent of the using amount of the concrete admixture, and is one of important technical approaches for reducing the using amount of the cement, improving the utilization rate of industrial waste residue and realizing the durability and high performance of the concrete. The polycarboxylic acid high-efficiency water reducing agent (PCE) is widely applied to the fields of high-speed rails, sea-crossing bridges, super high-rise buildings and the like. The PCE is developed very rapidly mainly because of the low doping amount of the ether polycarboxylic acid admixture, the cheap and easily available raw materials, the simple synthesis process, the low cost and the water reduction rate of 30-40%, so that the performances of cement and gelled materials can reach the optimal state, the setting retardation is hardly generated, and the slump of concrete is maintained (less than 1cm within 1 h). Therefore, the development of a novel high-performance polycarboxylate superplasticizer plays an important role.

At present, the production and application of the polycarboxylate water reducer are relatively wide, and in the prior art, the polycarboxylate water reducer is mainly produced by taking a 5C polyether (short for prenyl polyoxyethylene ether) macromonomer, a 4C polyether (short for isobutenol polyoxyethylene ether) macromonomer and various small monomers as main raw materials and adopting an oxidation-reduction initiation system to prepare the polycarboxylate water reducer. Redox initiation systems initiate polymerization of monomers by generating free radicals through redox reactions. In the process of preparing the polycarboxylate superplasticizer by free radical polymerization, the activity of the polyether macromonomer is far lower than that of the micromolecular unsaturated carboxylic acid monomer; in order to ensure the uniform copolymerization of the terminal alkenyl polyoxyethylene ether and the small molecular monomer, only the dripping time of the small molecular monomer can be prolonged, so that the preparation time of the polycarboxylic acid water reducing agent is generally more than 3 hours; the heating method is used for synthesizing the polycarboxylic acid water reducing agent, the polymerization reaction temperature is usually 40-60 ℃, and the higher temperature increases the energy consumption and increases the production cost, so that the market competitiveness of the product is reduced, and the dispersion performance, slump retention performance, durability and the like of the product are insufficient and defective.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides a method for synthesizing a polycarboxylic acid water reducer by manganese oxide heterogeneous catalysis quaternary copolymerization of a 6C polyether macromonomer (namely diethylene glycol monovinyl ether). Thus providing a method for synthesizing the polycarboxylic acid water reducer by manganese oxide heterogeneous catalysis quaternary copolymerization of 6C polyether macromonomer, which has the advantages of low synthesis temperature, short synthesis time, excellent cement dispersing performance and slump retaining performance over time, good compressive strength and durability and can be industrially produced.

The content of the invention is as follows: a method for synthesizing a polycarboxylate superplasticizer by manganese oxide heterogeneous catalysis quaternary copolymerization of a 6C polyether macromonomer is characterized by comprising the following steps:

a. preparing materials:

taking raw materials including a macromonomer, a small monomer A, a small monomer B, a small monomer C, a chain transfer agent, a reducing agent, an oxidizing agent, a catalyst and water, wherein: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 3.0-4.5: 0.01-0.1: 1, the chain transfer agent accounts for 0.18-0.58 percent of the total mass of the monomers (the total mass of the monomers is the sum of the small monomer A, the small monomer B, the small monomer C and the large monomer, and the same is applied later), the reducing agent accounts for 0.03-0.15 percent of the total mass of the monomers, the oxidizing agent accounts for 0.1-1.5 percent of the total mass of the monomers, and the catalyst accounts for 0.01-0.06 percent of the total mass of the monomers;

mixing the small monomer A, the small monomer B and the small monomer C with water, and uniformly stirring to prepare a solution A for later use; mixing a reducing agent, a chain transfer agent and water, and uniformly stirring to prepare a solution B for later use;

the macromonomer is diethylene glycol monovinyl ether (EPEG for short and 6C polyether macromonomer for short, and product production enterprises comprise Sichuan Hongcong new material company, Liaoning Oaku chemical company, Bailingwei science and technology company and Saen chemical technology (Shanghai) company), and the molecular weight is 1500-4000;

said small monomer A is acrylic acid, said small monomer B is acrylamide, said small monomer C is sodium allylsulfonate;

the chain transfer agent is one or a mixture of two of thioglycolic acid, mercaptopropionic acid and thioglycolic acid;

the catalyst is one or a mixture of two of manganese dioxide, manganous oxide, manganous manganic oxide and manganese monoxide;

the reducing agent is one or a mixture of more than two of sodium hypophosphite, sodium bisulfite, sodium sulfite and ascorbic acid;

the oxidant is one or a mixture of more than two of hydrogen peroxide, potassium persulfate and ammonium persulfate;

b. and (3) synthesis reaction:

adding the macromonomer and water into a reactor (such as a three-neck flask) with a thermometer, (gradually) cooling and stirring (dissolving), adding a catalyst and water, mixing and stirring for 10-20 min when the temperature is controlled to be 5-20 ℃ and the macromonomer is completely dissolved, (after uniform mixing) adding an oxidant and water, mixing and stirring for 5-10 min (uniform mixing), then (using a constant-pressure dropping funnel) simultaneously dropwise adding the solution A and the solution B at a constant speed, keeping the temperature at 5-20 ℃ for reaction for a total time of 1-2 h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer (namely the polycarboxylic acid water reducer synthesized by manganese oxide heterogeneous catalysis quaternary copolymerization of the 6C polyether macromonomer).

The invention comprises the following steps: step a, the ingredients are as follows: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is preferably 3.5:0.06:0.03:1, the chain transfer agent is preferably 0.2 to 0.4% of the total mass of the monomers, the reducing agent is preferably 0.08 to 0.12% of the total mass of the monomers, the oxidizing agent is preferably 0.85 to 1.15% of the total mass of the monomers, and the catalyst is preferably 0.02 to 0.04% of the total mass of the monomers.

The invention comprises the following steps: in the step a, the small monomer A, the small monomer B and the small monomer C are mixed with water to prepare a solution A, preferably: and mixing the small monomer A, the small monomer B and the small monomer C with water according to the mass ratio of the small monomer A, the small monomer B and the small monomer C to the mass ratio of water of 1: 5-15 to prepare a solution A.

The invention comprises the following steps: in the step a, the reducing agent, the chain transfer agent and water are mixed to prepare a solution B, preferably: and mixing the reducing agent and the chain transfer agent with water according to the mass ratio of the total mass of the reducing agent and the chain transfer agent to the mass of water of 1: 66-126 to prepare liquid B.

The invention comprises the following steps: the water in step a and step b is preferably distilled water, ultrapure water or deionized water.

The invention comprises the following steps: in step b the macromer and water are fed to a reactor with a thermometer, preferably: adding the macromonomer and water into a reactor with a thermometer according to the mass ratio of the macromonomer to the water of 1: 0.2-0.6.

The invention comprises the following steps: and c, adding the catalyst and water, mixing and stirring, namely adding the catalyst and the water according to the mass ratio of 1: 100-600 (preferably 1: 100-230) of the catalyst and the water, and mixing and stirring.

The catalyst generates free radicals through the change of the valence states of the supported oxidant and the supported reducer, so that the conversion and synthesis of large and small monomers are accelerated. The active components in the catalyst, other components and the carrier form a synergistic effect, and the catalytic oxidation process is enhanced. The catalyst has stable performance and structure, is suitable for continuous production, and can be regenerated after the catalyst is deactivated.

The inorganic material as heterogeneous catalyst has relatively great specific surface area, and the solid catalyst has active adsorption site for effective coordination of reactant molecule, so as to lower the reaction activity and speed and deepen the oxidation of oxidant. The organic matter can be adsorbed on the active center, and is deformed to generate an activated complex, so that the activation energy of the reaction is reduced, and the speed of the chemical reaction is accelerated.

The invention comprises the following steps: and b, adding the oxidant and the water, mixing and stirring, namely adding the oxidant and the water according to the mass ratio of 1: 0.7-10 (preferably 1: 0.7-3) of the oxidant to the water, and mixing and stirring.

The invention comprises the following steps: and (c) performing heat preservation reaction at the temperature of 5-20 ℃ in the step b, preferably at the temperature of 10-15 ℃.

The invention comprises the following steps: and c, in the step B, simultaneously dropwise adding the solution A and the solution B at a constant speed (by using a constant-pressure dropping funnel), wherein the total time of dropwise adding and heat preservation reaction at the temperature of 5-20 ℃ is 1-2 h, preferably: and (4) dropwise adding the liquid A and the liquid B at a constant speed (by using a constant-pressure dropping funnel), wherein the liquid A is dropwise added for 0.6h, the liquid B is dropwise added for 1.1h, and after the liquid B is dropwise added, the temperature is kept for 0.5h at 10-15 ℃. When the solution B is dripped, a reducing substance and an oxide react to generate active free radicals to initiate polymerization between monomers, a reducing component in the solution B must be separated from an oxidizing component in a base material, and the dripping time of the solution B is prolonged by half an hour compared with that of the solution A, so that the catalytic effect is best, the polymerization is more sufficient, and the performance of the obtained product is best.

The chemical reaction formula of the above polymerization reaction is as follows:

the invention comprises the following steps: the prepared polycarboxylic acid water reducing agent is subjected to infrared spectrum analysis (FT-IR); evaluating the performance by adopting a cement paste test and a concrete test;

the invention comprises the following steps: by infrared spectrum characterization (FT-IR analysis data, see figure description), the characteristic functional group of the polycarboxylate superplasticizer appears in the synthesized product.

The performance test of the prepared polycarboxylic acid water reducing agent comprises the following steps: the cement paste fluidity test is carried out 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 'test standard for the performance of common concrete mixture'; GB/T50081-2002 Standard test method for mechanical properties of common concrete carries out related tests.

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

(1) by adopting the invention, manganese oxide (which is one or a mixture of two of manganese dioxide, manganese sesquioxide, manganous manganic oxide and manganese monoxide and the same later) is used as the catalyst for the first time, the water reducing agent is synthesized by heterogeneous catalysis, and the catalyst can be recycled, so that the cost can be reduced; meanwhile, the reaction temperature is reduced to room temperature, the redox efficiency is higher, the total reaction time is about 2 hours, the initial dispersibility (the water reducing rate is improved by 4-8% under the same doping amount) and the slump retaining performance (the slump loss is reduced after 1 hour) are good, the raw materials for synthesis are cheap and easy to obtain, the synthesis process is simple and efficient, the prepared polycarboxylic acid water reducing agent can be directly used without adjusting the pH value, the industrial production is easy, and the practicability is strong;

(2) by adopting the invention, the EPEG (i.e. diethylene glycol monovinyl ether) macromonomer is copolymerized with the small monomer acrylic acid, acrylamide and sodium allylsulfonate, and the reactivity ratios of the EPEG macromonomer and the small monomer acrylic acid, the acrylamide and the sodium allylsulfonate determine that the reaction of the EPEG is closer to ideal constant ratio copolymerization, and the reaction process is easy to control;

(3) by adopting the invention, the catalyst generates free radicals through the change of the valence states of the loaded oxidant and the reducer, thereby accelerating the conversion synthesis of large and small monomers; the active components in the catalyst, other components and the carrier form a synergistic effect, so that the catalytic oxidation process is enhanced; the catalyst has stable performance and structure, is suitable for continuous production, and can be regenerated after the catalyst is deactivated; the inorganic material as heterogeneous catalyst has relatively great specific surface area, and the solid catalyst has active adsorption site for effective coordination of reactant molecule, so as to lower the reaction activity and speed and deepen the oxidation of oxidant. Organic matters can be adsorbed on the active center and deform to generate an activated complex, so that the activation energy of the reaction is reduced, and the speed of the chemical reaction is accelerated;

(4) by adopting the invention, the action mechanism of the catalyst manganese oxide (any one or a mixture of two of manganese dioxide, manganous oxide and manganese monoxide) on the free radical polymerization mainly has the following two aspects:

on one hand: catalyst manganese oxide can be used as a catalyst for redox initiation systems to make H₂O₂The decomposition rate is increased, so that the rate of generating free radicals is increased, the monomer is initiated to form monomer free radicals, and the synthesis temperature of the polycarboxylate superplasticizer is reduced, wherein the chemical reaction equation is as follows:

more monomer free radicals are generated in unit time, so that the chain initiation rate is increased, the chain free radicals are further generated, the chain growth is promoted, the molecular weight of the synthesized polycarboxylic acid water reducing agent is finally reduced, and the dispersibility of the water reducing agent with the same mixing amount is enhanced;

on the other hand: the carboxyl can not only be matched with the metal oxide in a plurality of coordination modes, but also can be combined with the metal oxide to form a polynuclear metal secondary structure unit, so that various coordination polymer network structures are constructed; manganese oxide can react with-COO^-A coordination reaction is carried out, electron deviation is caused through steric hindrance and an electronic effect, so that the double bond activity is increased, the polymerization reaction is promoted, and the molecular weight of the synthesized polycarboxylic acid water reducing agent is increased; the chemical reaction mechanism is shown as follows:

(5) by adopting the method, manganese oxide is added to improve the catalysis of free radical polymerization, the monomer conversion rate is improved, the polycarboxylic acid water reducing agent with an optimized molecular structure (shown as the following formula) is obtained, the prepared polycarboxylic acid water reducing agent has good dispersion performance and slump retaining performance, and different cement materials have excellent adaptability, and the polycarboxylic acid water reducing agent is particularly suitable for preparing concrete;

(6) according to the novel polyether macromonomer represented by the EPEG macromonomer, unsaturated double bonds in a molecular structure are directly connected with an oxygen atom in macromonomer ethylene glycol monovinyl ether to form a group of molecular structures with C-0 bonds, so that double bond electron cloud distribution is deviated, the charge environment of the unsaturated double bonds in the macromonomer is improved, the reaction activity of the double bonds in the macromonomer is far greater than that of the general macromonomer, and the polymerization reaction is easier to carry out. The double bonds in the molecules are of a substituted structure, so that the space resistance of swinging of the polyether side chains is further reduced, the swinging of the polyether side chains is more free, and the moving range is larger; the swinging freedom degree of the polyether side chain is increased, the wrapping property and the winding property of the polyether side chain are improved, namely the space free rotation degree of a synthesized product is high, and the wrapping effect on a concrete raw material is good, so that the synthesized polycarboxylate superplasticizer has higher adaptability, and particularly has obvious effect on the conditions of poor quality of sand and stone materials and high mud content; the production process of the initiator is pollution-free, the initiator can adapt to low-temperature synthesis of the polycarboxylate superplasticizer, and the initiator has the characteristics of high double bond activity, simple and convenient synthesis process and excellent performance of the polycarboxylate superplasticizer.

(7) The addition of acrylamide mainly introduces an amide group, the amphoteric group amide group can be adsorbed on the surfaces of cement minerals with different electrical properties so as to improve the dispersing performance of the cement and promote the hydration of the cement, and lone pair electrons on nitrogen atoms in the amide group molecular structure can generate a complex with higher water solubility with calcium ions, iron ions and the like in cement slurry through a complex reaction to generate a complex with higher water solubility, so that the hydration of tricalcium aluminate and the generation of ettringite can be promoted, the hydration process of the cement is accelerated, and the early strength of the concrete is enhanced; the action mechanism is shown in figure 2 and described;

(8) sulfonate (namely small monomer C sodium allyl sulfonate) is used as a strong ionic group, and the adsorption degree of the polymer on the surface of cement particles is influenced; when the addition amount of the sulfonate is in a proper range, the adsorption amount of cement particles to water reducer molecules is increased, the electrostatic repulsive force is enhanced, the cement dispersibility is improved, and the neat paste fluidity is higher;

(9) compared with the cement dispersing performance without the catalyst water reducing agent, the fluidity of the net slurry is increased by 30-60mm, and the loss of the fluidity is less within 10 mm; refer to the national standard GB/T50080-2002 Standard for testing the performance of the mixture of the common concrete, GB-T50081-2002 Standard for testing the mechanical properties of the common concrete, and GBT 50082-. The slump loss is small and is between 5 mm and 10mm, the slump loss is basically avoided, and the slump loss prevention effect is good; the compressive strength of the C30 concrete reaches more than 34.5MPa, the product is qualified, the 28d compressive strength of the product is 39.5-50.4MPa, and the compressive strength is higher than that of a blank group (22.3MPa) and a commercial group (35.6 MPa); the concrete freezing and thawing test has the quality loss rate below 5 percent, the product passes through 500 times of freezing and thawing resistance tests, the concrete freezing and thawing test has the quality loss rate below 0.5 percent, the quality loss rate is gradually reduced along with the increase of the test times, and the durability is good.

Drawings

FIG. 1 is an infrared spectrum of a polycarboxylic acid water-reducing agent prepared in example 6 of the present invention, the abscissa thereof being the wave number (cm)^-1) And the ordinate represents the transmittance (%); in the infrared spectrum, 3435.05cm^-1The part is a stretching vibration peak or an amido group of the hydroxyl at the tail end of the water reducing agent, which is 2885.66cm^-1The vibration peak of the expansion and contraction is the saturated C-H bond of the hydrocarbon, and the bending vibration peak is 1468.39cm^-1And 1347.88cm^-1；1965cm^-1The peak of (A) indicates that there is a nitrogen (-N-) containing group in the molecular structure, 1280.95cm^-1Is a characteristic peak of an amide III band, 1242.50cm^-1In the form of sulfonic acid group (-SO)₃-) Peak of stretching vibration, 1726.40cm^-1A stretching vibration peak of carboxylic acid C ═ O bond; 1113.19cm^-1、950.86cm^-1And 843.06cm^-1The absorption peak at (A) is a characteristic absorption peak of a long side chain polyoxyethylene group, wherein 1113.19cm^-1Is the stretching vibration peak of the ether bond C-O-C, 950.86cm^-1And 843.06cm^-1Respectively C-O and C-C stretching vibration peaks; the characteristic peaks can show that the small monomer and the polyether macromonomer are copolymerized in the solution to generate the polycarboxylic acid water reducing agent;

FIG. 2 is a diagram of the mechanism of action of acrylamide in the present invention and examples, which illustrates: in the molecular structure of the carboxyl-protective polycarboxylic acid water reducer, the slow-release component such as an amide group is less in adsorption groups such as-COOH compared with the common polycarboxylic acid water reducer at the beginning of the hydrolysis reaction, so that the initial adsorption capacity is weak, and the fluidity of cement paste using the common polycarboxylic acid water reducer is higher than that of cement paste using the carboxyl-protective polycarboxylic acid water reducer; however, in the process of continuous hydration reaction of cement, water reducing agent molecules which are dissociated in the slurry and not adsorbed by cement particles are continuously hydrolyzed in an alkaline environment provided by cement paste and release adsorption groups such as-COOH and the like, and the surfaces of the cement particles continuously adsorb the carboxyl groups, so that the dispersing performance of the cement slurry is improved, the fluidity of the cement slurry is not reduced, and the concrete slump is hardly lost; the process is continued until hydration products completely coat the water reducing agent which is adsorbed secondarily, and when no free polycarboxylic acid water reducing agent molecules remain in the water, the slump of the concrete begins to decrease; compared with the common polycarboxylic acid water reducing agent, the slow-release polycarboxylic acid water reducing agent can continuously exert a dispersing effect on cement paste, and the slump of concrete is kept not to be greatly lost;

Detailed Description

The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.

Example 1:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: respectively preparing solution A (3.56 g of small monomer A, 0.15g of small monomer B, 0.15g of small monomer C and 14.9g of distilled water) and solution B (0.028 g of ascorbic acid, 0.20g of thioglycolic acid and 18.87g of distilled water) for standby application, adding 36g of large monomer (namely ethylene glycol monovinyl ether, EPEG for short) and 15g of distilled water into a three-neck flask with a thermometer, gradually controlling the temperature and stirring to dissolve at room temperature, adding 0.005g of manganese oxide and 3g of water when the temperature is controlled to 10 ℃ and the large monomer is completely dissolved, mixing and stirring for 20min, adding 0.25g of hydrogen peroxide and 0.5g of water, uniformly mixing, simultaneously dropwise adding solution A (36min is dropwise added) and solution B (66min is dropwise added) by using a constant-pressure dropping funnel, keeping the temperature for 0.5h, standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer (namely the polycarboxylic acid water reducer synthesized by the manganese oxide heterogeneous catalysis copolymerization of the 6C polyether large monomer), the same applies later).

Example 2:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: respectively preparing solution A (3.62 g of small monomer A, 0.2g of small monomer B, 0.35g of small monomer C and 15g of distilled water) and solution B (0.04 g of ascorbic acid, 0.266g of thioglycolic acid and 18g of distilled water) for standby application, adding 30g of macromonomer (EPEG) and 15.9g of distilled water into a three-neck flask with a thermometer, gradually controlling the temperature and stirring to dissolve at room temperature, adding 0.015g of manganese oxide and 2g of water when the temperature is controlled to 15 ℃ and the macromonomer is completely dissolved, mixing and stirring for 10min, adding 0.22g of hydrogen peroxide and 0.5g of water, uniformly mixing, simultaneously dropwise adding solution A (38min is finished) and solution B (68min is finished) by using a constant-pressure dropping funnel, keeping the temperature for 0.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 3:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: respectively preparing solution A (3.1 g of small monomer A, 0.16g of small monomer B, 0.55g of small monomer C and 16.2g of distilled water) and solution B (0.05 g of ascorbic acid, 0.38g of thioglycolic acid and 19g of distilled water) for standby application, adding 38.02g of macromonomer (EPEG) and 18.66g of distilled water into a three-neck flask with a thermometer, gradually controlling the temperature and stirring for dissolution at room temperature, adding 0.02g of manganese oxide and 2g of water when the temperature is controlled to be 5 ℃ and the large monomer is completely dissolved, mixing and stirring for 28min, adding 0.38g of hydrogen peroxide and 0.5g of water, uniformly mixing, simultaneously dropwise adding solution A (35min is finished) and solution B (65min is finished) by using a constant-pressure dropping funnel, keeping the temperature for 0.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 4:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: respectively preparing solution A (3.888 g of small monomer A, 0.1062g of small monomer B, 0.58g of small monomer C and 17.285g of distilled water) and solution B (0.0445 g of ascorbic acid, 0.018g of thioglycolic acid and 19.87g of distilled water) for later use, adding 35.02g of macromonomer (EPEG) and 18.65g of distilled water into a three-neck flask with a thermometer, gradually controlling the temperature and stirring for dissolution at room temperature, adding 0.009g of manganese oxide and 2g of water when the temperature is controlled to be 8 ℃ and the macromonomer is completely dissolved, mixing and stirring for 22min, adding 0.68g of hydrogen peroxide and 0.5g of water, uniformly mixing, simultaneously dropwise adding solution A (40min is finished) and solution B (70min is finished) by using a constant-pressure dropping funnel, keeping the temperature for 0.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 5:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: respectively preparing solution A (3.28 g of small monomer A, 0.65g of small monomer B, 0.15g of small monomer C and 15.2g of distilled water) and solution B (0.06 g of ascorbic acid, 0.12g of thioglycolic acid and 20g of distilled water) for standby application, adding 40g of macromonomer (EPEG) and 20g of distilled water into a three-neck flask with a thermometer, gradually controlling the temperature and stirring to dissolve at room temperature, adding 0.019g of manganese oxide and 2g of water when the temperature is controlled to be 5 ℃ and the macromonomer is completely dissolved, mixing and stirring for 12min, adding 0.558g of hydrogen peroxide and 0.5g of water, uniformly mixing, simultaneously dropwise adding solution A (36min is finished) and solution B (66min is finished) by using a constant-pressure dropping funnel, keeping the temperature for 0.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 6:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: respectively preparing solution A (3.6 g of small monomer A, 0.2g of small monomer B, 0.75g of small monomer C and 13.680g of distilled water) and solution B (0.0925 g of ascorbic acid, 0.295g of thioglycolic acid and 21g of distilled water) for later use, adding 35.88g of large monomer (EPEG) and 20.65g of distilled water into a three-neck flask with a thermometer, gradually controlling the temperature and stirring for dissolving at room temperature, adding 0.02g of manganese oxide and 2g of water when the temperature is controlled to be 15 ℃ and the large monomer is completely dissolved, mixing and stirring for 26min, adding 0.66g of hydrogen peroxide and 0.5g of water, uniformly mixing, simultaneously dropwise adding solution A (39min is finished) and solution B (69min is finished) by using a constant-pressure dropping funnel, keeping the temperature for 0.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 7:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: respectively preparing solution A (3.5 g of small monomer A, 0.052g of small monomer B, 1.15g of small monomer C and 15.28g of distilled water) and solution B (0.062 g of ascorbic acid, 0.0152g of thioglycolic acid and 20.87g of distilled water) for later use, adding 38.141g of large monomer (EPEG) and 18.69g of distilled water into a three-neck flask with a thermometer, gradually controlling the temperature and stirring for dissolving at room temperature, adding 0.018g of manganese oxide and 2g of water when the temperature is controlled to be 8 ℃ and the large monomer is completely dissolved, mixing and stirring for 13min, adding 0.52g of hydrogen peroxide and 0.5g of water, uniformly mixing, simultaneously dropwise adding solution A (33min is completely dropwise added) and solution B (63min is completely added) by using a constant-pressure dropping funnel, keeping the temperature for 0.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 8:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: respectively preparing solution A (2.8 g of small monomer A, 0.2g of small monomer B, 0.95g of small monomer C and 16g of distilled water) and solution B (0.051 g of ascorbic acid, 0.052g of thioglycolic acid and 16g of distilled water) for later use, adding 37g of macromonomer (EPEG) and 16g of distilled water into a three-neck flask with a thermometer, gradually controlling the temperature and stirring to dissolve at room temperature, adding 0.015g of manganese oxide and 2g of water when the temperature is controlled to 15 ℃ and the macromonomer is completely dissolved, mixing and stirring for 25min, adding 0.05g of hydrogen peroxide and 0.5g of water, uniformly mixing, simultaneously dropwise adding solution A (32min is finished) and solution B (62min is finished) by using a constant-pressure dropping funnel, keeping the temperature for 0.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 9:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: respectively preparing solution A (4.6 g of small monomer A, 0.02g of small monomer B, 0.95g of small monomer C and 15g of distilled water) and solution B (0.08 g of ascorbic acid, 0.02g of thioglycolic acid and 17g of distilled water) for later use, adding 36g of large monomer (EPEG) and 16g of distilled water into a three-neck flask with a thermometer, gradually controlling the temperature and stirring to dissolve at room temperature, adding 0.018g of manganese oxide and 2g of water when the temperature is controlled to 15 ℃ and the large monomer is completely dissolved, mixing and stirring for 11min, adding 0.478g of hydrogen peroxide and 0.5g of water, uniformly mixing, simultaneously dropwise adding solution A (after 35min is finished) and solution B (after 65min is finished) by using a constant-pressure dropping funnel, keeping the temperature for 0.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 10:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: respectively preparing solution A (3.4 g of small monomer A, 0.86g of small monomer B, 0.15g of small monomer C and 15g of distilled water) and solution B (0.06 g of ascorbic acid, 0.19g of thioglycolic acid and 18g of distilled water) for later use, adding 36g of large monomer (EPEG) and 16g of distilled water into a three-neck flask with a thermometer, gradually controlling the temperature and stirring to dissolve at room temperature, adding 0.0198g of manganese oxide and 2g of water when the temperature is controlled to 15 ℃ and the large monomer is completely dissolved, mixing and stirring for 13min, adding 0.38g of hydrogen peroxide and 0.5g of water, uniformly mixing, simultaneously dropwise adding solution A (after 33min is finished) and solution B (after 63min is finished) by using a constant-pressure dropping funnel, keeping the temperature for 0.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

In examples 1-10 above: the macromonomer is diethylene glycol monovinyl ether (EPEG for short and 6C polyether macromonomer for short, and product production enterprises comprise Sichuan Hongcong new material company, Liaoning Oaku chemical company, Bailingwei science and technology company and Saen chemical technology (Shanghai) company), and the molecular weight is 1500-4000; the small monomer A is acrylic acid, the small monomer B is acrylamide, and the small monomer C is sodium allylsulfonate;

in examples 1-10 above: the catalyst (manganese oxide) is any one or a mixture of two of manganese dioxide, manganic oxide and manganese monoxide.

The application example is as follows:

and carrying out a cement paste test and a concrete test on the synthesized polycarboxylate superplasticizer. The performance index of the polycarboxylate superplasticizer is according to the industry standard JG/T223-2007 polycarboxylic acid high-performance water reducing agent; the cement paste fluidity test is carried out according to the national standard GB/T8077-2000 'concrete admixture homogeneity test method', the water reducing agent folded solid mixing amount is 0.12%, and the test results are shown in Table 1; according to the national standard GB/T50080-2002 performance test standards of common concrete mixture, the concrete test has the water reducing agent bending solid content of 0.22 percent; GB-T50081-2002 Standard test method for mechanical properties of common concrete carries out related tests.

Table 1: application performance test results:

description of the drawings: the breaking and mixing amount of the polycarboxylate superplasticizer is 0.12 percent, and the Czochralski method is P.O 42.5.5R cement. W/C is water/cement (mass ratio).

Table 2: c₃₀Concrete test results:

description of the drawings: the bending and consolidation blending amount of the polycarboxylic acid water reducer is tested to be 0.22%, the cement with the tensile modulus of P.O 42.5.5R, medium sand (machine-made sand) and 5-25 continuous granular macadam are adopted, the consumption of each side of the cement is 360 kg, and the sand rate is 45%.

Table 3: the concrete freeze-thaw test quality loss rate test result is as follows:

description of the drawings: the water-gel ratio of the polycarboxylic acid water reducer is tested to be 0.45, the bending and fixing parameters of the water reducer are 0.22%, cement of a drawing base P.O 42.5.5R, medium sand (machine-made sand) and 5-25 continuous granular rubbles are adopted, the consumption of each side of the cement is 360 kg, and the sand rate is 45%. (-representing no loss)

Example 11:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps:

a. preparing materials:

taking raw materials including a macromonomer, a small monomer A, a small monomer B, a small monomer C, a chain transfer agent, a reducing agent, an oxidizing agent, a catalyst and water, wherein: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 3: 6:0.03:0.02:1, the chain transfer agent accounts for 0.2 percent of the total mass of the monomers (the total mass of the monomers is the sum of the masses of the small monomer A, the small monomer B, the small monomer C and the large monomer, and the sum is the same), the reducing agent accounts for 0.03 percent of the total mass of the monomers, the oxidizing agent accounts for 0.12 percent of the total mass of the monomers, and the catalyst accounts for 0.02 percent of the total mass of the monomers; mixing the small monomer A, the small monomer B and the small monomer C with water, and uniformly stirring to prepare a solution A for later use; mixing a reducing agent, a chain transfer agent and water, and uniformly stirring to prepare a solution B for later use;

b. and (3) synthesis reaction:

adding the macromonomer and water into a reactor (such as a three-neck flask) with a thermometer, gradually cooling and stirring (dissolving), adding a catalyst and water to mix and stir for 20min when the temperature is controlled to be 5 ℃ and the macromonomer is completely dissolved, adding an oxidant and water to mix and stir for 8min, then (using a constant-pressure dropping funnel) simultaneously dropwise adding the solution A and the solution B at a constant speed, keeping the temperature at 5 ℃ for reaction for 1h, standing the reacted materials to room temperature, and thus obtaining the polycarboxylic acid water reducer (namely the polycarboxylic acid water reducer synthesized by manganese oxide heterogeneous catalytic quaternary copolymerization of 6C polyether macromonomer, and the like).

Refer to the national standard GB/T50080-2002 Standard for testing the performance of the mixture of the common concrete, GB-T50081-2002 Standard for testing the mechanical properties of the common concrete, and GBT 50082-. The loss of fluidity and slump is small, and the compressive strength of the C30 concrete reaches more than 34.5MPa and is qualified; the concrete freeze-thaw test is qualified when the mass loss rate is below 5 percent; the product prepared by the embodiment (namely the polycarboxylate water reducer prepared by the embodiment) is qualified.

Example 12:

a. preparing materials:

taking raw materials including a macromonomer, a small monomer A, a small monomer B, a small monomer C, a chain transfer agent, a reducing agent, an oxidizing agent, a catalyst and water, wherein: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 3.5:0.03:0.01:1, the chain transfer agent accounts for 0.3 percent of the total mass of the monomers (the total mass of the monomers is the sum of the small monomer A, the small monomer B, the small monomer C and the large monomer, and the chain transfer agent accounts for 0.05 percent of the total mass of the monomers, the oxidant accounts for 0.2 percent of the total mass of the monomers, and the catalyst accounts for 0.03 percent of the total mass of the monomers; mixing the small monomer A, the small monomer B and the small monomer C with water, and uniformly stirring to prepare a solution A for later use; mixing a reducing agent, a chain transfer agent and water, and uniformly stirring to prepare a solution B for later use;

b. and (3) synthesis reaction:

adding the macromonomer and water into a reactor (such as a three-neck flask) with a thermometer, (gradually) cooling and stirring (dissolving), adding a catalyst and water to mix and stir for 12min when the temperature is controlled to 10 ℃ and the macromonomer is completely dissolved, adding an oxidant and water to mix and stir for 5min, then (using a constant-pressure dropping funnel) simultaneously dropwise adding the solution A and the solution B at a constant speed, keeping the temperature at 10 ℃ for reaction for 1.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Refer to the national standard GB/T50080-2002 Standard for testing the performance of the mixture of the common concrete, GB-T50081-2002 Standard for testing the mechanical properties of the common concrete, and GBT 50082-. The loss of fluidity and slump is small, and the compressive strength of the C30 concrete reaches more than 34.5MPa and is qualified; the concrete freeze-thaw test is qualified when the mass loss rate is below 5 percent; the product obtained in this example was acceptable.

Example 13:

a. preparing materials:

taking raw materials including a macromonomer, a small monomer A, a small monomer B, a small monomer C, a chain transfer agent, a reducing agent, an oxidizing agent, a catalyst and water, wherein: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 4.5:0.04:0.06:1, the chain transfer agent accounts for 0.4 percent of the total mass of the monomers (the total mass of the monomers is the sum of the small monomer A, the small monomer B, the small monomer C and the large monomer, and the chain transfer agent accounts for 0.06 percent of the total mass of the monomers, the reducing agent accounts for 0.5 percent of the total mass of the monomers, and the catalyst accounts for 0.04 percent of the total mass of the monomers; mixing the small monomer A, the small monomer B and the small monomer C with water, and uniformly stirring to prepare a solution A for later use; mixing a reducing agent, a chain transfer agent and water, and uniformly stirring to prepare a solution B for later use;

b. and (3) synthesis reaction:

adding the macromonomer and water into a reactor (such as a three-neck flask) with a thermometer, (gradually) cooling and stirring (dissolving), adding a catalyst and water to mix and stir for 15min when the temperature is controlled to 15 ℃ and the macromonomer is completely dissolved, adding an oxidant and water to mix and stir for 8min, then (using a constant-pressure dropping funnel) simultaneously dropwise adding the solution A and the solution B at a constant speed, keeping the temperature at 15 ℃ for reaction for 1.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 14:

a. preparing materials:

taking raw materials including a macromonomer, a small monomer A, a small monomer B, a small monomer C, a chain transfer agent, a reducing agent, an oxidizing agent, a catalyst and water, wherein: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 3.8:0.05: 0.01-0.1: 1, the chain transfer agent accounts for 0.45 percent of the total mass of the monomers (the total mass of the monomers is the sum of the masses of the small monomer A, the small monomer B, the small monomer C and the large monomer, and the chain transfer agent accounts for 0.08 percent of the total mass of the monomers, the oxidant accounts for 0.9 percent of the total mass of the monomers, and the catalyst accounts for 0.05 percent of the total mass of the monomers;

b. and (3) synthesis reaction:

adding the macromonomer and water into a reactor (such as a three-neck flask) with a thermometer, gradually cooling and stirring (dissolving), adding a catalyst and water to mix and stir for 20min when the temperature is controlled to be 5 ℃ and the macromonomer is completely dissolved, adding an oxidant and water to mix and stir for 6min, then (using a constant-pressure dropping funnel) simultaneously dropwise adding the solution A and the solution B at a constant speed, keeping the temperature at the temperature of 5 ℃ for reaction for 1.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 15:

a. preparing materials:

taking raw materials including a macromonomer, a small monomer A, a small monomer B, a small monomer C, a chain transfer agent, a reducing agent, an oxidizing agent, a catalyst and water, wherein: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 4.2:0.05:0.08:1, the chain transfer agent accounts for 0.5 percent of the total mass of the monomers (the total mass of the monomers is the sum of the small monomer A, the small monomer B, the small monomer C and the large monomer, and the chain transfer agent is 0.13 percent of the total mass of the monomers, the oxidant accounts for 1.1 percent of the total mass of the monomers, and the catalyst accounts for 0.06 percent of the total mass of the monomers; mixing the small monomer A, the small monomer B and the small monomer C with water, and uniformly stirring to prepare a solution A for later use; mixing a reducing agent, a chain transfer agent and water, and uniformly stirring to prepare a solution B for later use;

b. and (3) synthesis reaction:

adding the macromonomer and water into a reactor (such as a three-neck flask) with a thermometer, gradually cooling and stirring (dissolving), adding a catalyst and water to mix and stir for 15min when the temperature is controlled to 10 ℃ and the macromonomer is completely dissolved, adding an oxidant and water to mix and stir for 5-10 min, then (using a constant pressure dropping funnel) simultaneously dropwise adding the solution A and the solution B at a constant speed, keeping the temperature at 10 ℃ for reaction for a total time of 1.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 16:

a. preparing materials:

taking raw materials including a macromonomer, a small monomer A, a small monomer B, a small monomer C, a chain transfer agent, a reducing agent, an oxidizing agent, a catalyst and water, wherein: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 3.8:0.05:0.09:1, the chain transfer agent accounts for 0.41 percent of the total mass of the monomers (the total mass of the monomers is the sum of the small monomer A, the small monomer B, the small monomer C and the large monomer, and the chain transfer agent accounts for 0.03 percent of the total mass of the monomers, the oxidant accounts for 1.3 percent of the total mass of the monomers, and the catalyst accounts for 0.05 percent of the total mass of the monomers; mixing the small monomer A, the small monomer B and the small monomer C with water, and uniformly stirring to prepare a solution A for later use; mixing a reducing agent, a chain transfer agent and water, and uniformly stirring to prepare a solution B for later use;

b. and (3) synthesis reaction:

adding the macromonomer and water into a reactor (such as a three-neck flask) with a thermometer, gradually cooling and stirring (dissolving), adding a catalyst and water to mix and stir for 12min when the temperature is controlled to be 8 ℃ and the macromonomer is completely dissolved, adding an oxidant and water to mix and stir for 5-10 min, then (using a constant pressure dropping funnel) simultaneously dropwise adding the solution A and the solution B at a constant speed, keeping the temperature at 8 ℃ for reaction for 1.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 17:

a. preparing materials:

taking raw materials including a macromonomer, a small monomer A, a small monomer B, a small monomer C, a chain transfer agent, a reducing agent, an oxidizing agent, a catalyst and water, wherein: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 3.0:0.01:0.01:1, the chain transfer agent accounts for 0.18 percent of the total mass of the monomers (the total mass of the monomers is the sum of the small monomer A, the small monomer B, the small monomer C and the large monomer, and the chain transfer agent is 0.03 percent of the total mass of the monomers, the oxidant accounts for 0.1 percent of the total mass of the monomers, and the catalyst accounts for 0.01 percent of the total mass of the monomers; mixing the small monomer A, the small monomer B and the small monomer C with water, and uniformly stirring to prepare a solution A for later use; mixing a reducing agent, a chain transfer agent and water, and uniformly stirring to prepare a solution B for later use;

b. and (3) synthesis reaction:

adding the macromonomer and water into a reactor (such as a three-neck flask) with a thermometer, gradually cooling and stirring (dissolving), adding a catalyst and water to mix and stir for 20min when the temperature is controlled to be 5 ℃ and the macromonomer is completely dissolved, adding an oxidant and water to mix and stir for 10min, then (using a constant-pressure dropping funnel) simultaneously dropwise adding the solution A and the solution B at a constant speed, keeping the temperature at 5 ℃ for reaction for 2h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 18:

a. preparing materials:

taking raw materials including a macromonomer, a small monomer A, a small monomer B, a small monomer C, a chain transfer agent, a reducing agent, an oxidizing agent, a catalyst and water, wherein: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 4.5:0.1:0.1:1, the chain transfer agent accounts for 0.58 percent of the total mass of the monomers (the total mass of the monomers is the sum of the small monomer A, the small monomer B, the small monomer C and the large monomer, and the chain transfer agent accounts for 0.15 percent of the total mass of the monomers, the oxidant accounts for 1.5 percent of the total mass of the monomers, and the catalyst accounts for 0.06 percent of the total mass of the monomers; mixing the small monomer A, the small monomer B and the small monomer C with water, and uniformly stirring to prepare a solution A for later use; mixing a reducing agent, a chain transfer agent and water, and uniformly stirring to prepare a solution B for later use;

b. and (3) synthesis reaction:

adding the macromonomer and water into a reactor (such as a three-neck flask) with a thermometer, gradually cooling and stirring (dissolving), adding a catalyst and water to mix and stir for 10min when the temperature is controlled to be 20 ℃ and the macromonomer is completely dissolved, adding an oxidant and water to mix and stir for 5min, then (using a constant-pressure dropping funnel) simultaneously dropwise adding the solution A and the solution B at a constant speed, keeping the temperature at 20 ℃ for reaction for 1h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 19:

a. preparing materials:

taking raw materials including a macromonomer, a small monomer A, a small monomer B, a small monomer C, a chain transfer agent, a reducing agent, an oxidizing agent, a catalyst and water, wherein: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 3.8:0.05:0.05:1, the chain transfer agent accounts for 0.38 percent of the total mass of the monomers (the total mass of the monomers is the sum of the small monomer A, the small monomer B, the small monomer C and the large monomer, and the chain transfer agent accounts for 0.08 percent of the total mass of the monomers, the oxidant accounts for 0.8 percent of the total mass of the monomers, and the catalyst accounts for 0.03 percent of the total mass of the monomers; mixing the small monomer A, the small monomer B and the small monomer C with water, and uniformly stirring to prepare a solution A for later use; mixing a reducing agent, a chain transfer agent and water, and uniformly stirring to prepare a solution B for later use;

b. and (3) synthesis reaction:

adding the macromonomer and water into a reactor (such as a three-neck flask) with a thermometer, (gradually) cooling and stirring (dissolving), adding a catalyst and water to mix and stir for 15min when the temperature is controlled to be 13 ℃ and the macromonomer is completely dissolved, adding an oxidant and water to mix and stir for 7min, then (using a constant-pressure dropping funnel) simultaneously dropwise adding the solution A and the solution B at a constant speed, keeping the temperature at 13 ℃ for reaction for 1.5h, and standing the reacted materials to room temperature to obtain the polycarboxylic acid water reducer.

Example 20:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 3.5:0.06:0.03:1, the chain transfer agent accounts for 0.4 percent of the total mass of the monomers, the reducing agent accounts for 0.12 percent of the total mass of the monomers, the oxidizing agent accounts for 1.15 percent of the total mass of the monomers, and the catalyst accounts for 0.04 percent of the total mass of the monomers; the same as any of embodiments 11 to 19, except that the above-mentioned embodiment is omitted.

Example 21:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 3.5:0.06:0.03:1, the chain transfer agent accounts for 0.4 percent of the total mass of the monomers, the reducing agent accounts for 0.08 percent of the total mass of the monomers, the oxidizing agent accounts for 0.85 percent of the total mass of the monomers, and the catalyst accounts for 0.03 percent of the total mass of the monomers; the same as any of embodiments 11 to 19, except that the above-mentioned embodiment is omitted.

Example 22:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 3.5:0.06:0.03:1, the chain transfer agent accounts for 0.25 percent of the total mass of the monomers, the reducing agent accounts for 0.12 percent of the total mass of the monomers, the oxidizing agent accounts for 0.95 percent of the total mass of the monomers, and the catalyst accounts for 0.02 percent of the total mass of the monomers; the same as any of embodiments 11 to 19, except that the above-mentioned embodiment is omitted.

Example 23:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 3.5:0.06:0.03:1, the chain transfer agent accounts for 0.2 percent of the total mass of the monomers, the reducing agent accounts for 0.08 percent of the total mass of the monomers, the oxidizing agent accounts for 0.85 percent of the total mass of the monomers, and the catalyst accounts for 0.02 percent of the total mass of the monomers; the same as any of embodiments 11 to 19, except that the above-mentioned embodiment is omitted.

Example 24:

Example 25:

a method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 3.5:0.06:0.03:1, the chain transfer agent accounts for 0.3 percent of the total mass of the monomers, the reducing agent accounts for 0.1 percent of the total mass of the monomers, the oxidizing agent accounts for 1 percent of the total mass of the monomers, and the catalyst accounts for 0.03 percent of the total mass of the monomers; the same as any of embodiments 11 to 19, except that the above-mentioned embodiment is omitted.

Example 26:

a method for synthesizing a polycarboxylate superplasticizer through heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps of mixing a small monomer A, a small monomer B and a small monomer C with water to prepare a solution A: mixing the small monomer A, the small monomer B and the small monomer C with water according to the mass ratio of the small monomer A, the small monomer B and the small monomer C to the mass ratio of water of 1:10 to prepare solution A; in the step a, the reducing agent, the chain transfer agent and water are mixed to prepare a solution B, which comprises the following steps: mixing the reducing agent and the chain transfer agent with water according to the mass ratio of the total mass of the reducing agent and the chain transfer agent to the mass of water being 1:80 to prepare liquid B; the addition of the macromonomer and water to the reactor with thermometer in step b is: adding the macromonomer and water into a reactor with a thermometer according to the mass ratio of the macromonomer to the water of 1: 0.5; the same as any of embodiments 11 to 25, except that the above-mentioned embodiment is omitted.

Example 27:

a method for synthesizing a polycarboxylate superplasticizer through heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps of mixing a small monomer A, a small monomer B and a small monomer C with water to prepare a solution A: mixing the small monomer A, the small monomer B and the small monomer C with water according to the mass ratio of the small monomer A, the small monomer B and the small monomer C to the mass ratio of water to be 1:8 to prepare solution A; in the step a, the reducing agent, the chain transfer agent and water are mixed to prepare a solution B, which comprises the following steps: mixing the reducing agent, the chain transfer agent and water according to the mass ratio of the total mass of the reducing agent and the chain transfer agent to the mass of water of 1:88 to prepare a solution B; the addition of the macromonomer and water to the reactor with thermometer in step b is: adding the macromonomer and water into a reactor with a thermometer according to the mass ratio of the macromonomer to the water of 1: 0.55; the same as any of embodiments 11 to 25, except that the above-mentioned embodiment is omitted.

Example 28:

a method for synthesizing a polycarboxylate superplasticizer through heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps of mixing a small monomer A, a small monomer B and a small monomer C with water to prepare a solution A: mixing the small monomer A, the small monomer B and the small monomer C with water according to the mass ratio of the small monomer A, the small monomer B and the small monomer C to the mass ratio of water of 1:5.6 to prepare solution A; in the step a, the reducing agent, the chain transfer agent and water are mixed to prepare a solution B, which comprises the following steps: mixing the reducing agent and the chain transfer agent with water according to the mass ratio of the total mass of the reducing agent and the chain transfer agent to the mass of water being 1:100 to prepare a solution B; the addition of the macromonomer and water to the reactor with thermometer in step b is: adding the macromonomer and water into a reactor with a thermometer according to the mass ratio of the macromonomer to the water of 1: 0.6; the same as any of embodiments 11 to 25, except that the above-mentioned embodiment is omitted.

Example 29:

a method for synthesizing a polycarboxylate superplasticizer through heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps of mixing a small monomer A, a small monomer B and a small monomer C with water to prepare a solution A: mixing the small monomer A, the small monomer B and the small monomer C with water according to the mass ratio of the small monomer A, the small monomer B and the small monomer C to the mass ratio of water of 1:5.8 to prepare solution A; in the step a, the reducing agent, the chain transfer agent and water are mixed to prepare a solution B, which comprises the following steps: mixing the reducing agent, the chain transfer agent and water according to the mass ratio of the total mass of the reducing agent and the chain transfer agent to the mass of water of 1:78 to prepare a solution B; the addition of the macromonomer and water to the reactor with thermometer in step b is: adding the macromonomer and water into a reactor with a thermometer according to the mass ratio of the macromonomer to the water of 1: 0.4; the same as any of embodiments 11 to 25, except that the above-mentioned embodiment is omitted.

Example 30:

a method for synthesizing a polycarboxylate superplasticizer through heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps of mixing a small monomer A, a small monomer B and a small monomer C with water to prepare a solution A: mixing the small monomer A, the small monomer B and the small monomer C with water according to the mass ratio of the small monomer A, the small monomer B and the small monomer C to the mass ratio of water of 1:5 to prepare solution A; in the step a, the reducing agent, the chain transfer agent and water are mixed to prepare a solution B, which comprises the following steps: mixing the reducing agent and the chain transfer agent with water according to the mass ratio of the total mass of the reducing agent and the chain transfer agent to the mass of water being 1:66 to prepare a solution B; the addition of the macromonomer and water to the reactor with thermometer in step b is: adding the macromonomer and water into a reactor with a thermometer according to the mass ratio of the macromonomer to the water of 1: 0.2; the same as any of embodiments 11 to 25, except that the above-mentioned embodiment is omitted.

Example 31:

a method for synthesizing a polycarboxylate superplasticizer through heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps of mixing a small monomer A, a small monomer B and a small monomer C with water to prepare a solution A: mixing the small monomer A, the small monomer B and the small monomer C with water according to the mass ratio of the small monomer A, the small monomer B and the small monomer C to the mass ratio of water of 1:15 to prepare solution A; in the step a, the reducing agent, the chain transfer agent and water are mixed to prepare a solution B, which comprises the following steps: mixing the reducing agent, the chain transfer agent and water according to the mass ratio of the total mass of the reducing agent and the chain transfer agent to the mass of water of 1:126 to prepare a solution B; the addition of the macromonomer and water to the reactor with thermometer in step b is: adding the macromonomer and water into a reactor with a thermometer according to the mass ratio of the macromonomer to the water of 1: 0.6; the same as any of embodiments 11 to 25, except that the above-mentioned embodiment is omitted.

Example 32:

a method for synthesizing a polycarboxylate superplasticizer through heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer comprises the following steps of mixing a small monomer A, a small monomer B and a small monomer C with water to prepare a solution A: mixing the small monomer A, the small monomer B and the small monomer C with water according to the mass ratio of the small monomer A, the small monomer B and the small monomer C to the mass ratio of water of 1:10 to prepare solution A; in the step a, the reducing agent, the chain transfer agent and water are mixed to prepare a solution B, which comprises the following steps: mixing the reducing agent and the chain transfer agent with water according to the mass ratio of the total mass of the reducing agent and the chain transfer agent to water of 1:96 to prepare solution B; the addition of the macromonomer and water to the reactor with thermometer in step b is: adding the macromonomer and water into a reactor with a thermometer according to the mass ratio of the macromonomer to the water of 1: 0.3; the same as any of embodiments 11 to 25, except that the above-mentioned embodiment is omitted.

Example 33:

a method for synthesizing a polycarboxylate superplasticizer by manganese oxide heterogeneous catalysis quaternary copolymerization of a 6C polyether macromonomer, wherein the catalyst and water are added in the step b for mixing and stirring, and the catalyst and the water are added in a mass ratio of 1: 100; adding an oxidant and water in the step b, mixing and stirring, namely adding the oxidant and the water according to the mass ratio of 1:0.7 of the oxidant to the water, mixing and stirring; the same as any of embodiments 11 to 32 is omitted.

Example 34:

a method for synthesizing a polycarboxylate superplasticizer by manganese oxide heterogeneous catalysis quaternary copolymerization of a 6C polyether macromonomer, wherein the catalyst and water are added in the step b for mixing and stirring, and the catalyst and the water are added in a mass ratio of 1:600 for mixing and stirring; adding an oxidant and water in a mass ratio of 1:10, mixing and stirring; the same as any of embodiments 11 to 32 is omitted.

Example 35:

a method for synthesizing a polycarboxylate superplasticizer by manganese oxide heterogeneous catalysis quaternary copolymerization of a 6C polyether macromonomer, wherein the catalyst and water are added in the step b for mixing and stirring, and the catalyst and the water are added in a mass ratio of 1: 230; adding an oxidant and water in a mass ratio of 1:5, mixing and stirring; the same as any of embodiments 11 to 32 is omitted.

Example 36:

a method for synthesizing a polycarboxylate superplasticizer by manganese oxide heterogeneous catalysis quaternary copolymerization of a 6C polyether macromonomer, wherein the catalyst and water are added in the step b for mixing and stirring, and the catalyst and the water are added in a mass ratio of 1:350 for mixing and stirring; adding an oxidant and water in a mass ratio of 1:3, and mixing and stirring; the same as any of embodiments 11 to 32 is omitted.

Example 37:

a method for synthesizing a polycarboxylate superplasticizer by manganese oxide heterogeneous catalysis quaternary copolymerization of a 6C polyether macromonomer, wherein the catalyst and water are added in the step b for mixing and stirring, and the catalyst and the water are added in a mass ratio of 1:160 for mixing and stirring; adding an oxidant and water in a mass ratio of 1:2, and mixing and stirring; the same as any of embodiments 11 to 32 is omitted.

Example 38:

in the step B, liquid A and liquid B are simultaneously dropwise added at a constant speed, and the total time of dropwise addition and heat preservation reaction at the temperature of 5-20 ℃ is 1-2 hours, wherein the method comprises the following steps: simultaneously dripping the solution A and the solution B at a constant speed, finishing dripping the solution A for 0.6h, finishing dripping the solution B for 1.1h, and keeping the temperature at 12 ℃ for 0.5h after finishing dripping the solution B; (ii) a The same as any of embodiments 11 to 37, however, are omitted.

In the above examples 11-38: the macromonomer is diethylene glycol monovinyl ether (EPEG for short and 6C polyether macromonomer for short, and product production enterprises comprise Sichuan Hongcong new material company, Liaoning Oaku chemical company, Bailingwei science and technology company and Saen chemical technology (Shanghai) company), and the molecular weight is 1500-4000; said small monomer A is acrylic acid, said small monomer B is acrylamide, said small monomer C is sodium allylsulfonate; the chain transfer agent is one or a mixture of two of thioglycolic acid, mercaptopropionic acid and thioglycolic acid; the catalyst is one or a mixture of two of manganese dioxide, manganous oxide, manganous manganic oxide and manganese monoxide; the reducing agent is one or a mixture of more than two of sodium hypophosphite, sodium bisulfite, sodium sulfite and ascorbic acid; the oxidant is one or a mixture of more than two of hydrogen peroxide, potassium persulfate and ammonium persulfate; the water is distilled water, ultrapure water or deionized water.

In the above embodiment: the percentages used, not specifically indicated, are percentages by weight or known to those skilled in the art; the parts by mass (by weight) may all be grams or kilograms.

In the above embodiment: the process parameters (temperature, time, etc.) and the numerical values of the components in each step are in the range, and any point can be applicable. All the raw materials are commercially available products.

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

The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.

Claims

1. A method for synthesizing a polycarboxylate superplasticizer by heterogeneous catalysis quaternary copolymerization of manganese oxide of a 6C polyether macromonomer is characterized by comprising the following steps:

a. preparing materials:

taking raw materials including a macromonomer, a small monomer A, a small monomer B, a small monomer C, a chain transfer agent, a reducing agent, an oxidizing agent, a catalyst and water, wherein: the mole ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 3.0-4.5: 0.01-0.1: 1, the chain transfer agent accounts for 0.18-0.58% of the total mass of the monomers, the reducing agent accounts for 0.03-0.15% of the total mass of the monomers, the oxidizing agent accounts for 0.1-1.5% of the total mass of the monomers, and the catalyst accounts for 0.01-0.06% of the total mass of the monomers;

mixing the small monomer A, the small monomer B and the small monomer C with water, and uniformly stirring to prepare a solution A for later use;

mixing a reducing agent, a chain transfer agent and water, and uniformly stirring to prepare a solution B for later use;

the macromonomer is diethylene glycol monovinyl ether;

b. and (3) synthesis reaction:

adding a macromonomer and water into a reactor with a thermometer, cooling and stirring, adding a catalyst and water, mixing and stirring for 10-20 min when the temperature is controlled to be 5-20 ℃ and the macromonomer is completely dissolved, adding an oxidant and water, mixing and stirring for 5-10 min, simultaneously dropwise adding the solution A and the solution B at a constant speed, wherein the total time of dropwise adding and heat preservation reaction at the temperature of 5-20 ℃ is 1-2 h, and standing the reacted material to room temperature to obtain the polycarboxylic acid water reducer.

2. The method for synthesizing the polycarboxylate superplasticizer by the heterogeneous catalysis quaternary copolymerization of the manganese oxide of the 6C polyether macromonomer according to claim 1 is characterized in that: step a, the ingredients are as follows: the molar ratio of the small monomer A to the small monomer B to the small monomer C to the large monomer is 3.5:0.06:0.03:1, the chain transfer agent accounts for 0.2-0.4% of the total mass of the monomers, the reducing agent accounts for 0.08-0.12% of the total mass of the monomers, the oxidizing agent accounts for 0.85-1.15% of the total mass of the monomers, and the catalyst accounts for 0.02-0.04% of the total mass of the monomers.

3. The method for synthesizing the polycarboxylic acid water reducer by the heterogeneous catalysis quaternary copolymerization of the manganese oxide of the 6C polyether macromonomer according to claim 1 or 2, which is characterized by comprising the following steps: in the step a, the small monomer A, the small monomer B and the small monomer C are mixed with water to prepare a solution A, which comprises the following steps: and mixing the small monomer A, the small monomer B and the small monomer C with water according to the mass ratio of the small monomer A, the small monomer B and the small monomer C to the mass ratio of water of 1: 5-15 to prepare a solution A.

4. The method for synthesizing the polycarboxylic acid water reducer by the heterogeneous catalysis quaternary copolymerization of the manganese oxide of the 6C polyether macromonomer according to claim 1 or 2, which is characterized by comprising the following steps: in the step a, the reducing agent, the chain transfer agent and water are mixed to prepare a solution B, which comprises the following steps: and mixing the reducing agent and the chain transfer agent with water according to the mass ratio of the total mass of the reducing agent and the chain transfer agent to the mass of water of 1: 66-126 to prepare liquid B.

5. The method for synthesizing the polycarboxylic acid water reducer by the heterogeneous catalysis quaternary copolymerization of the manganese oxide of the 6C polyether macromonomer according to claim 1 or 2, which is characterized by comprising the following steps: the water in step a and step b is distilled water, ultrapure water or deionized water.

6. The method for synthesizing the polycarboxylic acid water reducer by the heterogeneous catalysis quaternary copolymerization of the manganese oxide of the 6C polyether macromonomer according to claim 1 or 2, which is characterized by comprising the following steps: the addition of the macromonomer and water to the reactor with thermometer in step b is: adding the macromonomer and water into a reactor with a thermometer according to the mass ratio of the macromonomer to the water of 1: 0.2-0.6.

7. The method for synthesizing the polycarboxylic acid water reducer by the heterogeneous catalysis quaternary copolymerization of the manganese oxide of the 6C polyether macromonomer according to claim 1 or 2, which is characterized by comprising the following steps: and b, adding the catalyst and water, mixing and stirring, namely adding the catalyst and the water according to the mass ratio of 1: 100-600 of the catalyst and the water, and mixing and stirring.

8. The method for synthesizing the polycarboxylic acid water reducer by the heterogeneous catalysis quaternary copolymerization of the manganese oxide of the 6C polyether macromonomer according to claim 1 or 2, which is characterized by comprising the following steps: and b, adding an oxidant and water, mixing and stirring, namely adding the oxidant and the water according to the mass ratio of the oxidant to the water of 1: 0.7-10, and mixing and stirring.

9. The method for synthesizing the polycarboxylic acid water reducer by the heterogeneous catalysis quaternary copolymerization of the manganese oxide of the 6C polyether macromonomer according to claim 1 or 2, which is characterized by comprising the following steps: and (c) performing heat preservation reaction at the temperature of 5-20 ℃ in the step b, namely performing heat preservation reaction at the temperature of 10-15 ℃.

10. The method for synthesizing the polycarboxylic acid water reducer by the heterogeneous catalysis quaternary copolymerization of the manganese oxide of the 6C polyether macromonomer according to claim 1 or 2, which is characterized by comprising the following steps: and c, simultaneously dropwise adding the solution A and the solution B at a constant speed in the step B, wherein the total time of dropwise adding and heat preservation reaction at the temperature of 5-20 ℃ is 1-2 h, and the steps are as follows: and simultaneously dropwise adding the solution A and the solution B at a constant speed, wherein the solution A is completely dropwise after 0.6 hour, the solution B is completely dropwise after 1.1 hour, and after the solution B is completely dropwise, the temperature is kept at 10-15 ℃ for 0.5 hour.