阅读说明：本技术 一种用于降低高固含浆体黏度的聚合物及其制备方法 (Polymer for reducing viscosity of high-solid-content slurry and preparation method thereof ) 是由 吴伟 黄玉美 刘昭洋 王玉乾 王进春 田宇 石雄松 于 2021-08-15 设计创作，主要内容包括：一种用于降低高固含浆体黏度的聚合物及其制备方法,本发明提供了所述聚合物的结构式。制备方法：将大单体A即聚乙二醇单甲基醚溶于二氯甲烷置于冰盐浴中,缓慢滴加卤化剂,升温,反应,加入冰水终止反应,去掉溶剂二氯甲烷,再进行冷冻干燥得到单体A的卤化物；将其溶于乙醇中,加入烷基双胺,转入高压釜中,升温,反应,终止反应,恢复室温后蒸发浓缩干燥得到单体B；将单体B置于反应釜,加入磷化剂、催化剂对甲苯磺酸,搅拌均匀,控制温度同时开始滴加胺甲基化试剂,升温,反应,加入NaOH调节pH值,得到最终产物。本发明的聚合物性能良好,对于混凝土和砂浆等宾汉流体,有效地降低了其塑性粘度,解决了高固含浆体黏度过高的问题。(The invention provides a polymer for reducing viscosity of high-solid-content slurry and a preparation method thereof, and provides a structural formula of the polymer. The preparation method comprises the following steps: dissolving a macromonomer A, namely polyethylene glycol monomethyl ether, in dichloromethane, placing in an ice salt bath, slowly dropwise adding a halogenating agent, heating, reacting, adding ice water to terminate the reaction, removing the solvent dichloromethane, and then carrying out freeze drying to obtain a halide of the monomer A; dissolving the monomer B in ethanol, adding alkyl diamine, transferring into a high-pressure kettle, heating, reacting, terminating the reaction, recovering the room temperature, evaporating, concentrating and drying to obtain a monomer B; and (3) placing the monomer B in a reaction kettle, adding a phosphating agent and a catalyst p-toluenesulfonic acid, uniformly stirring, controlling the temperature, simultaneously dropwise adding an aminomethylating reagent, heating, reacting, adding NaOH to adjust the pH value, and obtaining a final product. The polymer has good performance, effectively reduces the plastic viscosity of Bingham fluids such as concrete, mortar and the like, and solves the problem of overhigh viscosity of high solid content slurry.)

1. A polymer for reducing the viscosity of a high solids slurry, wherein the polymer for reducing the viscosity of a high solids slurry has the following formula:

in the formula, R₁Selected from hydrogen atoms or C₁To C₁₈Alkyl groups of (a); r₂Selected from hydrogen atoms or C₁To C₅Alkyl groups of (a); m is selected from hydrogen atom or alkali metal or C₁To C₅Alkyl groups of (a); a is selected from C₁-C₅An alkylamine of (a); a is an integer of 8 to 150; b is an integer of 0 to 90.

2. A method of preparing a polymer for reducing the viscosity of high solids slurries as claimed in claim 1, characterized in that it comprises the following process steps: dissolving 30-90 parts of macromonomer A, namely polyethylene glycol monomethyl ether, in dichloromethane, placing in an ice salt bath, slowly dropwise adding 10-45 parts of a halogenating agent, heating to 70-100 ℃ after dropwise adding is finished, reacting for 1-4 hours, cooling and adding ice water to terminate the reaction when the reaction end point is reached, removing dichloromethane serving as a solvent by rotary evaporation at 30 ℃, and then carrying out freeze drying to obtain a halide of the monomer A; dissolving 30-90 parts of halide of the monomer A in 750 parts of ethanol, then placing in a cold salt bath, adding 60-270 parts of alkyl diamine, then transferring into a high-pressure kettle, heating to 80-100 ℃, reacting for 12-24 hours, cooling to 0 ℃ to terminate the reaction, recovering the room temperature, and then performing rotary evaporation, concentration and drying to obtain the monomer B, wherein the alkyl diamine is one or a mixture of any two of ethylenediamine, propylenediamine, 1, 4-butanediamine, 1, 5-pentanediamine and 1, 6-hexanediamine; placing 30-90 parts of monomer B at the bottom of a reaction kettle, adding 30-180 parts of a phosphating agent and 3-10 parts of catalyst p-toluenesulfonic acid, uniformly stirring, controlling the temperature to be 40-42 ℃, simultaneously beginning to dropwise add 30-200 parts of aminomethylating reagent, completing dropwise adding within 3-6 hours, heating to 90-120 ℃ after completing dropwise adding, reacting for 6-10 hours, and adding NaOH to adjust the pH value to be 5-7 after finishing the reaction to obtain a final product, namely the polymer for reducing the viscosity of the high solid content slurry; the structural formula of the polyethylene glycol monomethyl ether is as follows:

in the formula, m: represents the polymerization degree of oxirane oxygen, and m is 8-150; n: represents the polymerization degree of propylene oxide, n is 0 to 90; and n is 0-0.6.

3. The method of claim 2, wherein the halogenating agent is one or a mixture of any two of phosphorus trichloride, phosphorus tribromide and phosphorus triiodide.

4. The method according to claim 2, wherein the phosphating agent is one or a mixture of two or more of phosphorous acid, sodium phosphite, hypophosphorous acid, sodium hypophosphite, diester phosphite, and triester phosphite.

5. The method of claim 2, wherein the aminomethylating agent is one or a mixture of two of formaldehyde, acetaldehyde, paraformaldehyde, and acetone.

6. The method according to claim 2, wherein the recommended polymerization degree m of the polyethylene glycol monomethyl ether is 8-100; the recommended polymerization degree n is between 0 and 30; the ratio of n to m is preferably between 0 and 0.3.

7. Polymerization for reducing the viscosity of high solids slurries according to claim 2The preparation method of the compound is characterized by comprising the following process steps: dissolving 90 parts of macromonomer A, namely polyethylene glycol monomethyl ether MPEG, in dichloromethane, placing in an ice salt bath, and slowly dropwise adding 30 parts of halogenating agent, namely phosphorus tribromide PBr₃In the structural formula of the polyethylene glycol monomethyl ether, n is 23, m is 92, after the dropwise addition is finished, the temperature is raised to 70 ℃, the reaction lasts for 2 hours, when the reaction end point is reached, ice water is added for stopping the reaction by cooling, dichloromethane serving as a solvent is removed by rotary evaporation at 30 ℃, and then the mixture is frozen and dried to obtain halide of the monomer A, namely bromide of the MPEG; dissolving 90 parts of MPEG bromide in 750 parts of ethanol, placing the mixture in a salt bath with ice, adding 140 parts of alkyl diamine, namely ethylenediamine, transferring the mixture into a high-pressure kettle, heating to 100 ℃, reacting for 18 hours, cooling to 0 ℃ to terminate the reaction, recovering the room temperature, and performing rotary evaporation, concentration and drying to obtain a monomer B; putting 90 parts of monomer B at the bottom of a reaction kettle, adding 180 parts of phosphorizing agent namely phosphorous acid and 5 parts of catalyst p-toluenesulfonic acid, uniformly stirring, controlling the temperature to be 40 ℃, simultaneously beginning to dropwise add 180 parts of aminomethylating reagent namely formaldehyde, completing dropwise adding within 4 hours, heating to 100 ℃ after completing dropwise adding, reacting for 7 hours, and after finishing the reaction, adding NaOH to adjust the pH value to be 6-6.2, thus obtaining the final product, namely the polymer for reducing the viscosity of the high solid content slurry.

8. The method of claim 2, wherein the method comprises the following steps: dissolving 90 parts of macromonomer A, namely polyethylene glycol monomethyl ether MPEG, in dichloromethane, placing in an ice salt bath, and slowly dropwise adding 30 parts of halogenating agent, namely phosphorus tribromide PBr₃In the structural formula of the polyethylene glycol monomethyl ether, n is 50, m is 140, when the dropwise addition is completed, the temperature is raised to 70 ℃, the reaction lasts for 2 hours, when the reaction end point is reached, ice water is added for stopping the reaction by cooling, dichloromethane serving as a solvent is removed by rotary evaporation at 30 ℃, and then the mixture is frozen and dried to obtain halide of the monomer A, namely bromide of the MPEG; ② dissolving 90 parts of MPEG bromide in 750 parts of ethanol, placing in ice salt bath, adding 140 parts of alkyl diamine, namely ethylenediamine, then transferring into a high-pressure autoclave, heating to 100 ℃, reacting for 18 hours, cooling to 0 ℃, terminating the reaction, recoveringPerforming rotary evaporation, concentration and drying after room temperature recovery to obtain a monomer B; putting 90 parts of monomer B at the bottom of a reaction kettle, adding 180 parts of phosphorizing agent namely phosphorous acid and 5 parts of catalyst p-toluenesulfonic acid, uniformly stirring, controlling the temperature to be 40 ℃, simultaneously beginning to dropwise add aminomethylating reagent namely formaldehyde 185 parts, completing dropwise adding within 5 hours, heating to 100 ℃ after completing dropwise adding, reacting for 9 hours, and after finishing the reaction, adding NaOH to adjust the pH value to be 6.4-6.6, thus obtaining the final product, namely the polymer for reducing the viscosity of the high-solid slurry.

9. The method of claim 2, wherein the method comprises the following steps: dissolving 90 parts of macromonomer A, namely polyethylene glycol monomethyl ether MPEG, in dichloromethane, placing in an ice salt bath, and slowly dropwise adding 30 parts of halogenating agent, namely phosphorus tribromide PBr₃In the structural formula of the polyethylene glycol monomethyl ether, n is 90, m is 150, after the dropwise addition is finished, the temperature is raised to 70 ℃, the reaction lasts for 2 hours, when the reaction end point is reached, ice water is added for stopping the reaction by cooling, dichloromethane serving as a solvent is removed by rotary evaporation at 30 ℃, and then the mixture is frozen and dried to obtain halide of the monomer A, namely bromide of the MPEG; dissolving 90 parts of MPEG bromide in 750 parts of ethanol, placing the mixture in a salt bath with ice, adding 140 parts of alkyl diamine, namely ethylenediamine, transferring the mixture into a high-pressure kettle, heating to 100 ℃, reacting for 18 hours, cooling to 0 ℃ to terminate the reaction, recovering the room temperature, and performing rotary evaporation, concentration and drying to obtain a monomer B; putting 90 parts of monomer B at the bottom of a reaction kettle, adding 180 parts of phosphorizing agent namely phosphorous acid and 5 parts of catalyst p-toluenesulfonic acid, uniformly stirring, controlling the temperature to be 40 ℃, simultaneously beginning to dropwise add aminomethylating reagent namely formaldehyde 185 parts, completing dropwise adding within 5 hours, heating to 100 ℃ after completing dropwise adding, reacting for 10 hours, and after finishing the reaction, adding NaOH to adjust the pH value to be 6.5-6.7, thus obtaining the final product, namely the polymer for reducing the viscosity of the high-solid slurry.

10. The method of claim 2, wherein the method comprises the following steps: firstly, 90 parts of macromonomer A are polymerizedDissolving ethylene glycol monomethyl ether MPEG in dichloromethane, placing in ice salt bath, slowly dropwise adding 30 parts of halogenating agent, namely phosphorus tribromide PBr₃In the structural formula of the polyethylene glycol monomethyl ether, n is 50, m is 120, when the dropwise addition is completed, the temperature is raised to 70 ℃, the reaction lasts for 2 hours, when the reaction end point is reached, ice water is added for stopping the reaction by cooling, dichloromethane serving as a solvent is removed by rotary evaporation at 30 ℃, and then the mixture is frozen and dried to obtain halide of the monomer A, namely bromide of the MPEG; dissolving 90 parts of MPEG bromide in 750 parts of ethanol, placing the mixture in a salt bath with ice, adding 140 parts of alkyl diamine, namely ethylenediamine, transferring the mixture into a high-pressure kettle, heating to 100 ℃, reacting for 18 hours, cooling to 0 ℃ to terminate the reaction, recovering the room temperature, and performing rotary evaporation, concentration and drying to obtain a monomer B; putting 90 parts of monomer B at the bottom of a reaction kettle, adding 90 parts of phosphorizing agent namely phosphorous acid and 3 parts of catalyst p-toluenesulfonic acid, uniformly stirring, controlling the temperature to be 40 ℃, simultaneously beginning to dropwise add aminomethylating reagent namely 90 parts of formaldehyde, completing dropwise adding within 4 hours, heating to 100 ℃ after completing dropwise adding, reacting for 6 hours, and after finishing the reaction, adding NaOH to adjust the pH value to be 6.5-6.7, thus obtaining the final product, namely the polymer for reducing the viscosity of the high-solid slurry.

Technical Field

The invention relates to a polymer for reducing viscosity of high solid content slurry, belonging to the technical field of chemical additives of building materials. The invention also relates to a preparation method of the polymer for reducing the viscosity of the high-solid-content slurry.

Background

With increasing importance on environmental protection, energy-saving and carbon-reducing lives are being vigorously pursued at present. In order to respond to the call in the concrete industry, high-performance concrete is widely used, and meanwhile, fly ash, slag and the like are used as auxiliary cementing materials, and the aim of ensuring that the strength of the concrete is not reduced is often achieved by a method of reducing a water-cement ratio. However, such a high solid content slurry tends to increase the viscosity of the concrete, and is difficult to construct. Sometimes, workers often reflect that even if the slump of the high-strength concrete meets the requirement (more than 200mm), the high-strength concrete is difficult to turn over and shovel, the viscosity of the concrete is high, and pumping and construction are difficult. There are many studies aiming at the high viscosity of concrete, and the related patent documents: CN103833251A discloses an inorganic admixture for adjusting the strength and viscosity of ultra-high strength concrete. The composition comprises the following components in percentage by mass: 5% -10% of silica fume; 20-30% of mineral powder; 60 to 75 percent of superfine powder. The superfine powder is a mixture of I-grade fly ash and microbeads, has an average grain diameter of 1-10 microns and has continuous gradation; the mass ratio of the fly ash to the microbeads is 1 (0.5-3); the fly ash powder is compact spherical particles, and the microbead powder is compact perfect regular spherical particles. When in use, the cement is added into the concrete cementing material in an amount of 10-20% of the total mass of the cementing material instead of cement. CN104230270A discloses a low-viscosity reactive powder concrete, which comprises the following components in parts by weight: cement: 0.53-0.60 part; silica fume: 0.13-0.17 part; fly ash: 0.12-0.20 part; limestone powder: 0.10-0.18 part; high-performance water reducing agent: 0.009-0.011 part; quartz sand: 1.0-1.5 parts; steel fiber: 0.08-0.24 part; mixing water: 0.14 to 0.18 portion. The technology achieves the purpose of reducing the viscosity of concrete by adding inorganic components and increasing the ball effect of the concrete, but the mixing amount of the inorganic components is often large, so that the mixing proportion of the concrete is changed. Therefore, the popularization in construction sites is difficult, and inorganic materials often require particle size and particle shape, so that the preparation energy consumption is high. The development of organic viscosity reducer is in the initial research stage at home and abroad. CN1784369A discloses a polycarboxylic acid concrete admixture exhibiting properties such as reduced concrete viscosity, improved slump-retaining ability and inhibited bleeding water, and improved properties for cement compositions and the like. The above-mentioned polycarboxylic acid concrete admixture comprises a polycarboxylic acid polymer containing a polyalkylene glycol in a side chain, wherein said polycarboxylic acid polymer is obtained by polymerizing monomer components comprising an alkyl (meth) acrylate monomer and a specific polyalkylene glycol unsaturated monomer and an unsaturated carboxylic acid (salt) monomer, and has a specific weight average molecular weight. The technology is an additive for reducing the viscosity by introducing hydrophobic acrylates, but the technology has a condition of mutual conflict with a plurality of experimental phenomena, the research on the mechanism of organic viscosity reduction is still in an exploration stage in academia, and no acknowledged product capable of effectively reducing the viscosity exists in the market at present.

The technologies have good performance on the polymer for reducing the viscosity of the high-solid-content slurry, and can effectively reduce the plastic viscosity of Bingham fluid such as concrete, mortar and the like, so that the problem of overhigh viscosity of the high-solid-content slurry is solved, and no specific guidance scheme is provided.

Disclosure of Invention

The invention aims to provide a polymer for reducing the viscosity of high-solid-content slurry, which has good performance and can effectively reduce the plastic viscosity of Bingham fluid such as concrete, mortar and the like, thereby solving the problem of overhigh viscosity of the high-solid-content slurry.

To this end, another technical problem to be solved by the present invention is to provide a method for preparing the above polymer for reducing the viscosity of high solid content slurry.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

a polymer for reducing the viscosity of a high solids slurry (or a polymer for reducing the viscosity of a high solids slurry such as a Bingham fluid such as concrete or mortar) characterized in that the polymer for reducing the viscosity of a high solids slurry has the formula:

in the formula, R₁Selected from hydrogen atoms or C₁To C₁₈Alkyl groups of (a); r₂Selected from hydrogen atoms or C₁To C₅Alkyl groups of (a); m is selected from hydrogen atom or alkali metal or C₁To C₅Alkyl groups of (a); a is selected from C₁-C₅An alkylamine of (a); a is an integer of 8 to 150; b is an integer of 0 to 90.

The preparation method of the polymer for reducing the viscosity of the high-solid slurry is characterized by comprising the following process steps: dissolving 30-90 parts of macromonomer A, namely polyethylene glycol monomethyl ether, in dichloromethane, placing in an ice salt bath (the mass ratio of the macromonomer A to the dichloromethane is 1:2-3), slowly dropwise adding 10-45 parts of halogenating agent, heating to 70-100 ℃ after dropwise adding is finished, reacting for 1-4 hours, cooling and adding ice water to terminate the reaction when the reaction end point is reached, removing the dichloromethane solvent by rotary evaporation at 30 ℃ (separating an organic layer, washing with water twice), and then carrying out freeze drying to obtain the halide of the monomer A; dissolving 30-90 parts of halide of the monomer A in 750 parts of ethanol, then placing in a cold salt bath, adding 60-270 parts of alkyl diamine, then transferring into a high-pressure kettle, heating to 80-100 ℃, reacting for 12-24 hours, cooling to 0 ℃ to terminate the reaction, recovering the room temperature, and then performing rotary evaporation, concentration and drying to obtain the monomer B, wherein the alkyl diamine is one or a mixture of any two of ethylenediamine, propylenediamine, 1, 4-butanediamine, 1, 5-pentanediamine and 1, 6-hexanediamine; placing 30-90 parts of monomer B at the bottom of a reaction kettle, adding 30-180 parts of a phosphating agent and 3-10 parts of catalyst p-toluenesulfonic acid, uniformly stirring, controlling the temperature to be 40-42 ℃, simultaneously beginning to dropwise add 30-200 parts of aminomethylating reagent, completing dropwise adding within 3-6 hours, heating to 90-120 ℃ after completing dropwise adding, reacting for 6-10 hours, and adding NaOH to adjust the pH value to be 5-7 after finishing the reaction to obtain a final product, namely the polymer for reducing the viscosity of the high solid content slurry; the structural formula of the polyethylene glycol monomethyl ether is as follows (the structural formula of the raw material containing the long-chain monomer A is as follows):

in the formula, m: represents the polymerization degree of oxirane oxygen, m is 8-150, and the recommended polymerization degree m is 8-100; n: represents the polymerization degree of epoxypropyl, n is 0-90, and the recommended polymerization degree n is 0-30;

m is 0-0.6, and the recommended ratio is 0-0.3.

In the above technical solution, a preferable technical solution may be: the halogenating agent is phosphorus trichloride PCl₃PBr of phosphorus tribromide₃One or a mixture of any two of phosphorus triiodide. The phosphating agent is one or a mixture of any two of phosphorous acid, sodium phosphite, hypophosphorous acid, sodium hypophosphite, diester phosphite and triester phosphite. The amine methylation reagent is one or a mixture of any two of formaldehyde, acetaldehyde, paraformaldehyde and acetone.

In the above technical solution, a preferable technical solution may be that: the preparation method of the polymer for reducing the viscosity of the high-solid slurry comprises the following process steps: dissolving 90 parts of macromonomer A, namely polyethylene glycol monomethyl ether (MPEG, the structural formula of the polyethylene glycol monomethyl ether is n-23, m-92) in dichloromethane, placing in a ice salt bath, and slowly dropwise adding 30 parts of halogenating agent, namely phosphorus tribromide PBr₃When the temperature is raised to 70 ℃ after the dropwise addition is finished, the reaction lasts for 2 hours, and when the reaction end point is reached, ice water is cooled and added to terminate the reaction, the solvent dichloromethane is removed by rotary evaporation at 30 ℃, and then freeze drying is carried out to obtain the halide of the monomer A, namely the bromide of the MPEG; ② dissolving 90 parts of MPEG bromide in 750 parts of ethanol, then placing in ice salt bath, adding 140 parts ofTransferring alkyl diamine, namely ethylene diamine, into a high-pressure kettle, heating to 100 ℃, reacting for 18 hours, cooling to 0 ℃ to terminate the reaction, recovering the room temperature, and then performing rotary evaporation, concentration and drying to obtain a monomer B; putting 90 parts of monomer B at the bottom of a reaction kettle, adding 180 parts of phosphorizing agent namely phosphorous acid and 5 parts of catalyst p-toluenesulfonic acid, uniformly stirring, controlling the temperature to be 40 ℃, simultaneously beginning to dropwise add 180 parts of aminomethylating reagent namely formaldehyde, completing dropwise adding within 4 hours, heating to 100 ℃ after completing dropwise adding, reacting for 7 hours, and after finishing the reaction, adding NaOH to adjust the pH value to be 6-6.2, thus obtaining the final product, namely the polymer for reducing the viscosity of the high solid content slurry.

Among the above-described technical solutions, preferred technical solutions may be embodiment 2, embodiment 3, and embodiment 4.

The invention provides a polymer for reducing the viscosity of high-solid slurry, wherein the high-solid slurry can be concrete, mortar, gypsum and nanoparticle suspension. The invention has good performance, and can effectively reduce the plastic viscosity of Bingham fluid such as concrete, mortar and the like. The invention is different from the traditional polycarboxylic acid dispersant which selects carboxyl as an anchoring group, and selects phosphoric acid as an anchoring group, so that the polycarboxylic acid dispersant has higher affinity to particles and can effectively reduce the friction force when the particles move. It is different from the traditional polycarboxylic acid which adopts a comb structure, but adopts a gemini structure, and has higher particle surface coverage rate.

For Bingham fluids, its shear force should satisfy the following equation:

τ＝τ₀+γ·μ

in the formula, gamma is shear stress and gamma₀Yield stress, gamma, shear rate, mu, plastic viscosity.

The physical meaning of yield stress is the value at which the concrete begins to flow under the influence of its own weight, which can be well characterized by slump or expansion tests. The plastic viscosity indicates the time required under flowing conditions such as concrete pouring or pumping, and cannot be characterized by slump. According to the results of the foreign rheological application research and the combination of Bingham theory, the water reducing agents (naphthalene series, sulfamic acid, aliphatic series and polycarboxylic acids) are found to be effective and obvious in reducing the yield stress of the slurry, and the slump increase and the expansion degree are increased, but the water reducing agents hardly contribute to the reduction of the plastic viscosity of the slurry, and the research also finds that the water reducing agents can even increase the plastic viscosity of the slurry. Therefore, polymers effective in reducing plastic viscosity must be found to effectively reduce the viscosity of concrete slurry.

In order to test the viscosity of the concrete, the inventor tests the outflow time of the V-shaped groove or the outflow distance of the L-shaped groove of the concrete on the premise of initially controlling the concrete to have the same expansion degree, slump and air content to characterize the plastic viscosity of the concrete. However, this is a relatively qualitative method, which cannot accurately measure the actual value of the plastic viscosity, and the polymer adsorbed on the surface of the particles is covered by the hydration product due to the non-stop hydration of the cement during the measurement, resulting in the loss of concrete. And each polymer is not consistently sensitive to such losses, which can cause different errors in testing. In order to more accurately test the plastic viscosity of the concrete, the inventor adopts a mortar rheometer to test, and the mortar is used for simulating the concrete to test. The torque of the mortar under different shear rates is tested by a rheometer, and then the torque is plotted against the shear rate, and the slope and intercept of a regression line can be obtained by linear regression, which respectively represent the yield stress and the plastic viscosity.

Adopt the beneficial effect that above-mentioned scheme had: under the condition that the common water reducing agent cannot well solve the problem of high viscosity of high-solid slurry, the surface coverage rate of particles is increased by changing the molecular structure into a gemini structure, and phosphate groups with strong anchoring capacity are selected as charged groups, so that the anchoring capacity of the particles is improved, and meanwhile, the friction force among the particles is reduced. The shaping viscosity in the Bingham fluid can be effectively reduced, the flow rate and the plasticity of the fluid are increased, and powerful guarantee is provided for configuring high-solid-content slurry in engineering application.

In conclusion, the invention provides the polymer for reducing the viscosity of the high-solid-content slurry, the polymer has good performance, and the plastic viscosity of Bingham fluids such as concrete, mortar and the like is effectively reduced, so that the problem of overhigh viscosity of the high-solid-content slurry is solved.

Drawings

Fig. 1 is a schematic view showing compressive strengths of concrete at different ages.

FIG. 2 is a graph of shear rate (plotted by apparent viscosity versus shear rate).

FIG. 3 is a shear rate graph (shear torque vs. shear rate).

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1: the preparation method of the polymer for reducing the viscosity of the high-solid slurry comprises the following process steps: 90 parts of macromonomer A, namely polyethylene glycol monomethyl ether (MPEG, the structural formula of the polyethylene glycol monomethyl ether is n-23, and m-92) is dissolved in dichloromethane and placed in a ice salt bath, and the mass ratio of the macromonomer A to the dichloromethane is 1:2. Slowly dripping 30 parts of halogenating agent PBr₃When the temperature is raised to 70 ℃ after the dropwise addition is finished, the reaction lasts for 2 hours, and when the reaction end point is reached, ice water is cooled and added to terminate the reaction, the solvent dichloromethane is removed by rotary evaporation at 30 ℃, and then freeze drying is carried out to obtain the halide of the monomer A, namely the bromide of the MPEG; dissolving 90 parts of MPEG bromide in 750 parts of ethanol, placing the mixture in a salt bath with ice, adding 140 parts of alkyl diamine, namely ethylenediamine, transferring the mixture into a high-pressure kettle, heating to 100 ℃, reacting for 18 hours, cooling to 0 ℃ to terminate the reaction, recovering the room temperature, and performing rotary evaporation, concentration and drying to obtain a monomer B; thirdly, 90 parts of monomer B is placed at the bottom of a reaction kettle, 180 parts of phosphorizing agent namely phosphorous acid and 5 parts of catalyst p-toluenesulfonic acid are added, the mixture is uniformly stirred, the temperature is controlled to be 40 ℃, 180 parts of aminomethylating reagent namely formaldehyde is added dropwise at the same time, and the mixture is added dropwise within 4 hoursAnd after finishing the dropwise addition, heating to 100 ℃, reacting for 7 hours, and after finishing the reaction, adding NaOH to adjust the pH value to 6-6.2 to obtain a final product, namely the polymer for reducing the viscosity of the high-solid-content slurry, which is recorded as 23EO 2P.

Example 2: the preparation method of the polymer for reducing the viscosity of the high-solid slurry comprises the following process steps: 90 parts of macromonomer A, namely polyethylene glycol monomethyl ether (MPEG, n is 50, m is 140) are dissolved in dichloromethane and placed in an ice salt bath, and the mass ratio of the macromonomer A to the dichloromethane is 1: 2.5. Slowly dripping 30 parts of halogenating agent PBr₃When the temperature is raised to 70 ℃ after the dropwise addition is finished, the reaction lasts for 2 hours, and when the reaction end point is reached, ice water is cooled and added to terminate the reaction, the solvent dichloromethane is removed by rotary evaporation at 30 ℃, and then freeze drying is carried out to obtain the halide of the monomer A, namely the bromide of the MPEG; dissolving 90 parts of MPEG bromide in 750 parts of ethanol, placing the mixture in a salt bath with ice, adding 140 parts of alkyl diamine, namely ethylenediamine, transferring the mixture into a high-pressure kettle, heating to 100 ℃, reacting for 18 hours, cooling to 0 ℃ to terminate the reaction, recovering the room temperature, and performing rotary evaporation, concentration and drying to obtain a monomer B; putting 90 parts of monomer B at the bottom of a reaction kettle, adding 180 parts of phosphorizing agent namely phosphorous acid and 5 parts of catalyst p-toluenesulfonic acid, uniformly stirring, controlling the temperature to be 40 ℃, simultaneously beginning to dropwise add aminomethylating reagent namely formaldehyde 185 parts, completing dropwise adding within 5 hours, heating to 100 ℃ after completing dropwise adding, reacting for 9 hours, adding NaOH to adjust the pH value to be 6.4-6.6 after finishing the reaction, and obtaining a final product, namely the polymer for reducing the viscosity of the high-solid slurry, which is marked as 50EO 2P.

Example 3: the preparation method of the polymer for reducing the viscosity of the high-solid slurry comprises the following process steps: 90 parts of macromonomer A, namely polyethylene glycol monomethyl ether (MPEG, n is 90, m is 150) are dissolved in dichloromethane and placed in an ice salt bath, and the mass ratio of the macromonomer A to the dichloromethane is 1: 3. Slowly dripping 30 parts of halogenating agent PBr₃When the temperature is raised to 70 ℃ after the dropwise addition is finished, the reaction lasts for 2 hours, and when the reaction end point is reached, ice water is added for cooling to stop the reaction, the dichloromethane serving as a solvent is removed by rotary evaporation at 30 ℃, and then the freeze drying is carried out to obtain the compoundHalides to monomer a, i.e. MPEG bromide; dissolving 90 parts of MPEG bromide in 750 parts of ethanol, placing the mixture in a salt bath with ice, adding 140 parts of alkyl diamine, namely ethylenediamine, transferring the mixture into a high-pressure kettle, heating to 100 ℃, reacting for 18 hours, cooling to 0 ℃ to terminate the reaction, recovering the room temperature, and performing rotary evaporation, concentration and drying to obtain a monomer B; putting 90 parts of monomer B at the bottom of a reaction kettle, adding 180 parts of phosphorizing agent namely phosphorous acid and 5 parts of catalyst p-toluenesulfonic acid, uniformly stirring, controlling the temperature to be 40 ℃, simultaneously beginning to dropwise add aminomethylating reagent namely formaldehyde 185 parts, completing dropwise adding within 5 hours, heating to 100 ℃ after completing dropwise adding, reacting for 10 hours, adding NaOH to adjust the pH value to be 6.5-6.7 after finishing the reaction, and obtaining a final product, namely the polymer for reducing the viscosity of the high-solid slurry, which is marked as 100EO 2P.

Example 4: the preparation method of the polymer for reducing the viscosity of the high-solid slurry comprises the following process steps: 90 parts of macromonomer A, namely polyethylene glycol monomethyl ether (MPEG, n is 50, m is 120) are dissolved in dichloromethane and placed in an ice salt bath, and the mass ratio of the macromonomer A to the dichloromethane is 1:2. Slowly dripping 30 parts of halogenating agent PBr₃When the temperature is raised to 70 ℃ after the dropwise addition is finished, the reaction lasts for 2 hours, and when the reaction end point is reached, ice water is cooled and added to terminate the reaction, the solvent dichloromethane is removed by rotary evaporation at 30 ℃, and then freeze drying is carried out to obtain the halide of the monomer A, namely the bromide of the MPEG; dissolving 90 parts of MPEG bromide in 750 parts of ethanol, placing the mixture in a salt bath with ice, adding 140 parts of alkyl diamine, namely ethylenediamine, transferring the mixture into a high-pressure kettle, heating to 100 ℃, reacting for 18 hours, cooling to 0 ℃ to terminate the reaction, recovering the room temperature, and performing rotary evaporation, concentration and drying to obtain a monomer B; putting 90 parts of monomer B at the bottom of a reaction kettle, adding 90 parts of phosphorizing agent namely phosphorous acid and 3 parts of catalyst p-toluenesulfonic acid, uniformly stirring, controlling the temperature to be 40 ℃, simultaneously beginning to dropwise add aminomethylating reagent namely 90 parts of formaldehyde, completing dropwise adding within 4 hours, heating to 100 ℃ after completing dropwise adding, reacting for 6 hours, adding NaOH to adjust the pH value to be 6.5-6.7 after finishing the reaction, and obtaining a final product, namely the polymer for reducing the viscosity of the high-solid slurry, which is marked as 50EO 1P.

Example 5: the polymer for reducing the viscosity of the high-solid slurry has the following structural formula:

in the formula, R₁Selected from hydrogen atoms or C₁To C₁₈Alkyl groups of (a); r₂Selected from hydrogen atoms or C₁To C₅Alkyl groups of (a); m is selected from hydrogen atom or alkali metal or C₁To C₅Alkyl groups of (a); a is selected from C₁-C₅An alkylamine of (a); a is an integer of 8 to 150; b is an integer of 0 to 90.

In this example, R₁Selected from hydrogen atoms, R₂Is selected from C₅M is selected from C₃A is selected from C₃An alkylamine of (a); a is 100 and b is 50.

The structural formula of the monomer B obtained by activating and end-capping the hydroxyl group of the structure A is as follows:

in the formula, m: represents the polymerization degree of oxirane oxygen, m is 8-150, and the recommended polymerization degree is 8-100;

n: represents the polymerization degree of propylene oxide, n is 0 to 90, and the recommended polymerization degree is 0 to 30;

m is 0-0.6, and the recommended ratio is 0-0.3;

q: represents an alkyl group having 1 to 12 carbons, preferably ethane, propane and butane;

a: represents a secondary amino group.

In the embodiment, m is 100, n is 30 and q is selected from propane

The solid particle adsorption group structure C is as follows:

a: represents a secondary amino group; r is a hydrogen atom orC₁To C₅Alkyl groups of (a); m is a hydrogen atom or an alkali metal or C₁To C₅Alkyl group of (1). In this embodiment, R is selected from C₅Alkyl groups of (a); m is selected from C₅Alkyl group of (1).

The blending amount (fracture blending amount) of the polymer for reducing the viscosity of the high-solid content slurry can be 0.15-0.4% of the cementing material.

The following are the experimental part of the invention:

and (3) testing mortar: and evaluating the dispersing capacity of the polymer to the mortar according to GB8076-2008, and testing the mortar expansion degree to represent the dispersing capacity of the polymer to the mortar. The cement adopts Nymph cement P.O 42.5; sand: and Mx is 2.2-1.6 fine sand (powder content is 15%). The blending amounts (folding and fixing blending amounts) in the tables below (of the polymer of the present invention) are the mass percentages of the gelled material.

TABLE 1

EO: represents ethylene oxide; p: represents a phosphate group.

As can be seen from Table 1, the dispersing ability of the polymer was enhanced with the increase in the degree of polymerization of EO, and when it exceeded 50 degrees, the increase in the dispersing ability was retarded without significant change. From the anchoring group, 50EO2P (bisphosphate) has a better dispersibility than 50EO1P (monophosphorate). EO having a low degree of polymerization has better dispersion retention ability in terms of retention ability. The 50EO2P has the best dispersing and retaining ability overall, and the following experiments were carried out with the 50EO2P being selected.

Testing the performance of the concrete: the concrete performance test is carried out according to GB/T50080-2002 Standard of common concrete mixture Performance test methods and GB/T50081-2002 Standard of common concrete mechanical Performance test methods, different water reducing agents are selected to ensure that the concrete slump reaches 210mm and the expansion reaches 500mm, and the air content of the concrete is controlled by using a defoaming agent to keep 1.5 percent, so that the concrete has the same yield stress. And testing the concrete V-shaped groove outflow time under the same yield stress condition, and using the concrete V-shaped groove outflow time to represent the plastic viscosity of the concrete. The mixing proportion of the concrete is shown in a table 2, and the cement adopts Emenstrophe cement P.O 42.5; fly ash: tao Peak 2 class; mineral powder: adult Doujiafeng; sand: 2.2-1.6% of Mx fine sand (powder content is 15%); (ii) a Small stones: crushed stone with the particle size of 5-10 mm; big stones: crushed stone with the particle size of 10-25 mm. The mass of the large stones is 4: 6.

TABLE 2

A blank sample is compared with a water reducing agent X sold in the market (traditional PCE, products of different manufacturers at home and abroad), the water reducing agent X sold in the market can be a polymerization product of a free radical unsaturated carboxyl monomer and a macromonomer, and the macromonomer is TPEG, HPEG, MPEG and APEG respectively. See table 3. The components of each commercially available water reducer X product were as follows:

X-TPEG: the polycarboxylate superplasticizer is prepared from the following raw materials in parts by mass: 90 parts of polyoxyethylene ether macromonomer (prenyl alcohol polyoxyethylene ether TPEG-3000), 8.65 parts of acrylic acid, 0.95 part of chain transfer agent (sodium methallylsulfonate), 0.53 part of initiator (0.38 part of hydrogen peroxide and 0.15 part of ascorbic acid), 0.9 part of defoaming monomer and 150 parts of deionized water. The defoaming monomer is polyoxyethylene-polyoxypropylene segmented copolymer, the polyoxyethylene-polyoxypropylene segmented copolymer is AP type, and the molecular weight is 7000. The deionized water is divided into deionized water X₁Deionized water Y, deionized water Z, deionized water X for dissolving polyoxyethylene ether macromonomer and chain transfer agent₁The mass portion of the acrylic acid-defoaming monomer is 60 portions, the mass portion of the deionized water Y used for dissolving the initiator is 50 portions, and the mass portion of the deionized water Z used for dissolving the acrylic acid and the defoaming monomer is 40 portions; the preparation method of the polycarboxylate superplasticizer comprises the following process steps: firstly, according to the mass ratio, the prenyl alcohol polyoxyethylene ether TPEG-3000 and the deionized water X₁Pouring into a three-neck flask, stirring in a water bath, heating to 40 ℃, and then adding sodium methallyl sulfonate into the three-neck flask; in a container (beaker)) Dissolving an initiator into deionized water Y to prepare a solution A; dissolving acrylic acid, (defoaming monomer) AP type polyoxyethylene-polyoxypropylene block copolymer into deionized water Z in another container (another beaker) to prepare solution B; secondly, after the solid in the three-mouth flask is completely dissolved, respectively and simultaneously dripping the solution A and the solution B into the three-mouth flask by using a constant flow pump at the temperature of 40 ℃, controlling the dripping time to be 2.5 hours, then continuously preserving the temperature (the temperature is still 40 ℃) to react for 1.5 hours, naturally cooling to a certain temperature (can be 20 ℃), adjusting the pH value of the obtained product to be 7.0 by using an alkaline solution (can be a 30 wt% sodium hydroxide solution), and obtaining a (solid content is 42%) polycarboxylic acid water reducing agent product (the initiator ascorbic acid is dissolved into deionized water Y when the solution A is prepared, and after the solid in the three-mouth flask is completely dissolved, adding a 30% hydrogen peroxide aqueous solution into the deionized water Y by mass percent to prepare the solution A).

X-APEG: the GK-3000-A2 type water reducing agent comprises the following synthetic process: polymerization reaction: 220g of acrylic acid are metered in, together with 210g of deionized water, and pumped into the titration flask A for further use (as charge A). 2g of vitamin C and 7.60g of thioglycolic acid are metered and added with 420g of deionized water and pumped into a titration tank B for standby (serving as a material B). Adding 2300g of deionized water and 1800g of allyl alcohol polyoxyethylene ether into a reaction kettle, stirring, heating from room temperature to 55 ℃, adding 12.0g of hydrogen peroxide, simultaneously titrating the material A and the material B, titrating the material A for 2.5 hours, titrating the material B for 3 hours, keeping the temperature for 1.5 hours, and controlling the temperature to be 60 +/-2 ℃ to obtain the polymer. Neutralization reaction: and (3) cooling the polymer to below 50 ℃ (45 ℃), adding a sodium hydroxide aqueous solution (with the mass percentage concentration of 30%) while stirring, adjusting the pH value to 6-7, and finishing the reaction to obtain the polyether polycarboxylic acid high-performance water reducing agent with the solid content of about 40%.

X-HPEG: the polycarboxylate superplasticizer is prepared from the following raw materials in parts by mass: 88 parts of polyoxyethylene ether macromonomer (methyl allyl polyoxyethylene ether HPEG-2400), 8 parts of acrylic acid, 1.0 part of chain transfer agent (mercaptopropionic acid), 0.45 part of initiator (ammonium persulfate), 0.85 part of defoaming monomer and 148 parts of deionized water. The defoaming monomer is polyoxyethylene-polyoxypropylene block copolymerThe copolymer, polyoxyethylene-polyoxypropylene block copolymer, is of the AE type, with a molecular weight of 6000. The deionized water is divided into deionized water X₂59 parts by mass of deionized water X for dissolving polyoxyethylene ether macromonomer and chain transfer agent, 51 parts by mass of deionized water Y for dissolving initiator, and 38 parts by mass of deionized water Z for dissolving acrylic acid and defoaming monomer; the preparation method of the polycarboxylate superplasticizer comprises the following process steps: firstly, polyoxyethylene ether macromonomer (methyl allyl polyoxyethylene ether) and deionized water X are mixed according to the mass ratio₂Pouring into a three-neck flask, stirring in a water bath, heating to 39 ℃, and then adding mercaptopropionic acid into the three-neck flask; dissolving ammonium persulfate in deionized water Y in a container (beaker) to prepare a solution A; dissolving acrylic acid, AE type polyoxyethylene-polyoxypropylene block copolymer in deionized water Z in another container (another beaker) to prepare solution B; secondly, after the solid in the three-mouth flask is completely dissolved, respectively and simultaneously dripping the solution A and the solution B into the three-mouth flask by using a constant flow pump at the temperature of 39 ℃, controlling the dripping time to be 3.0 hours, then continuously preserving the temperature (the temperature is still 39 ℃) for reaction for 2.0 hours, naturally cooling to 20 ℃, and adjusting the pH value of the obtained product to 6.5 by using an alkaline solution (which can be 30 wt% of sodium hydroxide solution) to obtain the polycarboxylic acid water reducing agent product.

X-MPEG, wherein the water reducing agent is prepared by the following preparation method: esterification: taking 300g of methoxypolyethylene glycol monomethyl ether MPEG (molecular weight of 3000), putting the methoxypolyethylene glycol monomethyl ether into a 1000ml four-neck flask provided with a breakpoint thermometer, a condenser tube and a stirrer, adding 0.4g of each of hydroquinone and hydroquinone monomethyl ether as a polymerization inhibitor when the reaction temperature reaches 70 ℃, uniformly stirring, then adding 57.6g of acrylic acid, continuously heating to 90 ℃, adding 4.29g of concentrated sulfuric acid as a catalyst, introducing nitrogen as a water carrying agent, and reacting for 10 hours at 120 ℃ to obtain methoxypolyethylene glycol monomethyl ether acrylate (esterified macromonomer). (ii) polymerization: adding a proper amount of distilled water into a 1000ml four-mouth flask provided with a breakpoint thermometer, a condenser pipe and a stirrer, introducing nitrogen, dropwise adding an esterified macromonomer solution with the concentration of 66.7% and an initiator (an ammonium persulfate solution with the concentration of 6%) by using a constant flow pump at the temperature of 85 ℃, finishing dropwise adding the esterified macromonomer within 4 hours, finishing dropwise adding the initiator after 0.5 hour lag, and preserving the temperature for 1 hour at 95 ℃ after finishing dropwise adding the esterified macromonomer and the initiator. And thirdly, after the reaction is finished, cooling, and then adjusting the pH value by using a sodium hydroxide aqueous solution with the mass percentage concentration of 30% to keep the pH value at 7-8 to obtain the water reducing agent.

TABLE 3

As can be seen from Table 3, the 50EO2P was used in higher loadings than X to achieve the same slump, indicating that the 50EO2P dispersing ability was weaker than that of the conventional PCE. For different types of PCEs, the HPEG requirement is minimal, and the MPEG requirement is maximal. As can be seen from the outflow time of the V-groove, different types of PCEs have little influence on the outflow time, which is about 250s, and the outflow time is reduced by only 55s by using 50EO2P, which shows that the outflow time can be obviously reduced. Since the concrete used in the test had the same slump and air content, i.e. the same yield stress, and the reduction in the flow-out time indicated a reduction in the plastic viscosity of the concrete, it can be shown that 50EO2P can significantly reduce the viscosity of the concrete, reducing the frictional resistance of the concrete under shear stress.

FIG. 1 is a schematic diagram showing the compressive strength of concrete at different ages, wherein the compressive strength of X-TPEG, 50EO2P, X-HPEG, X-APEG and X-MPEG in FIG. 1 correspond from left to right. As can be seen from the compressive strength of concrete at different ages, the 3d strength of 50EO2P is lower than that of PCE, probably because of the retarding effect on concrete caused by using bisphosphonic acid as an anchoring group. But its 7d strength is comparable to the PCE and 28d strength is higher than all types of PCEs.

And (3) testing the rheology of the mortar:

(1) and selecting the middle-linked cement P.O.42.5 to perform mortar test under the condition of a water-cement ratio of 0.29, operating the test process according to GB8076, and controlling the fluidity of the net slurry to be 230 +/-15 mm. Table 4 shows the neat paste test data for different water reducers.

TABLE 4

(2) Preparation of a static paste 600mL was placed in a rheometer (Schleiblinger Viskomat NT-LT9-005) for testing, with a shear rate of 40 to 160S^-1Controlling the shear rate to be increased by 40S every 2min^-1When prompting to the highest speed 160S^-1Then 40S^-1Reducing the shear rate to 40S^-1。

By plotting apparent viscosity versus shear rate, FIG. 2 was obtained. As can be seen from FIG. 2, the viscosity of 50EO2P is significantly less than other types of polycarboxylate water reducers, both in the low shear rate and high shear rate regions, consistent with the concrete experimental data. In order to more accurately illustrate the plastic viscosity, the inventors plotted the shear torque against the shear rate and performed a linear regression to obtain the yield stress and the plastic viscosity. As shown in fig. 3. Linear regression calculations gave the data of table 5.

TABLE 5

From the regressed yield stress and plastic viscosity, it can be seen that 50EO2P has a lower plastic viscosity than PCE (a different commercially available monomer product). Compared with MPEG, the plastic viscosity is reduced by 36%, which can obviously reduce the plastic viscosity of the slurry under the condition of high solid content, but not just reduce the yield stress. The rheological structure of the mortar is also consistent with the result of a concrete experiment, which shows that the novel polymer can effectively reduce the plastic viscosity of the slurry and reduce the friction force among solid particles, thereby reducing the viscosity of the slurry, improving the flow rate of the slurry and reducing the flowing friction force of the slurry.

In conclusion, the invention provides the polymer for reducing the viscosity of the high-solid-content slurry, the polymer has good performance, and the plastic viscosity of Bingham fluids such as concrete, mortar and the like is effectively reduced, so that the problem of overhigh viscosity of the high-solid-content slurry is solved.