Search

CN-122011400-A - High-performance crosslinking type cationic concrete air entraining agent and preparation method thereof

CN122011400ACN 122011400 ACN122011400 ACN 122011400ACN-122011400-A

Abstract

The application relates to the technical field of concrete additives, in particular to a high-performance cross-linked cationic concrete air entraining agent and a preparation method thereof. The preparation process of the air entraining agent comprises the steps of carrying out reflux reaction on a polyamine compound and bromoalkane under the protection of inert atmosphere, mixing and emulsifying the polyamine compound and bromoalkane with an emulsifier and a sodium citrate solution to obtain a pre-emulsion, mixing the pre-emulsion, hydrophilic polyoxyethylene ether, an initiator and a phosphate modifier, adopting ultraviolet irradiation to initiate a crosslinking reaction to obtain an intermediate product, mixing and stirring the intermediate product, a micro-nano bubble solution, pretreated nano cellulose and a foam stabilizer, and then carrying out reduced pressure distillation and filtration to obtain the air entraining agent.

Inventors

  • YU FEIYU
  • LI WEITENG
  • PENG XIAOBIN
  • ZHU SHAOHONG
  • WANG YANGJIE
  • WU JINSONG
  • GUAN MENGQIN
  • JIANG ZHUOJUN
  • WU WENXIAN
  • CHEN LIYUAN

Assignees

  • 科之杰新材料集团有限公司
  • 科之杰新材料集团浙江有限公司

Dates

Publication Date
20260512
Application Date
20251226

Claims (10)

  1. 1. The preparation method of the high-performance cross-linked cationic concrete air entraining agent is characterized by comprising the following steps of: S1, under the protection of inert atmosphere, carrying out reflux reaction on a polyamine compound and bromoalkane in an organic solvent, then mixing the obtained reaction liquid with an emulsifier and a sodium citrate solution, and carrying out dispersion treatment and heating for emulsification to obtain a homogeneous pre-emulsion; S2, mixing the pre-emulsion with hydrophilic polyoxyethylene ether, an initiator and a phosphate modifier, and initiating by ultraviolet irradiation under the conditions of deoxidization and temperature control to enable a system to undergo polymerization and crosslinking reaction to obtain an intermediate product; S3, mixing and stirring the intermediate product, the micro-nano bubble solution, the pretreated nano cellulose and the foam stabilizer, then removing volatile unreacted monomer components through reduced pressure distillation, and finally filtering to obtain the air entraining agent; wherein the pretreated nanocellulose is obtained by modifying nanocellulose by a silane coupling agent.
  2. 2. The method of manufacturing according to claim 1, characterized in that: S1, under the protection of inert atmosphere, carrying out reflux reaction on a polyamine compound and bromoalkane in an organic solvent at 60-70 ℃ for 2-4 days, then mixing the obtained reaction liquid with an emulsifying agent and a sodium citrate solution, carrying out ultrasonic dispersion treatment, heating to 60-80 ℃ and stirring for 1-3 hours to carry out emulsification treatment, thus obtaining a homogeneous pre-emulsion; Wherein the reaction raw material comprises 2-5 parts of polyamine compound, 10-12 parts of bromoalkane, 40-50 parts of organic solvent, 1-2 parts of sodium citrate solution and 5-8 parts of emulsifier by weight.
  3. 3. The process according to claim 1 or 2, wherein, The polyamine compound is one or more of N- (3-aminopropyl) -1, 3-propylene diamine, N, N ' -methylene bisacrylamide, 1,1,4,7,10,10-hexamethyl triethylene tetramine, N, N, N ', N ' -tetramethyl ethylenediamine and 1,4, 7-pentamethyl diethylene triamine; the bromoalkane is one or more of 1-bromooctadecane, 1-bromopentadecane, 1, 14-dibromotetradecane, 1-bromotetradecane and 1-bromododecane; The emulsifier is one or more of sodium stearate, sodium dodecyl sulfate, benzalkonium chloride and polysorbate-80; The organic solvent is tetrahydrofuran; the concentration of the sodium citrate solution is 1% -2%.
  4. 4. The method according to claim 1, wherein, S2, mixing part of the pre-emulsion with hydrophilic polyoxyethylene ether, an initiator and a phosphate modifier, introducing inert gas to remove oxygen in a reaction environment, controlling the temperature of a reaction system to be 23-27 ℃, and irradiating with ultraviolet light with the wavelength of 365nm for 3-5 hours under a constant temperature condition to obtain an intermediate product; Wherein, the reaction raw material components of the S2 comprise 20-25 parts of pre-emulsion, 15-20 parts of hydrophilic polyoxyethylene ether, 1-2 parts of initiator and 10-15 parts of phosphate modifier according to parts by weight; S3, adding the micro-nano bubble solution, the pretreated nano cellulose suspension and the foam stabilizer into the intermediate product, stirring and mixing uniformly, then removing volatile unreacted monomer components by reduced pressure rotary evaporation at 40-60 ℃, and finally filtering to obtain the air entraining agent; the S3 comprises, by weight, 10-15 parts of micro-nano bubble solution, 8-10 parts of pretreated nano cellulose suspension and 1-5 parts of foam stabilizer.
  5. 5. The method according to claim 1, wherein the stirring and mixing time in S3 is 30-50 minutes, and the filtration is performed by using a microporous filter membrane with a pore size of 0.22 μm.
  6. 6. The method of manufacturing according to claim 1, characterized in that: The hydrophilic polyoxyethylene ether is one or more of polyoxyethylene oleyl alcohol ether, polyoxyethylene lauryl alcohol ether, polyoxyethylene fatty alcohol ether and polyoxyethylene alkylphenol ether; The initiator is one or more of azodiisobutyronitrile, azodiisoheptonitrile, dibenzoyl peroxide, lauroyl peroxide, potassium persulfate and ammonium persulfate; the phosphate modifier is one or more of triisopropylphosphate, acrylic acid phosphate, tri (2, 4-di-tert-butylphenyl) phosphate, 2- (m-tolyloxy) ethyl potassium phosphate and hydroxyethyl methacrylate phosphate; The foam stabilizer is one or more of dodecyl dimethyl amine oxide, alkanolamide, polyethylene glycol, polyvinylpyrrolidone and coconut oil diethanolamide.
  7. 7. The method of manufacturing according to claim 1, characterized in that: Treating water by adopting a micro-bubble generating device to generate micro-nano bubble solution, wherein the bubble size distribution is 0.1-50 mu m, and the bubble concentration is 10 7 -10 8 /mL; The pretreated nanocellulose is obtained by carrying out surface modification reaction on nanocellulose and a silane coupling agent in an alcohol solution, and carrying out solid-liquid separation and washing.
  8. 8. The method according to claim 1, wherein the pretreatment nanocellulose suspension is prepared by the following steps: uniformly mixing nanocellulose with an alcohol solution, adding a silane coupling agent, stirring for 2-4 hours at room temperature, centrifugally filtering and separating, and washing with the alcohol solution to remove unreacted coupling agent to obtain the nano-cellulose; Wherein, the raw material components comprise 10-15 parts of nano cellulose, 100-150 parts of alcohol solution and 1-3 parts of silane coupling agent by weight.
  9. 9. The preparation method according to claim 7 or 8, characterized in that: The silane coupling agent is one or more of gamma- (methacryloyloxy) propyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane, octadecyl dimethyl trimethoxysilylpropyl ammonium chloride, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane and bis- (gamma-triethoxysilylpropyl) tetrasulfide; the alcohol solution is ethanol solution.
  10. 10. A high performance cross-linked cationic concrete air entraining agent prepared by the preparation method of any one of claims 1 to 9.

Description

High-performance crosslinking type cationic concrete air entraining agent and preparation method thereof Technical Field The application relates to the technical field of concrete additives, in particular to a high-performance cross-linked cationic concrete air entraining agent and a preparation method thereof. Background Concrete is used as a core material of modern buildings, and the durability and the working performance of the concrete are important. The air entraining agent is a key additive, and can obviously improve the freeze thawing resistance, the impermeability and the workability of the concrete by introducing a large amount of uniform and closed micro-bubbles into the concrete. However, conventional air entraining agents generally suffer from poor bubble stability, insufficient compatibility with cement paste, and the like, which makes them limited in their performance in severe environments or high-strength concrete applications. Currently, the main products in the concrete admixture market comprise traditional air entraining agents such as rosin resins, alkylbenzene sulfonates and the like. However, the existing anionic air entraining agent is sensitive, and is easy to deactivate in the environment of high-alkalinity concrete, and the nonionic air entraining agent is large in dosage and poor in bubble stability, so that the compressive strength of the concrete is poor. Current air entraining agents fail to address the problem of long term stability of the air entraining agent in complex concrete systems, resulting in insufficient durability of the concrete. The research and development of the air entraining agent of the high-performance concrete with stable and durable air bubbles, good compatibility with cement paste and adaptability to severe working conditions has important value and significance. In addition, along with the promotion of environmental protection related policies and the rising of the demands of solid waste recycling, the concrete air entraining agent preparation industry also needs to develop innovative materials with high performance and ecological benefits. Therefore, developing a high-performance concrete air entraining agent with mild preparation process, recycling of solid waste resources, stable and durable air bubbles and good environmental compatibility becomes a technical problem to be solved in the field. Disclosure of Invention The application aims to overcome the defects in the prior art and provides a high-performance crosslinking cationic concrete air entraining agent and a preparation method thereof, and the technical scheme is as follows: the application provides a preparation method of a high-performance cross-linked cationic concrete air entraining agent, which comprises the following steps: S1, under the protection of inert atmosphere, carrying out reflux reaction on a polyamine compound and bromoalkane in an organic solvent, then mixing the obtained reaction liquid with an emulsifier and a sodium citrate solution, and carrying out dispersion treatment and heating for emulsification to obtain a homogeneous pre-emulsion; S2, mixing the pre-emulsion with hydrophilic polyoxyethylene ether, an initiator and a phosphate modifier, and initiating by ultraviolet irradiation under the conditions of deoxidization and temperature control to enable a system to undergo polymerization and crosslinking reaction to obtain an intermediate product; S3, mixing and stirring the intermediate product, the micro-nano bubble solution, the pretreated nano cellulose and the foam stabilizer, then removing volatile unreacted monomer components through reduced pressure distillation, and finally filtering to obtain the air entraining agent; wherein the pretreated nanocellulose is obtained by modifying nanocellulose by a silane coupling agent. In some embodiments, S1, under the protection of inert atmosphere, a polyamine compound and bromoalkane are subjected to reflux reaction in an organic solvent at 60-70 ℃ for 2-4 days, then the obtained reaction solution is mixed with an emulsifying agent and a sodium citrate solution, after ultrasonic dispersion treatment, the mixture is heated to 60-80 ℃ and stirred for 1-3 hours to carry out emulsification treatment, and a homogeneous pre-emulsion is obtained, wherein the reaction raw material comprises, by weight, 2-5 parts of the polyamine compound, 10-12 parts of bromoalkane, 40-50 parts of the organic solvent, 1-2 parts of the sodium citrate solution and 5-8 parts of the emulsifying agent. In some embodiments, the polyamine compound is N- (3-aminopropyl) -1, 3-propanediamine, N ' -methylenebisacrylamide, 1,1,4,7,10,10-hexamethyl triethylene tetramine, N, one or more of N, N ', N ' -tetramethyl ethylenediamine, 1,4, 7-pentamethyl diethylenetriamine. In some embodiments, the bromoalkane is one or more of 1-bromooctadecane, 1-bromopentadecane, 1, 14-dibromotetradecane, 1-bromotetradecane, 1-bromododecane. In some embodiments, the emulsifier i