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CN-122012183-A - Water-based cleaning agent and preparation method and application thereof

CN122012183ACN 122012183 ACN122012183 ACN 122012183ACN-122012183-A

Abstract

The invention relates to the technical field of water-based cleaning agents, in particular to a water-based cleaning agent and a preparation method and application thereof, wherein the water-based cleaning agent is prepared by taking an amphiphilic molecule formed by chemical grafting of a beta-cyclodextrin-PEO derivative and siloxane as a core component, and a bio-based solubilizer and a corrosion inhibitor as auxiliary materials through a three-step method, wherein the cyclodextrin-PEO derivative is prepared by ring-opening polymerization of ethylene oxide; the invention provides molecular recognition inclusion capacity through cyclodextrin cavities, the silicone chain segment enhances the interfacial permeability, the biological base component ensures the environment friendliness, and the practical application proves that the invention is particularly suitable for precise cleaning in high-end fields such as semiconductor manufacturing, aerospace and the like.

Inventors

  • LI XIANLONG
  • GUO TIANZHI
  • ZHAI HONGFENG
  • LI ANNAN

Assignees

  • 广东波达机电设备有限公司

Dates

Publication Date
20260512
Application Date
20260121

Claims (10)

  1. 1. The preparation method of the water-based cleaning agent is characterized by comprising the following steps of: S1, reacting beta-cyclodextrin with ethylene oxide at a molar ratio of 1:6.8 at a temperature of 85+/-2 ℃, adding NaOH accounting for 0.5% of the mass of the beta-cyclodextrin as a catalyst, maintaining a stirring speed of 300rpm for 4 hours, cooling the system to 40 ℃ after the reaction is finished, neutralizing the system to pH=7.0+/-0.2 by dilute hydrochloric acid, purifying the system by dialysis through a dialysis membrane with a molecular weight cutoff of 1000Da for 24-36 hours, pre-freezing the system at-50 ℃ for 4 hours, and sublimating and drying the system at-30 ℃ for 24 hours to obtain the beta-cyclodextrin-PEO derivative, wherein the polymerization degree of PEO chain segments is n=3; s2, mixing the beta-cyclodextrin-PEO derivative obtained in the S1 with 3-aminopropyl trimethoxy silane according to a molar ratio of 1:1.2-1.5, adding an EDC/NHS condensing agent in a deionized water environment, wherein the molar ratio of EDC to aminosiloxane is 1:1.2-1.5, firstly carrying out light-shielding reaction for 4 hours under the conditions of pH=7.0-7.5 and 25+/-2 ℃, then regulating the pH to 5.5-6.0, and continuously carrying out reaction for 2 hours to obtain the cyclodextrin-siloxane grafting with the grafting rate of more than or equal to 90%; And S3, heating deionized water to 40 ℃, adding creatine phosphate sodium accounting for 1.2% of the total mass of the system as a buffering agent, stirring until the creatine phosphate sodium is completely dissolved, sequentially adding octyl citrate accounting for 2.5% of the total mass of the system as a bio-based solubilizer and 1.0% of lauroyl sarcosine sodium as an auxiliary surfactant, stirring for 30min, slowly adding the cyclodextrin-siloxane graft of S2, stirring for 1h to be homogeneous, adding a 10% citric acid solution to adjust the pH value to 7.5+/-0.2, then performing ultrasonic dispersion treatment, and finally removing impurities through a 0.45 mu m microporous membrane to obtain the water-based cleaning agent.
  2. 2. The method for preparing a water-based detergent according to claim 1, wherein the cyclodextrin derivative is an etherified derivative of beta-cyclodextrin, wherein the hydrophilic segment is a polyethylene oxide segment, the polymerization degree n=3-5, and the cyclodextrin cavity pore diameter is expanded to 1.0-1.2nm after etherification reaction, so as to enhance the inclusion capacity of greasy dirt with molecular weight 500-1000.
  3. 3. The method for preparing the water-based cleaning agent according to claim 1, wherein the siloxane compound is an aminosiloxane oligomer, the structure of the siloxane compound is an oligomer with the polymerization degree of aminopropyl trimethoxy silane of 3-5, and an amidation reaction is carried out between amino groups and carboxyl groups of cyclodextrin derivatives to form a functional synergistic decontamination system, wherein the main attack molecules of the cyclodextrin are identified and included, the siloxane is subjected to side-by-side interfacial penetration and damage, and a siloxane chain segment accounts for 35-45% of the total mass of the grafted material.
  4. 4. The method for preparing the water-based cleaning agent according to claim 1, wherein the covalent grafting reaction is an amidation reaction and is carried out in the presence of condensing agent EDC/NHS, wherein the molar ratio of EDC to aminosilicone is 1:1.2-1.5, the pH of a reaction system is controlled to be 5.3-5.7, so that the amide bond formation efficiency is optimized, and the grafting rate is more than or equal to 90%.
  5. 5. The method for preparing the water-based cleaning agent according to claim 1, wherein the bio-based solvent is octyl citrate, the addition amount of the bio-based solvent is 2.0-3.0% of the total mass of the system, and the octanol/water distribution coefficient of the bio-based solvent is 2.5-3.0, so that the bio-based solvent is used for enhancing the solubility of hydrophobic greasy dirt, and the biodegradation rate is more than or equal to 80% within 28 days.
  6. 6. The method for preparing a water-based cleaning agent according to claim 1, wherein the buffer agent is creatine phosphate sodium, the addition amount of the buffer agent is 1.0-1.5% of the total mass of the system, and the buffer capability stabilizes the final pH of the cleaning agent at 7.0-8.0, so as to replace the traditional silicate to avoid white spots on the metal surface.
  7. 7. The method for preparing the water-based cleaning agent according to claim 1, wherein the surfactant is sodium lauroyl sarcosinate, the addition amount of the surfactant is 0.5-1.5% of the total mass of the system, and after the surfactant is compounded with a cyclodextrin-siloxane grafting material, the foam height is reduced to below 10mm within 5min, so that the water-based cleaning agent is suitable for a spray cleaning process.
  8. 8. The method for preparing a water-based detergent as claimed in claim 1, wherein the homogenizing treatment comprises ultrasonic dispersion or mechanical stirring, wherein the ultrasonic dispersion is carried out at a frequency of 40+ -2 kHz and a power density of 0.5+ -0.1W/cm 2 for 15+ -1 min, the mechanical stirring is carried out at a rotation speed of 400-600rpm for 30+ -2 min, so that the viscosity of the detergent is controlled at 10-15 mPa.s at normal temperature of 25+ -2 ℃ and the micelle size D90 is ensured to be less than or equal to 100nm.
  9. 9. The method for preparing a water-based cleaning agent according to claim 1, wherein the aqueous solution is deionized water with conductivity less than or equal to 5 μs/cm, the amount of the deionized water is 80-90% of the total mass of the system, and the calcium and magnesium ion content in the water is less than or equal to 10ppm, so as to prevent hard water from affecting the stability of the cleaning agent.
  10. 10. The method for preparing the water-based cleaning agent according to claim 1, wherein the preparation method is carried out under the heating condition of normal temperature of 25+/-5 ℃ or less than or equal to 60 ℃, the pH value is controlled by real-time pH monitoring in the reaction process, the deviation is within +/-0.2, and the final product is stored in a closed container for 12 months under the environment of-5 ℃ to 40 ℃ without layering.

Description

Water-based cleaning agent and preparation method and application thereof Technical Field The invention relates to the technical field of water-based cleaning agents, in particular to a water-based cleaning agent and a preparation method and application thereof. Background The water-based cleaning agent technology is taken as a core component in the industrial cleaning field, the development level of the water-based cleaning agent technology is directly related to the cleaning efficiency and the product quality of key industries such as manufacturing industry, electronic industry, precision instruments and the like, and along with the increasing strictness of environmental protection regulations and the continuous improvement of high-end manufacturing requirements, the water-based cleaning agent is gradually replaced by the traditional solvent-based cleaning agent, so that the water-based cleaning agent becomes an important way for realizing green cleaning. The traditional water-based cleaning agent mainly depends on the physical compounding of a surfactant, realizes the decontamination function through the effects of emulsification, dispersion and the like, generally adopts simple mixing of an anionic surfactant and a nonionic surfactant, has a certain effect on basic decontamination, but has obvious limitations that firstly, the cleaning efficiency of complex greasy dirt is low, the requirement of precision manufacture is difficult to meet, secondly, a large amount of foam is easy to generate in the use process, the implementation of efficient processes such as spray cleaning and the like is influenced, thirdly, part of the formula has corrosion risk on a metal substrate, biodegradability is poor, waste water treatment cost is high, and the root of the problems is that the traditional technology lacks the precise design of a molecular level, the components are mainly physically mixed, the synergistic effect is weak, and phase separation or performance attenuation is easy to occur. In the high-end fields of semiconductor manufacturing, electronic component cleaning and the like, more stringent requirements are put forward on the performance of water-based cleaning agents, for example, the cleaning agents in the wafer processing process are required to have multiple characteristics of high-efficiency decontamination, low foam, no residue, corrosion resistance and the like, meanwhile, the environmental protection standards of low toxicity and biodegradability must be met, the targets are difficult to achieve simultaneously in the prior art, and especially the deep problems of antagonism among components, insufficient interface behavior regulation and the like cannot be solved by simple stacking of surfactants in the traditional formula. Therefore, a novel water-based cleaning agent based on the molecular engineering concept is developed, the synergy among components is realized through means of chemical grafting, structural design and the like, the defects of the traditional technology are fundamentally overcome, and the novel water-based cleaning agent becomes an urgent technical demand in the field. Disclosure of Invention In order to solve the problems mentioned in the background art, the invention provides a water-based cleaning agent, and a preparation method and application thereof. In order to achieve the above purpose, the present invention adopts the following technical scheme: the preparation method of the water-based cleaning agent comprises the following steps: S1, reacting beta-cyclodextrin with ethylene oxide at a molar ratio of 1:6.8 at a temperature of 85+/-2 ℃, adding NaOH accounting for 0.5% of the mass of the beta-cyclodextrin as a catalyst, maintaining a stirring speed of 300rpm for 4 hours, cooling the system to 40 ℃ after the reaction is finished, neutralizing the system to pH=7.0+/-0.2 by dilute hydrochloric acid, purifying the system by dialysis through a dialysis membrane with a molecular weight cutoff of 1000Da for 24-36 hours, pre-freezing the system at-50 ℃ for 4 hours, and sublimating and drying the system at-30 ℃ for 24 hours to obtain the beta-cyclodextrin-PEO derivative, wherein the polymerization degree of PEO chain segments is n=3; s2, mixing the beta-cyclodextrin-PEO derivative obtained in the S1 with 3-aminopropyl trimethoxy silane according to a molar ratio of 1:1.2-1.5, adding an EDC/NHS condensing agent in a deionized water environment, wherein the molar ratio of EDC to aminosiloxane is 1:1.2-1.5, firstly carrying out light-shielding reaction for 4 hours under the conditions of pH=7.0-7.5 and 25+/-2 ℃, then regulating the pH to 5.5-6.0, and continuously carrying out reaction for 2 hours to obtain the cyclodextrin-siloxane grafting with the grafting rate of more than or equal to 90%; And S3, heating deionized water to 40 ℃, adding creatine phosphate sodium accounting for 1.2% of the total mass of the system as a buffering agent, stirring until the creatine phosphate sodi