An active grinding molecular level additive of alkenylated phenylsilane and its preparation method and application

Abstract

The application provides an enal-phenylsilane active grinding molecular grade additive and a preparation method and application thereof, and belongs to the technical field of functional additive detection. The enal-phenylsilane active grinding molecular grade additive is obtained by mixing a myrtle enal solution and a dehydrating agent dispersion liquid, and then adding a 4-anilino triethoxysilane solution to carry out a dehydration condensation reaction. The enal-phenylsilane active grinding molecular grade additive contains enal-conjugated bridging and a phenylsilane flexible chain segment, forms a conjugated color system which can rotate freely, has good conjugated coupling characteristics and chemical stability, has excellent light stability, low hygroscopicity, is convenient to store and is not easy to be caked.

Description

Technical Field

[0001] This invention relates to the field of functional additive detection technology, and in particular to an enolized phenylsilane active grinding molecular-level additive, its preparation method, and its application. Background Technology

[0002] Active grinding aids for silicon micropowder are core functional components in the production of silicon micropowder. Their core function is to optimize the dispersion of silicon micropowder particles, aid grinding, and prevent agglomeration during the grinding process, thereby improving grinding efficiency. Simultaneously, they ensure the uniformity, distribution, and purity of the silicon micropowder product, making them suitable for various silicon micropowder grinding processes, including wet, dry, conventional, and ultrafine grinding. Their component system is complex and diverse. Besides core polycarboxylic acid dispersants, silane coupling agents (with phenyltriethoxysilane derivatives being an important category), and functional inorganic salts, they also contain natural plant extracts and various thickening and regulating components. The thickening components can flexibly adjust the viscosity characteristics of the aid system. The ratio and content of different components directly affect the flowability, suspension, solids, and anti-settling properties of the aid, thus adapting it to the different process requirements of silicon micropowder grinding.

[0003] The micro-viscosity of active grinding aids for silicon micropowder is a core process indicator determining the grinding effect, and it is highly correlated with the efficiency of grinding production and product quality. Low-viscosity aid systems have good flowability, facilitating pipeline transport and particle dispersion, but are prone to silicon micropowder particle agglomeration and insufficient grinding. High-viscosity aid systems offer excellent anti-settling and anti-agglomeration effects, making them suitable for ultrafine silicon micropowder grinding, but they increase the energy consumption of grinding equipment and may even affect the powder discharge efficiency. Therefore, precisely adjusting the micro-viscosity of active grinding aids for silicon micropowder allows the aids to accurately match the actual needs of different grinding processes, significantly improving the quality and production efficiency of silicon micropowder products. Furthermore, accurate and efficient detection and control of the micro-viscosity of the aids are key requirements for the refinement and upgrading of silicon micropowder grinding processes, the optimization of aid formulations, and the realization of large-scale, efficient production.

[0004] Traditional viscosity measurement methods mostly rely on devices such as falling ball viscometers, rotational viscometers, and vibrational viscometers. These devices are designed for macroscopic viscosity measurement and suffer from problems such as large sample requirements, insufficient sensitivity in low viscosity ranges, and susceptibility to errors in sensing micro-region viscosity changes, making it difficult to achieve precise molecular-level measurement of micro-region viscosity. Although a small number of molecular probes have been developed for viscosity detection, most of these probes rely on artificially synthesized chemical raw materials. The preparation process is complex and requires multiple reaction steps, with cumbersome post-processing and low yield, making them unsuitable for the needs of industrial-scale production. At the same time, there are few functionalized molecular-level viscosity measurement tools based on phenyltriethoxysilane derivatives of silicon micropowder active grinding aids, combined with natural product reconstruction, which has become a technical bottleneck for the refinement of silicon micropowder grinding processes. The DHTPM, an enaldehyde-modified phenylsilane active grinding molecular-level aid of the present invention, is based on phenyltriethoxysilane derivatives in silicon micropowder active grinding aids. It is a molecular-level measuring tool obtained by reconstructing the natural product myrtle enaldehyde, which fills this technological gap. It can realize the precise in-situ molecular-level detection of the viscosity of the micro-area of ​​silicon micropowder active grinding aids, providing accurate data support for the formulation of aids, process control of production, and quality control of the entire grinding process. It has irreplaceable and great practical benefits for the fine formulation of silicon micropowder active grinding aids and the optimization and upgrading of grinding processes. Summary of the Invention

[0005] The purpose of this invention is to provide an enaldehyde-modified phenylsilane active grinding molecular-level aid, its preparation method, and its application, in order to solve the technical problem that the physical micro-region viscosity of existing functional grinding aids is difficult to measure and accurately modulate.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides an enaldehyde-modified phenylsilane active grinding molecular-level aid, having the following structural formula: .

[0007] This invention also provides a method for preparing the above-mentioned enaldehyde phenylsilane active grinding molecular-level aid, comprising the following steps: Under a protective atmosphere, myrtle aldehyde solution is mixed with dehydrating agent dispersion, and then 4-phenylaminotriethoxysilane solution is added to carry out dehydration condensation reaction to obtain enaldehyde-modified phenylsilane active grinding molecular-level aid.

[0008] Furthermore, the concentration of the myrtol solution is 1-5 mol / L, and the solvent in the myrtol solution is a mixture of alcohol and organic solvent. The alcohol includes one or more of methanol, propanol, ethanol, ethylene glycol and 1,2-propanediol; the organic solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate and acetone, and the volume ratio of alcohol to organic solvent is 1-5:1.

[0009] Furthermore, the concentration of the 4-anilinotriethoxysilane solution is 1~3 mol / L, and the solvent in the 4-anilinotriethoxysilane solution is a mixture of ethanol, ethylene glycol and N,N-dimethylformamide, wherein the volume ratio of ethanol, ethylene glycol and N,N-dimethylformamide is 1:1:1.

[0010] Furthermore, the solvent in the dehydrating agent dispersion is selected from one or more of methanol, ethanol, and ethylene glycol, and the concentration of the dehydrating agent dispersion is 1~6 mol / L; The dehydrating agent in the dehydrating agent dispersion contains one or more of sodium carbonate, sodium bicarbonate, potassium bicarbonate, or magnesium hydroxide.

[0011] Furthermore, the molar ratio of 4-anilinetriethoxysilane, myrtol, and dehydrating agent is 1:1~3:1~6.

[0012] Furthermore, the myrtle aldehyde solution and the dehydrating agent dispersion are mixed as follows: stirring at 100-900 rpm for 0.5-2 h, then heating to 70-90 °C at a rate of 1-5 °C / min, while simultaneously increasing the stirring rate to 900-1800 rpm; adding 4-anilinetriethoxysilane solution to the mixture using a uniform spray method at a spray rate of 2-6 mL / min; after spraying, evacuating and pressurizing to 2-8 atm, continuing stirring at 1200-2200 rpm, and maintaining the temperature at 90-120 °C for 2.0-6.0 h to complete the dehydration condensation reaction.

[0013] Furthermore, after the dehydration condensation reaction is completed, the product is purified by sequentially performing nitrogen distillation, extraction dehydration, cold crystallization, and freeze drying.

[0014] This invention also provides the application of the above-mentioned enaldehyde phenylsilane active grinding molecular-level aid in the physical micro-region viscosity detection of silicon micro powder grinding dispersion.

[0015] The beneficial effects of this invention are: The additive of this invention contains enaldehyde-based conjugated bridging segments and phenylsilane flexible segments in its molecular structure, forming a typical "rotatable conjugated chromogenic system": In low-viscosity silica powder grinding dispersions, the conjugated segments can rotate freely, and the excited-state energy is mainly dissipated through mechanical rotation, resulting in a weak apparent optical signal. As the viscosity of the dispersion micro-regions increases, the molecular chain rotation is inhibited by steric hindrance, and the energy dissipation mode changes to radiative transition. The optical signal intensity increases significantly with increasing viscosity, exhibiting a logarithmic function relationship, resulting in a "turn-on" visual detection effect. This chromogenic mode switching caused by changes in micro-region viscosity is a typical molecular-level viscosity response mechanism, which can accurately capture viscosity fluctuations in the micro-regions of silica powder grinding dispersions.

[0016] The enaldehyde-modified phenylsilane active grinding molecular-level additive provided by this invention is based on the reconstruction of natural enaldehyde derivatives and phenylsilane functional molecules. It appears as a white powder and is readily soluble in common solvents such as ethylene glycol, tetrahydrofuran, and dimethyl sulfoxide. Its core advantage lies in its unique molecular structure design—containing enaldehyde-modified conjugated bridging and flexible phenylsilane segments, forming a freely rotating conjugated chromogenic system. This system possesses both excellent conjugated coupling properties and chemical stability, exhibiting superior photostability, low hygroscopicity, convenient storage, and resistance to clumping. The flexible conjugated single and double bonds in this additive molecule can rotate freely in low-viscosity silica powder grinding dispersions. The excited-state energy is dissipated through mechanical motion, resulting in a weak light signal. As the viscosity of the dispersion increases, the molecular chain rotation is inhibited by steric hindrance, and the energy is released through radiative transitions. The light signal intensity significantly increases logarithmically with viscosity, exhibiting a clear "turn-on" visualization effect. Under external excitation light of 310nm, this additive can emit a bright blue fluorescence with a peak of 410nm in the wavelength range of 250~350nm. It can accurately capture the micro-region viscosity changes of the silicon micropowder grinding aid dispersion, providing real-time, in-situ visual detection support for the control of dispersion viscosity.

[0017] The additive of this invention possesses strong environmental adaptability and anti-interference capabilities, providing reliable assurance for viscosity detection of silicon micropowder grinding dispersions. It exhibits excellent compatibility with common components in dispersions such as polycarboxylic acid grinding aids, silane coupling agents, and polyethylene glycol, without affecting its color-generating function due to the presence of these additives. It demonstrates good tolerance to solvent polarity, maintaining stable absorbance in systems of different polarities, with the absorption spectrum peak concentrated around 410 nm without significant shift. Simultaneously, its optical signal remains stable within the conventional pH range (6.0~11.0) of silicon micropowder grinding dispersions, and its Stokes shift exceeds 110 nm, effectively avoiding interference from excitation light and scattered light from silicon micropowder particles, significantly improving the signal-to-noise ratio. Furthermore, this additive has a viscosity sensitivity coefficient of 0.64 and a detection limit as low as 1.015 cP, accurately identifying minute viscosity fluctuations in the microenvironment of low-viscosity liquids, adapting to the detection needs of all scenarios from low-viscosity flow dynamics to high-viscosity pastes.

[0018] Silica powder grinding dispersions often contain pseudoplastic components such as sodium polymethacrylate and polyethylene glycol. Traditional viscometers are prone to distorting results due to shear thinning caused by shear action. However, the enaldehyde-modified phenylsilane active grinding molecular-level additive of this invention does not rely on rotational shear action. It directly senses micro-region viscosity through a molecular-level viscosity response mechanism, effectively avoiding interference from pseudoplastic components and accurately reflecting the microscopic steady-state viscosity of the dispersion. This characteristic makes it particularly suitable for detecting silica powder grinding dispersions containing complex polymeric components. It can accurately distinguish viscosity differences caused by particle agglomeration, adjustments in the amount of grinding aid added, or changes in solid content, providing reliable data for process modulation.

[0019] This additive is prepared via a one-step dehydration condensation reaction. The required raw materials are derived from the reconstruction of natural products and silane derivatives. The preparation process is simple and easy to implement, requires no complex equipment, has a high yield, and is environmentally friendly, aligning with the concept of low-carbon and sustainable development. Its application requires extremely small amounts (optimal concentration of only 10 μM), resulting in low detection costs, making it suitable for large-scale chemical production and industrial testing scenarios. With its high sensitivity, strong stability, and excellent anti-interference response performance, this additive can be widely used for optimizing the preparation process and quality control of silicon micropowder grinding dispersions. It provides real-time feedback on whether the dispersion viscosity is suitable for grinding efficiency, helping to avoid particle agglomeration at low viscosity or a surge in equipment energy consumption at high viscosity. It efficiently matches the needs of different grinding processes (wet / dry, conventional / ultrafine grinding), demonstrating broad application prospects in the industrial production of silicon micropowder. Attached Figure Description

[0020] Figure 1 This is a schematic diagram illustrating the response mechanism of the enaldehyde-modified phenylsilane active grinding molecular-level aid in Example 1 to the physical micro-region viscosity. Figure 2 This is a high-resolution mass spectrum of the enaldehyde-modified phenylsilane active grinding molecular-level aid in Example 1; Figure 3 The emission spectra of the enaldehyde phenylsilane active grinding molecular-level aid in Example 1 in glycerol / water mixed solutions of different volume fractions are shown. Figure 4 This is a logarithmic function graph of fluorescence intensity versus viscosity value for the enaldehyde-modified phenylsilane active grinding molecular-level aid in Example 1; Figure 5 The images show the photostability test results of the enaldehyde-modified phenylsilane active grinding molecular-level aid in Example 1 in high-viscosity and low-viscosity solutions, respectively. Figure 6 The absorption spectra of the enaldehyde-modified phenylsilane active grinding molecular-level aid in Example 1 in solutions of different polarities are shown. Figure 7The values ​​of luminescence intensity of the enaldehyde-modified phenylsilane active grinding molecular-level aid in Example 1 in solutions with different pH values; Figure 8 This is a Stokes displacement test diagram of the enaldehyde-modified phenylsilane active grinding molecular-level aid in Example 1; Figure 9 This is a test chart showing the detection limit of the alkenyl phenylsilane active grinding molecular-level aid in Example 1; Figure 10 The emission spectra of the enaldehyde-modified phenylsilane active grinding molecular-level aid in Example 1 in different commercially available silicon micropowder grinding active aids are shown. Detailed Implementation

[0021] This invention provides an enaldehyde-modified phenylsilane active grinding molecular-level aid, having the following structural formula: .

[0022] This invention also provides a method for preparing the above-mentioned enaldehyde phenylsilane active grinding molecular-level aid, comprising the following steps: Under a protective atmosphere, myrtle aldehyde solution is mixed with dehydrating agent dispersion, and then 4-phenylaminotriethoxysilane solution is added to carry out dehydration condensation reaction to obtain enaldehyde-modified phenylsilane active grinding molecular-level aid.

[0023] In this invention, the concentration of the myrtol solution is 1-5 mol / L, preferably 2-4 mol / L, and more preferably 3 mol / L; the solvent in the myrtol solution is a mixture of alcohol and organic solvent, wherein the alcohol includes one or more of methanol, propanol, ethanol, ethylene glycol and 1,2-propanediol; the organic solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate and acetone, and the volume ratio of alcohol to organic solvent is 1-5:1, preferably 2-4:1, and more preferably 3:1.

[0024] In this invention, the concentration of the 4-anilinotriethoxysilane solution is 1~3 mol / L, preferably 2 mol / L; the solvent in the 4-anilinotriethoxysilane solution is a mixture of ethanol, ethylene glycol and N,N-dimethylformamide, and the volume ratio of ethanol, ethylene glycol and N,N-dimethylformamide is 1:1:1.

[0025] In this invention, the solvent in the dehydrating agent dispersion is selected from one or more of methanol, ethanol, and ethylene glycol, and the concentration of the dehydrating agent dispersion is 1~6 mol / L, preferably 2~5 mol / L, and more preferably 3~4 mol / L. The dehydrating agent in the dehydrating agent dispersion contains one or more of sodium carbonate, sodium bicarbonate, potassium bicarbonate, or magnesium hydroxide.

[0026] In this invention, the molar ratio of 4-anilinetriethoxysilane, myrtol, and dehydrating agent is 1:1 to 3:1 to 6, preferably 1:1.5 to 2.5:2 to 5, and more preferably 1:2:3 to 4.

[0027] In this invention, the myrtle aldehyde solution and the dehydrating agent dispersion are mixed as follows: stirring at 100-900 rpm for 0.5-2 h, then heating to 70-90 °C at a rate of 1-5 °C / min, while simultaneously increasing the stirring rate to 900-1800 rpm; adding 4-anilinetriethoxysilane solution to the mixture using a uniform spray method at a spray rate of 2-6 mL / min; after spraying, evacuating and pressurizing to 2-8 atm, continuing stirring at 1200-2200 rpm, and maintaining the temperature at 90-120 °C for 2.0-6.0 h to complete the dehydration condensation reaction. Preferably, the myrtle aldehyde solution and the dehydrating agent dispersion are mixed as follows: stirring at 200-800 rpm for 1 hour, then heating to 80°C at a rate of 2-4°C / min while simultaneously increasing the stirring rate to 1000-1500 rpm; adding 4-anilinetriethoxysilane solution to the mixture using a uniform spray method at a spray rate of 3-4 mL / min; after spraying, evacuating and pressurizing to 4-6 atm, continuing stirring at 1500-2000 rpm, and maintaining the temperature at 100-110°C for 3.0-5.0 hours to complete the dehydration condensation reaction.

[0028] In this invention, after the dehydration condensation reaction is completed, the product is purified. The purification is carried out in sequence by nitrogen blowing distillation, extraction dehydration, cold precipitation crystallization and freeze drying.

[0029] In this invention, the nitrogen blowing distillation involves transferring the cooled reaction material into the sample tube of a nitrogen blowing apparatus, using a nitrogen flow rate of 30-50 mL / min, a blowing temperature of 30-50°C, and a blowing time of 30-60 min, until the solution volume is concentrated to 1 / 6-1 / 3 of its original volume. The concentrated nitrogen solution is then transferred to a flask in a rotary evaporator, with a vacuum degree of -0.09 to -0.07 MPa, a water bath temperature of 50-60°C, a rotation speed of 60-400 rpm, and a distillation time of 1-3 h. Preferably, the nitrogen blowing distillation involves transferring the cooled reaction material into the sample tube of a nitrogen blowing apparatus, using a nitrogen flow rate of 35-45 mL / min, a blowing temperature of 40°C, and a blowing time of 40-50 min, until the solution volume is concentrated to 1 / 6-1 / 3 of its original volume. The concentrated nitrogen solution is then transferred to a flask in a rotary evaporator, with a vacuum of -0.09 to -0.07 MPa, a water bath temperature of 55°C, a rotation speed of 100-300 rpm, and a distillation time of 2 h.

[0030] In this invention, the extraction and dehydration involves adding an extraction system (ethyl acetate: purified water = 1~10:1, volume ratio) to the crude product after distillation, with the total amount of extractant being 5~8 times the mass of the crude product; transferring the extract to a separatory funnel, shaking at a frequency of 120~150 times / min for 10~15min, then allowing it to stand for 20~30min to separate the layers, collecting the upper organic phase; repeating the extraction 2~3 times, combining all organic phases, adding anhydrous sodium sulfate to the combined organic phase at 5%~8% (g / mL) of the organic phase volume, stirring at a speed of 300~500rpm at room temperature for 30~45min; filtering at normal pressure using medium-speed qualitative filter paper (pore size 1~3μm), controlling the filtration flow rate at 5~10mL / min, collecting the filtrate, and removing the anhydrous sodium sulfate desiccant; adding 0.1%~0.5% (mass fraction) of activated carbon to the filtrate, stirring at room temperature for 5~20min, and filtering again. Preferably, the extraction and dehydration involves adding an extraction system (ethyl acetate: purified water = 2~8:1, volume ratio) to the crude product after distillation, with the total amount of extractant being 6~7 times the mass of the crude product; transferring the extract to a separatory funnel, shaking at a frequency of 130~140 times / min for 12~15min, then allowing it to stand for 20~30min to separate the layers, collecting the upper organic phase; repeating the extraction 2~3 times, combining all organic phases, adding anhydrous sodium sulfate to the combined organic phase at 6%~7% (g / mL) of the organic phase volume, stirring at a speed of 300~500rpm at room temperature for 30~45min; filtering at normal pressure using medium-speed qualitative filter paper (pore size 1~3μm), controlling the filtration flow rate at 6~8mL / min, collecting the filtrate, and removing the anhydrous sodium sulfate desiccant; adding 0.2%~0.4% (mass fraction) of activated carbon to the filtrate, stirring at room temperature for 5~20min, and filtering again.

[0031] In this invention, the cold crystallization involves transferring the filtered organic phase into a rotary evaporator, setting the vacuum level to -0.09 to -0.07 MPa, the water bath temperature to 35 to 55°C, and the rotation speed to 80 to 300 rpm, concentrating the solution until the solid content is 8 to 12 mg / mL to obtain a concentrated solution. The concentrated solution is then slowly transferred to a clean crystallization flask, and while stirring, an ethanol-purified water mixture (ethanol:purified water = 1:5 to 20, volume ratio) is added at a stirring speed of 200 to 600 rpm and a dropping rate of 2 to 5 mL / mL. Mix thoroughly; place the crystallization flask in a low-temperature constant temperature oven, set the temperature to 1~10℃, and let it stand for 8~16 hours for cold precipitation. After the cold precipitation is completed, install the Buchner funnel and the vacuum filtration flask, and lay 1~3 layers of neutral fast filter paper (pore size 0.45~1.0μm). Moisten the filter paper in advance with a frozen ethanol-purified water mixture (same as the cold precipitation system). The vacuum degree is -0.09~-0.07MPa, the vacuum filtration flow rate is 2~10mL / min, and the crystals are washed 2~3 times with 5~10mL of frozen mixture. After each washing, filter until dry. Preferably, the cold crystallization involves transferring the filtered organic phase into a rotary evaporator, setting the vacuum level to -0.08 MPa, the water bath temperature to 40-50°C, and the rotation speed to 80-300 rpm, concentrating the solution until the solid content is 9-11 mg / mL to obtain a concentrated solution. The concentrated solution is then slowly transferred to a clean crystallization flask, and while stirring, an ethanol-purified water mixture (ethanol:purified water = 1:5-20, volume ratio) is added at a stirring speed of 300-500 rpm and a dropping rate of 3-4 mL / mL. Mix thoroughly; place the crystallization flask in a low-temperature constant temperature oven, set the temperature to 3~8℃, and let it stand for 8~16 hours for cold precipitation. After the cold precipitation is completed, install the Buchner funnel and the vacuum filtration flask, and lay 1~3 layers of neutral fast filter paper (pore size 0.45~1.0μm). Moisten the filter paper in advance with a frozen ethanol-purified water mixture (same as the cold precipitation system), set the vacuum degree to -0.08MPa, and the vacuum filtration flow rate to 2~10mL / min. Wash the crystals 2~3 times with 5~10mL of frozen mixture, and filter to dryness after each wash.

[0032] In this invention, the freeze-drying process involves transferring the crystalline product obtained by vacuum filtration into a freeze-drying bottle, setting the pre-freezing temperature to -40 to -30°C, and the pre-freezing time to 2-4 hours. After pre-freezing, the freeze dryer vacuum system is activated, setting the vacuum degree to ≤10 Pa, the sublimation temperature to -30 to -10°C, and the total freeze-drying time to 10-36 hours. After freeze-drying, the product is quickly removed under nitrogen protection, transferred to a mortar and gently ground, and passed through an 80-100 mesh sieve to obtain a uniform, light yellow powder. Preferably, the freeze-drying process involves transferring the crystalline product obtained by vacuum filtration into a freeze-drying bottle, setting the pre-freezing temperature to -35°C, and the pre-freezing time to 3 hours. After pre-freezing, the freeze dryer vacuum system is activated, setting the vacuum degree to ≤10 Pa, the sublimation temperature to -25 to -10°C, and the total freeze-drying time to 24-30 hours. After freeze-drying, the product is quickly removed under nitrogen protection, transferred to a mortar and gently ground, and passed through an 80-100 mesh sieve to obtain a uniform, light yellow powder.

[0033] This invention also provides the application of the above-mentioned enaldehyde phenylsilane active grinding molecular-level aid in the physical micro-region viscosity detection of silicon micro powder grinding dispersion.

[0034] In this invention, the application includes the following steps: In this invention, the solvent of the enaldehyde phenylsilane active grinding molecular-level auxiliary agent solution is preferably an ethylene glycol solution. This solvent has good compatibility with the silicon micropowder grinding dispersion system, does not interfere with it, and can ensure uniform dispersion of the auxiliary agent. The concentration of the auxiliary agent solution is preferably 10 μM.

[0035] In this invention, the excitation wavelength for measuring the light signal intensity is preferably 310 nm, and the peak emission wavelength is around 410 nm, presenting a typical bright blue light signal with high visibility. It can effectively avoid the light absorption interference of other components in the silicon micropowder grinding dispersion. The test process does not rely on shearing action and can be directly monitored in situ.

[0036] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0037] Example 1

[0038] Myrtol (300.44 g) was added to a mixed solution of ethanol and N,N-dimethylformamide, wherein the volume ratio of ethanol to N,N-dimethylformamide was 3:1. The mixture was stirred and sonicated at a stirring speed of 1100 rpm and an ultrasonic power of 300 W at room temperature (25 °C) for 1.25 h to obtain a myrtol solution with a concentration of 3 mol / L. 255.39 g of 4-anilinotriethoxysilane was added to a mixed solution of ethanol, ethylene glycol and N,N-dimethylformamide (in equal volume ratio), stirred until homogeneous, and the stirring speed was controlled at 1300 rpm for 0.55 h. The mixing was carried out at 40 °C to obtain a 2 mol / L 4-anilinotriethoxysilane solution. Sodium carbonate (370.97 g) was added to ethanol and stirred at 1500 rpm at 42.5 °C until it was evenly dispersed, thus preparing a dehydrating agent dispersion with a concentration of 3.5 mol / L. Under a nitrogen protective atmosphere, the prepared myrtle aldehyde solution was first mixed with the dehydrating agent dispersion and stirred at a low speed of 500 rpm for 1.25 h at room temperature. Then, the temperature was increased to 80 °C at a rate of 3 °C / min, while the stirring rate was increased to 1350 rpm. Subsequently, the prepared 4-anilinetriethoxysilane solution was added to the mixture by uniform spraying at a rate of 4 mL / min until spraying was complete. After spraying, a vacuum was applied and the pressure was increased to 5 atm. Stirring was continued at 1700 rpm, and the temperature was maintained at 105 °C for 4.0 h until the reaction was completed. After the reaction was completed, the pressure was reduced to atmospheric pressure and cooled, with a purging rate of 0.35 m / s, until the temperature was cooled to room temperature.

[0039] After the condensation reaction is completed, the product is purified. The purification process consists of nitrogen blowing distillation, extraction and dehydration, cold crystallization and freeze drying in sequence. Nitrogen blowing distillation: the material after the reaction is cooled is transferred into the sample tube of a nitrogen blowing apparatus, the nitrogen flow rate is 40 mL / min, the blowing temperature is 40℃, and the blowing time is 45 min, until the solution volume is concentrated to 1 / 4 of the original volume; then the nitrogen blowing concentrate is transferred to the eggplant flask of a rotary evaporator, the distillation pressure is -0.08 MPa, the water bath temperature is 55℃, the rotation speed is 230 rpm, and the distillation time is 2 h. The extraction and dehydration process involved adding an extraction system (ethyl acetate: purified water = 5.5:1, volume ratio) to the crude product after distillation, with the total amount of extractant being 6.5 times the mass of the crude product. The mixture was then transferred to a separatory funnel, oscillated at 135 times / min for 12.5 min, and allowed to stand for 25 min to separate into layers. The upper organic phase was collected. This extraction was repeated twice, and all organic phases were combined. Anhydrous sodium sulfate was added to the combined organic phase at 6.5% (g / mL) of the organic phase volume, and the mixture was stirred at 400 rpm at room temperature for 37.5 min. The mixture was then filtered at atmospheric pressure using medium-speed qualitative filter paper (2 μm pore size) at a flow rate of 7.5 mL / min, and the filtrate was collected. 0.3% (mass fraction) of activated carbon was added to the filtrate, and the mixture was stirred at room temperature for 12.5 min before being filtered again. The cold crystallization process involved: transferring the filtered organic phase into a rotary evaporator, setting the vacuum to -0.08 MPa, the water bath temperature to 45°C, and the rotation speed to 190 rpm, concentrating the solution until the solid content was 10 mg / mL, and obtaining a concentrated solution. The concentrated solution was then slowly transferred into a clean crystallization flask, and while stirring, an ethanol-purified water mixture (ethanol:purified water = 1:12.5, volume ratio) was added at a stirring speed of 400 rpm and a dropping rate of 3.5 mL / min until homogeneous. The crystallization flask was then placed in a low-temperature constant-temperature oven at 5.5°C and allowed to stand for 12 hours for cold crystallization. After the cold crystallization was complete, a Buchner funnel and a vacuum filtration flask were installed, and two layers of neutral rapid filter paper (pore size 0.725 μm) were laid on top. The filter paper was pre-wetted with a frozen ethanol-purified water mixture (same as the cold crystallization system), and the vacuum was set to -0.08 MPa with a vacuum flow rate of 6 mL / min. The crystals were washed twice with 7.5 mL of the frozen mixture, and after each wash, the mixture was filtered until dry. The freeze-drying process involved transferring the crystalline product obtained by vacuum filtration into a freeze-drying bottle, setting the pre-freezing temperature to -35°C for 3 hours, and then starting the vacuum system of the freeze dryer with a vacuum level of ≤10Pa, a sublimation temperature of -20°C, and a total freeze-drying time of 23 hours. After freeze-drying, the product was quickly removed under nitrogen protection, transferred to a mortar and gently ground, and passed through a 90-mesh sieve to obtain a uniform, light yellow powder (yield 92.3%). After purification, the enaldehyde-modified phenylsilane active grinding molecular-level aid, 356.9 g of powder (yield 92.1%), was obtained and designated as DHTPM.

[0040] The mechanism by which the enaldehyde-modified phenylsilane active grinding molecular-level aid affects the viscosity of silicon micropowder grinding dispersion in this embodiment is as follows: Figure 1 As shown, the core molecular structure of this additive contains enaldehyde-based conjugated bridging and phenylsilane flexible segments, forming a freely rotating single and double bond conjugated system. It possesses both good structural flexibility and conjugated color-forming properties. Its response color-forming mechanism is highly compatible with the micro-region viscosity changes of the silicon micropowder grinding aid dispersion: In low-viscosity grinding aid dispersions, the conjugated segments can rotate freely, and the excited-state energy is efficiently dissipated through non-radiative transitions, exhibiting only a weak light signal; as the micro-region viscosity of the dispersion increases, the molecular chain rotation is suppressed by steric hindrance, and the energy dissipation path switches to radiative transitions, releasing a strong green light signal with a peak value of 410 nm. Moreover, the light signal intensity and viscosity show a significantly enhanced logarithmic function relationship. Therefore, the viscosity of the silicon micropowder grinding aid dispersion can be intuitively judged by the light signal intensity, achieving a precise correspondence between viscosity and light signal.

[0041] The enaldehyde-modified phenylsilane active grinding molecular-level aid prepared in this embodiment was analyzed by high-resolution mass spectrometry, and the results are as follows: Figure 2 As shown, from Figure 2It can be seen that the relative molecular mass of the natural product prepared in this embodiment and the active molecular tool reconstructed from traditional silanes is 387.58775 [M]. + Its theoretical relative mass estimate is 387.59500, which confirms that the obtained product has the same relative molecular mass as the enaldehyde-modified phenylsilane active grinding molecular-level aid 1-(6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)-N-(4-(triethoxysilyl)phenyl)methyleneamine (DHTPM), with the molecular formula C. 22 H 33 NO3Si.

[0042] The performance of the enaldehyde-modified phenylsilane active grinding molecular-level aid prepared in this embodiment was tested.

[0043] 1. Viscosity response test of acetalized phenylsilane activated grinding molecular-level additive (DHTPM)

[0044] To investigate the detection efficiency of the enaldehyde-modified phenylsilane active grinding molecular-level additive DHTPM on the micro-region viscosity of silicon micropowder grinding dispersion, a mixed solution of glycerol and deionized water (simulating silicon micropowder grinding dispersions with different viscosity gradients) was prepared. The volume fraction of deionized water ranged from 0% to 99%, and the DHTPM concentration was controlled at 10 μM. The external excitation wavelength was set to 310 nm, and viscosity response tests were conducted at room temperature. The test results are as follows: Figure 3 As shown. From Figure 3 It is clearly evident that DHTPM exhibits extremely high sensitivity to changes in solution viscosity. As the viscosity of the mixed solution gradually increases (corresponding to an increase in the viscosity of the silicon micropowder grinding dispersion), the intensity of the emitted light signal shows a significant increasing trend. In particular, when the volume fraction of glycerol exceeds 70%, the viscosity of the mixed system rises sharply, and the light signal intensity of DHTPM shows an explosive increase. Compared with the low-viscosity system containing only deionized water (simulating a dilute phase grinding dispersion), the light signal intensity is increased by up to about 70.8 times. This fully demonstrates that DHTPM can accurately capture the minute fluctuations in the viscosity of the silicon micropowder grinding dispersion from low to high, and its detection sensitivity far exceeds that of conventional molecular-level detection tools.

[0045] Furthermore, analysis of the test data shows that the logarithmic function of the light signal intensity and the viscosity of the mixed solution can be fitted to a straight line with excellent linearity, specifically as follows: Figure 4 As shown. By Figure 4It can be seen that the intensity of the light signal emitted by DHTPM increases regularly with the increase of solution viscosity. Its response characteristics are in high agreement with the Förster-Hoffmann relation. The viscosity sensitivity coefficient of DHTPM is 0.64 and the coefficient of determination of the fit is 0.98, indicating that the linear correlation between the light signal intensity and the logarithm of viscosity is extremely strong. The detection results are accurate, reliable and have excellent repeatability. The above test results fully demonstrate that the enaldehyde-modified phenylsilane active grinding molecular-level additive DHTPM possesses excellent viscosity detection performance. It can be used as a dedicated molecular-level tool for detecting the micro-area viscosity of silicon micropowder grinding dispersions. Its extremely high sensitivity and good linear response characteristics can provide solid data support for the precise modulation of silicon micropowder grinding processes. It can provide real-time feedback on the viscosity of the grinding dispersion, helping staff to quickly determine whether the dispersion viscosity is suitable for grinding equipment and grinding requirements. This effectively avoids the problems of silicon micropowder agglomeration at low viscosity and the surge in equipment energy consumption at high viscosity, and significantly improves the particle size uniformity of silicon micropowder products. At the same time, its simple testing conditions and accurate detection results are suitable for the in-situ, real-time monitoring needs in the large-scale industrial production of silicon micropowder, demonstrating great application potential and irreplaceable practical value in the quality control and process optimization of grinding dispersions.

[0046] 2. Light stability test of diethyl phenyl silane activated grinding molecular-level additive (DHTPM)

[0047] 1.16 mg of the enaldehyde-modified phenylsilane active grinding molecular-level aid DHTPM prepared in Example 1 was added to ethylene glycol to prepare a 4 mM stock solution. For testing, the stock solution was diluted to 10 μM and then added to simulated silicon micropowder grinding dispersion systems of different viscosities. The solution was continuously irradiated under a 310 nm excitation light source for 60 min, and the changes in its optical signal intensity were monitored. The test results are as follows: Figure 5 As shown.

[0048] Depend on Figure 5 Data shows that DHTPM exhibits excellent photostability in solutions of varying viscosities. Even under prolonged excitation, it continues to release stable, unaffected light signals without significant photobleaching. This characteristic makes it highly promising for industrial monitoring of silicon micropowder grinding dispersions. It can meet the requirements for long-term, in-situ, real-time viscosity detection without frequent calibration or reagent replacement, significantly improving the continuity and reliability of viscosity monitoring during silicon micropowder grinding. This provides crucial support for stable control of the grinding process and ensuring product quality uniformity, making it suitable for long-term, continuous viscosity detection scenarios in large-scale silicon micropowder production, demonstrating significant practical value.

[0049] 3. Universality test of enaldehyde-modified phenylsilane activated grinding molecular-level aid

[0050] 1.55 mg of the enaldehyde-modified phenylsilane active grinding molecular-level aid DHTPM prepared in this example was added to an ethylene glycol mixed solution to prepare a 4 mM stock solution. For testing, the solution was further diluted to 10 μM and added to eight common solvents of different polarities: N,N-dimethylformamide, dimethyl sulfoxide, dichloromethane, purified water, methanol, tetrahydrofuran, ethanol, and ethyl acetate. The absorbance changes were tested at room temperature. The test results are as follows: Figure 6 As shown.

[0051] Depend on Figure 6 The results show that the absorbance of DHTPM in the eight different polar solvents is similar with no significant difference, indicating that its ability to absorb excitation light energy is not affected by the polarity of the solution. The absorption spectrum does not shift or change significantly due to changes in solution polarity, demonstrating excellent polarity tolerance. This characteristic gives it strong detection versatility in silicon micropowder grinding aid dispersions with complex solvent systems and diverse component polarities. Whether the grinding aid is water as the main solvent or is compounded with auxiliary solvents of different polarities such as ethanol, methanol, and ethyl acetate, DHTPM can stably absorb light and accurately respond to viscosity changes without the need to adjust detection parameters for different formulations. This greatly improves the versatility and reliability of viscosity detection for silicon micropowder grinding aid dispersions, making it suitable for silicon micropowder grinding processes with multiple formulations and solvent systems. It provides solid support for viscosity monitoring of diverse grinding aids in industrial production and has outstanding application value.

[0052] 4. pH tolerance test of diethyl phenyl silane activated grinding molecular-level additive (DHTPM)

[0053] Weigh 3.10 mg of the enaldehyde-modified phenylsilane active grinding molecular-level additive (DHTPM) prepared in Example 1, dissolve it in an appropriate amount of ethanol to prepare a DHTPM stock solution with a concentration of 8 mmol / L. This stock solution was then added to a series of buffer solutions simulating the actual pH environment (6.0~11.0) of a silicon micropowder grinding dispersion. The specific buffer system design was tailored to the industrial application requirements of silicon micropowder grinding: a potassium dihydrogen phosphate / dipotassium hydrogen phosphate mixed buffer solution with pH = 6.0~8.0, and a Tris-sodium bicarbonate mixed buffer solution with pH = 8.0~11.0. The final concentration of DHTPM in all test systems was adjusted to 10 μM. The change in optical signal intensity was measured at room temperature. The test results are as follows: Figure 7 As shown. By Figure 7Test results show that DHTPM exhibits weak and stable light signal release characteristics within the wide pH range of 6.0~11.0, which is commonly used in silicon micropowder grinding dispersions. The light signal intensity fluctuations are minimal, demonstrating excellent pH tolerance. This characteristic is highly compatible with the industrial application requirements of silicon micropowder grinding aids: the conventional pH control range for silicon micropowder grinding dispersions (for wet / dry grinding) is 6.0~11.0. During production, preparation, storage, transportation, and actual grinding processes, slight pH fluctuations can easily occur due to the addition of polycarboxylic acid grinding aids, silane coupling agents, or changes in the solid content of the system. DHTPM maintains a stable light signal within this pH fluctuation range, and its response to the micro-region viscosity of the grinding dispersion is not affected by environmental pH changes, ensuring the accuracy and repeatability of viscosity detection results. This superior characteristic gives DHTPM strong industrial adaptability in the field of silicon micron powder grinding aids. It eliminates the need for additional pH adjustment of the grinding aid dispersion for adaptability testing, greatly improving the convenience and efficiency of industrial testing. It can be stably applied to viscosity testing of silicon micron powder grinding aid dispersions with different formulations and grinding processes, providing key performance support for silicon micron powder grinding aid formulation optimization, production process quality control, and in-situ real-time monitoring of grinding processes. It effectively ensures the reliability of viscosity testing in silicon micron powder grinding industrial production, adapts to the needs of large-scale and continuous industrial production, and has outstanding application value.

[0054] 5. Stokes displacement test of diethyl phenyl silane activated grinding molecular-level aid (DHTPM)

[0055] 1.93 mg of the enaldehyde-modified phenylsilane active grinding molecular-level aid DHTPM prepared in this example was added to an ethylene glycol mixed solution to prepare a 5 mM stock solution. For testing, the solution was further diluted to 10 μM, added to purified water, and its absorption and emission spectra were measured. The Stokes shift was calculated. The tests were conducted at room temperature, and the results are as follows: Figure 8 As shown.

[0056] Depend on Figure 8 The results show that the DHTPM exhibits a Stokes shift of 113.4 nm, demonstrating a significant advantage of a large Stokes shift. This effectively reduces the interference of the excitation wavelength on detection and significantly improves the signal-to-noise ratio. This characteristic makes it highly promising for viscosity detection in silicon micropowder grinding dispersions. It can effectively avoid interference from background light scattered by silicon micropowder particles and excitation light, preventing signal distortion and ensuring accurate and reliable detection results. It is suitable for in-situ, real-time viscosity monitoring of complex silicon micropowder grinding dispersion systems, improving the accuracy and stability of viscosity detection in industrial production. It provides key technical support for the optimization of silicon micropowder grinding processes and product quality control, demonstrating outstanding application value.

[0057] 6. Detection limit test of diethyl etherified phenylsilane activated grinding molecular-level additive (DHTPM)

[0058] 2.33 mg of the enaldehyde-modified phenylsilane active grinding molecular-level additive (DHTPM) prepared in Example 1 was added to ethylene glycol to prepare a DHTPM stock solution with a concentration of 6 mmol / L. For testing, this stock solution was diluted to 10 μmol / L and then added to a water-glycerol mixture with extremely low viscosity (simulating the low viscosity conditions of the silicon micropowder grinding dispersion). The sensitivity of this stock solution to the viscosity of the micro-area was tested. The above tests were conducted at room temperature, and a linear fitting graph of the DHTPM detection limit was obtained (e.g., ...). Figure 9 As shown, where I max This refers to the optical signal intensity value corresponding to the peak wavelength. Figure 9 It can be seen that in the ultra-low viscosity system, the solution viscosity of DHTPM exhibits an excellent linear relationship with the logarithm of the light signal emission intensity, with a fitting coefficient of determination as high as 0.99, indicating that its response stability and accuracy in the low viscosity range are excellent. Calculations based on this linear relationship show that the viscosity detection limit of DHTPM is as low as 1.019 cP, fully demonstrating its extremely high sensitivity to minute changes in micro-region viscosity. Especially in low viscosity solution systems, it can still accurately capture viscosity fluctuations, resulting in outstanding detection performance. This significant advantage of a low detection limit makes it highly promising and practical for viscosity testing of silicon micropowder grinding aids. During silicon micropowder grinding, low-viscosity grinding aids are prone to particle agglomeration and insufficient grinding efficiency. DHTPM can accurately detect micro-viscosity changes as low as 1.033 cP, providing real-time feedback on minute fluctuations in the grinding aid dispersion from extremely low to suitable viscosity. This provides reliable data support for precise control of the silicon micropowder grinding process, effectively avoiding problems such as agglomeration and uneven dispersion of silicon micropowder at low viscosity, and helping to improve the uniformity of silicon micropowder products. Furthermore, its excellent low-viscosity detection performance is suitable for monitoring different low-viscosity conditions in wet and dry grinding of silicon micropowder, covering the entire viscosity range of grinding aid dispersions. This provides key technical support for quality control in large-scale industrial production, with broad application prospects.

[0059] Example 2

[0060] Myrtol (150.22 g) was added to a mixed solution of ethanol and N,N-dimethylformamide, wherein the volume ratio of ethanol to N,N-dimethylformamide was 1:1. The mixture was stirred and sonicated at a stirring speed of 600 rpm and an ultrasonic power of 100 W at room temperature (25 °C) for 0.5 h to obtain a myrtol solution with a concentration of 1 mol / L. 255.39 g of 4-anilinotriethoxysilane was added to a mixed solution of ethanol, ethylene glycol and N,N-dimethylformamide (in equal volume ratio), stirred until homogeneous, and the stirring speed was controlled at 800 rpm for 1.0 h. The mixing was carried out at 30 °C to obtain a 1 mol / L 4-anilinotriethoxysilane solution. Sodium carbonate (105.99 g) was added to methanol and stirred at 1000 rpm at 25 °C until it was evenly dispersed to prepare a dehydrating agent dispersion with a concentration of 1 mol / L. Under an argon protective atmosphere, the prepared myrtle aldehyde solution was first mixed with the dehydrating agent dispersion and stirred at a low speed of 100 rpm for 0.5 h at room temperature. Then, the temperature was increased to 70 °C at a rate of 1 °C / min, while the stirring rate was increased to 900 rpm. Subsequently, the prepared 4-anilinetriethoxysilane solution was added to the mixture using a uniform spray method, with the spray rate controlled at 2 mL / min, until spraying was completed. After spraying, a vacuum was drawn and pressurized to 2 atm, and stirring was continued at 1200 rpm, maintaining the temperature at 90 °C for 6.0 h until the reaction was completed. After the reaction was completed, the pressure was reduced to atmospheric pressure and cooled, with the purging rate controlled at 0.1 m / s, until it cooled to room temperature.

[0061] After the condensation reaction is completed, the product is purified; the purification is carried out sequentially by nitrogen distillation, extraction dehydration, cold crystallization, and freeze drying. The nitrogen blowing distillation process involves transferring the cooled reaction material into a sample tube of a nitrogen blowing apparatus, using a nitrogen flow rate of 30 mL / min, a blowing temperature of 30°C, and a blowing time of 30 min, until the solution volume is concentrated to 1 / 6 of its original volume. The concentrated nitrogen solution is then transferred to a flask in a rotary evaporator, with a distillation pressure of -0.09 MPa, a water bath temperature of 50°C, a rotation speed of 60 rpm, and a distillation time of 3 h. The extraction and dehydration process involves adding an extraction system (ethyl acetate: purified water = 1:1, volume ratio) to the crude product after distillation, with the total amount of extractant being 5 times the mass of the crude product. The mixture is then transferred to a separatory funnel, oscillated at 120 times / min for 10 min, and allowed to stand for 20 min to separate into layers. The upper organic phase is collected. This extraction is repeated twice, and all organic phases are combined. Anhydrous sodium sulfate is added to the combined organic phase at 5% (g / mL) of the organic phase volume, and the mixture is stirred at 300 rpm at room temperature for 45 min. The mixture is then filtered at atmospheric pressure using medium-speed qualitative filter paper (1 μm pore size) at a flow rate of 5 mL / min, and the filtrate is collected. 0.1% (mass fraction) activated carbon is added to the filtrate, and the mixture is stirred at room temperature for 20 min before being filtered again. The cold crystallization process involves: transferring the filtered organic phase into a rotary evaporator, setting the vacuum to -0.09 MPa, the water bath temperature to 35°C, and the rotation speed to 80 rpm, concentrating the solution until the solid content is 8 mg / mL to obtain a concentrated solution; slowly transferring the concentrated solution into a clean crystallization flask, while stirring, adding an ethanol-purified water mixture (ethanol:purified water = 1:5, volume ratio), stirring at 200 rpm, and dropping at a rate of 2 mL / min, until the mixture is homogeneous; placing the crystallization flask in a low-temperature constant temperature chamber, setting the temperature to 1°C, and allowing it to stand for cold crystallization for 8 hours; after cold crystallization, installing a Buchner funnel and a vacuum filtration flask, laying a layer of neutral rapid filter paper (pore size 0.45 μm), pre-wetting the filter paper with a frozen ethanol-purified water mixture (same as the cold crystallization system), setting the vacuum to -0.09 MPa, and the filtration flow rate to 2 mL / min; washing the crystallized solution twice with 5 mL of the frozen mixture, filtering to dryness after each wash; The freeze-drying process involves transferring the crystalline product obtained by vacuum filtration into a freeze-drying bottle, setting the pre-freezing temperature to -40℃ and the pre-freezing time to 4 hours. After pre-freezing, the vacuum system of the freeze dryer is started, setting the vacuum degree to ≤10Pa, the sublimation temperature to -30℃, and the total freeze-drying time to 10 hours. After freeze-drying, the product is quickly removed under nitrogen protection, transferred to a mortar and gently ground, and passed through an 80-mesh sieve to obtain a uniform light yellow powder. After purification, the enaldehyde-modified phenylsilane active grinding molecular-level aid is obtained, 350.0 g of powder (yield 90.3%), denoted as DHTPM.

[0062] The mass spectrometry results of the enaldehyde phenylsilane active grinding molecular-level aid (DHTPM) obtained in this example are the same as those in Example 1.

[0063] Example 3

[0064] Myrtol (450.66 g) was added to a mixed solution of ethanol and N,N-dimethylformamide, wherein the volume ratio of ethanol to N,N-dimethylformamide was 5:1. The mixture was stirred and sonicated at a stirring speed of 1600 rpm and an ultrasonic power of 500 W at room temperature (25 °C) for 2.0 h to obtain a myrtol solution with a concentration of 5 mol / L. 255.39 g of 4-anilinotriethoxysilane was added to a mixed solution of ethanol, ethylene glycol and N,N-dimethylformamide (equal volume ratio), stirred until homogeneous, and the stirring speed was controlled at 1800 rpm for 0.1 h. The mixing was carried out at 50 °C to obtain a 3 mol / L 4-anilinotriethoxysilane solution. Sodium carbonate (635.94 g) was added to ethanol and stirred at 2000 rpm at 60 °C until it was evenly dispersed to prepare a dehydrating agent dispersion with a concentration of 6 mol / L. Under a nitrogen protective atmosphere, the prepared myrtle aldehyde solution was first mixed with the dehydrating agent dispersion and stirred at a low speed of 900 rpm for 2.0 h at room temperature. Then, the temperature was increased to 90 °C at a rate of 5 °C / min, while the stirring rate was increased to 1800 rpm. Subsequently, the prepared 4-anilinetriethoxysilane solution was added to the mixture by uniform spraying at a controlled spray rate of 6 mL / min until spraying was complete. After spraying, a vacuum was drawn and pressurized to 8 atm, and stirring was continued at 2200 rpm while maintaining the temperature at 120 °C for 2.0 h until the reaction was complete. After the reaction was completed, the pressure was reduced to atmospheric pressure and cooled, with a purging rate of 0.6 m / s, until the temperature cooled to room temperature.

[0065] After the condensation reaction is completed, the product is purified; the purification is carried out sequentially by nitrogen distillation, extraction dehydration, cold crystallization, and freeze drying. The nitrogen blowing distillation process involves transferring the cooled reaction material into a sample tube of a nitrogen blowing apparatus, using a nitrogen flow rate of 50 mL / min, a blowing temperature of 50°C, and a blowing time of 60 min, until the solution volume is concentrated to 1 / 3 of its original volume. The concentrated nitrogen solution is then transferred to a flask in a rotary evaporator, with a distillation pressure of -0.07 MPa, a water bath temperature of 60°C, a rotation speed of 400 rpm, and a distillation time of 1 h. The extraction and dehydration process involved adding an extraction system (ethyl acetate: purified water = 10:1, volume ratio) to the crude product after distillation, with the total amount of extractant being 8 times the mass of the crude product. The mixture was then transferred to a separatory funnel, oscillated at 150 times / min for 15 min, and allowed to stand for 30 min to separate into layers. The upper organic phase was collected. This extraction was repeated three times, and all organic phases were combined. Anhydrous sodium sulfate was added to the combined organic phase at 8% (g / mL) of the organic phase volume, and the mixture was stirred at 500 rpm at room temperature for 45 min. The mixture was then filtered at atmospheric pressure using medium-speed qualitative filter paper (3 μm pore size) at a flow rate of 10 mL / min, and the filtrate was collected. The cold crystallization process involves: transferring the filtered organic phase into a rotary evaporator, setting the vacuum to -0.07 MPa, the water bath temperature to 55°C, and the rotation speed to 300 rpm, concentrating the solution until the solid content is 12 mg / mL to obtain a concentrated solution; slowly transferring the concentrated solution into a clean crystallization flask, while stirring, adding an ethanol-purified water mixture (ethanol:purified water = 1:20, volume ratio), stirring at 600 rpm, and dropping at a rate of 5 mL / min, until the mixture is homogeneous; placing the crystallization flask in a low-temperature constant temperature oven, setting the temperature to 10°C, and allowing it to stand for 16 hours for cold crystallization; after the cold crystallization is complete, installing a Buchner funnel and a vacuum filtration flask, laying three layers of neutral rapid filter paper (pore size 1.0 μm), pre-wetting the filter paper with a frozen ethanol-purified water mixture (same as the cold crystallization system), setting the vacuum to -0.07 MPa, and the filtration flow rate to 10 mL / min; washing the crystallizer three times with 10 mL of the frozen mixture, filtering to dryness after each wash; The freeze-drying process involved transferring the crystalline product obtained by vacuum filtration into a freeze-drying bottle, setting the pre-freezing temperature to -30°C for 2 hours, and then starting the vacuum system of the freeze dryer with a vacuum level of ≤10Pa and a sublimation temperature of -10°C for a total freeze-drying time of 36 hours. After freeze-drying, the product was quickly removed under nitrogen protection, transferred to a mortar and gently ground, and passed through a 100-mesh sieve to obtain a uniform pale yellow powder. After purification, the enaldehyde-modified phenylsilane active grinding molecular-level aid was obtained, 354.6 g of powder (yield 91.5%), denoted as DHTPM.

[0066] The mass spectrometry results of the enaldehyde phenylsilane active grinding molecular-level aid (DHTPM) obtained in this example are the same as those obtained in Example 1.

[0067] Application Example 1

[0068] 2.71 mg of the enaldehyde-modified phenylsilane active grinding molecular-level aid (DHTPM) prepared in Example 1 was dissolved in ethylene glycol to prepare a 7 mM stock solution. For testing, the solution was diluted to 10 μM. Three commercially available silicon micropowder grinding aids with different viscosities (Aiyota SMP-60 (grinding aid 1), viscosity 60.0 cP; Wacker Silres BS 200 (grinding aid 2), viscosity 200.0 cP; Evonik TEGO Dispers 750W (grinding aid 3), viscosity 400.0 cP) were selected as test subjects. DHTPM was added to each of the three aids, and the tests were conducted at room temperature with an excitation wavelength of 320 nm. The results are as follows: Figure 10 As shown. By Figure 10It can be seen that the light signal release intensity of the three silicon micropowder grinding aids differs significantly. Aiyota SMP-60 has the weakest light signal, WackerSilres BS 200 has a medium light signal, and Evonik TEGO Dispers 750W has the strongest light signal. This fully demonstrates that DHTPM can accurately sense the micro-area viscosity differences of different silicon micropowder grinding aids, intuitively distinguish the viscosity grade of the aids through visual light signals, and the detection results are highly consistent with the actual viscosity of the aids. Different viscosities of silicon micropowder grinding aids are suitable for different grinding scenarios. The 60cP low-viscosity aid has excellent flowability and is suitable for pipeline transportation and conventional silicon micropowder grinding. The 200cP medium-viscosity aid balances suspension and flowability and is suitable for grinding systems with medium to high solid content. The 400cP high-viscosity aid has excellent anti-settling properties and is suitable for ultrafine silicon micropowder grinding. The precise detection capability of DHTPM can provide key data support for the formulation and viscosity optimization of silicon micropowder grinding aids, helping R&D personnel to quickly adjust the aid formulation according to different grinding needs. At the same time, it can realize in-situ, real-time, and visual monitoring of the viscosity of silicon micropowder grinding aids in industrial production, effectively ensuring the stability of the grinding process and the uniformity of silicon micropowder particle size. It has extremely high application potential and practical value in the R&D, production, and process optimization of silicon micropowder grinding aids.

[0069] As can be seen from the above embodiments and test results, the enaldehyde-modified phenylsilane active grinding molecular-level additive (DHTPM) provided by the present invention, with its flexible conjugated structure, can convert the micro-region viscosity changes of the silicon micropowder grinding dispersion into a visible optical signal, achieving precise photochemical representation of the molecular-level micro-region viscosity. Comprehensive tests show that it has excellent spectroscopic properties, chemical stability, photostability, large Stokes shift, and wide pH tolerance. The emission wavelength is stable around 410 nm, and the Stokes shift is as high as 113.4 nm, which can effectively avoid the scattering light, excitation light background, and volume of silicon micropowder particles. The fluorescence interference from multiple components within the system is significantly reduced, improving the signal-to-noise ratio. Absorbance shows no significant difference in various polar solvents, and it remains stable within the typical pH range (6.0–11.0) of the silica powder grinding aid dispersion. It is unaffected by polycarboxylic acid grinding aids, polyethylene glycol, and other components. Even after continuous irradiation with a 320nm excitation light source for 60 minutes, it maintains a stable light signal without significant photobleaching. The viscosity detection limit is as low as 1.019 cP, and the linear fitting coefficient of determination between the solution viscosity and the logarithm of the light signal intensity in the extremely low viscosity range exceeds 0.98. It can accurately distinguish between 60 cP (Aiyota SMP-60), 200 cP (Wacker Silres BS 200), and 400 cP (Evonik TEGO Dispers). The viscosity differences of three commercially available silicon micropowder grinding aids (750W) were analyzed, and the light signal intensity showed a significant and regular change with increasing viscosity. Meanwhile, DHTPM, prepared using a one-step dehydration condensation process, is simple, requiring no complex equipment or cumbersome post-processing. The raw materials are partly derived from natural products, making them inexpensive and readily available. The preparation process is environmentally friendly, low-carbon, and energy-saving, with high yield and controllable cost, making it suitable for large-scale industrial chemical production. It can be widely used for viscosity detection, formulation adjustment, and industrial production quality control of silicon micropowder grinding dispersions. It provides real-time feedback on the viscosity of the grinding dispersion, offering precise data support for grinding process optimization. This effectively avoids the problems of silicon micropowder agglomeration at low viscosity and the surge in equipment energy consumption at high viscosity, helping to improve the particle size uniformity of silicon micropowder products. Furthermore, it is suitable for different grinding scenarios such as wet / dry and conventional / ultrafine grinding, eliminating the need to adjust detection parameters for different formulations, significantly improving detection efficiency and reducing detection costs. It provides key technical support for process upgrading and quality control in the silicon micropowder grinding industry, with broad application prospects.

[0070] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A molecular-level grinding aid for enaldehyde-modified phenylsilane, characterized in that, It has the following structural formula: 。 2. The method for preparing the enaldehyde-modified phenylsilane active grinding molecular-level aid according to claim 1, characterized in that, Includes the following steps: Under a protective atmosphere, myrtle aldehyde solution is mixed with dehydrating agent dispersion, and then 4-phenylaminotriethoxysilane solution is added to carry out dehydration condensation reaction to obtain enaldehyde-modified phenylsilane active grinding molecular-level aid.

3. The preparation method according to claim 2, characterized in that, The concentration of the myrtol solution is 1-5 mol / L. The solvent in the myrtol solution is a mixture of alcohol and organic solvent. The alcohol includes one or more of methanol, propanol, ethanol, ethylene glycol and 1,2-propanediol. The organic solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate and acetone. The volume ratio of alcohol to organic solvent is 1-5:

1.

4. The preparation method according to claim 2 or 3, characterized in that, The concentration of the 4-anilinotriethoxysilane solution is 1~3 mol / L, and the solvent in the 4-anilinotriethoxysilane solution is a mixture of ethanol, ethylene glycol and N,N-dimethylformamide, wherein the volume ratio of ethanol, ethylene glycol and N,N-dimethylformamide is 1:1:

1.

5. The preparation method according to claim 4, characterized in that, The solvent in the dehydrating agent dispersion is selected from one or more of methanol, ethanol, and ethylene glycol, and the concentration of the dehydrating agent dispersion is 1~6 mol / L; The dehydrating agent in the dehydrating agent dispersion contains one or more of sodium carbonate, sodium bicarbonate, potassium bicarbonate, or magnesium hydroxide.

6. The preparation method according to claim 5, characterized in that, The molar ratio of 4-anilinetriethoxysilane, myrtol, and dehydrating agent is 1:1~3:1~6.

7. The preparation method according to claim 2 or 6, characterized in that, The myrtle aldehyde solution and the dehydrating agent dispersion were mixed as follows: stirring at 100-900 rpm for 0.5-2 h, then heating to 70-90 °C at a rate of 1-5 °C / min, while simultaneously increasing the stirring rate to 900-1800 rpm; adding 4-anilinetriethoxysilane solution to the mixture using a uniform spray method at a spray rate of 2-6 mL / min; after spraying, evacuating and pressurizing to 2-8 atm, continuing stirring at 1200-2200 rpm, and maintaining the temperature at 90-120 °C for 2.0-6.0 h to complete the dehydration condensation reaction.

8. The preparation method according to claim 2, characterized in that, After the dehydration condensation reaction is completed, the product is purified by sequential nitrogen distillation, extraction dehydration, cold crystallization and freeze drying.

9. The application of the enaldehyde-modified phenylsilane active grinding molecular-level aid as described in claim 1 in the physical micro-region viscosity detection of silicon micropowder grinding dispersion.

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