Natural silane rotor and preparation method and application thereof

Abstract

The invention belongs to the technical field of industrial silane preparation, and provides a natural silane rotor and a preparation method and application thereof.The preparation method comprises the steps that a pyridoxal phosphate solution and a 4-amino ethyl cinnamate solution are mixed and then react to obtain pyridoxal phosphate cinnamyl ester; and mixing the pyridoxal phosphate cinnamyl ester solution and the amino silane solution, and reacting to obtain the natural silane rotor. The silane rotor has a good conjugated structure, is stable in chemical structure, can be stored for a long time, is good in light stability, and is not liable to cause a photobleaching phenomenon. Besides, conjugated single and double bonds capable of freely rotating exist in the molecular structure, a typical flexible intramolecular rotation characteristic is presented, the conjugated structure can freely rotate in a dilute solution, a surface sightseeing signal is weak, the free rotation phenomenon is limited in a thick solution, the surface sightseeing signal is strong, and the surface sightseeing signal is strong. Therefore, the device can be used as a molecular tool for monitoring the change of the thin consistency of the silane, and can provide real-time, lossless and visual detection support for the development of a silane modulation process.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of industrial silane preparation, and particularly relates to a natural silane rotor, a preparation method and application thereof. BACKGROUND

[0002] Industrial silane solution plays a huge role in the modification and modification process of inorganic mineral powder, and its viscosity control and structure control are closely related to the comprehensive function of the final composite powder. Generally, in the preparation process of industrial silane solution, the dilution size is closely related to the modification and modification efficiency, the micro-viscosity, a property that can resist deformation or prevent adjacent fluid layers from flowing, as a physical parameter, has a deep connection with the spreading, wetting, covering and other apparent properties of silane solution on the surface of inorganic mineral powder. For example: when the micro-viscosity of silane solution is low, the apparent presents good fluidity, which can fully penetrate and adhere between the inorganic mineral powder under high-speed stirring, and can fully wet the inorganic mineral powder; when the micro-viscosity of silane solution is high, it presents a paste, and its fluidity decreases significantly, and it is difficult to fully disperse and penetrate, but it can better stay and anchor on the surface of inorganic mineral powder, forming a relatively complete coating layer, so the control of the dilution of silane solution has a good promoting effect on the subsequent modification and activation of inorganic mineral powder. The change of micro-viscosity of silane solution often occurs in the micro area, and the traditional viscosity measurement mostly depends on various types of viscometers (falling ball viscometer, rotary viscometer, vibration viscometer, etc.). These viscometers are designed for macro-viscosity, and have strong equipment dependence in measurement, and have large sample requirements, and are not sensitive in low viscosity range, and the perception of micro-viscosity change is also prone to error, and it is difficult to finely control the micro-viscosity of silane solution, that is, it is difficult to measure the micro-viscosity at the molecular level, especially for the silane solution containing part of silane polymer, which will appear significant shear thinning phenomenon, and the viscometer is helpless. Therefore, it is urgent to develop a molecular-level tool suitable for silane solution to measure the change of micro-viscosity. SUMMARY

[0003] The present application relates to the technical field of industrial silane preparation, and particularly relates to a natural silane rotor, a preparation method and application thereof.

[0004] In order to achieve the above-mentioned application purpose, the present application provides the following technical scheme: The present application provides a natural silane rotor, the structure of the natural silane rotor is as follows: ; X is 、 、 、 , 、 、 or .

[0005] The application also provides a preparation method of the natural silane rotor, comprising the following steps: (1) mixing a pyridoxal phosphate solution and an ethyl 4-aminocinnamate solution, and then reacting to obtain a pyridoxal phosphate cinnamate ester; (2) mixing a pyridoxal phosphate cinnamate ester solution and an aminosilane solution, and then reacting to obtain the natural silane rotor.

[0006] Preferably, the concentration of the pyridoxal phosphate solution in step (1) is 1-5 M; The solvent of the pyridoxal phosphate solution comprises solvent a and dimethyl sulfoxide; The solvent a is one or more of ethyl acetate, N,N-dimethylformamide, acetonitrile and tetrahydrofuran; The volume ratio of the solvent a and dimethyl sulfoxide is 2-10:1.

[0007] Preferably, the concentration of the ethyl 4-aminocinnamate solution in step (1) is 1-3 M; The solvent of the ethyl 4-aminocinnamate solution is one or more of ethyl acetate, methanol, ethanol, N,N-dimethylformamide, acetonitrile, tetrahydrofuran and dimethyl sulfoxide.

[0008] Preferably, the molar ratio of pyridoxal phosphate and ethyl 4-aminocinnamate in step (1) is 1:1-3; The mixing mode in step (1) is to add the ethyl 4-aminocinnamate solution into the pyridoxal phosphate solution, and the adding rate is 1-5 mL / min; The temperature rising rate of the reaction in step (1) is 1-5 ℃ / min, the reaction temperature is 75-95 ℃, the stirring rate is 1200-2000 rpm, the ultrasonic power is 100-500 W, and the time is 1-12 h.

[0009] Preferably, the concentration of the pyridoxal phosphate cinnamate ester solution in step (2) is 1-3 M; The solvent of the pyridoxal phosphate cinnamate ester solution is one or more of ethyl acetate, N,N-dimethylformamide, acetonitrile and tetrahydrofuran.

[0010] Preferably, the concentration of the aminosilane solution in step (2) is 1-6 M; The aminosilane is 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, or 3-diethylenetriaminopropyltrimethoxysilane; The solvents for aminosilane solutions include alcohol and water; The alcohol is one or more of ethanol, methanol, and ethylene glycol; The volume ratio of alcohol to water is 1 to 5:1.

[0011] Preferably, the molar ratio of pyridoxalated cinnamon ester phosphate to aminosilane in step (2) is 1:1~6.

[0012] Preferably, the heating rate of the reaction in step (2) is 2~6℃ / min, the temperature is 60~90℃, the rotation speed is 1000~1800rpm, and the time is 1~4h.

[0013] The present invention also provides the application of the natural silane rotor in the micro-area viscosity detection of silane active additives.

[0014] This invention provides a natural silane rotor, which is obtained by reconstructing various natural products and further modifying traditional silanes. The resulting product is a light white powder, readily soluble in a mixture of ethanol, methanol, and purified water, suitable for industrial dilution. This silane rotor possesses a favorable conjugated structure, exhibits chemical stability and long-term storage capability, good photostability, and is not prone to photobleaching. Furthermore, its molecular structure contains freely rotating conjugated single and double bonds, exhibiting typical flexible intramolecular rotational characteristics. This conjugated structure can rotate freely in dilute solutions with weak apparent signals, while this free rotation phenomenon is restricted in viscous solutions with strong apparent signals. Therefore, it can serve as a molecular tool for monitoring changes in the dilution and viscosity of silanes, providing real-time, non-destructive, and visualized detection support for the development of silane modulation processes.

[0015] This invention provides a natural silane rotor, which, as an improved silane functional additive, can also be used for the modification and surface passivation of natural inorganic mineral powders, further enhancing the synergistic effect of inorganic mineral powders and their multiple functionalities.

[0016] Compared with the prior art, the present invention has the following advantages: The natural silane rotor of this invention enables visualized monitoring of the silane modulation process, filling the gap in traditional silane detection which is difficult to perform in situ, in real time, and conveniently. At the same time, it avoids the shear thinning effect that exists in the viscosity detection of traditional silane oligomers and even polymers. That is, this type of silane rotor can be used as a molecular-level tool for controlling the viscosity of silane functional solutions. This method is very effective for monitoring and controlling the viscosity of silane functional solutions and can provide a useful reference for the development of additives for composite powders.

[0017] The natural silane rotor of this invention has good pH stability and photostability. The logarithmic function of the intensity of the emitted light signal and the viscosity value of conventional silanes matches the Förster-Hoffmann relationship function. The viscosity sensitivity coefficient reaches 0.54, indicating that it has high sensitivity to viscosity and is very suitable for measuring the viscosity of conventional silanes. At the same time, the natural silane rotor can perform well in photodetection in a variety of representative silanes.

[0018] The natural silane rotor provided by this invention has a green apparent signal, high visual sensitivity, good visualization effect, and typical electron donation-withdrawal effect, exhibiting good turn-on detection effect. Its wavelength peak is 512 nm, which can effectively avoid the blue-violet light emission band range of traditional silanes, greatly improving the signal-to-noise ratio. Its Stokes shift exceeds 100 nm, which can effectively avoid interference from excitation light.

[0019] The natural silane rotor of the present invention is also an improved silane, which contains aromatic heterocycles, phosphates, and a large conjugated structure. It can not only serve as an external modification layer for natural inorganic mineral powders, but also provide sufficient multifunctionality, including flame retardancy, promoting char formation, and enhancing thermal stability. This allows it to work synergistically with the internal natural inorganic mineral powders to enhance the comprehensive function of the composite powder.

[0020] This invention also provides a method for preparing the natural silane rotor. The method is a two-step process, and the raw materials required are mainly from nature. The price is controllable, the overall application and preparation cost is low, and it is suitable for large-scale chemical preparation. Moreover, the whole process does not require complicated preparation processes, and the final yield is also high. The process is relatively green and environmentally friendly, and it is a typical natural product reconstruction and cross-border high-value application. Attached Figure Description

[0021] Figure 1 This is a schematic diagram illustrating the mechanism of micro-area viscosity detection using a natural silane rotor in Example 1; Figure 2 The emission spectra of the natural silane rotor in Example 1 in glycerol / water mixed solutions of different volume fractions are shown. Figure 3 This is a logarithmic function graph of fluorescence intensity versus viscosity value for the natural silane rotor in Example 1; Figure 4 The graphs show the photostability of the natural silane rotor in Example 1 in glycerol and purified water, respectively. Figure 5 The emission spectra of the natural silane rotor in Example 1 in solutions with different pH values ​​are shown below. Figure 6 The Stokes displacement diagram of the natural silane rotor in Experiment Example 1; Figure 7 The emission spectra of the natural silane rotor in Example 1 in different commercially available silane solutions are shown. Detailed Implementation

[0022] This invention provides a natural silane rotor, the structure of which is shown below: ; X is , , , , , , or .

[0023] This invention provides a method for preparing the natural silane rotor, comprising the following steps: (1) Pyridoxal phosphate solution and ethyl 4-aminocinnamate solution were mixed and reacted to obtain pyridoxal-modified cinnamate phosphate; (2) The natural silane rotor is obtained by mixing pyridoxal cinnamon ester phosphate solution and aminosilane solution and then reacting them.

[0024] In this invention, the concentration of the pyridoxal phosphate solution in step (1) is preferably 1~5M, more preferably 1.5~4.5M, and even more preferably 2~4M.

[0025] In this invention, the solvent of the pyridoxal phosphate solution comprises solvent a and dimethyl sulfoxide.

[0026] In this invention, solvent a is one or more of ethyl acetate, N,N-dimethylformamide, acetonitrile, and tetrahydrofuran.

[0027] In this invention, the volume ratio of solvent a to dimethyl sulfoxide is preferably 2 to 10:1, more preferably 3 to 9:1, and even more preferably 4 to 8:1.

[0028] In this invention, pyridoxal phosphate and solvent are mixed and stirred. The stirring speed is preferably 600-1200 rpm, more preferably 700-1100 rpm, and even more preferably 900-1000 rpm. The temperature is preferably 45-70℃, more preferably 50-65℃, and even more preferably 55-60℃. The stirring time is preferably 0.5-2 h, more preferably 1-1.5 h, and even more preferably 1.2-1.3 h. After stirring, a pyridoxal phosphate solution is obtained.

[0029] In this invention, the concentration of the 4-aminocinnamic acid ethyl ester solution in step (1) is preferably 1~3M, more preferably 1.5~2.5M, and even more preferably 1.8~2.3M.

[0030] In this invention, the solvent for the ethyl 4-aminocinnamate solution is one or more of ethyl acetate, methanol, ethanol, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, and dimethyl sulfoxide.

[0031] In this invention, ethyl 4-aminocinnamate and a solvent are mixed and stirred. The stirring speed is preferably 1000-1800 rpm, more preferably 1100-1700 rpm, and even more preferably 1200-1500 rpm. The temperature is preferably 40-75℃, more preferably 45-70℃, and even more preferably 55-60℃. The stirring time is preferably 0.2-1 h, more preferably 0.3-0.9 h, and even more preferably 0.4-0.8 h. After stirring, an ethyl 4-aminocinnamate solution is obtained.

[0032] In this invention, the molar ratio of pyridoxal phosphate and ethyl 4-aminocinnamate in step (1) is preferably 1:1 to 3, more preferably 1:1.5 to 2.5, and even more preferably 1:1.7 to 2.3.

[0033] In this invention, the mixing method in step (1) is to add ethyl 4-aminocinnamate solution to pyridoxal phosphate solution, and the addition rate is preferably 1~5 mL / min, more preferably 2~4 mL / min, and even more preferably 2.5~3 mL / min.

[0034] In this invention, the heating rate of the reaction in step (1) is preferably 1~5℃ / min, more preferably 1.5~4.5℃ / min, and more preferably 2~4℃ / min; the 4-aminocinnamate ethyl ester solution is added while the temperature is increased until the reaction temperature is reached; the reaction temperature is preferably 75~95℃, more preferably 80~90℃, and more preferably 84~86℃; stirring and sonication are maintained throughout the addition and reaction process; the stirring rate is preferably 1200~2000rpm, more preferably 1300~1900rpm, and more preferably 1400~1700rpm; the ultrasonic power is preferably 100~500W, more preferably 200~400W, and more preferably 250~350W; the time is preferably 1~12h, more preferably 2~10h, and more preferably 4~6h.

[0035] In this invention, after the reaction in step (1) is completed, the mixture is cooled to room temperature and the solvent is removed by vacuum distillation; the distillation pressure is preferably -0.07 to -0.09 MPa, more preferably -0.075 to -0.085 MPa, and more preferably -0.078 to -0.082 MPa; the evaporation rate is preferably 50 to 300 rpm, more preferably 100 to 200 rpm, and more preferably 140 to 160 rpm; the crude product is added to a mixture of ethanol and water, the volume ratio of ethanol to water is preferably 1 to 10:1, more preferably 2 to 8:1, and more preferably 4 to 6:1; the solid content is preferably 5 to 10 mg / mL, more preferably 6 to 9 mg / mL, and more preferably 7 to 8 mg / mL; The crystals are allowed to stand and precipitate. The preferred temperature for standing is 1-10°C, more preferably 2-8°C, and even more preferably 4-6°C. The preferred time is 5-24 h, more preferably 10-20 h, and even more preferably 14-16 h. The precipitated crystals are then filtered in a mixed solution of water and ethanol. The volume ratio of water to ethanol is preferably 1-10:1, more preferably 2-8:1, and even more preferably 4-6:1. The filter paper used for filtration is medium-speed or high-speed filter paper, and the number of filter paper layers is 1-3. The preferred filtration flow rate is 0.3-2 mL / s, more preferably 0.5-1.5 mL / s, and even more preferably 0.8-1.2 mL / s. The preferred number of filtrations is 1-5 times, and even more preferably 2-3 times. After filtration, pyridoxal-formaldehyde cinnamon phosphate is obtained.

[0036] In this invention, the concentration of the pyridoxal cinnamon ester phosphate solution in step (2) is preferably 1~3M, more preferably 1.5~2.5M, and even more preferably 1.8~2.3M.

[0037] In this invention, the solvent for the pyridoxal cinnamon ester phosphate solution is one or more of ethyl acetate, N,N-dimethylformamide, acetonitrile, and tetrahydrofuran.

[0038] In this invention, pyridoxal cinnamyl phosphate and solvent are mixed and stirred. The stirring speed is preferably 500-900 rpm, more preferably 600-800 rpm, and even more preferably 650-700 rpm. The temperature is preferably 40-70℃, more preferably 45-65℃, and even more preferably 50-60℃. The stirring time is preferably 0.5-1.5h, more preferably 0.6-1.4h, and even more preferably 0.8-1.2h.

[0039] In this invention, the concentration of the aminosilane solution in step (2) is preferably 1~6M, more preferably 2~5M, and even more preferably 3~4M.

[0040] In this invention, the aminosilane is 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, or 3-diethylenetriaminopropyltrimethoxysilane.

[0041] In this invention, the solvent for the aminosilane solution comprises alcohol and water.

[0042] In this invention, the alcohol is one or more of ethanol, methanol and ethylene glycol.

[0043] In this invention, the volume ratio of alcohol to water is preferably 1 to 5:1, more preferably 2 to 4:1, and even more preferably 2.5 to 3.5:1.

[0044] In this invention, aminosilane and solvent are mixed and stirred. The mixing and stirring temperature is preferably 20~30℃, more preferably 22~28℃, and even more preferably 24~26℃; the stirring speed is preferably 400~800rpm, more preferably 500~700rpm, and even more preferably 550~650rpm; and the stirring time is preferably 0.1~1h, more preferably 0.2~0.8h, and even more preferably 0.4~0.6h.

[0045] In this invention, the molar ratio of pyridoxal cinnamon ester phosphate and aminosilane in step (2) is preferably 1:1 to 6, more preferably 1:2 to 5, and even more preferably 1:3 to 4.

[0046] In this invention, step (2) involves mixing a pyridoxalated cinnamon ester phosphate solution into an aminosilane solution, followed by heating. The heating rate in step (2) is preferably 2-6°C / min, more preferably 3-5°C / min, and even more preferably 3.5-4°C / min; the temperature is preferably 60-90°C, more preferably 65-85°C, and even more preferably 70-80°C; the rotation speed is preferably 1000-1800 rpm, more preferably 1100-1700 rpm, and even more preferably 1200-1500 rpm; and the time is preferably 1-4 h, more preferably 1.5-3.5 h, and even more preferably 2-3 h.

[0047] In this invention, after the reaction in step (2) is completed, cooling is performed. The target cooling temperature is preferably 20-30°C, more preferably 22-28°C, and even more preferably 24-26°C. Then, secondary cooling is performed. The target temperature for secondary cooling is preferably 1-5°C, more preferably 1.5-4.5°C, and even more preferably 2-4°C. After reaching the target temperature for secondary cooling, the mixture is allowed to stand for 3-12 hours, more preferably 4-10 hours, and even more preferably 6-8 hours. After standing, filtration is performed using medium-speed or high-speed filter paper with 1-3 layers. The filtration flow rate is preferably 1-3 mL / s, more preferably 1.5-2.5 mL / s, and even more preferably 1.8-2.2 mL / s. During the filtration process, a mixture of water and ethanol is used for rinsing, wherein the volume ratio of water to ethanol is preferably 1~10:1, more preferably 2~8:1, and even more preferably 4~6:1; the vacuum degree of filtration is preferably -0.1~-0.08MPa, more preferably -0.09~-0.085MPa, and even more preferably -0.089~-0.088MPa; the number of filtrations is preferably 2~5 times; after filtration, drying is carried out, the drying temperature is preferably -40~-5℃, more preferably -30~-10℃, and even more preferably -25~-20℃; the drying time is preferably 24~72h, more preferably 30~65h, and even more preferably 40~50h; after drying, a natural silane rotor is obtained.

[0048] The present invention also provides the application of the natural silane rotor in the micro-area viscosity detection of silane active additives.

[0049] 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.

[0050] Example 1

[0051] (1) 247.14 g of pyridoxal phosphate was added to a mixed solution of tetrahydrofuran and dimethyl sulfoxide, wherein the volume ratio of tetrahydrofuran to dimethyl sulfoxide solvent was 4:1, the stirring rate was 900 rpm, the mixing temperature was 55℃, and the stirring time was 1.0 h, to obtain a pyridoxal phosphate solution with a concentration of 2 mol / L. (2) 382.46 g of ethyl 4-aminocinnamate was added to tetrahydrofuran, with a stirring rate of 1400 rpm, a mixing temperature of 55℃, and a stirring time of 0.5 h, to obtain a 2 mol / L ethyl 4-aminocinnamate solution. (3) Ethyl 4-aminocinnamate solution was added to pyridoxal phosphate solution at a rate of 3 mL / min, wherein the molar ratio of pyridoxal phosphate to natural cinnamate was 1:2. The temperature was increased simultaneously with the addition, with a heating rate of 3℃ / min, a reaction temperature of 85℃, and a stirring rate of 1600 rpm. Ultrasound was used during stirring, with a power of 300 W. After reaching the reaction temperature, stirring was continued for 6.0 h, followed by cooling to room temperature. The solvent was removed by vacuum distillation, with a distillation pressure of -0.08 MPa and a evaporation rate of 150 r / min. The resulting crude product was then added to a mixture of ethanol and purified water at a volume ratio of 5:1, with a solid content of 7 mg / mL. The mixture was allowed to stand at 5℃ for 12 h to precipitate crystals. The crystals were then filtered through a mixture of purified water and ethanol (volume ratio of purified water to ethanol 5:1) using fast filter paper with two layers, at a flow rate of 1.0 rpm. The concentration was increased by 10 mL / s, and the filtration was repeated twice to obtain 383.0 g of pyridoxal-formed cinnamon ester powder, with a yield of 91.1%. Repeat the above steps to obtain 840.8g of pyridoxalated cinnamon ester phosphate.

[0052] The obtained 840.8 g of pyridoxal cinnamon phosphate was added to tetrahydrofuran, stirred at 700 rpm, mixed at 50 °C for 1.0 h, to obtain a 2 mol / L pyridoxal cinnamon phosphate solution. (4) 653.2 g of 3-aminopropylmethyldimethoxysilane was added to a mixed solution of ethanol and purified water, wherein the volume ratio of ethanol to purified water was 2:1, the aminosilane solution was mixed at 25°C, the stirring rate was 600 rpm, the stirring time was 0.5 h, and the concentration of the aminosilane solution was 4 M. The pyridoxal-formed cinnamon phosphate solution and the aminosilane solution were directly mixed (molar ratio of pyridoxal-formed cinnamon phosphate to aminosilane was 1:2). The pyridoxal-formed cinnamon phosphate solution was poured directly into the aminosilane solution. Mixing was carried out at room temperature. After pouring, the temperature was raised at a rate of 4℃ / min to a reaction temperature of 70℃. The stirring rate was 1200 rpm. After reaching the reaction temperature, stirring was continued for 2.0 h. Then, the mixture was cooled to 25℃ and further lowered to 3℃. After standing for 6 h, it was filtered using medium-speed filter paper with two layers. The filtration flow rate was controlled at 2.0 mL / s. During filtration, the mixture was rinsed with a mixture of purified water and ethanol (volume ratio of purified water to ethanol was 5:1) under a vacuum of -0.09 MPa. This process was repeated three times. Finally, the mixture was dried using a freeze dryer at -15℃ for 48 h to obtain 782.8. The natural silane rotor powder of g (yield of 93.1%) is designated as HMPPMP-Silane1.

[0053] The mechanism of the natural silane rotor for detecting the micro-area viscosity of silane solution in this embodiment is as follows: Figure 1 As shown, this natural silane rotor contains a freely rotatable single- and double-bond conjugated structure. This type of conjugated structure exhibits certain flexibility and intramolecular rotational properties. In low-viscosity silane solutions, it can rotate freely, dissipating excited-state energy through non-radiative transitions. In high-viscosity silane solutions, it is difficult to rotate, dissipating excited-state energy through radiative transitions. This difference is reflected in the significant difference in light signal emission intensity, allowing the viscosity of the silane solution to be determined based on the light signal emission intensity. It also exhibits a high sensitivity coefficient to micro-region viscosity (x=0.54). Furthermore, the natural silane rotor of this invention has a stable chemical structure, good photostability, and good pH tolerance. Even under prolonged irradiation, it maintains good light signal intensity and a large Stokes shift.

[0054] The performance of the natural silane rotor prepared in this embodiment was tested.

[0055] Mixed solutions containing different volume fractions of glycerol and purified water were prepared, with the purified water volume fraction ranging from 0% to 99%. The external excitation wavelength was set to 400 nm, and the concentration of the natural product-modified silane rotor in the test solution was controlled at 10 μM. The test was conducted at room temperature, and the test results are as follows: Figure 2 As shown. From Figure 2 It can be seen that as the viscosity of the micro-regions of the mixed solution gradually increases, the intensity of the emitted light signal also gradually increases. In particular, when the volume fraction of glycerol exceeds 70%, the viscosity of the mixed system increases more significantly, and its light signal intensity increases significantly, reaching nearly 50 times higher than that of the solution system without added glycerol.

[0056] Furthermore, tests revealed that the logarithmic function of the light signal intensity and solution viscosity of the mixed solution can be fitted to a straight line, as shown below. Figure 3 As shown, from Figure 3 As can be seen, the natural silane rotor HMPPMP-Silane1 provided by this invention emits a stronger light signal as the viscosity increases, which is consistent with the Förster-Hoffmann relationship. Therefore, the viscosity sensitivity coefficient of HMPPMP-Silane1 is 0.54, and the coefficient of determination is 0.99. The test results show that the natural silane rotor HMPPMP-Silane1 provided by this invention has good detection sensitivity for the micro-region viscosity of solutions and can be used as supporting data for the micro-region viscosity (thickness) adjustment process of silane solutions. Specific logarithmic function values ​​are shown in Table 1.

[0057] Table 1. Logarithmic values ​​of viscosity and fluorescence intensity

[0058] Light stability test of natural silane rotor (HMPPMP-Silane1)

[0059] 1.74 mg of the natural silane rotor prepared in Example 1 was dissolved in a mixed solution of ethanol and purified water (volume ratio 1:5) to control its concentration at 3 mM. For subsequent testing, it was diluted to 10 μM and added to purified water and glycerol respectively. The mixture was continuously excited under a 400 nm excitation light source for 60 min, and the change in its optical signal intensity was tested. The test results are as follows: Figure 4 As shown, the obtained data is collected in Table 2.

[0060] Table 2 Fluorescence intensity test results

[0061] Depend on Figure 4 As shown in Table 2, the natural silane rotor (HMPPMP-Silane1) has good photostability and can release stable light signals under long-term excitation light source irradiation.

[0062] pH stability test of natural silane rotor (HMPPMP-Silane1)

[0063] 3.48 mg of the natural silane rotor prepared in this example was dissolved in a mixed solution of ethanol and purified water (volume ratio 1:5) to control its concentration at 6 mM. For testing, it was further diluted to 10 μM, and the solution was added to solutions with pH values ​​ranging from 5.0 to 10.0 to test the changes in fluorescence intensity. This test was conducted at room temperature, and the results are as follows: Figure 5 As shown.

[0064] Depend onFigure 5 The test results show that the fluorescence intensity of the natural silane rotor (HMPPMP-Silane1) does not change significantly over a relatively wide pH range, and it exhibits good stability in light signal release within this pH range, indicating that the natural silane rotor has high pH tolerance.

[0065] Universality testing of natural silane rotors

[0066] 4.64 mg of the natural silane rotor prepared in this example was dissolved in a mixed solution of ethanol and purified water (volume ratio 1:5) to control its concentration at 8 mM. For testing, it was further diluted to 10 μM and added to purified water to test its absorption and emission spectra, and its Stokes shift was further measured. All tests were conducted at room temperature, and the results are as follows: Figure 6 As shown. By Figure 6 The results show that its Stokes shift is 101 nm, indicating that it is not easily affected by the excitation wavelength and can effectively improve the signal-to-noise ratio.

[0067] 876 g of natural silane rotor powder was dissolved in a mixed solution of ethanol and purified water (1:1) and sprayed onto 10 kg of natural brucite. The mixture was stirred continuously and then flash-dried to obtain natural silane rotor modified natural brucite composite powder.

[0068] The oil absorption values ​​of this material and unmodified natural brucite were tested according to DB / T5211.15-2014. The activation rates of the modified natural brucite and unmodified brucite were tested by weighing method, and the results are recorded in Table 3.

[0069] Table 3. Oil absorption value and activation rate of powders before and after modification.

[0070] As can be seen from the test results in Table 3, the oil absorption value of the natural brucite composite powder modified by the natural silane rotor (HMPPMP-Silane1) decreased significantly, from a maximum of 39 mL / 100g to 24 mL / 100g, and the activation rate increased from a maximum of 18.9% to 90.3%. This indicates that after modification by the natural silane rotor, the hydroxyl groups on the surface of natural brucite were significantly shielded, the surface polarity decreased significantly, the adsorption of subsequent processing aids also decreased significantly, the overall processing cost was controlled, and the surface activation degree increased significantly.

[0071] Unmodified and modified natural brucite were added to PLA / TPU composite substrates to verify their mechanical properties, thermal stability, dynamic mechanical properties, limiting oxygen index, and vertical combustion performance. Specifically, PLA and TPU particles were dried in a vacuum drying oven at 80℃ for 12 hours. Then, 78 parts of PLA, 10 parts of TPU, and 12 parts of unmodified and modified natural brucite were added to a torque rheometer. The temperature was set at 190℃, the rotation speed at 60 rpm, and the mixing time at 10 min. All component samples were molded on a flat vulcanizing machine at 200℃ and 10 MPa, and prepared into specimens according to different requirements. The results are recorded in Table 4.

[0072] Mechanical properties: tested according to GB / T528-2009 standard, with a tensile speed of 50 mm / min; Thermal stability: Heated from 30°C to 800°C at a heating rate of 20°C / min in a nitrogen atmosphere; Limiting oxygen index: tested according to ASTM D2863-77 standard; Vertical burning performance: tested according to ASTM D6413 standard.

[0073] Table 4. Test results of PLA / TPU composite substrates before and after powder modification.

[0074] As shown in Table 4, the mechanical properties of the PLA / TPU composite substrate were significantly improved after the addition of natural brucite composite powder modified with natural silane rotor (HMPPMP-Silane1), increasing from 28.4 MPa to 58.6 MPa, indicating a better interface and significantly improved compatibility. At high temperatures, the char content also improved significantly, increasing from a maximum of 6.15 wt% to 17.98 wt%, indicating that the natural silane rotor (HMPPMP-Silane1) can form a good internal-external synergistic effect with the internal natural brucite and exhibit good char-promoting properties during combustion. This may be due to the presence of more nitrogen-containing aromatic heterocycles and multi-conjugated structures in its structure, enabling it to quickly char and adhere to the internal MgO ceramic precursor pyrolysis framework during combustion. Regarding the pyrolysis temperature, T... 50%The thermal stability was significantly improved from 357.8℃ to 374.6℃, which may be attributed to the good dispersibility and synergistic effect between the internal and external components, making it more difficult for pyrolysis fragments generated during the pyrolysis of PLA / TPU composite substrate to diffuse in the matrix, and severely restricting the mobility of its molecular chains. In terms of limiting oxygen index (LOI), with the addition of modified natural brucite composite powder, the LOI of the composite substrate increased from 20.3% to 29.8%. This may be because the good dispersibility of the composite powder makes it more difficult for the molecular chains to move, and the molecular fragments generated by the pyrolysis of these powders are more likely to form coke that adheres to the molecular chains, blocking the transfer of airflow, mass flow, and heat flow, forming a good physical barrier layer, and effectively inhibiting the rapid development of the combustion process. In terms of vertical combustion, after adding modified natural brucite composite powder, it can pass the V-0 rating without dripping, while after adding unmodified natural brucite composite powder, it is difficult to pass the vertical combustion rating. In summary, the natural silane rotor (HMPPMP-Silane1) provided by this invention, after modifying natural brucite, can be used as a functional composite powder to improve the multiple properties of PLA / TPU composite substrates, significantly enhancing the synergistic effect between internal and external components.

[0075] 2.33 mg of the natural silane rotor (HMPPMP-Silane1) from Example 1 was dissolved in a mixed solution of purified water and ethanol at a volume ratio of 4:1, resulting in a concentration of 4 mM. This solution was then diluted to 10 μM for testing. Three commercially available silane solutions were selected as test subjects. The aforementioned natural silane rotor (HMPPMP-Silane1) was added to these three silane solutions, and the test was conducted at room temperature with an external light source excitation wavelength of 400 nm. The test results are as follows: Figure 7 As shown.

[0076] Depend on Figure 7It can be seen that the light signal emission intensities of the three silane solutions are different, indicating that there are certain viscosity differences among them. This may be related to the different types and components of the silane solutions. The different components contained in the three silane solutions will greatly affect their spreading, wetting, and coating effects on the surface of inorganic mineral powders. Generally, silane solutions with higher micro-area viscosity have weaker spreading and wetting properties for inorganic mineral powders, but stronger adhesion and anchoring abilities. High-speed stirring can effectively achieve multi-level modification of inorganic mineral powders. In contrast, silane solutions with lower viscosity have stronger wetting and penetration properties for inorganic mineral powders, and better fluidity during high-speed stirring, but lack adhesion and anchoring properties. The final test results show that silane solution 1 is a low-viscosity silane solution, exhibiting a relatively thin appearance, which is more suitable for rapid wetting and penetration; silane solution 2 is a medium-viscosity silane solution, with a medium overall consistency; and silane solution 3 is a high-viscosity silane solution, exhibiting good overall viscosity, which is more suitable for anchoring and adhesion. The test results show that the natural silane rotor (HMPPMP-Silane1) provided by this invention can fully sense the changes in micro-region viscosity in silane solutions and release them through visualized light signals. This is of great significance for studying the thickening process of different types of silane solutions and can help develop more products that meet the needs of different customers.

[0077] Example 2

[0078] (1) 247.14 g of pyridoxal phosphate was added to a mixed solution of tetrahydrofuran and dimethyl sulfoxide, wherein the volume ratio of tetrahydrofuran to dimethyl sulfoxide solvent was 2:1, the stirring rate was 600 rpm, the mixing temperature was 45℃, the stirring time was 2.0 h, and the concentration of the pyridoxal phosphate solution was 1 mol / L. (2) 191.23 g of ethyl 4-aminocinnamate was added to tetrahydrofuran, with a stirring rate of 1000 rpm, a mixing temperature of 40℃, a stirring time of 1.0 h, and the concentration of the ethyl 4-aminocinnamate solution was 1 mol / L. (3) Ethyl 4-aminocinnamate solution was added to pyridoxal phosphate solution at a rate of 1 mL / min, wherein the molar ratio of pyridoxal phosphate to ethyl 4-aminocinnamate was 1:1. The temperature was increased simultaneously with the addition, with a heating rate of 1℃ / min, a reaction temperature of 75℃, and a stirring rate of 1200 rpm. Ultrasonication with a power of 100 W was performed during stirring. After reaching the reaction temperature, stirring was continued for 12.0 h. The mixture was then cooled to room temperature, and the solvent was removed by vacuum distillation at a pressure of -0.07 MPa and a evaporation rate of 50 r / min. The resulting crude product was then added to a mixture of ethanol and purified water at a volume ratio of 1:1, with a solid content of 5 mg / mL. The mixture was allowed to stand at 1℃ for 5 h to precipitate crystals. The crystals were then filtered through a mixture of purified water and ethanol (volume ratio of purified water to ethanol 1:1) using high-speed filter paper with one layer and a filtration flow rate of 0.3%. The concentration was increased by 10 mL / s, and the filtration was repeated four times to obtain 379.2 g of pyridoxal-formyl cinnamon phosphate powder, with a yield of 90.2%. Repeat the above steps to obtain 420.4g of pyridoxalated cinnamon ester phosphate.

[0079] The obtained 420.4 g of pyridoxal cinnamon phosphate was added to tetrahydrofuran, the stirring rate was 500 rpm, the mixing temperature was 40℃, the stirring time was 1.5 h, and the concentration of the pyridoxal cinnamon phosphate solution was controlled at 1 mol / L. (4) 163.3 g of 3-aminopropylmethyldimethoxysilane was added to a mixed solution of ethanol and purified water, wherein the volume ratio of ethanol to purified water was 1:1, the aminosilane solution was mixed at 25°C, the stirring rate was 800 rpm, the stirring time was 0.1 h, and the concentration of the aminosilane solution was 1 M. The pyridoxal-formed cinnamon phosphate solution and the aminosilane solution were directly mixed (molar ratio of pyridoxal-formed cinnamon phosphate to aminosilane was 1:1). The pyridoxal-formed cinnamon phosphate solution was poured directly into the aminosilane solution. Mixing was carried out at room temperature. After pouring, the temperature was raised at a rate of 2℃ / min to a reaction temperature of 60℃. The stirring rate was 1000 rpm. After reaching the reaction temperature, stirring was continued for 4.0 h. Then, the mixture was cooled to 25℃ and further lowered to 1℃. After standing for 3 h, it was filtered using medium-speed filter paper with one layer. The filtration flow rate was controlled at 3.0 mL / s. During filtration, the mixture was rinsed with a mixture of purified water and ethanol (volume ratio of purified water to ethanol was 1:1) under a vacuum of -0.1 MPa. This process was repeated twice. Afterward, the mixture was dried using a freeze dryer at -40℃ for 24 h to obtain 535.8. The natural silane rotor powder of g (yield of 91.8%) is designated as HMPPMP-Silane1.

[0080] The spectral results of the natural silane rotor (HMPPMP-Silane1) obtained in this embodiment are the same as those obtained in Example 1.

[0081] Example 3

[0082] (1) 247.14 g of pyridoxal phosphate was added to a mixed solution of tetrahydrofuran and dimethyl sulfoxide, wherein the volume ratio of tetrahydrofuran to dimethyl sulfoxide solvent was 10:1, the stirring rate was 1200 rpm, the mixing temperature was 70℃, the stirring time was 0.5 h, and the concentration of the pyridoxal phosphate solution was 5 mol / L. (2) 573.69 g of ethyl 4-aminocinnamate was added to tetrahydrofuran, with a stirring rate of 1800 rpm, a mixing temperature of 75 °C, a stirring time of 0.2 h, and a concentration of ethyl 4-aminocinnamate solution of 3 mol / L. (3) Ethyl 4-aminocinnamate solution was added to pyridoxal phosphate solution at a rate of 5 mL / min, wherein the molar ratio of pyridoxal phosphate to ethyl 4-aminocinnamate was 1:3. The temperature was increased simultaneously with the addition, with a heating rate of 5℃ / min. The reaction temperature was 95℃, and the stirring rate was 2000 rpm. Ultrasonication with a power of 500 W was performed during stirring. After reaching the reaction temperature, stirring was continued for 1.0 h, followed by cooling to room temperature. The solvent was removed by vacuum distillation, with a distillation pressure of -0.09 MPa and a evaporation rate of 300 r / min. The resulting crude product was then added to a mixture of ethanol and purified water at a volume ratio of 10:1, with a solid content controlled at 10%. The concentration of pyridoxalyl cinnamon phosphate was increased by mg / mL and allowed to stand at 10℃ for 24 h to precipitate crystals. The crystals were then filtered through a mixture of purified water and alcohol (volume ratio of purified water to ethanol was 10:1) using high-speed filter paper with 3 layers. The filtration flow rate was 2.0 mL / s, and the filtration was repeated once to obtain 381.7 g of pyridoxalyl cinnamon phosphate powder, with a yield of 90.8%. Repeat the above steps to obtain 420.4 g of pyridoxal-modified cinnamon ester. The obtained 420.4 g of pyridoxal cinnamon phosphate was added to tetrahydrofuran, the stirring rate was 900 rpm, the mixing temperature was 70℃, the stirring time was 0.5 h, and the concentration of the pyridoxal cinnamon phosphate solution was controlled at 3 mol / L. (4) 979.8 g of 3-aminopropylmethyldimethoxysilane was added to a mixed solution of ethanol and purified water, wherein the volume ratio of ethanol to purified water was 5:1, the aminosilane solution was mixed at room temperature (25°C) with a stirring rate of 800 rpm and a stirring time of 0.1 h, and the concentration of the aminosilane solution was 6 M. The pyridoxal-formed cinnamon phosphate solution and the aminosilane solution were directly mixed (molar ratio of pyridoxal-formed cinnamon phosphate to aminosilane was 1:6). The pyridoxal-formed cinnamon phosphate solution was poured directly into the aminosilane solution. Mixing was carried out at room temperature. After pouring, the temperature was raised at a rate of 6℃ / min to a reaction temperature of 90℃. The stirring rate was 1800 rpm. After reaching the reaction temperature, stirring was continued for 1.0 h. The mixture was then cooled to 25℃ and further lowered to 5℃. After standing for 12 h, it was filtered using medium-speed filter paper with 3 layers. The filtration flow rate was controlled at 1.0 mL / s. During filtration, the mixture was rinsed with a mixture of purified water and ethanol (volume ratio of purified water to ethanol was 10:1) under a vacuum of -0.08 MPa. This process was repeated 4 times. The mixture was then dried using a freeze dryer at -5℃ for 72 h to obtain 539.3. The natural silane rotor powder of g (yield of 92.4%) is designated as HMPPMP-Silane1.

[0083] The spectral results of the natural silane rotor (HMPPMP-Silane1) obtained in this embodiment are the same as those obtained in Example 1.

[0084] As can be seen from the above embodiments, the natural silane rotor provided by the present invention has a flexible conjugated structure, which can exhibit different rotational states in environments with different micro-region viscosities. Changes in the micro-region viscosity of silane solutions can be converted into optical signals, achieving effective detection of the physical index of silane solution micro-region viscosity from a completely new molecular-level perspective. Various test results show that the natural silane rotor (HMPPMP-Silane1) can maintain good optical signal intensity even under long-term irradiation, maintain stable optical signal over a wide pH range, exhibits a green apparent optical signal color, and has high visual sensitivity. Its viscosity sensitivity coefficient is 0.54, making it suitable for detecting the micro-region viscosity of silane solutions in complex liquid environments containing multiple components. Its emission wavelength of 512 nm effectively avoids background fluorescence signal interference that may be caused by various additives in the silane solution. The Stokes shift exceeds 100 nm, effectively avoiding interference caused by the excitation wavelength and significantly improving the signal-to-noise ratio. The natural silane rotor itself is a modified silane containing aromatic heterocycles, phosphates, and a highly conjugated structure. It not only serves as an external modification layer for natural inorganic mineral powders but also provides a wide range of functionalities, including flame retardancy, char formation promotion, and enhanced thermal stability. This allows it to work synergistically with the internal natural inorganic mineral powders, strengthening the overall functionality of the composite powder. Furthermore, this naturally modified silane rotor is produced via a one-step process, which is green and environmentally friendly, yielding a high final output. The required raw materials are natural products, inexpensive, readily available, and of low cost. Post-processing is also simple and easy, resulting in an overall low-carbon, environmentally friendly, and cost-effective product suitable for industrial applications.

[0085] 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 natural silane rotor, characterized in that, The structure of the natural silane rotor is shown below: ； X is , , , , , , or .

2. The method for preparing the natural silane rotor according to claim 1, characterized in that, Includes the following steps: (1) Pyridoxal phosphate solution and ethyl 4-aminocinnamate solution were mixed and reacted to obtain pyridoxal-modified cinnamate phosphate; (2) The natural silane rotor is obtained by mixing pyridoxal cinnamon ester phosphate solution and aminosilane solution and then reacting them.

3. The method for preparing the natural silane rotor as described in claim 2, characterized in that, The concentration of the pyridoxal phosphate solution mentioned in step (1) is 1~5M; The solvent for pyridoxal phosphate solution contains solvent a and dimethyl sulfoxide; Solvent a is one or more of ethyl acetate, N,N-dimethylformamide, acetonitrile, and tetrahydrofuran; The volume ratio of solvent a to dimethyl sulfoxide is 2~10:

1.

4. The method for preparing the natural silane rotor as described in claim 3, characterized in that, The concentration of the ethyl 4-aminocinnamate solution in step (1) is 1~3M; The solvent for the ethyl 4-aminocinnamate solution is one or more of ethyl acetate, methanol, ethanol, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, and dimethyl sulfoxide.

5. The method for preparing the natural silane rotor as described in claim 4, characterized in that, In step (1), the molar ratio of pyridoxal phosphate to ethyl 4-aminocinnamate is 1:1~3; The mixing method described in step (1) is to add ethyl 4-aminocinnamate solution to pyridoxal phosphate solution at a rate of 1~5 mL / min; The heating rate of the reaction in step (1) is 1~5℃ / min, the reaction temperature is 75~95℃, the stirring rate is 1200~2000rpm, the ultrasonic power is 100~500W, and the time is 1~12h.

6. The method for preparing the natural silane rotor as described in claim 5, characterized in that, The concentration of the pyridoxal cinnamon ester phosphate solution in step (2) is 1~3M; The solvent for the pyridoxal-modified cinnamon ester phosphate solution is one or more of ethyl acetate, N,N-dimethylformamide, acetonitrile, and tetrahydrofuran.

7. The method for preparing the natural silane rotor as described in claim 6, characterized in that, The concentration of the aminosilane solution in step (2) is 1~6M; The aminosilane is 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, or 3-diethylenetriaminopropyltrimethoxysilane; The solvents for aminosilane solutions include alcohol and water; The alcohol is one or more of ethanol, methanol, and ethylene glycol; The volume ratio of alcohol to water is 1 to 5:

1.

8. The method for preparing the natural silane rotor as described in claim 7, characterized in that, In step (2), the molar ratio of pyridoxal cinnamon ester phosphate to aminosilane is 1:1~6.

9. The method for preparing the natural silane rotor as described in claim 8, characterized in that, The heating rate of the reaction in step (2) is 2~6℃ / min, the temperature is 60~90℃, the rotation speed is 1000~1800rpm, and the time is 1~4h.

10. The application of the natural silane rotor of claim 1 in the micro-area viscosity detection of silane active additives.

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