Syringaldehyde glycosyl chromophore as well as preparation method and application thereof

Abstract

The invention provides a syringaldehyde glycosyl chromophore as well as a preparation method and application thereof, and belongs to the technical field of detection and analysis of inorganic mineral powder infiltrating fluid. The syringyl glycosyl chromophore disclosed by the invention is 3-((4-hydroxy-3, 5-dimethoxybenzylidene) amino)-4-((1-methoxy-1-oxo-3-phenylpropyl-2-yl) amino)-4-oxobutyric acid, and the structural formula of the syringyl glycosyl chromophore is shown in the specification. A structural formula of the syringaldehyde glycosyl color producing agent is shown as a formula I. The syringaldehyde glycosyl color producing agent can realize visual monitoring on a preparation process of an inorganic mineral powder infiltrating solution, and fills the blank that a traditional inorganic mineral infiltrating solution is difficult to detect in situ, in real time and efficiently.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of inorganic mineral powder infiltration liquid detection and analysis, and particularly relates to a syringaldehyde glycosyl color developing agent and a preparation method and application thereof. BACKGROUND

[0002] An inorganic mineral powder infiltration liquid is a kind of infiltration liquid with excellent stability and good fluidity, which can provide good wetting, adhesion, smoothness and other functional properties for inorganic mineral powder, and is commonly used as a powder lubricant, a stirring agent, a release agent and the like, especially widely used in the modification and compounding of inorganic mineral powder. As a kind of high value-added powder post-modification functional additive, the relative consistency of the inorganic mineral powder infiltration liquid can be controlled to improve the wetting performance in the post-modification process of the inorganic mineral powder, so as to better improve the wettability, dispersibility and fluidity of the powder. The inorganic mineral powder infiltration liquid with high consistency is easier to store and shape, and is more significant in thickness, but has poor fluidity, poor wettability and infiltration, and poor permeability. In contrast, the inorganic mineral powder infiltration liquid with low consistency performs better in fluidity, has good spreading and permeability, and has strong wetting capacity, but the thickness may be poor, and the long-term storage and shaping ability is poor. At present, the consistency of the inorganic mineral powder infiltration liquid is effectively measured by various viscometers, but there are certain defects, such as: a large amount of sample is required, a long measurement time is required, and it is difficult to accurately measure the micro-viscosity of the inorganic mineral powder infiltration liquid containing a large amount of pseudoplastic macromolecular components (there is a shear thinning effect). Therefore, in-situ, visual and rapid measurement methods need to be developed.

[0003] Many aldehyde derivatives are derived from natural plant extracts, widely exist in nature, and have good aromatic conjugate properties. In addition, the functions of natural aldehyde derivatives can be further expanded through multi-component natural product reconstruction, especially the color developing function in multiple applications. Photochemical technology is a kind of in-situ, efficient and visual detection method for measuring the micro-viscosity of inorganic mineral powder infiltration liquid by using molecular-level color developing tools. The final performance is to release the strength of the light signal. This in-situ static response method can effectively avoid the error caused by traditional shear thinning, and can effectively improve the modulation effect of the consistency of the inorganic mineral powder infiltration liquid. At present, there are few natural aldehyde-based sugar color developing functional molecules constructed by multiple plant extracts used for monitoring and modulation of inorganic mineral powder infiltration liquid.

[0004] Therefore, it is of great significance to provide a natural aldehyde-based sugar color developing functional molecule constructed by multiple plant extracts for accurately measuring the micro-viscosity of inorganic mineral powder infiltration liquid. SUMMARY

[0005] The present application aims to provide a syringaldehyde glycosyl colorant, a preparation method and application thereof, so as to solve the technical problem of difficulty in accurately measuring micro-viscosity of inorganic mineral powder infiltration liquid in the prior art.

[0006] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions.

[0007] The present application provides a syringaldehyde glycosyl colorant, which is 3-((4-hydroxy-3,5-dimethoxybenzylidene)amino)-4-((1-methoxy-1-oxo-3-phenylpropan-2-yl)amino)-4-oxobutanoic acid (HDMPAO), and a structural formula of the syringaldehyde glycosyl colorant is shown as formula I.

[0008]

[0009] The present application provides a preparation method of a syringaldehyde glycosyl colorant, which comprises the following steps.

[0010] 1) mixing an amino acid dipeptide derivative and a solvent under ultrasonic conditions to obtain solution 1;

[0011] 2) mixing a natural aldehyde derivative and a solvent to obtain solution 2;

[0012] 3) adding solution 2 into solution 1 to react, so as to obtain the syringaldehyde glycosyl colorant.

[0013] Further, in the step 1), the amino acid dipeptide derivative comprises aspartyl phenylalanine methyl ester;

[0014] The solvent comprises one or more of methanol, ethanol, propanol, ethylene glycol and 1,2-propanediol;

[0015] The molar concentration of the solution 1 is 1-5 M.

[0016] Further, in the step 1), the power of ultrasonic is 100-600 W;

[0017] The mixing is carried out in stirring, the stirring rate is 600-1800 rpm, the stirring temperature is 25-50 DEG C, and the stirring time is 0.1-1.0 h.

[0018] Further, in the step 2), the natural aldehyde derivative is syringaldehyde;

[0019] The solvent is an alcohol solution, wherein the alcohol in the alcohol solution comprises one or more of methanol, ethanol, propanol, ethylene glycol and 1,2-propanediol,

[0020] The volume ratio of the alcohol in the alcohol solution to water is 2-9:1;

[0021] The molar concentration of the solution 2 is 1-3 M.

[0022] Further, in the step 2), the mixing is carried out under stirring, the stirring rate is 1000-2000 rpm, the stirring time is 0.1-1.2 h, and the stirring temperature is 35-60 DEG C.

[0023] Further, the molar ratio of the natural aldehyde derivative and the amino acid dipeptide derivative is 1-3:1.

[0024] Further, in the step 3), the solution 2 is added at a uniform speed by spraying, and the spraying rate is 1-5 mL / min.

[0025] Further, in the step 3), the reaction temperature is 100-120 DEG C, the temperature rising rate is 1-5 DEG C / min, the reaction time is 1.0-3.0 h, and the reaction pressure is 2-6 atm.

[0026] The reaction is carried out under stirring, and the stirring rate is 800-1600 rpm.

[0027] The application also provides an application of the syringaldehyde glycosyl color reagent in detection of micro-viscosity change of inorganic mineral powder infiltration liquid.

[0028] The application has the following beneficial effects:

[0029] 1) The HDMPAO (syringaldehyde glycosyl color reagent) of the application is obtained by introducing a natural aldehyde derivative to couple with a sugar sweetener, realizes introduction and functional reconstruction of natural products, and the required raw materials are widely available in nature, have a wide source and a low price, and have typical green environmental protection and sustainable use characteristics.

[0030] 2) The HDMPAO of the application can effectively respond to the micro-viscosity of inorganic mineral powder infiltration liquid, is helpful for efficient regulation of inorganic mineral powder infiltration liquid formula process, can release a visual light signal to the change of micro-viscosity, the light signal intensity gradually increases with the increase of micro-viscosity, the inorganic mineral powder infiltration liquid can be conveniently observed and real-time controlled, the sensitive coefficient of the HDMPAO to viscosity is higher (x=0.65), the chemical structure is relatively stable, is suitable for long-term stable existence in complex inorganic mineral powder infiltration liquid, the color wavelength peak is 422 nm, has a typical bright blue light, is convenient to observe, has better light stability, has good solvent polarity resistance, has a lower detection lower limit (as low as 1.017 cP), has a Stokes shift of 109 nm, can effectively avoid the interference of excitation light, and is suitable for fine monitoring and modulation reference of inorganic mineral powder infiltration liquid micro-viscosity.

[0031] 3) The HDMPAO of the present application can realize visual monitoring of the modulation process of inorganic mineral powder infiltration liquid, filling the blank of traditional inorganic mineral infiltration liquid which is difficult to detect in situ, in real time and efficiently, at the same time, avoiding the shear thinning effect existing in viscosity detection of the oligomer even the high polymer containing in the inorganic mineral infiltration liquid, that is, the eugenol glycoside device can be used as a molecular level tool for monitoring the dilution process of inorganic mineral powder infiltration liquid, which can provide effective reference for the surface activation and functional development of composite powder;

[0032] 4) The HDMPAO of the present application is a modified surface active modifier, which contains aromatic ring, flexible ester group, carboxyl group and rotatable Schiff base conjugated structure, which can not only be anchored on the outside of inorganic powder as an external modification layer of natural inorganic mineral powder, but also provide sufficient multifunctionality, including flame retardant, promoting carbon formation, improving matrix compatibility, so that it can play the internal and external synergistic effect with the internal natural inorganic mineral powder, and strengthen the comprehensive function of the composite powder;

[0033] 5) The HDMPAO of the present application is prepared by one-step method, which is simple, fast, efficient and high-yield, suitable for large-scale industrial production, the chemical process is simple and easy to operate, the main product is green and environmentally friendly and the source is abundant, the whole process has high yield, the main solvents involved in the post-processing process are alcohol and purified water, which will not have negative impact on the environment, and it is a typical application of natural product reconstruction across the border and high value. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 The preparation route map of the HDMPAO described in the present application;

[0035] Figure 2 The high resolution mass spectrum of the HDMPAO prepared in Example 1;

[0036] Figure 3 The nuclear magnetic resonance carbon spectrum of the HDMPAO prepared in Example 1;

[0037] Figure 4 The fluorescence spectrum of the HDMPAO prepared in Example 1 in glycerol solution with different proportions;

[0038] Figure 5 The fitting graph of the light signal intensity of the HDMPAO prepared in Example 1 at 422 nm and the logarithmic function of the solution viscosity;

[0039] Figure 6 The light stability test graph of the HDMPAO prepared in Example 1;

[0040] Figure 7 The detection lower limit graph of the HDMPAO prepared in Example 1;

[0041] Figure 8 Stokes shift of HDMPAO prepared for Example 1 in purified water;

[0042] Figure 9 Absorption spectra of HDMPAO prepared for Example 1 in different polar solutions;

[0043] Figure 10 Fluorescence spectra of HDMPAO prepared for Example 1 in different inorganic mineral powder infiltrate samples. DETAILED DESCRIPTION

[0044] The present application provides a syringaldehyde glycosyl color reagent, which is 3-((4-hydroxy-3,5-dimethoxybenzylidene)amino)-4-((1-methoxy-1-oxo-3-phenylpropan-2-yl)amino)-4-oxobutanoic acid, and the structural formula of the syringaldehyde glycosyl color reagent is shown as formula I:

[0045]

[0046] The present application provides a preparation method of a syringaldehyde glycosyl color reagent, which comprises the following steps:

[0047] 1) mixing an amino acid dipeptide derivative and a solvent under ultrasonic conditions to obtain solution 1;

[0048] 2) mixing a natural aldehyde derivative and a solvent to obtain solution 2;

[0049] 3) adding solution 2 into solution 1 to react, so as to obtain the syringaldehyde glycosyl color reagent.

[0050] In the present application, in the step 1), the amino acid dipeptide derivative is preferably aspartyl phenylalanine methyl ester;

[0051] The solvent comprises one or more of methanol, ethanol, propanol, ethylene glycol and 1,2-propanediol, preferably one or more of methanol, ethanol, ethylene glycol and 1,2-propanediol, and further preferably one or more of methanol, ethanol and 1,2-propanediol;

[0052] The molar concentration of the solution 1 is 1-5 M, preferably 2-4 M, and further preferably 3 M.

[0053] In the present application, in the step 1), the power of the ultrasonic is 100-600 W, preferably 200-500 W, and further preferably 300-400 W;

[0054] The mixing is carried out by stirring at a speed of 600–1800 rpm, preferably 800–1600 rpm, and more preferably 1000–1400 rpm; the stirring temperature is 25–50°C, preferably 30–45°C, and more preferably 35–40°C; and the stirring time is 0.1–1.0 h, preferably 0.3–0.8 h, and more preferably 0.4–0.7 h.

[0055] In this invention, in step 2), the natural aldehyde derivative is preferably syringaldehyde;

[0056] The solvent is an alcohol solution, wherein the alcohol in the alcohol solution includes one or more of methanol, ethanol, propanol, ethylene glycol and 1,2-propanediol, preferably one or more of methanol, ethanol, ethylene glycol and 1,2-propanediol, and more preferably one or more of methanol, ethanol and 1,2-propanediol.

[0057] The volume ratio of alcohol to water in the alcohol solution is 2 to 9:1, preferably 3 to 8:1, and more preferably 4 to 7:1;

[0058] The molar concentration of solution 2 is 1–3 M, preferably 1.5–2.5 M, and more preferably 2 M.

[0059] In this invention, in step 2), mixing is carried out by stirring at a speed of 1000-2000 rpm, preferably 1200-1800 rpm, and more preferably 1400-1600 rpm; the stirring time is 0.1-1.2 h, preferably 0.3-1 h, and more preferably 0.5-0.8 h; and the stirring temperature is 35-60°C, preferably 40-55°C, and more preferably 45-50°C.

[0060] In this invention, the molar ratio of the natural aldehyde derivative and the amino acid dipeptide derivative is 1 to 3:1, preferably 1.5 to 2.5:1, and more preferably 2:1.

[0061] In this invention, in step 3), solution 2 is added by uniform spraying, with a spraying rate of 1 to 5 mL / min, preferably 2 to 4 mL / min, and more preferably 3 mL / min.

[0062] In the present application, in the step 3), the temperature of the reaction is 100-120℃, preferably 105-115℃, further preferably 110℃; the rate of temperature rise is 1-5℃ / min, preferably 2-4℃ / min, further preferably 3℃ / min; the time of the reaction is 1.0-3.0h, preferably 1.2-2.8h, further preferably 1.5-2.5h; the pressure of the reaction is 2-6atm, preferably 3-5atm, further preferably 4atm;

[0063] The reaction is carried out under stirring, and the rate of stirring is 800-1600rpm, preferably 900-1500rpm, further preferably 1000-1400rpm.

[0064] In the present application, after the reaction, pressure relief and air cooling are further included, and the rate of purging is controlled to be 0.1-0.5m / s until cooling to room temperature.

[0065] In the present application, a separation and purification step is further included: the reaction solution cooled to room temperature is subjected to solvent removal under reduced pressure, and the reduced pressure range is -0.09 to -0.07MPa; the obtained solid is washed with an alcohol solvent 1-3 times during the reduced pressure distillation, and the alcohol solvent is a mixed solution of ethanol, methanol and ethylene glycol in a volume ratio of 1-10:1-5:1; the obtained solid is subjected to extraction in a mixed solution of ethyl acetate and purified water, and the organic phase is collected and dried with anhydrous sodium sulfate, and then the solvent is removed by reduced pressure distillation, and the obtained solid is washed with an ethanol solution 1-3 times during the reduced pressure distillation, and the volume ratio of ethanol and water in the ethanol solution is 1:1-5; after washing, the solid is dispersed in an ethanol solution, and the volume ratio of ethanol and water in the ethanol solution is 1:5-20, and the solid content is 3-8mg / mL, and then the ethanol solution is left to stand at a low temperature environment of 1-10℃ for 4-8h, and then the ethanol solution is removed by suction filtration, and the reduced pressure range during suction filtration is -0.09 to -0.07MPa, and 1-2 layers of neutral rapid filter paper are used for suction filtration, and the flow rate of suction filtration is 2-8mL / s; after suction filtration, the obtained solid is placed in a low-temperature dryer for sublimation treatment, and the temperature of sublimation treatment is -30 to -10℃, and the time of sublimation treatment is 10-24h.

[0066] The present application further provides an application of the syringaldehyde glycosyl color reagent in the detection of the micro-viscosity change of the inorganic mineral powder infiltration solution.

[0067] In the present application, the application of the syringaldehyde glycosyl color reagent in the detection of the micro-viscosity change of the inorganic mineral powder infiltration solution includes the following steps:

[0068] The syringaldehyde glycoside color reagent is dissolved in an ethanol solution to prepare a syringaldehyde glycoside mother liquor; different concentrations of syringaldehyde glycoside are added dropwise into a mixed solution of glycerol and water to simulate the change of micro-viscosity in the inorganic mineral powder infiltration liquid base solution preparation technology, and the response effect of the syringaldehyde glycoside to the change of viscosity is tested.

[0069] In the present application, the mechanism of the application of the syringaldehyde glycoside color reagent in the detection of the change of micro-viscosity of the inorganic mineral powder infiltration liquid is as follows:

[0070]

[0071] The technical solutions provided by the present application will be described in detail below in combination with the embodiments, but they should not be understood as limitations to the protection scope of the present application.

[0072] Example 1

[0073] 2 mol of aspartyl phenylalanine methyl ester and ethanol are mixed under ultrasonic conditions at 35℃, the ultrasonic power is 300 W, the mixing is carried out under stirring, the stirring rate is 1200 rpm, and the stirring time is 0.5 h to obtain a solution 1 with a molar concentration of 2M;

[0074] 1 mol of syringaldehyde and an ethanol solution (the volume ratio of ethanol to water in the ethanol solution is 5:1) are mixed at 45℃, the mixing is carried out under stirring, the stirring rate is 1500 rpm, and the stirring time is 0.6 h to obtain a solution 2 with a molar concentration of 2M;

[0075] The solution 2 is added to the solution 1 by uniform spraying at a rate of 3 mL / min until the spraying is completed, after the spraying is completed, the pressure is increased to 4 atm, and the reaction is carried out by increasing the temperature to 110℃ at a rate of 3℃ / min during the pressurization process, the mechanical stirring rate is controlled to be 1200 rpm, and after the addition is completed, the stirring is continued for 2.0 h, after the reaction is completed, the pressure is released and the air cooling is carried out, the blowing rate is controlled to be 0.3 m / s until the temperature is cooled to room temperature;

[0076] The reaction solution cooled to room temperature was removed of solvent under reduced pressure, the range of which was -0.08 MPa, the solid obtained during the reduced pressure distillation was washed twice with an alcoholic solvent, which was a mixed solution of ethanol, methanol and ethylene glycol in a volume ratio of 5:3:1, the solid obtained was extracted in a mixed solution of ethyl acetate and purified water, the organic phase was collected and dried with anhydrous sodium sulfate, and then the solvent was removed by reduced pressure distillation, the solid was washed twice with an ethanol solution during the reduced pressure distillation, the volume ratio of ethanol and water in the ethanol solution was 1:3; after the washing, the solid was dispersed in an ethanol solution, the volume ratio of ethanol and water in the ethanol solution was 1:12, the solid content was 5 mg / mL, and then it was placed in a low-temperature environment at 5°C for 6 h, followed by removing the ethanol solution by suction filtration, the range of reduced pressure during the suction filtration was -0.08 MPa, 1 layer of neutral rapid filter paper was used for the suction filtration, and the flow rate of the suction filtration was 5 mL / s; after the suction filtration, the solid obtained was placed in a low-temperature dryer for sublimation treatment, the temperature of the sublimation treatment was -20°C, and the time of the sublimation treatment was 15 h, to obtain 426.8 g of 3-((4-hydroxy-3,5-dimethoxybenzylidene)amino)-4-((1-methoxy-1-oxo-3-phenylpropan-2-yl)amino)-4-oxobutanoic acid, denoted as HDMPAO, with a yield of 93.1%.

[0077] The molecular weight of the HDMPAO prepared in Example 1 was tested by high resolution liquid chromatography mass spectrometry, and the results are shown in Figure 2 The test data are as follows: HR-MS (ESI): calcd for C 23 H 26 N2O8([M]) + 458.50, found: 458.4720.

[0078] The HDMPAO prepared in Example 1 was characterized by nuclear magnetic resonance carbon spectrum, and the results are shown in Figure 3 13 CNMR (101 MHz, DMSO-d6) δ 178.6, 171.8, 162.6, 160.3, 148.9, 139.2, 137.8, 136.8, 129.0, 128.1, 126.7, 104.8, 65.1, 57.3, 56.2, 52.2, 37.4, 36.5. Through the analysis of nuclear magnetic resonance and mass spectrometry, it can be determined that the product prepared is the target compound 3-((4-hydroxy-3,5-dimethoxybenzylidene)amino)-4-((1-methoxy-1-oxo-3-phenylpropan-2-yl)amino)-4-oxobutanoic acid.

[0079] ​0.92 mg of HDMPAO prepared in Example 1 was dissolved in 2 mL of ethanol to prepare a fluorescent compound mother liquor with a concentration of 1 mM, and the fluorescent compound concentration was kept at 10 μM during the test, and the total volume of the test system was kept at 3 mL.

[0080] The response of micro-viscosity to HDMPAO was tested by preparing glycerol-water test systems with glycerol volume fractions of 0%, 10%, 30%, 50%, 70%, and 99%, and keeping the total volume of the test system at 3 mL and the test temperature at room temperature, with 320 nm as the excitation wavelength. The test results are shown in Figure 4 and Figure 5 .

[0081] Generally, the viscosity of purified water is only 1.0 cP, while the viscosity of glycerol is as high as 956.0 cP, and it can be seen from Figure 4 that the luminescence intensity increases as the viscosity increases, and when the glycerol concentration reaches 99%, the luminescence intensity at 422 nm increases by 89.2 times.

[0082] It can be seen from Figure 5 that the HDMPAO of the present application has good sensitivity to viscosity, and the log value of its luminescence intensity and the log value of the viscosity show a good linear relationship, that is, as the viscosity increases, the luminescence intensity also gradually increases, and the sensitivity calculated by the Forster-Hoffmann formula is 0.65, and the fitting coefficient of determination is 0.99. It can be seen from the test results that the HDMPAO of the present application can have a good response to micro-viscosity, has high sensitivity, and is suitable for detecting micro-viscosity in inorganic mineral powder infiltration liquid, and is beneficial to the precise regulation of the consistency of the inorganic mineral powder infiltration liquid.

[0083] The light stability of HDMPAO was tested by dissolving 1.37 mg of HDMPAO prepared in Example 1 in ethanol, wherein the concentration of HDMPAO was 3 mM, and then adding it into low-viscosity purified water (1.0 cP) and high-viscosity 99% volume fraction glycerol solution (956.0 cP) to make the concentration of HDMPAO 10 μM, and under the continuous irradiation of an external excitation light source at 320 nm, the change of the light signal intensity within 60 min was tested. The test results are shown in Figure 6 .

[0084] It can be seen from Figure 6 that HDMPAO can maintain good light stability in both high-viscosity glycerol and low-viscosity purified water, and is not greatly affected even under long-time irradiation.

[0085] The detection limit of HDMPAO prepared in Example 1 was tested. The test method was as follows: 2.29 mg of HDMPAO prepared in Example 1 was dissolved in linoleic acid to obtain an HDMPAO solution with a concentration of 5 mmol / L. For testing, the concentration was diluted to 10 μmol / L, and then added to a mixed solution of water and glycerol with very low viscosity. The detection sensitivity to viscosity was tested. The above tests were carried out at room temperature. A linear fitting graph of the detection limit of HDMPAO obtained in Example 1 was obtained, as shown below. Figure 7 As shown (I) max This refers to the I value corresponding to the peak value at the wavelength.

[0086] from Figure 7 As can be seen from the data, in solutions with extremely low viscosity, the viscosity value of HDMPAO has a good linear relationship with the logarithm of the light signal emission intensity (y = 0.91 + 1.70x), and the coefficient of determination of the fit is 0.99. Based on this linear relationship, the detection limit of HDMPAO is 1.017 cP, indicating that it is very sensitive to changes in micro-region viscosity and is suitable for the regulation and monitoring of changes in the viscosity of inorganic mineral powder wetting solutions.

[0087] The Stokes shift of the HDMPAO prepared in Example 1 was tested. The method was as follows: 2.75 mg of HDMPAO was dissolved in an ethanol solution (ethanol to water volume ratio of 1:5) to a concentration of 6 mM. For testing, the solution was further diluted to 10 μM and added to purified water to measure its absorption and emission spectra. The Stokes shift was then further measured. The tests were conducted at room temperature, and the results are as follows: Figure 8 As shown.

[0088] Depend on Figure 8 The results show that its Stokes shift is 109 nm, indicating that it is not easily affected by the excitation wavelength and can effectively improve the signal-to-noise ratio.

[0089] The polarity tolerance of HDMPAO prepared in Example 1 was tested. The test method was as follows: 3.21 mg of HDMPAO was dissolved in ethanol to a concentration of 7 mM, and then added to solvents of different polarities (dimethyl sulfoxide, tetrahydrofuran, toluene, ethanol, ethyl acetate, and dichloromethane) to achieve a HDMPAO concentration of 10 μM. The light signal absorption characteristics under different polarity solvent atmospheres were tested. The tests were conducted at room temperature, and the results are as follows. Figure 9 As shown.

[0090] Depend on Figure 9It can be seen that the absorbance of HDMPAO is around 0.45 in various solvents, and the peak value of its absorption spectrum is around 320 nm. The overall results show that HDMPAO is not sensitive to the polarity of the solution and is suitable for use in the wetting solution of inorganic mineral powder containing multiple polar components.

[0091] 3.67 mg of HDMPAO prepared in Example 1 was dissolved in purified water to obtain an HDMPAO solution with a concentration of 8 mmol / L. Then, the HDMPAO solution was added to inorganic mineral wetting solution 1, inorganic mineral wetting solution 2, and inorganic mineral wetting solution 3 at room temperature, respectively, where the concentration of HDMPAO was 10 μmol / L. Emission spectra of the three inorganic mineral wetting solutions were measured using an external excitation source of 320 nm. The test results are shown below. Figure 10 As shown.

[0092] Depend on Figure 10 It can be seen that the viscosities of the three inorganic mineral wetting solutions differ significantly, resulting in a large difference in the intensity of the light signal. Specifically, inorganic mineral wetting solution 1 has the lowest light signal intensity, indicating that its consistency is relatively thin, with a viscosity of 7.5 cP as shown in the test data. Inorganic mineral wetting solution 2 has a medium light signal intensity, indicating that its consistency is somewhat improved, with an overall medium consistency, and a viscosity of 20.2 cP as shown in the test data. Inorganic mineral wetting solution 3 has a further increase in light signal intensity, with an overall larger consistency, and a viscosity of 34.8 cP as shown in the test data. It is evident that the HDMPAO provided by this invention can exhibit different intensities of light signal intensity for inorganic mineral powder wetting solutions of different viscosities, with a peak emission wavelength of 422 nm, which is bright blue light, providing a good visualization and monitoring effect.

[0093] 458.5g of HDMPAO was dissolved in an ethanol solution (the volume ratio of ethanol to water in the ethanol solution was 1:1), and then sprayed onto 10kg of natural hydromagnesite. After continuous stirring and flash drying, eugenolized and glycosylated natural hydromagnesite composite powder was obtained.

[0094] The oil absorption values ​​of this material and unmodified natural hydromagnesite were tested according to DB / T5211.15-2014.

[0095] The activation rates of the modified natural hydromagnesite and the unmodified natural hydromagnesite were tested using a gravimetric method. The test results are shown in Table 1.

[0096] Table 1. Oil absorption value and activation rate of composite powder before and after modification.

[0097] Powder type Oil absorption value (mL / 100g) Activation rate (%) Modified natural hydromagnesite 25 91.2 Unmodified natural hydromagnesite 38 19.8

[0098] As can be seen from Table 1, the oil absorption value of the natural water magnesite composite powder modified by HDMPAO is greatly reduced, and the maximum value is reduced from 38 mL / 100 g to 25 mL / 100 g, and the activation rate is increased from 19.8% to 91.2%, indicating that the surface hydroxyl group of the natural water magnesite is greatly shielded after modification by HDMPAO, the surface polarity is significantly reduced, the adsorption degree of subsequent processing aids is greatly reduced, the overall processing cost is controlled, and the surface activation degree is greatly increased.

[0099] The unmodified and modified natural water magnesite was added to the polylactic acid PLA and methyl vinyl silicone rubber MVQ composite substrate respectively, and the method was as follows: the PLA was dried in a vacuum drying box at 60°C for 8h, then 80 parts of PLA and 15 parts of MVQ, antioxidant 1010 (0.5 parts) and 14 parts of unmodified and modified natural water magnesite were added to the internal mixer, the temperature was set to 190°C, the rotation speed was 50 rpm, and the mixing time was 5 min, then the silicone rubber vulcanizing agent DBPMH (1 part) was added and mixed for 5 min, all the samples of components were molded on a flat plate vulcanizing machine under the conditions of 200°C and 10 MPa, and test samples were prepared according to different requirements. The mechanical properties, thermal stability, dynamic mechanical properties, limiting oxygen index and vertical combustion performance of the test samples were tested.

[0100] Mechanical properties: according to ASTM D256 standard, the tensile speed was 10 mm / min;

[0101] Thermal stability: heated from 40°C to 800°C at a heating rate of 10°C / min in a nitrogen atmosphere;

[0102] Limiting oxygen index: tested according to GB / T2406-2008 standard;

[0103] Vertical combustion performance: tested according to GB / T2408-2008 standard. The test results are shown in Table 2.

[0104] Table 2 PLA / MVQ composite substrate test results after adding modified powder

[0105]

[0106]

[0107] As can be seen from Table 2, when the natural water magnesite composite powder modified by HDMPAO is added, the mechanical properties of the PLA / MVQ composite substrate are significantly improved, from 31.2 MPa to 48.5 MPa, indicating that the interface is improved to a better degree, and the compatibility is significantly improved; at high temperature, the residual carbon content is also significantly improved, from 3.2wt% to 12.8wt%, indicating that HDMPAO can form a good internal and external synergistic effect with the internal natural water magnesite, and can exhibit good carbon formation promotion during combustion, which may be due to the structure containing more aromatic rings and multiple conjugated structures, so that it can quickly form carbon during combustion and adhere to the internal MgO ceramic precursor pyrolysis skeleton; in terms of pyrolysis temperature, T 50％ As can be seen from Table 2, when the natural water magnesite composite powder modified by HDMPAO is added, the mechanical properties of the PLA / MVQ composite substrate are significantly improved, from 31.2 MPa to 48.5 MPa, indicating that the interface is improved to a better degree, and the compatibility is significantly improved; at high temperature, the residual carbon content is also significantly improved, from 3.2wt% to 12.8wt%, indicating that HDMPAO can form a good internal and external synergistic effect with the internal natural water magnesite, and can exhibit good carbon formation promotion during combustion, which may be due to the structure containing more aromatic rings and multiple conjugated structures, so that it can quickly form carbon during combustion and adhere to the internal MgO ceramic precursor pyrolysis skeleton; in terms of pyrolysis temperature, T

[0108] Example 2

[0109] 1 mol of aspartyl phenylalanine methyl ester and ethanol were mixed under ultrasonic conditions at 25°C, the ultrasonic power was 100 W, the mixing was carried out under stirring, the stirring rate was 600 rpm, and the stirring time was 1.0 h, to obtain a solution 1 with a molar concentration of 1M;

[0110] 1 mol of aspartyl phenylalanine methyl ester and ethanol were mixed under ultrasonic conditions at 25°C, the ultrasonic power was 100 W, the mixing was carried out under stirring, the stirring rate was 600 rpm, and the stirring time was 1.0 h, to obtain a solution 1 with a molar concentration of 1M;

[0111] Solution 2 was added to Solution 1 by uniform spraying at a rate of 1 mL / min until the spraying was completed, and then the pressure was increased to 2 atm, and the reaction was carried out by increasing the temperature to 100°C at a rate of 1°C / min while the mechanical stirring rate was controlled at 800 rpm. After the addition was completed, the stirring was continued for 3.0 h, and then the pressure was released and the solution was cooled by air blowing at a rate of 0.1 m / s until the temperature reached room temperature.

[0112] The reaction solution cooled to room temperature was subjected to solvent removal under reduced pressure at -0.09 MPa, and the obtained solid was washed once with an alcoholic solvent, which was a mixed solution of ethanol, methanol, and ethylene glycol at a volume ratio of 1:1:1. The obtained solid was extracted in a mixed solution of ethyl acetate and purified water, and the organic phase was collected and dried with anhydrous sodium sulfate, and then the solvent was removed by distillation under reduced pressure. The solid was washed once with an ethanol solution in which the volume ratio of ethanol to water was 1:1, and then dispersed in an ethanol solution in which the volume ratio of ethanol to water was 1:5 and the solid content was 3 mg / mL. The solution was then left to stand for 4 h at a low temperature of 1°C, and then the ethanol solution was removed by suction filtration under reduced pressure at -0.09 MPa using 2 layers of neutral rapid filter paper at a flow rate of 2 mL / s. The obtained solid was then subjected to sublimation treatment in a low-temperature dryer at a temperature of -30°C for 10 h, and 413.1 g of 3-((4-hydroxy-3,5-dimethoxybenzylidene)amino)-4-((1-methoxy-1-oxo-3-phenylpropan-2-yl)amino)-4-oxobutanoic acid, denoted as HDMPAO, was obtained at a yield of 90.1%.

[0113] Example 3

[0114] Aspartyl phenylalanine methyl ester (3 mol) and ethanol were mixed under ultrasonic conditions at 50°C, the power of the ultrasonic was 600 W, the mixing was carried out with stirring at a rate of 1800 rpm for 0.1 h, and a solution 1 having a molar concentration of 5 M was obtained.

[0115] Syringaldehyde (1 mol) and an ethanol solution (in which the volume ratio of ethanol to water was 2:1) were mixed at 35°C, the mixing was carried out with stirring at a rate of 1000 rpm for 1.2 h, and a solution 2 having a molar concentration of 3 M was obtained.

[0116] Solution 2 was added to solution 1 by uniform spraying at a rate of 5 mL / min until spraying was complete. After spraying, the pressure was increased to 6 atm, and the temperature was increased to 120°C at a rate of 5°C / min during the pressurization process. The mechanical stirring rate was controlled at 1600 rpm. After the addition was completed, stirring was continued for 1.0 h. After the reaction was completed, the pressure was released and the solution was suspended and cooled by air cooling at a rate of 0.5 m / s until it cooled to room temperature.

[0117] The reaction solution, cooled to room temperature, was subjected to reduced pressure (-0.07 MPa) to remove the solvent. The resulting solid was washed once with an alcohol solvent (a mixture of ethanol, methanol, and ethylene glycol in a volume ratio of 10:5:1). The solid was then extracted with a mixture of ethyl acetate and purified water. The organic phase was collected, dried over anhydrous sodium sulfate, and the solvent was removed by reduced pressure distillation. The solid was washed three times with an ethanol solution in a volume ratio of 1:5 (ethanol to water). After washing, the solid was dispersed in an ethanol solution in a volume ratio of 1:20 (ethanol to water). The solid content was [not specified]. The solution was prepared at 8 mg / mL and then allowed to stand at 10°C for 8 h. The ethanol solution was then removed by vacuum filtration at a reduced pressure of -0.07 MPa using a single layer of neutral, fast-drying filter paper at a flow rate of 8 mL / s. After filtration, the resulting solid was placed in a low-temperature desiccator for sublimation at -10°C for 24 h, yielding 420.9 g of 3-((4-hydroxy-3,5-dimethoxybenzyl)amino)-4-((1-methoxy-1-oxo-3-phenylprop-2-yl)amino)-4-oxobutyric acid, denoted as HDMPAO, with a yield of 91.8%.

[0118] As can be seen from the above embodiments, the present invention provides a eugenolized glycosyl chromogenic agent, its preparation method and application, wherein the eugenolized glycosyl chromogenic agent is 3-((4-hydroxy-3,5-dimethoxybenzyl)amino)-4-((1-methoxy-1-oxo-3-phenylprop-2-yl)amino)-4-oxobutyric acid, and the structural formula of the eugenolized glycosyl chromogenic agent is shown in Formula I: Formula I. The eugenol glycoside chromogen of the present invention enables visualized monitoring of the preparation process of inorganic mineral powder wetting solution, filling the gap in the traditional in-situ, real-time, and efficient detection of inorganic mineral wetting solutions.

[0119] 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 eugenol-based glycosyl colorant, characterized in that, The eugenolized glycosyl chromogen is 3-((4-hydroxy-3,5-dimethoxybenzyl)amino)-4-((1-methoxy-1-oxo-3-phenylprop-2-yl)amino)-4-oxobutyric acid, and the structural formula of the eugenolized glycosyl chromogen is shown in Formula I:

2. A method for preparing the eugenol-based glycosyl chromogen according to claim 1, characterized in that, Includes the following steps: 1) The amino acid dipeptide derivative and the solvent were mixed under ultrasonic conditions to obtain solution 1; 2) Mix the natural aldehyde derivative with a solvent to obtain solution 2; 3) Add solution 2 to solution 1 to react and obtain eugenol glycoside colorant.

3. The method for preparing the eugenol-based glycosyl colorant according to claim 2, characterized in that, In step 1), the amino acid dipeptide derivative includes aspartic phenylalanine methyl ester. The solvent includes one or more of methanol, ethanol, propanol, ethylene glycol and 1,2-propanediol; The molar concentration of solution 1 is 1–5 M.

4. The method for preparing the eugenol-based glycosyl colorant according to claim 2 or 3, characterized in that, In step 1), the power of the ultrasound is 100-600W; The mixing is carried out by stirring at a speed of 600–1800 rpm, at a temperature of 25–50°C, and for a time of 0.1–1.0 h.

5. The method for preparing the eugenol-based glycosyl colorant according to claim 4, characterized in that, In step 2), the natural aldehyde derivatives include syringaldehyde; The solvent is an alcohol solution, wherein the alcohol in the alcohol solution includes one or more of methanol, ethanol, propanol, ethylene glycol, and 1,2-propanediol. The volume ratio of alcohol to water in the alcohol solution is 2 to 9:1; The molar concentration of solution 2 is 1–3 M.

6. The method for preparing the eugenol-based glycosyl colorant according to claim 5, characterized in that, In step 2), the mixing is carried out by stirring at a speed of 1000-2000 rpm for 0.1-1.2 h and at a temperature of 35-60 °C.

7. The method for preparing the eugenol-based glycosyl colorant according to claim 6, characterized in that, The molar ratio of the natural aldehyde derivative and the amino acid dipeptide derivative is 1 to 3:

1.

8. The method for preparing the eugenol-based glycosyl chromogen according to claim 6 or 7, characterized in that, In step 3), solution 2 is added by uniform spraying at a rate of 1 to 5 mL / min.

9. The method for preparing the eugenol-based glycosyl colorant according to claim 8, characterized in that, In step 3), the reaction temperature is 100–120°C, the heating rate is 1–5°C / min, the reaction time is 1.0–3.0 h, and the reaction pressure is 2–6 atm. The reaction is carried out under stirring at a speed of 800–1600 rpm.

10. The application of the eugenol glycoside colorant of claim 1 in the detection of micro-region viscosity changes in the wetting solution of inorganic mineral powder.

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