A natural patulin-based cinnamyl derivative, its preparation method and application

Abstract

The application belongs to the technical field of industrial analysis and detection, and provides a cinnamon derivative based on natural mycotoxin, a preparation method and application thereof.The preparation method comprises the following steps: mixing anatumomycin solution and trans-4-methoxy acrylate solution, and then reacting to obtain the cinnamon derivative based on natural mycotoxin; the molar ratio of anatumomycin and trans-4-methoxy acrylate is 1:1-80.The cinnamon derivative based on natural mycotoxin provided by the application can be applied in inorganic powder grinding and dispersing agents containing a large number of pseudoplastic components as a molecular tool, as an in-situ molecular level viscosity sensing tool, the size of relative viscosity can be obtained without the help of external shearing, and the viscosity change can be effectively presented in a visual way, which is helpful to realize the rapid, efficient and controllable preparation of inorganic powder grinding and dispersing agents.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of industrial analysis and detection, and particularly relates to a cinnamyl derivative based on natamycin, a preparation method and application thereof. BACKGROUND

[0002] Inorganic powder grinding dispersant is widely used in the grinding process of various inorganic mineral powders, and is an important chemical additive. It plays an important role in the grinding process of inorganic mineral powders. A small amount of grinding dispersant can significantly improve the grinding efficiency of mineral powders, effectively reduce the energy consumption in the grinding process of powders, save grinding time, and effectively improve the service life of grinding balls and grinding equipment, thereby greatly saving production costs. There are various types of grinding dispersants. Among the numerous grinding dispersants, various oligomers or polymer grinding dispersants have been developed, including polyurethane, epoxy resin, alkyd resin, acrylic acid system, etc. Only a small amount of grinding dispersant is needed to be adsorbed on the surface of a large amount of powder particles to help build a three-dimensional structure between the powder-powder and the powder-resin, shield the accumulation and hardening between the powders, improve the flow leveling of the powders, and reduce the adsorption between the powder particles. Therefore, grinding dispersant has become a necessary component to improve the grinding efficiency of natural mineral powders. In addition, the added value brought by grinding dispersant is greater. As a liquid dispersant, the improvement of the micro-viscosity of the grinding dispersant can effectively improve the grinding efficiency and particle size of the powder. By selecting a suitable base, the grinding dispersant with appropriate viscosity can significantly change the long-term storage precipitation and cementation problem of the powder. When it is necessary to enhance the flowability of the grinding dispersant, reducing the micro-viscosity of the grinding dispersant can make it better wet the inorganic powder. When it is necessary to enhance the friction and adhesion of the grinding dispersant, increasing the micro-viscosity of the grinding dispersant can make it better assist the grinding of the powder and improve the efficiency. Therefore, the micro-viscosity of the grinding dispersant is a property that can resist deformation or prevent the relative flow of adjacent fluid layers. The viscosity measurement method of traditional inorganic powder grinding dispersant mostly uses various types of viscometers for measurement, which is time-consuming and requires a large amount of material, and is highly dependent on equipment. The test results obtained are macroscopic results, which are difficult to measure the change of micro-viscosity, and are also strongly dependent on the measurement of viscosity change in the process of rotary shear, which is difficult to measure at the molecular level.

[0003] In the field of industrial analysis and detection, photochemical technology can use molecular tools to measure micro-viscosity. By controlling the emission wavelength, the viscosity change of the grinding dispersant can be visualized. This light force conversion method can be used to develop more suitable inorganic powder grinding dispersants. At present, there are few simple natural product reconstruction methods to prepare molecular tools for measuring the micro-viscosity of inorganic powder grinding dispersants. Therefore, how to use natural products to prepare a molecular tool for measuring the micro-viscosity of grinding dispersants has become a problem that needs to be solved by those skilled in the art. SUMMARY

[0004] Therefore, the application provides a cinnamon derivative based on natural mycotoxin, a preparation method and application thereof.

[0005] To achieve the above object, the application adopts the following technical scheme:

[0006] The application provides a cinnamon derivative based on natural mycotoxin, and a structural formula of the cinnamon derivative is shown as formula 1.

[0007]

[0008] The application provides a preparation method of the above-mentioned cinnamon derivative based on natural mycotoxin, comprising the following steps:

[0009] The cinnamon derivative based on natural mycotoxin is obtained by mixing and reacting aneurysmal fungus solution and trans-4-methoxy acrylate solution.

[0010] The molar ratio of aneurysmal fungus and trans-4-methoxy acrylate is 1:1-80.

[0011] Further, the temperature of the reaction is 50-120 DEG C, and the reaction time is 1-48 h.

[0012] Further, the concentration of the aneurysmal fungus solution is 1-75 mol / L, and the concentration of the trans-4-methoxy acrylate solution is 1-400 mol / L.

[0013] Further, the aneurysmal fungus solution comprises aneurysmal fungus and an alcohol solvent, and the trans-4-methoxy acrylate solution comprises trans-4-methoxy acrylate and an alcohol solvent; the alcohol solvent independently comprises one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, 1,2-propanediol and 1,3-propanediol.

[0014] Further, the mixing step is that the trans-4-methoxy acrylate solution is added to the aneurysmal fungus solution by dropwise adding.

[0015] Further, the dropwise adding rate is 1 drop / 15 s-1 drop / s, the dropwise adding temperature is 25-50 DEG C, and the dropwise adding is accompanied by stirring, and the stirring speed is 100-1000 rpm.

[0016] The application also provides application of the above-mentioned cinnamon derivative based on natural mycotoxin as a molecular tool in measuring the viscosity of inorganic powder grinding dispersant, comprising the following steps:

[0017] The cinnamyl derivative based on natural mycotoxin is mixed with an organic solvent to obtain a mixed solution as a molecular tool, and the molecular tool is mixed with an inorganic powder grinding dispersant.

[0018] Further, the organic solvent includes one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, 1,2-propanediol and 1,3-propanediol, and the concentration of the mixed solution is 1-100 mol / L.

[0019] Further, the concentration of the molecular tool in the inorganic powder grinding dispersant is 1-80 μmol / L.

[0020] According to the above technical solution, compared with the prior art, the application has the following beneficial effects:

[0021] (1) The cinnamyl derivative based on natural mycotoxin is obtained by one-step conjugate coupling of natural mycotoxin orange rubber mold and natural cinnamyl aldehyde derivative trans-4-methoxy acrylate, both of which are natural products and widely available in nature, and are green and environmentally friendly. The one-step reaction improves the yield of the target product, effectively reduces the production and preparation cost, and uses alcohol solvents throughout the process, effectively reducing the use of toxic organic solvents, suitable for large-scale preparation, and the way of reconfiguring the molecular tool from natural products is very suitable for the concept of low-carbon and sustainable development.

[0022] (2) The cinnamyl derivative based on natural mycotoxin as a molecular tool has the advantages of stable chemical structure, effectively discarding the weak bond of the molecule, and using ether bond raw materials for active hydroxyl groups, which can exist in complex inorganic powder grinding dispersants for a long time, and the light signal release performance is stable. It can also be applied to inorganic powder grinding dispersants of various pH values, and can maintain good light signal output even after long-term irradiation. It also has a high annual sensitivity coefficient (x=0.41), especially for low viscosity, with a detection lower limit of 1.157 cP, suitable for measuring the viscosity changes of inorganic powder grinding dispersants in micro areas.

[0023] (3) The cinnamyl derivative based on natural mycotoxin as a molecular tool can be applied to inorganic powder grinding dispersants containing a large amount of pseudoplastic components, as an in-situ molecular level viscosity sensing tool, without the need for external shearing to obtain the size of relative viscosity, and the viscosity change can be effectively presented in a visual way. The molecular tool can release light signals in the wavelength range of 370-680 nm under external excitation of 350 nm, which can be used for visual measurement of the micro area viscosity of inorganic powder grinding dispersants, and has a great promoting effect on the control of the dilution of inorganic powder grinding dispersants, which helps to realize the rapid, efficient and controllable preparation of inorganic powder grinding dispersants. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 Schematic diagram of the mechanism of the natural mycotoxin-based cinnamon derivative as a molecular tool to measure microviscosity provided by the present application;

[0025] Figure 2 High-resolution mass spectrum of the natural mycotoxin-based cinnamon derivative prepared for Example 1;

[0026] Figure 3 Spectrogram of the natural mycotoxin-based cinnamon derivative prepared for Example 1 in different viscosity solution atmospheres;

[0027] Figure 4 Linear fitting graph between the light signal intensity and the viscosity size of the natural mycotoxin-based cinnamon derivative prepared for Example 1 as a molecular tool;

[0028] Figure 5 Spectrogram of the natural mycotoxin-based cinnamon derivative prepared for Example 1 as a molecular tool in different commercially available inorganic powder grinding dispersants;

[0029] Figure 6 Spectrogram of the natural mycotoxin-based cinnamon derivative prepared for Example 1 as a molecular tool in different pH atmospheres;

[0030] Figure 7 Light stability test results of the natural mycotoxin-based cinnamon derivative prepared for Example 1 as a molecular tool in glycerol and purified water;

[0031] Figure 8 Lower limit detection graph of the natural mycotoxin-based cinnamon derivative prepared for Example 1 as a molecular tool. DETAILED DESCRIPTION

[0032] The present application provides a natural mycotoxin-based cinnamon derivative, the structural formula of which is shown as Formula 1:

[0033]

[0034] In the present application, the natural mycotoxin-based cinnamon derivative can be named as 2,3-dimethoxy-5,6-bis(4-(4-methoxyphenyl)buta-1,3-dien-1-yl)cyclohexa-2,5-diene-1,4-dione, with a molecular formula of C 30 H 28O6, with a relative molecular mass of 484.18, has a light yellow powder appearance, and is easily soluble in ethanol, methanol, propanol, N,N-dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, acetonitrile, acetone and other common solvents. The cinnamon derivative has a typical single-double bond alternating conjugated structure, low hygroscopicity and is suitable for long-term storage; the chemical structure does not contain weak bonds, and a large conjugated flexible structure is adopted, and the conjugated structure can present different rotating states in inorganic powder grinding dispersants with different viscosities, and the released light signal intensity is different, so that the dilution process control of the inorganic powder grinding dispersant becomes visual. Meanwhile, the cinnamon derivative is electrically neutral and does not interact with various components in the inorganic powder grinding dispersant. In addition, the inorganic powder grinding dispersant contains a large amount of polymer components, including: polyurethane system, epoxy system, acrylic system, alkyd resin system and the like. The cinnamon derivative as a molecular tool can realize the viscosity measurement of such pseudoplastic fluid without relying on rotary shear, and is not easily disturbed by various components in the inorganic powder grinding dispersant, such as triethanolamine, ammonium acetate, ethylene glycol, propylene glycol and the like, has a wide pH application range and a low detection lower limit, and is thus particularly suitable for fine measurement of micro-zone viscosity changes of the inorganic powder grinding dispersant.

[0035] The application provides a preparation method of the cinnamon derivative based on natural mycotoxin.

[0036] The cinnamon derivative based on natural mycotoxin is obtained by mixing the solution of the citrinin and the solution of the trans-4-methoxy acrylate and then performing reaction.

[0037] In the application, the molar ratio of the citrinin to the trans-4-methoxy acrylate is 1:1-80, preferably 1:10-70, and more preferably 1:20-60.

[0038] In the application, the structural formula of the citrinin is shown as formula 2, and the structural formula of the trans-4-methoxy acrylate is shown as formula 3.

[0039]

[0040] In the application, the temperature of the reaction is 50-120 DEG C, preferably 60-100 DEG C, and more preferably 70-90 DEG C; and the reaction time is 1-48 h, preferably 10-40 h, and more preferably 20-30 h.

[0041] In the application, the heating rate of the room temperature to the reaction temperature is 15-60 DEG C / h, preferably 20-50 DEG C / h, and more preferably 30-40 DEG C / h.

[0042] In the application, the reaction process is as follows:

[0043]

[0044] In the present application, the reaction is accompanied by stirring, and the stirring rate is 500-2000 rpm, preferably 600-1800 rpm, and further preferably 800-1500 rpm.

[0045] In the present application, the concentration of the citrinin solution is 1-75 mol / L, preferably 2-70 mol / L, and further preferably 5-60 mol / L; and the concentration of the trans-4-methoxycinnamate solution is 1-400 mol / L, preferably 5-300 mol / L, and further preferably 10-200 mol / L.

[0046] In the present application, the citrinin solution comprises citrinin and an alcohol solvent, and the trans-4-methoxycinnamate solution comprises trans-4-methoxycinnamate and an alcohol solvent; the alcohol solvent independently comprises one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, 1,2-propanediol and 1,3-propanediol, preferably one or more of methanol, ethanol, propanol, ethylene glycol, 1,2-propanediol and 1,3-propanediol, and further preferably one or more of methanol, ethanol, 1,2-propanediol and 1,3-propanediol; when multiple solvents are selected, they are preferably mixed in equal volumes.

[0047] In the present application, the mixing step is adding the trans-4-methoxycinnamate solution to the citrinin solution by dropwise addition.

[0048] In the present application, the dropwise addition rate is 1 drop / 15 s-1 drop / s, preferably 1 drop / 10 s-1 drop / s, and further preferably 1 drop / 5 s; the dropwise addition temperature is 25-50°C, preferably 30-45°C, and further preferably 35-40°C; and the dropwise addition is accompanied by stirring, and the stirring rate is 100-1000 rpm, preferably 200-800 rpm, and further preferably 300-600 rpm.

[0049] In the present application, after the reaction is completed, the obtained product is sequentially subjected to vacuum distillation, extraction, cold separation and drying, the vacuum distillation is carried out in a rotary evaporator, the pressure of the rotary evaporator is -0.09 to -0.08 MPa; the step of extraction is that the crude product of the reaction is dissolved in a mixed system of ethyl acetate and water, and is repeatedly extracted 1 to 4 times, preferably 2 to 3 times, the organic phase is collected and removed by vacuum distillation, the volume ratio of the ethyl acetate and water is 1 to 10:1, preferably 2 to 8:1, and further preferably 4 to 6:1; the step of cold separation is that the extraction product is dissolved in ethyl acetate, the solid content is controlled to be 1 to 30 mg / mL, preferably 5 to 25 mg / mL, and further preferably 10 to 20 mg / mL, then is dispersed in ethanol, the volume ratio of the ethyl acetate and ethanol is controlled to be 1:1 to 30, preferably 1:5 to 25, and further preferably 1:10 to 20; is placed at 0 to 15℃ for 1 to 60 h, the temperature of the placement is preferably 3 to 12℃, preferably 5 to 10℃, the time of the placement is 10 to 50 h, and further preferably 20 to 40 h, a large amount of solid can be separated out, and is subjected to suction filtration, the obtained solution is poured into a funnel, a medium-speed or fast filter paper is used, the number of layers is 1 to 3, preferably 2, the adding rate is controlled to be 6 to 100 mL / min, preferably 10 to 80 mL / min, and further preferably 20 to 60 mL / min, until the suction filtration is completed, then is dispersed in the aforementioned mixed solution of ethyl acetate and ethanol, and the above-mentioned suction filtration step is repeated 1 to 5 times, preferably 2 to 4 times, and further 3 times, and a precipitate is obtained; the drying temperature is -30 to 0℃, preferably -25 to -5℃, and further preferably -20 to -10℃, and the drying time is 1 to 68 h, preferably 10 to 50 h, and further preferably 20 to 40 h.

[0050] The present application also provides the use of the above-mentioned natural mycotoxin-based cinnamic acid derivative as a molecular tool for measuring the viscosity of an inorganic powder grinding aid dispersant, comprising the following steps:

[0051] The natural mycotoxin-based cinnamic acid derivative is mixed with an organic solvent to obtain a mixed solution as a molecular tool, and the molecular tool is mixed with the inorganic powder grinding aid dispersant.

[0052] In the present application, the organic solvent includes one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, 1,2-propanediol and 1,3-propanediol, preferably one or more of methanol, ethanol, ethylene glycol, 1,2-propanediol and 1,3-propanediol, and further preferably one or more of methanol, ethanol and 1,3-propanediol, and when multiple solvents are selected, the solvents are preferably mixed in equal volumes; the concentration of the mixed solution is 1 to 100 mol / L, preferably 10 to 80 mol / L, and further preferably 20 to 60 mol / L.

[0053] In the present application, the concentration of the molecular tool in the inorganic powder grinding dispersant is 1-80 μmol / L, preferably 10-70 μmol / L, and further preferably 30-50 μmol / L.

[0054] In the present application, the inorganic powder grinding dispersant includes any one of phosphates, carboxylic acids, amino acids, basic amines and silicates, preferably any one of phosphates, carboxylic acids, amino acids and silicates, and further preferably phosphates or carboxylic acids.

[0055] In the present application, the natural patulin-based cinnamic acid derivative finally presents a chemical structure with a single-double bond conjugate and an electron-withdrawing effect, as shown in the following formula: Figure 1 As shown in the formula, the resulting conjugate structure can rotate freely in the inorganic powder grinding dispersant with low viscosity, at this time, the excitation state energy is mainly dissipated through mechanical rotation, and the apparent optical signal is weak or even non-existent; when the composition of the inorganic powder grinding dispersant changes to cause the viscosity to rise, the mechanical rotation of the resulting molecular tool is limited, at this time, the excitation state energy is mainly dissipated through radiation transition, and the light signal released is relatively strong, and there is a positive correlation between the signal intensity and the viscosity. The stronger the apparent optical signal, the higher the viscosity of the inorganic powder grinding dispersant, the stronger its flowability, adhesion, friction and cohesion, at this time, it can better grind part of the inorganic powder that is difficult to disperse; in contrast, the weaker the apparent optical signal, the thinner the inorganic powder grinding dispersant at this time, the stronger its flowability, but its cohesion, friction and lubricity decrease. Therefore, the molecular tool as a signal switch can realize the recognition of the micro-area viscosity of the inorganic powder grinding dispersant, and as one of the data presentation methods of its deployment process, that is, the apparent optical signal strength and weakness is used to visually monitor the thinness, which more efficiently meets the grinding and lubrication needs of different inorganic powders.

[0056] The technical solutions provided by the present application will be described in detail below in conjunction with the embodiments, but they should not be understood as limiting the scope of protection of the present application.

[0057] Example 1

[0058] 16.2 g of trans-4-methoxy acrylate was dissolved in ethanol, stirred uniformly to obtain a trans-4-methoxy acrylate solution with a concentration of 100 mol / L, 0.98 g of citrinin was dissolved in ethanol, stirred uniformly to obtain a citrinin solution with a concentration of 5 mol / L;

[0059] The trans-4-methoxy acrylate solution is added to the natamycin solution by dropwise addition, the dropwise addition rate is 1 drop / 5 s, the stirring rate is controlled at 500 r / min during dropwise addition, the temperature is raised while stirring during dropwise addition, the temperature raising rate is 30 ℃ / h, the target temperature is 80 ℃, until the dropwise addition is completed, continue to react for 24 h, the stirring rate during reaction is 1200 rpm, to obtain the target product crude product;

[0060] The target product crude product is purified, and the purification process is sequentially carried out by vacuum distillation, extraction, cold separation and drying, wherein the vacuum distillation is carried out in a rotary evaporator, and the pressure of the rotary evaporator is-0.09 MPa; in the extraction process, the aforementioned obtained crude product is redissolved in a mixed system of ethyl acetate and purified water, the volume ratio of the ethyl acetate and the purified water is 5:1, the extraction is repeated 2 times, the organic phase is collected and removed by vacuum distillation; the cold separation is that the obtained extraction product is dissolved in ethyl acetate, the solid content is controlled to be 15 mg / mL, and it is dispersed in ethanol, the volume ratio of ethyl acetate and ethanol is controlled to be 1:15, it is placed at 8 ℃ for 30 h, a large amount of solid can be separated out, and it is suction filtered, the obtained solution is poured into a funnel, fast filter paper is used, the layer number is 2, the adding rate is controlled to be 50 mL / min, until the suction filtration is completed, then it is dispersed in the aforementioned mixed solution of ethyl acetate and ethanol, and the above-mentioned suction filtration step is repeated 3 times, to obtain the precipitate; the drying process adopts low-temperature drying, the temperature of the low-temperature drying is-15 ℃, and the time of the low-temperature drying is 36 h; after the drying is completed, the yield of the cinnamic derivative based on natamycin is 2.18 g, and the yield is 90.1%.

[0061] The relative molecular mass of the obtained cinnamic derivative based on natamycin is analyzed, and the results are shown in Table 1. Figure 2 The relative molecular mass of the obtained cinnamic derivative based on natamycin is analyzed, and the results are shown in Table 1. + The relative molecular mass of the obtained cinnamic derivative based on natamycin is analyzed, and the results are shown in Table 1.

[0062] Example 2

[0063] 0.16 g of trans-4-methoxy acrylate is dissolved in ethanol to obtain a trans-4-methoxy acrylate solution with a concentration of 1 mol / L, and 0.2 g of citrinin is dissolved in ethanol to obtain a citrinin solution with a concentration of 1 mol / L;

[0064] The trans-4-methoxy acrylate solution is added to the natamycin solution by dropwise addition, the dropwise addition rate is 1 drop / 15 s, the stirring rate is controlled at 100 r / min during dropwise addition, the temperature is increased while stirring during dropwise addition, the temperature increasing rate is 15 ℃ / h, the target temperature is 50 ℃, until the dropwise addition is completed, continue to react for 48 h, the stirring rate during the reaction is 600 rpm, to obtain the target product crude product;

[0065] The target product crude product is purified, and the purification process is sequentially carried out by vacuum distillation, extraction, cold separation and drying, wherein the vacuum distillation is carried out in a rotary evaporator, and the pressure of the rotary evaporator is-0.08 MPa; in the extraction process, the aforementioned obtained crude product is redissolved in a mixed system of ethyl acetate and purified water, the volume ratio of the ethyl acetate and the purified water is 1:1, the extraction is repeated 1 time, the organic phase is collected and removed by vacuum distillation; the cold separation is that the obtained extraction product is dissolved in ethyl acetate, the solid content is controlled to be 1 mg / mL, and it is dispersed in ethanol, the volume ratio of ethyl acetate and ethanol is controlled to be 1:1, and it is placed at 0 ℃ for 1 h, a large amount of solid can be separated out, and it is suction filtered, the obtained solution is poured into a funnel, a rapid filter paper is used, the layer number is 1 layer, the adding rate is controlled to be 6 mL / min, until the suction filtration is completed, then it is dispersed in the aforementioned mixed solution of ethyl acetate and ethanol, and the above-mentioned suction filtration step is repeated 1 time, to obtain the precipitate; the drying process adopts low-temperature drying, the temperature of the low-temperature drying is-30 ℃, and the time of the low-temperature drying is 1 h; after the drying is completed, the yield of the cinnamic derivative based on natamycin is 0.2 g, and the yield is 83.5%.

[0066] The mass spectrum result of the cinnamic derivative based on natamycin prepared in the example is the same as that of example 1.

[0067] Example 3

[0068] 64.8 g of trans-4-methoxy acrylate is dissolved in ethanol to obtain a trans-4-methoxy acrylate solution with a concentration of 400 mol / L, 0.98 g of citrinin is dissolved in ethanol to obtain a citrinin solution with a concentration of 75 mol / L;

[0069] The trans-4-methoxy acrylate solution is added to the natamycin solution by dropwise addition, the dropwise addition rate is 1 drop / s, the stirring rate is controlled at 800 r / min during dropwise addition, the temperature is increased while stirring during dropwise addition, the temperature increasing rate is 60 ℃ / h, the target temperature is 100 ℃, until the dropwise addition is completed, continue to react for 1 h, the stirring rate during the reaction is 1800 rpm, to obtain the target product crude product;

[0070] The crude target product was purified by sequentially performing vacuum distillation, extraction, refrigeration, and drying. Vacuum distillation was conducted in a rotary evaporator at a pressure of -0.09 MPa. During extraction, the crude product was redissolved in a mixture of ethyl acetate and purified water at a volume ratio of 10:1, and the extraction was repeated four times. The organic phase was collected and removed by vacuum distillation. Refrigeration involved dissolving the extracted product in ethyl acetate, controlling the solid content to 30 mg / mL, and dispersing it in ethanol, controlling the concentration of ethyl acetate and ethanol. The volume ratio was 1:30. After standing at 15℃ for 60 hours, a large amount of solid precipitated. This solid was then filtered, and the resulting solution was poured into a funnel. Using rapid filter paper with 3 layers, the addition rate was controlled at 100 mL / min until filtration was complete. The solid was then dispersed in the aforementioned ethyl acetate and ethanol mixed solution. The above filtration steps were repeated 5 times to obtain the precipitate. The drying process was carried out at low temperature, with a drying temperature of 0℃ and a drying time of 68 hours. After drying, the yield of the cinnamon derivative based on natural mycotoxin was 2.12 g, with a yield of 87.6%.

[0071] The mass spectrometry results of the cinnamon derivative based on natural mycotoxin prepared in this embodiment are the same as those in Example 1.

[0072] Performance testing

[0073] The cinnamon derivative based on natural mycotoxin prepared in Example 1 was subjected to viscosity sensitivity testing, detection limit testing, pH stability and light stability testing.

[0074] 1. Viscosity sensitivity test of cinnamon derivatives based on natural mycotoxins (DBMCDD):

[0075] Solutions with viscosity gradients were prepared by adding glycerol and purified water in different volume ratios (see Table 1). The external excitation wavelength was controlled at 365 nm. The concentration of the added cinnamon derivative based on natural mycotoxin was 10 μmol / L. The tests were conducted at room temperature, and the results are as follows: Figure 3 As shown.

[0076] Table 1. Correspondence between the ratio of glycerol to purified water and viscosity.

[0077]

[0078]

[0079] like Figure 3As shown, with the gradual increase of solution viscosity, the apparent optical signal intensity gradually increases, and the DBMCDD reaches the maximum in the glycerol solution. Compared with the solution system without adding purified water, the apparent optical signal intensity increases by 463 times at the highest.

[0080] In addition, after converting the optical signal intensity and the solution viscosity into logarithmic functions, it can be found that in the low viscosity range, the sensitivity of the molecular tool to viscosity is higher, and then with the gradual increase of viscosity, the sensitivity coefficient decreases, but it can also maintain a viscosity sensitivity coefficient of 0.41. At this time, the fitting coefficient of determination is 0.99, as shown in Figure 4 The corresponding logarithmic function values are shown in Table 2.

[0081] Table 2 Logarithm of viscosity and logarithm of fluorescence intensity

[0082] logarithm of the viscosity (log η) 0.01 0.24 0.57 1.03 1.77 2.99 logarithm of the fluorescence intensity (log I) 1.0 2.51 263 2.84 3.13 3.63

[0083] 2. Detection lower limit test of natural mycotoxin-based cinnamon derivative (DBMCDD):

[0084] 1.45 mg of DBMCDD prepared in Example 1 was dissolved in water-soluble alkyd resin, and the concentration was controlled to be 3 mmol / L. During the test, it was diluted to 10 μmol / L, and it was added to the purified water and glycerol mixed solution with very low viscosity, respectively, to test the detection lower limit of the viscosity sensitivity. The above test was carried out at room temperature, and the results are shown in Figure 5 .

[0085] From the results Figure 5 It can be seen that in the solution with very low viscosity, the viscosity value of DBMCDD and the logarithmic value of the optical signal release intensity have a good linear relationship, and the fitting coefficient of determination is 0.99. The detection lower limit of the molecular tool DBMCDD to viscosity is 1.157 cP, which indicates that it is very sensitive to the micro-viscosity change of the inorganic powder grinding dispersant, and is suitable for the regulation and visual monitoring of the dilution of the inorganic powder grinding dispersant.

[0086] 3. pH stability test of natural mycotoxin-based cinnamon derivative (DBMCDD):

[0087] 1.94 mg of DBMCDD prepared in Example 1 was dissolved in water-soluble alkyd resin, and the concentration was controlled to be 4 mmol / L. During the test, the concentration was diluted to 10 μmol / L, and it was added to the solution with different pH atmosphere, respectively, to verify its resistance to pH. The test results are shown in Figure 6 .

[0088] From the results Figure 6The test results show that the fluorescence intensity of DBMCDD does not change significantly in the pH range of 3-12 in which inorganic powder grinding dispersants are generally present, and can exhibit good light stability, indicating that it is not easily affected by pH and is suitable for use in inorganic powder grinding dispersants in complex pH environments.

[0089] 4. Light stability test of the cinnamon derivative (DBMCDD) based on natural mycotoxin:

[0090] 3.39 mg of DBMCDD prepared in Example 1 was dissolved in water-soluble alkyd resin to control the concentration to 7 mmol / L, and then diluted to 10 μmol / L during testing. The light signal intensity was tested for changes within 60 min under continuous irradiation of an external excitation light source at 365 nm, in low-viscosity purified water and high-viscosity glycerol, respectively. The test results are shown in Figure 7 , and the obtained data are shown in Table 3.

[0091] Table 3. Fluorescence test results

[0092] Time / min 0 10 20 30 60 Fluorescence intensity in glycerol / a.u. 9.27 9.12 8.92 8.76 8.60 Fluorescence intensity in glycerol / a.u. 4301.2 4290.6 4282.3 4269.7 4258.0

[0093] As shown by Figure 7 and the data in Table 3, DBMCDD can still maintain good light signal release intensity under continuous irradiation of an external light source. This light signal stability indicates that it is not prone to photobleaching and is suitable for use in the micro-viscosity response of inorganic powder grinding dispersants, and will not be greatly affected under long-term irradiation.

[0094] Application Example 1

[0095] 2.42 mg of the cinnamon derivative based on natural mycotoxin prepared in Example 1 was dissolved in a certain volume of water-soluble alkyd resin to obtain a molecular tool solution with a concentration of 5 mmol / L. Then the molecular tool solution was added to common wax emulsions with different viscosities, and after addition, the concentration of the added molecular tool was diluted to 10 μmol / L. The test was carried out at room temperature, and the external excitation light source was 365 nm. The obtained spectral results are shown in Figure 8 , and the typical values of the specific test data are shown in Table 4.

[0096] Table 4. Light signal intensity and viscosity of different wax emulsions

[0097] Test sample Light signal intensity Viscosity Grinding aid 1 680.2 10.1 Grinding aid 2 1621.9 101.2 Grinding aid 3 3087.2 510.2

[0098] As shown by Figure 8As can be seen from Table 4, the apparent optical signals released by the three solutions are quite different, which is caused by the different viscosities of the three water-soluble alkyd resins. Specifically, the optical signal intensity of the grinding aid 1 (DH-5038) is the lowest, indicating that the viscosity is small, and the test data shows that the viscosity is 10.1 cP; the optical signal of the grinding aid 2 (AKN-2076) is at moderate intensity, indicating that the viscosity is improved to a certain extent, and the test data shows that the viscosity is 101.2 cP; the optical signal intensity of the grinding aid 3 (OROTAN) further rises and the whole presents a sticky state, and the viscosity is large, and the test data shows that the viscosity is 510.2 cP. The test results show that the natural natamycin-based cinnamon derivative molecular tool (DBMCDD) provided by the application can release optical signals of different intensities for grinding aids with different viscosities, and the wavelength peak of the released light is 450 nm, which is within the visual perception range, so that the visual monitoring effect can be achieved.

[0099] The above test and application results show that the natural natamycin-based cinnamon derivative molecular tool (DBMCDD) provided by the application is a single-double bond alternating conjugated compound with multiple chromophores. The flexible rotatable conjugated structure can present different rotating states in inorganic powder grinding dispersants with different viscosities, and then be converted into different optical signals to be released, so that the viscosity of the inorganic powder grinding dispersant microzone can be quickly, efficiently and visually detected. Various test results show that the molecular tool DBMCDD has a high sensitivity coefficient in the low viscosity range, the detection lower limit is as low as 1.157 cP, and has good resistance to various pH values, excellent anti-photobleaching property and good light stability. In addition, the DBMCDD is a molecular tool, which is particularly suitable for in-situ measurement and is suitable for viscosity measurement of inorganic powder grinding dispersants containing a large amount of pseudoplastic fluid components. Moreover, the natural natamycin-based cinnamon derivative is prepared by a simple one-step method, and the preparation process does not require expensive metal catalysts and highly toxic organic solvents, and the preparation process is simple, environmentally friendly and easy to implement, and the final yield is also high. The raw material source is abundant, and the natural product is reconstructed, the amount is extremely small, and it is suitable for large-scale industrialized production and application.

[0100] The above only describes the preferred embodiments of the application, and it should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the application, and these improvements and refinements should also be considered as the protection scope of the application.

Claims

1. A cinnamon derivative based on natural mycotoxins, characterized in that, The structural formula of the cinnamon derivative is shown in Formula 1: Formula 1.

2. The method for preparing cinnamon derivatives based on natural mycotoxins according to claim 1, characterized in that, Includes the following steps: containing compounds solutions and compounds The cinnamon derivative based on natural mycotoxins is obtained by reacting the solutions after mixing. compound and compounds The molar ratio is 1:1~80.

3. The preparation method according to claim 2, characterized in that, The reaction temperature is 50~120℃, and the reaction time is 1~48h.

4. The preparation method according to claim 3, characterized in that, The compound-containing The concentration of the solution is 1~75 mol / L; containing compounds The concentration of the solution is 1~400mol / L.

5. The preparation method according to claim 3 or 4, characterized in that, The compound-containing The solution includes compounds And alcohol solvents, containing compounds The solution includes compounds And alcohol solvents; the alcohol solvents are one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, 1,2-propanediol and 1,3-propanediol.

6. The preparation method according to claim 5, characterized in that, The mixing step is as follows: [The mixture contains compounds] The solution is added dropwise to the compound. In the solution.

7. The preparation method according to claim 6, characterized in that, The dropping rate is 1 drop / 15s to 1 drop / s, the dropping temperature is 25 to 50°C, and the dropping is accompanied by stirring at a speed of 100 to 1000 rpm.

8. The application of the cinnamon derivative based on natural mycotoxin as a molecular tool in measuring the viscosity of inorganic powder grinding aids and dispersants, as described in claim 1, is characterized in that... Includes the following steps: A cinnamon derivative based on natural mycotoxins is mixed with an organic solvent to obtain a mixed solution, which is then used as a molecular tool. This molecular tool is then mixed with an inorganic powder grinding aid and dispersant.

9. The application according to claim 8, characterized in that, The organic solvent is one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, 1,2-propanediol and 1,3-propanediol, and the concentration of the mixed solution is 1~100 mol / L.

10. The application according to claim 9, characterized in that, The concentration of the molecular tool in the inorganic powder grinding aid dispersant is 1~80 μmol / L.

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