A kind of cloud base silane and its preparation method and a metasilicate composite powder

Abstract

The application belongs to the technical field of functional materials, and provides a cloudine silane, a preparation method thereof and a metasilicate composite powder. The first solution is obtained by mixing a cloudine solution and an alcohol solution of inorganic salt; the cloudine silane is obtained by mixing the first solution and an aromatic bromosilane solution for substitution reaction; the second solution is obtained by mixing the cloudine silane and an organic solvent; and the metasilicate composite powder is obtained by mixing the second solution and a metasilicate slurry for reaction. The method is simple and low in cost, the cloudine silane prepared by the method can greatly improve the functionality of the natural mineral powder, and the metasilicate composite powder prepared by the method has excellent chemical stability, oil absorption value, dispersibility, carbon formation property and mechanical property, and can be added into a polymer matrix as a multifunctional composite filler to play the roles of filling, strengthening, toughening and promoting carbon formation.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functional materials, and in particular to a yunnankaine silane, a preparation method thereof and a metasilicate composite powder. BACKGROUND

[0002] By reasonably developing and applying natural mineral powders, the problems of fossil energy depletion and high carbon consumption can be effectively alleviated. By adopting the design concept of multifunctionalization, the application value and potential of these natural mineral powders can be significantly enhanced. In addition, the simple and efficient preparation process not only saves time and cost, but also supports large-scale production and utilization in diversified application scenarios.

[0003] However, most natural mineral powders face the problem of compatibility when combined with low-polarity polyolefin elastomer substrates due to their strong surface polarity and rich hydroxyl groups. Traditionally, silanes are often used to modify the surface of natural mineral powders, but this method often cannot meet the more extensive application requirements. For example, calcareous metasilicates, as a mineral commonly found in nature, have excellent physical filling properties, but still have many limiting factors in practical applications. For example, calcareous metasilicates prepared by physical methods have problems such as excessively high surface polarity, easy caking, poor processing performance, and easy precipitation. Traditional silane coupling agents can improve these problems to some extent, but their functionality is still limited.

[0004] Therefore, there is an urgent need to provide a modified material that can greatly enhance the functionality of natural mineral powders. SUMMARY

[0005] Therefore, the present application provides a yunnankaine silane, a preparation method thereof and a metasilicate composite powder to solve the problem of poor functionality of natural mineral powders modified by traditional silane coupling agents.

[0006] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0007] The present application provides a yunnankaine silane, the structural formula of which is shown as formula I:

[0008]

[0009] The present application also provides a preparation method of a yunnankaine silane, comprising the following steps:

[0010] 1) mixing a yunnankaine solution with an alcohol solution of an inorganic salt to obtain a first solution;

[0011] 2) mixing the first solution with an aromatic bromosilane solution to perform a substitution reaction to obtain a yunnankaine silane;

[0012] The structure of the roemerine in the roemerine solution is shown as formula II:

[0013]

[0014] The structure of the aromatic bromosilane in the aromatic bromosilane solution is shown as formula III:

[0015]

[0016] Preferably, the molar ratio of the roemerine in the roemerine solution to the inorganic salt in the alcohol solution of the inorganic salt in step 1) is 1:1-5; the concentration of the roemerine solution is 1-3 mol / L; and the concentration of the alcohol solution of the inorganic salt is 1-5 mol / L.

[0017] Preferably, the mixing in step 1) is dropwise adding the roemerine solution into the alcohol solution of the inorganic salt, and the dropwise adding rate is 5 mL / s-1 mL / s.

[0018] Preferably, the molar ratio of the aromatic bromosilane in the aromatic bromosilane solution to the roemerine in the roemerine solution in step 2) is 1-3:1; and the concentration of the aromatic bromosilane solution is 1-3 mol / L.

[0019] Preferably, the mixing in step 2) is dropwise adding the aromatic bromosilane solution into the first solution, and the dropwise adding rate is 5 mL / s-1 mL / s; the temperature of the substitution reaction in step 2) is 55-100 ℃, the temperature increasing rate is 5-20 ℃ / h, and the time is 1-24 h.

[0020] Preferably, the inorganic salt in the alcohol solution of the inorganic salt includes one or more of sodium carbonate, cesium carbonate, sodium bicarbonate, potassium carbonate, calcium carbonate, magnesium hydroxide and aluminum hydroxide; the alcohol in the alcohol solution of the inorganic salt includes one or more of ethanol, methanol, n-butanol, ethylene glycol, neopentyl alcohol, isopropyl alcohol and propyl alcohol; and the solvent in the roemerine solution and the solvent in the aromatic bromosilane solution independently include one or more of water, N,N-dimethylformamide, ethyl acetate, tetrahydrofuran, dimethyl sulfoxide, methanol, ethanol and propyl alcohol.

[0021] The application further provides a preparation method of a metasilicate composite powder, including the following steps:

[0022] S1: mixing the roemerine silane in claim 1 with an organic solvent to obtain a second solution;

[0023] S2: mixing the second solution with a metasilicate slurry to react, to obtain a metasilicate composite powder.

[0024] Preferably, the concentration of the second solution in S1 is 1-5 mol / L; the temperature of the mixing in S1 is 25-50 DEG C, and the time is 10-180 min.

[0025] Preferably, the mass molar ratio of metasilicate to cloud base silane in the metasilicate slurry in S2 is 1-20 kg:1 mol; the concentration of the metasilicate slurry is 1-5 kg / L.

[0026] Preferably, the mixing in S2 is spraying the second solution into the metasilicate slurry, the spraying rate of the second solution into the metasilicate slurry is 1-30 mL / min, and the temperature is 25-45 DEG C; the temperature of the reaction in S2 is 50-95 DEG C, the temperature rising rate is 5-30 DEG C / h, and the time is 0.2-6.0 h.

[0027] Preferably, the organic solvent comprises one or more of N,N-dimethylformamide, ethyl acetate, dimethyl sulfoxide and tetrahydrofuran; the median particle size D50 of the metasilicate in the metasilicate slurry is 1.0-4.0 mu m; the dispersing liquid in the metasilicate slurry comprises one or more of methanol, ethylene glycol, ethanol, propanol, n-butanol, isopropyl alcohol, neopentyl alcohol and isopropyl alcohol; and the metasilicate comprises natural calcareous metasilicate. 50 Preferably, the organic solvent comprises one or more of N,N-dimethylformamide, ethyl acetate, dimethyl sulfoxide and tetrahydrofuran; the median particle size D50 of the metasilicate in the metasilicate slurry is 1.0-4.0 mu m; the dispersing liquid in the metasilicate slurry comprises one or more of methanol, ethylene glycol, ethanol, propanol, n-butanol, isopropyl alcohol, neopentyl alcohol and isopropyl alcohol; and the metasilicate comprises natural calcareous metasilicate.

[0028] The application further provides a metasilicate composite powder prepared by the preparation method of the metasilicate composite powder.

[0029] According to the technical solution, compared with the prior art, the application has the following beneficial effects:

[0030] 1. The application adopts natural product cloud base silane and aromatic bromosilane to obtain cloud base silane (BMPMMP) through one-step substitution reaction, the cloud base silane (BMPMMP) is a nitrogen hetero large conjugate silane compound, the large conjugate nitrogen hetero borate in the metasilicate composite powder modified by the nitrogen hetero large conjugate silane compound has a polycyclic conjugate aromatic ring structure, low surface energy, can effectively shield the hydroxyl group on the surface of the natural calcareous metasilicate mineral powder, reduce the surface polarity, and reduce the oil absorption value of the natural mineral powder; at the same time, the cloud base silane as a low-polarity natural product post-modifier can greatly save the processing cost after modifying the natural metasilicate, effectively improve the dispersibility of the obtained metasilicate composite powder in the polyolefin matrix, promote the high value and functionality of the natural mineral powder, and the whole preparation process can be prepared by one-step method, which is suitable for large-scale industrial production.

[0031] 2. The metasilicate composite powder (BMPMMP-NMS) described in the application is a white artificial functionalized natural inorganic composite powder with a core-shell structure, and is a restructured product of multiple natural products (psilocin and natural calcareous silicate). The BMPMMP-NMS has excellent chemical stability, a low oil absorption value, high dispersibility, good carbon formation and reinforcement and toughening properties, and can be added to a polymer matrix as a multifunctional composite filler to achieve the effects of filling, reinforcement, toughening and carbon formation promotion. The application range of natural mineral powder can be effectively expanded, and the natural mineral powder can play a role in more fields and exhibit greater value.

[0032] 3. The BMPMMP-NMS described in the application contains N elements and Si elements on the outside of the core-shell structure, and these elements can better improve the flame retardant effect. The large conjugated aromatic ring on the surface can effectively form carbon during the combustion process. The natural calcareous metasilicate in the core-shell structure has strong stability and a certain aspect ratio, which can effectively improve the tear resistance and tensile resistance of the composite material. During the combustion process, a large amount of carbon can be attached to the internal calcareous metasilicate skeleton to form a reinforced carbon layer with excellent thermal stability and strong impact resistance, which is beneficial to strengthening the physical barrier effect. The internal and external synergistic effect can effectively improve the flame retardant, carbon formation and smoke suppression properties of the BMPMMP-NMS material, and greatly expand the functionality of the BMPMMP-NMS material. BRIEF DESCRIPTION OF DRAWINGS

[0033] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed in the embodiments or prior art description will be briefly introduced below. Obviously, the drawings in the following description are only embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor on the basis of the provided drawings.

[0034] Figure 1 The structure schematic diagram of the metasilicate composite powder (BMPMMP-NMS) prepared in Example 1.

[0035] Figure 2 The particle size distribution diagram of the metasilicate composite powder (BMPMMP-NMS) prepared in Example 1.

[0036] Figure 3 The SEM diagram of the metasilicate composite powder (BMPMMP-NMS) prepared in Example 1. DETAILED DESCRIPTION

[0037] The present application provides a psilocin silane, and the structural formula of the psilocin silane is shown as formula I:

[0038]

[0039] The present application also provides a preparation method of the silane of yohimbine, comprising the following steps:

[0040] 1) mixing the solution of yohimbine with the alcohol solution of inorganic salt to obtain a first solution;

[0041] 2) mixing the first solution with the solution of aromatic bromosilane to carry out substitution reaction to obtain the silane of yohimbine;

[0042] The structural formula of yohimbine in the solution of yohimbine is shown as formula II:

[0043]

[0044] The structural formula of aromatic bromosilane in the solution of aromatic bromosilane is shown as formula III:

[0045]

[0046] In the present application, the molecular formula of the silane of yohimbine is C 24 H 28 N2O2Si, and the relative molecular mass is 404.19.

[0047] In the present application, the alcohol solution of inorganic salt in step 1) is a dispersion liquid of inorganic salt.

[0048] In the present application, the molar ratio of yohimbine in the solution of yohimbine to inorganic salt in the alcohol solution of inorganic salt in step 1) is 1:1-5, preferably 1:2-4, and more preferably 1:3; the concentration of the solution of yohimbine is 1-3 mol / L, preferably 2 mol / L; and the concentration of the dispersion liquid of inorganic salt is 1-5 mol / L, preferably 2-4 mol / L, and more preferably 3 mol / L.

[0049] In the present application, the mixing in step 1) is to drop the solution of yohimbine into the alcohol solution of inorganic salt, the dropping rate is 5 mL / s-1 mL / s, preferably 4 mL / s-2 mL / s, and more preferably 3 mL / s; the mixing temperature is preferably room temperature; the stirring speed of the mixing is preferably 100-1200 rpm, further preferably 150-1000 rpm, and more preferably 200-500 rpm; and the mixing time is preferably 1-18 h, further preferably 5-15 h, and more preferably 10-12 h.

[0050] In the present application, the molar ratio of aromatic bromosilane in the solution of aromatic bromosilane to yohimbine in the solution of yohimbine in step 2) is 1-3:1, and preferably 2:1; and the concentration of the solution of aromatic bromosilane is 1-3 mol / L, and preferably 2 mol / L.

[0051] In the present application, the preparation method of the aromatic bromosilane solution in step 2) is preferably dissolving the aromatic bromosilane in a solvent; the stirring speed of the dissolving is preferably 100-700 rpm, further preferably 150-650 rpm, more preferably 200-450 rpm; the time of the dissolving is preferably 1-12 h, further preferably 2-10 h, more preferably 5-8 h.

[0052] In the present application, the mixing in step 2) is dropping the aromatic bromosilane solution into the first solution, the dropping rate is 5-1 mL / s, preferably 4-2 mL / s, more preferably 3 mL / s; the temperature of the substitution reaction in step 2) is 55-100℃, preferably 60-90℃, further preferably 65-85℃, more preferably 70-80℃; the temperature rising rate is 5-20℃ / h, preferably 6-18℃ / h, further preferably 8-15℃ / h, more preferably 10-13℃ / h; the time is 1-24 h, preferably 2-20 h, further preferably 3-15 h, more preferably 5-10 h.

[0053] In the present application, the temperature of the mixing in step 2) is preferably room temperature; the stirring speed of the mixing is preferably 100-1600 rpm, further preferably 200-1200 rpm, more preferably 300-500 rpm.

[0054] In the present application, after the substitution reaction in step 2) ends, it is further preferably including the operation of centrifugal washing and drying.

[0055] In the present application, the centrifugal washing is preferably placing the yunnanshuang silane in a centrifugal tube for centrifugal treatment; the solid content of the centrifugal treatment is preferably 0.1-1 g / mL, further preferably 0.2-0.8 g / mL, more preferably 0.3-0.5 g / mL; the centrifugal speed of the centrifugal treatment is preferably 1000-10000 r / min, further preferably 1500-9500 r / min, more preferably 2000-7000 r / min; the centrifugal time of the centrifugal treatment is preferably 5-60 min, further preferably 10-50 min, more preferably 20-30 min; the centrifugal frequency of the centrifugal treatment is preferably 1-5 times, further preferably 2-4 times, more preferably 3 times.

[0056] In the present application, the drying is preferably drying the centrifuged yohimbine silane in a vacuum oven; the temperature of the drying is preferably 25-60℃, further preferably 30-55℃, more preferably 35-40℃; the time of the drying is preferably 1-48h, further preferably 5-40h, more preferably 10-35h; the power of the drying is preferably 100-500W, further preferably 150-400W, more preferably 200-300W.

[0057] In the present application, the inorganic salt includes one or several of sodium carbonate, cesium carbonate, sodium bicarbonate, potassium carbonate, calcium carbonate, magnesium hydroxide and aluminum hydroxide; the alcohol in the alcohol solution of the inorganic salt includes one or several of ethanol, methanol, n-butanol, ethylene glycol, neopentyl alcohol, isopropyl alcohol and propyl alcohol; the solvent in the yohimbine solution and the solvent in the aromatic bromosilane solution independently includes one or several of water, N,N-dimethylformamide, ethyl acetate, tetrahydrofuran, dimethyl sulfoxide, methanol, ethanol and propyl alcohol.

[0058] The present application also provides a preparation method of metasilicate composite powder, comprising the following steps:

[0059] S1: mixing the yohimbine silane in claim 1 with an organic solvent to obtain a second solution;

[0060] S2: mixing the second solution with a metasilicate slurry to react, to obtain metasilicate composite powder.

[0061] In the present application, the concentration of the second solution in S1 is 1-5mol / L, preferably 2-4mol / L, more preferably 3mol / L; the temperature of the mixing in S1 is 25-50℃, preferably 28-45℃, further preferably 30-42℃, more preferably 35-40℃; the time is 10-180min, preferably 15-150min, further preferably 20-120min, more preferably 30-80min; the rotating speed of the mixing is preferably 100-800rpm, further preferably 200-700rpm, more preferably 300-500rpm.

[0062] In the present application, the mass molar ratio of metasilicate to yohimbine silane in the metasilicate slurry in S2 is 1-20kg:1mol, preferably 3-15kg:1mol, further preferably 5-12kg:1mol, more preferably 8-10kg:1mol; the concentration of the metasilicate slurry is 1-5kg / L, preferably 1.5-4kg / L, further preferably 2-3.5kg / L, more preferably 2.5-3kg / L.

[0063] In the present application, when the mass molar ratio of metasilicate in the metasilicate slurry to the benzylated methyl methylsilane is higher than 20 kg: 1 mol, the amount of the benzylated methyl methylsilane (BMPMMP) added is too low, it is difficult to effectively modify and surface modify the metasilicate, and it is also difficult to effectively reduce the polarity of the surface of the metasilicate; and when the mass molar ratio of metasilicate in the metasilicate slurry to the benzylated methyl methylsilane is lower than 1 kg: 1 mol, the benzylated methyl methylsilane (BMPMMP) is enriched on the surface of the metasilicate, and even most of the benzylated methyl methylsilane is adsorbed on the surface of the composite powder, and the metasilicate particles may be wrapped together, causing the particle size of part of the powder to increase, and further causing the dispersion effect of the composite powder in the polyolefin elastomer matrix to be poor due to the poor wrapping effect in the processing process.

[0064] In the present application, the preparation step of the metasilicate slurry in S2 is preferably adding the dispersion liquid to the metasilicate for stirring and infiltration; the stirring speed is preferably 500-2000 rpm, further preferably 550-1500 rpm, and more preferably 650-1000 rpm; the stirring time is preferably 1-12 h, 2-10 h, and more preferably 5-8 h; and the stirring temperature is preferably 25-80℃, further preferably 30-60℃, and more preferably 35-50℃.

[0065] In the present application, the mixing in S2 is spraying the second solution into the metasilicate slurry, the spraying rate of the second solution into the metasilicate slurry is 1-30 mL / min, preferably 3-28 mL / min, further preferably 5-25 mL / min, and more preferably 10-20 mL / min; the temperature is 25-45℃, preferably 28-42℃, further preferably 30-40℃, and more preferably 32-38℃; the reaction temperature in S2 is 50-95℃, preferably 55-90℃, further preferably 60-85℃, and more preferably 65-70℃; the temperature rising rate is 5-30℃ / h, preferably 10-25℃ / h, further preferably 12-20℃ / h, and more preferably 15-18℃ / h; the time is 0.2-6.0 h, preferably 0.5-5.0 h, further preferably 0.8-4.5 h, and more preferably 1.0-3.0 h; and the stirring rate of the reaction is preferably 1000-3000 r / min, further preferably 1200-2500 r / min, and more preferably 1500-2000 r / min.

[0066] In the present application, the organic solvent includes one or more of N,N-dimethylformamide, ethyl acetate, dimethyl sulfoxide, and tetrahydrofuran; the median particle size D 50is 1.0-4.0 μm, preferably 1.2-3.6 μm, further preferably 1.5-3.0 μm, more preferably 2.0-2.5 μm; the dispersion liquid in the metasilicate slurry comprises one or more of methanol, ethylene glycol, ethanol, propanol, n-butanol, isopropanol, neopentyl alcohol, and isopropanol; and the metasilicate comprises natural calcareous metasilicate.

[0067] In the present application, after the reaction in S2 is completed, operations of suction filtration, centrifugation, precipitation, and drying are further preferably included.

[0068] In the present application, the suction filtration is preferably vacuum distillation of the metasilicate composite powder to remove the organic solvent, and ethanol suction filtration washing is added; the pressure of the vacuum distillation is preferably -0.07 to -0.09 MPa, more preferably -0.08 MPa; the filter paper of the suction filtration washing is preferably rapid filter paper; the number of layers of the rapid filter paper is preferably 1-3 layers, more preferably 2 layers; and the number of times of the suction filtration washing is preferably 1-5 times, further preferably 2-4 times, more preferably 3 times.

[0069] In the present application, the centrifugation is preferably centrifugation treatment of the metasilicate composite powder after suction filtration in a centrifuge; the solvent of the centrifugation treatment is preferably water; the solid content of the centrifugation treatment is preferably 1-30 mg / mL, further preferably 5-25 mg / mL, more preferably 10-20 mg / mL; the rate of the centrifugation treatment is preferably 1000-10000 r / min, further preferably 2000-8000 r / min, more preferably 3000-5000 r / min; and the time of the centrifugation treatment is preferably 5-60 min, further preferably 10-50 min, more preferably 20-30 min.

[0070] In the present application, the temperature of the precipitation is preferably 1-15 ℃, further preferably 2-12 ℃, more preferably 5-10 ℃; and the solid content of the precipitation is preferably 1-50 mg / mL, further preferably 5-45 mg / mL, more preferably 10-25 mg / mL.

[0071] In the present application, the drying is preferably flash drying; the temperature of the drying is preferably 90-160 ℃, further preferably 100-150 ℃, more preferably 120-130 ℃; and the time of the drying is preferably 1-45 min, further preferably 5-40 min, more preferably 10-25 min.

[0072] The present application further provides a metasilicate composite powder prepared by the above method.

[0073] In the present application, the metasilicate composite powder has a median particle size (D50 ) is 1.0-4.0 μm, preferably 1.2-3.6 μm, further preferably 1.5-3.0 μm, and more preferably 2.0-2.5 μm; and the metasilicate composite powder is a white powder.

[0074] The technical solutions provided by the present application are described in detail below in conjunction with examples, but they should not be understood as limiting the scope of protection of the present application.

[0075] Example 1

[0076] 1. 212.25 g of ephedrine was mixed with methanol to obtain a ephedrine solution with a concentration of 2 mol / L, and 210.0 g of sodium bicarbonate was dispersed in ethanol to obtain a sodium bicarbonate dispersion solution with a concentration of 2.5 mol / L, then the ephedrine solution was added to the sodium bicarbonate dispersion solution at a dropping rate of 3 mL / s, and then stirred at a stirring rate of 1000 rpm at room temperature (25℃) for 6 h to obtain a first solution;

[0077] 2. 546.48 g of aromatic bromosilane was dissolved in propyl alcohol and stirred at a stirring rate of 300 rpm for 8 h to obtain an aromatic bromosilane solution with a concentration of 2 mol / L; then the aromatic bromosilane solution was added to the first solution at a dropping rate of 3 mL / s at room temperature (25℃) and a stirring rate of 1000 rpm, and then heated to 80℃ at a heating rate of 10℃ / h, and a substitution reaction was carried out for 10 h; after the reaction was completed, the product was placed in a centrifugal tube, the solid content was controlled to be 0.5 g / mL, and centrifugal treatment was carried out at a centrifugal rate of 6000 r / min for 30 min; after centrifugal treatment for 3 times, the product was placed in a vacuum oven and dried at a temperature of 40℃ and a power of 300 W for 24 h to obtain ephedrine silane (BMPMMP);

[0078] 3. 404.19 g of ephedrine silane was mixed with a solution of N,N-dimethylformamide and ethyl acetate with a volume ratio of 1:1, the mixing temperature was controlled to be 30℃, the stirring rate was 400 rpm, and the mixing time was 100 min to obtain a second solution with a concentration of 2 mol / L;

[0079] 4. Ethanol was added to 10 kg of medium particle size D 50For 1.6 μm natural calcareous metasilicate (NMS), fully stirring infiltration, control the stirring rate to be 1000 rpm, the stirring time to be 6 h, the stirring temperature to be 45℃, and the concentration of the metasilicate slurry to be 2 kg / L; then the second solution is added to the metasilicate slurry in the form of spraying, wherein the spraying rate is 15 mL / min, the spraying temperature is 30℃, and the temperature is raised to 75℃ at a temperature raising rate of 15℃ / h, and the reaction is carried out at a stirring rate of 2000 r / min for 2.5 h; then the product is removed of the organic solvent at a pressure of -0.09 MPa, and ethanol is added for repeated suction filtration and washing 3 times, wherein the filter paper for suction filtration and washing is 2 layers of quick filter paper; then the product after suction filtration and washing is placed in a centrifuge, deionized water is added, and the solid content is controlled to be 20 mg / mL, the centrifugal rate is 6000 r / min, and the centrifugal treatment is carried out for 30 min; then the precipitation is carried out at a temperature of 10℃, the solid content is controlled to be 30 mg / mL, and finally the drying is carried out at a temperature of 120℃ for 25 min, and the metasilicate composite powder (BMPMMP-NMS) is obtained.

[0080] It is detected that the structure diagram of the metasilicate composite powder BMPMMP-NMS obtained in the embodiment is as shown in Figure 1 From Figure 1 It can be seen that the surface of the metasilicate composite powder obtained in the embodiment is attached with a layer of functional outer layer modified by the benzyl protected metformin silane (BMPMMP), wherein the natural calcareous sheet silicate is a micro-fiber with a certain aspect ratio, and the BMPMMP uniformly covers the surface of the natural calcareous metasilicate powder to form a better core-shell structure.

[0081] The particle size distribution diagram of the metasilicate composite powder obtained in the embodiment is as shown in Figure 2 From Figure 2 It can be seen that the particle size distribution of the metasilicate composite powder prepared in the embodiment is relatively uniform, presents a unimodal shape, and is concentrated near 1.8 μm.

[0082] The SEM diagram of the metasilicate composite powder obtained in the embodiment is as shown in Figure 3 From Figure 3 It can be seen that the surface of the metasilicate composite powder obtained in the embodiment exists a sheet-shaped wrapper, and the sheet-shaped wrapper is uniformly dispersed on the surface of the metasilicate composite powder, and the overall modification effect is good.

[0083] Example 2

[0084] 1. 212.25 g of the meat leaf cloud base was mixed with ethanol to obtain a solution of the meat leaf cloud base with a concentration of 1 mol / L, and 106.00 g of sodium carbonate was dispersed in ethylene glycol to obtain a dispersion of sodium carbonate with a concentration of 1 mol / L, then the meat leaf cloud base solution was added to the sodium carbonate dispersion at a drop rate of 1 mL / s, and then stirred at room temperature (25°C) at a stirring rate of 1200 rpm for 1 h to obtain a first solution;

[0085] 2. 273.24 g of aromatic bromosilane was mixed with propanol and stirred at a stirring rate of 100 rpm for 12 h to obtain an aromatic bromosilane solution with a concentration of 1 mol / L; then the aromatic bromosilane solution was added to the first solution at a drop rate of 1 mL / s at room temperature (25°C) and a stirring rate of 1600 rpm, and then heated to 55°C at a heating rate of 5°C / h, and a substitution reaction was carried out for 1 h; after the reaction was completed, the product was placed in a centrifuge tube, the solid content was controlled to be 0.1 g / mL, and centrifugal treatment was carried out at a centrifugal rate of 1000 r / min for 60 min; after the centrifugal treatment was carried out once, the product was placed in a vacuum oven and dried at a temperature of 25°C and a power of 100 W for 48 h to obtain a cloud base silane (BMPMMP);

[0086] 3. 404.19 g of the cloud base silane was mixed with a solution of ethyl acetate and dimethyl sulfoxide with a volume ratio of 1:1, the temperature of the mixture was controlled to be 25°C, the stirring rate was 800 rpm, and the mixing time was 10 min to obtain a second solution with a concentration of 1 mol / L;

[0087] 4. Methanol was added to 1 kg of natural calcareous metasilicate (NMS) with a median particle size D 50 of 1.6 μm, the stirring was fully infiltrated, the stirring rate was controlled to be 500 rpm, the stirring time was 12 h, and the stirring temperature was 25°C to obtain a metasilicate slurry with a concentration of 1 kg / L; then the second solution was added to the metasilicate slurry in the form of spraying, wherein the spraying rate was 1 mL / min and the spraying temperature was 25°C; then the temperature was increased to 50°C at a heating rate of 5°C / h, and the reaction was carried out at a stirring rate of 3000 r / min for 6.0 h; then the organic solvent was removed from the product at a pressure of -0.09 MPa, and ethanol was added for repeated filtration and washing once, wherein the filter paper for filtration and washing was 3 layers of quick filter paper; then the product after filtration and washing was placed in a centrifuge, deionized water was added, and the solid content was controlled to be 1 mg / mL, and centrifugal treatment was carried out at a centrifugal rate of 1000 r / min for 60 min; then the product was precipitated at a temperature of 1°C and the solid content was controlled to be 1 mg / mL, and finally the product was dried at a temperature of 90°C for 45 min to obtain a metasilicate composite powder (BMPMMP-NMS).

[0088] Example 3

[0089] 1. Mix 212.25 g of the meat leaf cloud magnolia alkaline with ethanol to obtain a solution of the meat leaf cloud magnolia alkaline with a concentration of 3 mol / L, and disperse 500.0 g of calcium carbonate in n-butanol to obtain a dispersion of the calcium carbonate with a concentration of 5 mol / L, then add the solution of the meat leaf cloud magnolia alkaline to the dispersion of the calcium carbonate at a drop rate of 5 mL / s, and then stir at a stirring rate of 100 rpm at room temperature (25 °C) for 18 h to obtain a first solution;

[0090] 2. Mix 819.72 g of the aromatic bromosilane with ethyl acetate to obtain a solution of the aromatic bromosilane with a concentration of 3 mol / L, and stir at a stirring rate of 700 rpm for 1 h, then add the solution of the aromatic bromosilane to the first solution at a drop rate of 5 mL / s at room temperature (25 °C) and a stirring rate of 100 rpm, and then heat to 100 °C at a heating rate of 20 °C / h, and carry out a substitution reaction for 24 h, after the reaction is completed, place the product in a centrifuge tube, control the solid content to be 1 g / mL, and centrifuge at a centrifugal speed of 10,000 r / min for 5 min, after centrifugation for 5 times, place the product in a vacuum oven, and dry at a temperature of 60 °C and a power of 500 W for 1 h to obtain a cloud magnolia alkaline silane (BMPMMP);

[0091] 3. Mix 404.19 g of the cloud magnolia alkaline silane with a solution of ethyl acetate and tetrahydrofuran in a volume ratio of 1:1, control the mixing temperature to be 50 °C, the stirring rate to be 100 rpm, and the mixing time to be 180 min to obtain a second solution with a concentration of 5 mol / L;

[0092] 4. Add ethylene glycol to 20 kg of natural calcareous metasilicate (NMS) with a medium particle size D 50 of 1.6 μm, fully stir to soak, control the stirring rate to be 2,000 rpm, the stirring time to be 1 h, and the stirring temperature to be 80 °C to obtain a metasilicate slurry with a concentration of 5 kg / L, then add the second solution to the metasilicate slurry in the form of spraying, wherein the spraying rate is 30 mL / min, the spraying temperature is 45 °C, and the temperature is then raised to 95 °C at a heating rate of 30 °C / h, and the reaction is carried out at a stirring rate of 1,000 r / min for 0.2 h, then remove the organic solvent at a pressure of -0.09 MPa, and add ethanol to repeatedly filter and wash 5 times, wherein the filter paper for filter and washing is 1 layer of quick filter paper, then place the product after filter and washing in a centrifuge, add deionized water and control the solid content to be 30 mg / mL, and centrifuge at a centrifugal speed of 10,000 r / min for 5 min, then precipitate at a temperature of 15 °C and control the solid content to be 50 mg / mL, and finally dry at a temperature of 160 °C for 1 min to obtain a metasilicate composite powder (BMPMMP-NMS).

[0093] Comparative Example 1

[0094] The only difference between Comparative Example 1 and Example 1 is that the amount of cloudine silane (BMPMMP) added in Step 3 is 202.10 g; and the amount of natural calcareous metasilicate (NMS) added in Step 4 is 20 kg.

[0095] Comparative Example 2

[0096] The only difference between Comparative Example 2 and Example 1 is that the amount of cloudine silane (BMPMMP) added in Step 3 is 606.29 g; and the amount of natural calcareous metasilicate (NMS) added in Step 4 is 1 kg.

[0097] Experimental Example 1

[0098] The metasilicate composite powder (BMPMMP-NMS) prepared in Examples 1-3, the metasilicate composite powder (BMPMMP-NMS) prepared in Comparative Examples 1-2, and the natural calcareous metasilicate (NMS) without any modification are subjected to activation rate and oil absorption value tests, and the test results are shown in Table 1.

[0099] The activation rate is tested by weighing the dry powder;

[0100] The oil absorption value is tested according to the standard of DB / T5211.15-2014.

[0101] Table 1 Test results of activation rate and oil absorption value

[0102]

[0103] As can be seen from Table 1, through the test results of Examples 1-3 and the natural calcareous metasilicate (NMS) without any modification, the activation rate of the metasilicate composite powder BMPMMP-NMS after the metasilicate is hybridized by BMPMMP is significantly increased from the original 23.4% to 96.3%, indicating that BMPMMP can greatly improve the surface polarity of natural calcareous metasilicate. Moreover, the oil absorption value of the metasilicate composite powder is also significantly reduced, indicating that the metasilicate composite powder modified by BMPMMP can effectively shield the surface hydroxyl group of natural calcareous metasilicate, significantly reduce its polarity, and greatly reduce the processing cost. As can be seen from the test results of Comparative Examples 1-2, when the mass molar ratio of metasilicate to BMPMMP in the metasilicate slurry is higher than 20 kg: 1 mol, i.e. the addition amount of BMPMMP is too low, the final shielding effect is general, and the modification effect on the natural calcareous metasilicate powder is poor. When the mass molar ratio of metasilicate to BMPMMP in the metasilicate slurry is lower than 1 kg: 1 mol, i.e. the addition amount of BMPMMP is too high, too much BMPMMP may wrap multiple natural calcareous metasilicate particles together, so that the excess BMPMMP is adsorbed on the surface and may fall off or peel off during the processing, resulting in poor final modification effect. In summary, after the addition of BMPMMP, the activation rate and oil absorption value of the composite powder can be significantly improved, which is beneficial to the functional performance of the composite powder and the improvement of compatibility and dispersibility.

[0104] Experimental Example 2

[0105] The metasilicate composite powder (BMPMMP-NMS) prepared in Examples 1-3 and Comparative Examples 1-2 and the natural calcareous metasilicate (NMS) without any modification were added to the polyolefin elastomer. Specifically, the hydrogenated styrene-butadiene block copolymer SEBS (60 parts) was mixed with white oil (8 parts) for 5 min, and then 1:1 antioxidant 1010 and antioxidant 1076 (1 part), lubricant silicone lubricating ester (1 part) and BMPMMP-NMS (or natural calcareous metasilicate NMS without any modification) 40 parts were added in sequence, and the mixture was mixed at a temperature of 170°C for 7 min to obtain six polyolefin elastomer composite material samples. The mechanical properties, carbon residue rate and melt index of the six composite material samples were tested. The test results are shown in Table 2.

[0106] Among them, the mechanical property test: according to GB / T 528-2009, the butadiene rubber composite material was prepared into a corresponding test sample, and the tensile strength and elongation at break were tested.

[0107] Residual carbon rate test: The ratio of residual carbon mass and initial mass was measured at 600℃ with a heating rate of 10℃ / min under nitrogen atmosphere.

[0108] Melt index test: The test condition was controlled according to the standard of American ASTM D1238, the temperature was 190℃, the pressure was 2.16kg, and the test time was 10min.

[0109] Table 2: Test results of mechanical and carbonization properties of composite samples

[0110]

[0111]

[0112] As can be seen from Table 2, the test results of the composite samples prepared by Comparative Examples 1-3 and natural calcareous metasilicate (NMS) without any modification (NMS) show that when the composite powder hybridized by yunnanocaine silane BMPMMP is added to the polyolefin elastomer, the elongation at break of the polyolefin elastomer increases significantly, and the tensile strength is significantly improved, with the highest increase from 11.28MPa to 24.75MPa. Furthermore, the residual carbon rate of Examples 1-3 also increases significantly, from 14wt% to about 31wt%, and the melt index also increases significantly, indicating that the introduction of BMPMMP can effectively improve the surface properties of natural calcareous metasilicate powder, making its dispersion in the polyolefin elastomer better, and significantly improving the mechanical properties of the composite material.

[0113] BMPMMP itself has a large conjugated aromatic ring, which can significantly improve its carbonization property as the heat rises, which helps to improve the physical barrier property in the combustion process, and better plays the condensed phase barrier effect, effectively inhibiting the volatilization of smoke and flammable molecular chain fragments. In addition, the introduction of low-polarity BMPMMP can also significantly improve the processing fluidity of the composite material, which may be due to the reduction of the surface energy of natural calcareous metasilicate, so that the composite powder can play a certain internal lubrication effect during the processing process; however, when the mass molar ratio of metasilicate to BMPMMP in the metasilicate slurry is too high or too low (Comparative Examples 1-2), the mechanical property improvement effect of the polyolefin elastomer is general, which may be due to the poor modification effect of BMPMMP on the natural calcareous metasilicate powder.

[0114] When the mass molar ratio of metasilicate in metasilicate slurry to BMPMMP is too high, the surface energy decreases limitedly; when it is too low, multiple natural calcareous metasilicate powders may be wrapped together, causing passive increase of particle size, and the BMPMMP on the surface is easy to fall off in the processing process, and the dispersibility and compatibility cannot be effectively improved, at the same time, the carbonization of the polyolefin elastomer composite is also limitedly improved, which may be because the BMPMMP on the surface cannot well play the synergistic carbonization effect with the natural calcareous metasilicate, and it is difficult to form a co-force to promote carbonization, not only that, the melt index also generally increases, indicating that when the BMPMMP is too low or too high, the composite powder is not good at improving the processing fluidity of the polyolefin elastomer, which is closely related to the poor dispersibility and compatibility caused by the surface energy. The above results show that the introduction of BMPMMP can improve the mechanical properties, carbonization and processing fluidity of the composite powder in the polyolefin elastomer, effectively improve the application value and application potential of the composite powder, and also can develop multiple functional powders suitable for polyolefin elastomer.

[0115] The above only describes the preferred embodiments of the present application, and it should be pointed out that for ordinary skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A silane for yunnano, characterized in that, The structural formula of the silane in the alkaloid is shown in Formula I:

2. A method for preparing the silane of styrax as described in claim 1, characterized in that, Includes the following steps: 1) Mix the solution of caryophyllum alkaloid with an alcoholic solution of inorganic salt to obtain the first solution; 2) The first solution was mixed with an aromatic bromosilane solution to carry out a substitution reaction, yielding styraxine silane; The structural formula of the myristin in the myristin solution is shown in Formula II: The structural formula of the aromatic bromosilane in the aromatic bromosilane solution is shown in Formula III:

3. The method for preparing a silane of styrax alkaloid according to claim 2, characterized in that, In step 1), the molar ratio of myristica fragrans alkaloid in the myristica fragrans alkaloid solution to the inorganic salt in the alcoholic solution of the inorganic salt is 1:1 to 5. The concentration of the myrobalanine solution is 1–3 mol / L; The concentration of the alcoholic solution of the inorganic salt is 1–5 mol / L; The mixing described in step 1) involves adding a solution of physalisine to an alcoholic solution of inorganic salts at a rate of 5 mL / s to 1 mL / s.

4. The method for preparing a silane according to any one of claims 1 to 3, characterized in that, In step 2), the molar ratio of aromatic bromosilane in the aromatic bromosilane solution to myristophylline in the myristophylline solution is 1 to 3:

1. The concentration of the aromatic bromosilane solution is 1–3 mol / L; The mixing described in step 2) involves adding an aromatic bromosilane solution dropwise to the first solution at a rate of 5 mL / s to 1 mL / s. The substitution reaction in step 2) is carried out at a temperature of 55–100°C, a heating rate of 5–20°C / h, and a time of 1–24h.

5. The method for preparing a silane of styrax alkaloid according to claim 4, characterized in that, The inorganic salt in the alcohol solution of the inorganic salt includes one or more of sodium carbonate, cesium carbonate, sodium bicarbonate, potassium carbonate, calcium carbonate, magnesium hydroxide, and aluminum hydroxide. The alcohol in the inorganic salt alcohol solution includes one or more of ethanol, methanol, n-butanol, ethylene glycol, neopentyl alcohol, isopropanol, and propanol; The solvents in the *Lysimachia foenum-graecum* alkaloid solution and the aromatic bromosilane solution independently include one or more of water, N,N-dimethylformamide, ethyl acetate, tetrahydrofuran, dimethyl sulfoxide, methanol, ethanol, and propanol.

6. A method for preparing metasilicate composite powder, characterized in that, Includes the following steps: S1: Mix the silane of cinnamic acid described in claim 1 with an organic solvent to obtain a second solution; S2: Mix the second solution with the metasilicate slurry and react to obtain metasilicate composite powder.

7. The method for preparing a metasilicate composite powder according to claim 6, characterized in that, The concentration of the second solution in S1 is 1–5 mol / L; The mixing temperature in S1 is 25–50°C, and the mixing time is 10–180 min.

8. The method for preparing a metasilicate composite powder according to claim 7, characterized in that, The mass molar ratio of metasilicate to silane in the metasilicate slurry described in S2 is 1-20 kg: 1 mol. The concentration of the metasilicate slurry is 1–5 kg / L; The mixing described in S2 involves spraying the second solution into the metasilicate slurry at a rate of 1–30 mL / min and at a temperature of 25–45 °C. The reaction described in S2 is carried out at a temperature of 50–95°C, a heating rate of 5–30°C / h, and a time of 0.2–6.0h.

9. A method for preparing a metasilicate composite powder according to any one of claims 6 to 8, characterized in that, The organic solvent includes one or more of N,N-dimethylformamide, ethyl acetate, dimethyl sulfoxide, and tetrahydrofuran; The median particle size D of the metasilicate in the metasilicate slurry 50 Its thickness ranges from 1.0 to 4.0 μm; The dispersion in the metasilicate slurry includes one or more of methanol, ethylene glycol, ethanol, propanol, n-butanol, isopropanol, neopentyl alcohol, and isopropanol. The metasilicates include natural calcium metasilicates.

10. The metasilicate composite powder prepared by the method for preparing metasilicate composite powder according to any one of claims 6 to 9.

Images