A cinnamic acid derivative, its preparation method and application, and a hydromagnesite composite powder, its preparation method and application

Abstract

The present invention belongs to the technical field of functional materials, and provides a cinnamic acid derivative, a preparation method and application thereof, and a hydromagnesite composite powder, a preparation method and application thereof, comprising the following steps: reacting a solution of the cinnamic acid derivative, a solution of hydromagnesite and an inorganic powder to obtain the hydromagnesite composite powder. The preparation process provided by the present invention does not require large-scale equipment and has low energy consumption, which conforms to the current popular low-carbon environmental protection strategy. In addition, the cinnamic acid derivative can greatly reduce the oil absorption value of the powder, which is beneficial to reducing the consumption of additives and resins during processing, and also helps to improve the interfacial bonding strength in the polymer matrix. The hydromagnesite composite powder D provided by the present invention 50 are all maintained in the range of 1.6 - 2.0 μm, and the oil absorption values are all maintained in the range of 30 - 36 mL / 100 g.

Description

Technical Field

[0001] The present invention relates to the technical field of functional materials, and particularly to a cinnamic acid derivative, a preparation method and application thereof, and a hydromagnesite composite powder, a preparation method and application thereof. Background Art

[0002] The emerging energy revolution has greatly promoted the development and design of functional materials. In particular, the superfine and high-value application of traditional inorganic powders is the only way for many enterprises to transform and upgrade. The application of natural products (minerals) is becoming increasingly widespread in the new energy field. In particular, many common stone ores in nature can obtain extremely valuable subsidiary functions after simple processing and shaping. Hydromagnesite ore, as a basic magnesium carbonate, whose chemical structure is a complex of magnesium carbonate and magnesium hydroxide, has been tried in the fields of flame retardancy and smoke suppression. However, there are still many problems in its current application. For example, the mesh number is not high, making it difficult to meet the needs of fine applications, and it is difficult to be applied in many energy precision device fields. The actual dispersion effect and smoke suppression effect are limited, and even the surface of the product is rough, causing difficulties in processing. Secondly, there are a large number of hydroxyl groups and even bound water on its surface. With the increasing requirement of mesh number, its oil absorption value has even reached 60 mL / 100 g, which is very unfavorable for its application in the polymer matrix. Thirdly, its surface is slightly alkaline due to excessive polarity, and the exposed groups may have an adverse effect on the stability of the polymer matrix during processing and subsequent use. Based on this, designing and preparing an effective surface shielding layer to meet many requirements such as controllable cost, simple preparation, and large-scale application can greatly promote the rapid development of such stone ores.

[0003] Cinnamic acid, a natural aromatic product, is widely sourced and inexpensive, and is often used as a fragrance in food additives and the daily chemical and beauty industries. However, it is rarely used in the modification of stone ore powders and the fields of flame retardancy and smoke suppression. The high-value application of traditional powder materials is a long-term evolving proposition. Especially in the case where many natural stone ore materials cannot be quickly regenerated in a short time, how to apply them more efficiently, at low cost, and targeted is particularly important. Summary of the Invention

[0004] The purpose of the present invention is to provide a cinnamic acid derivative, a preparation method and application thereof, and a hydromagnesite composite powder, a preparation method and application thereof.

[0005] In order to achieve the above-mentioned invention purpose, the present invention provides the following technical solutions:

[0006] The present invention provides a cinnamic acid derivative, whose structure is shown in Formula I:

[0007]

[0008] The present invention also provides a preparation method of the cinnamic acid derivative, comprising the following steps:

[0009] Mix a 4-bromophenyl diphenylphosphine solution, a p-bromocinnamic acid solution, an inorganic powder, and a palladium bis(pinacolato)borate solution, and then carry out a reaction to obtain the cinnamic acid derivative.

[0010] Preferably, the solvents of the 4-bromophenyl diphenylphosphine solution and the p-bromocinnamic acid solution are independently methanol, ethanol, ethyl acetate, dimethyl sulfoxide, or N,N-dimethylformamide;

[0011] The concentration of the 4-bromophenyl diphenylphosphine solution is 1 to 20 mol / L;

[0012] The concentration of the p-bromocinnamic acid solution is 1 to 30 mol / L;

[0013] The molar ratio of 4-bromophenyl diphenylphosphine to p-bromocinnamic acid is 1:1 to 10;

[0014] The inorganic powder is one or more of sodium carbonate, calcium carbonate, cesium carbonate, and potassium carbonate;

[0015] The molar ratio of 4-bromophenyl diphenylphosphine to the inorganic powder is 1:1 to 100;

[0016] The palladium bis(pinacolato)borate solution contains bis(pinacolato)borane, a palladium source, and a solvent;

[0017] The molar ratio of bis(pinacolato)borane to 4-bromophenyl diphenylphosphine is 1 to 10:1;

[0018] The palladium source is palladium acetate, palladium chloride, tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloropalladium, di(triphenylphosphine)chloropalladium, di(benzonitrile)dichloropalladium, 1,4-bis(diphenylphosphino)butane-palladium chloride, bis(acetonitrile)dichloropalladium, bis(methyldiphenylphosphine)dichloropalladium, di(tritert-butylphosphine)palladium, or dichloro-bis(ditert-butylphenylphosphine)palladium;

[0019] The molar ratio of the palladium source to 4-bromophenyl diphenylphosphine is 0.005 to 0.1:1;

[0020] The solvent is one or more of N,N-dimethylformamide, tetrahydrofuran, ethanol, ethyl acetate, dimethyl sulfoxide, methanol, and acetonitrile.

[0021] Preferably, the temperature of the reaction is 25 to 100 °C, the stirring rate of the reaction is 500 to 1200 rpm, and the reaction time is 1 to 36 h.

[0022] The present invention also provides the application of the cinnamic acid derivative in the hydromagnesite composite powder.

[0023] The present invention also provides a hydromagnesite composite powder, which is prepared from raw materials comprising the following molar ratios:

[0024] A cinnamic acid derivative, hydromagnesite and an inorganic powder;

[0025] The molar ratio of the hydromagnesite to the cinnamic acid derivative is from 1:0.1 to 20;

[0026] The molar ratio of the inorganic powder to the cinnamic acid derivative is from 1 to 100:1.

[0027] The present invention also provides a preparation method of the hydromagnesite composite powder, which comprises the following steps:

[0028] Reacting a solution of the cinnamic acid derivative, a solution of hydromagnesite and the inorganic powder to obtain the hydromagnesite composite powder.

[0029] Preferably, the solvent of the solution of the cinnamic acid derivative is one or more of ethanol, methanol and ethyl acetate;

[0030] The concentration of the solution of the cinnamic acid derivative is from 1 to 40 M;

[0031] The solvent of the solution of the hydromagnesite is ethanol, methanol or water;

[0032] The concentration of the solution of the hydromagnesite is from 1 to 10 M.

[0033] Preferably, the stirring rate of the reaction is from 100 to 1200 rpm, the temperature of the reaction is from 25 to 60 °C, and the time of the reaction is from 1 to 24 h.

[0034] The present invention also provides the application of the hydromagnesite composite powder in energy devices.

[0035] The present invention has the following advantages:

[0036] The present invention provides a cinnamic acid derivative, the structure of which is shown in Formula I:

[0037]

[0038] The cinnamic acid derivative provided by the present invention contains P element, which endows the cinnamic acid derivative with excellent flame retardancy. The introduction of a large number of aromatic rings further expands the conjugated structure of the surface shielding layer molecules, which has a certain promoting effect on the charring performance during the combustion process.

[0039] The present invention also provides a method for preparing a cinnamic acid derivative, which comprises the following steps: mixing a 4-bromophenyl diphenylphosphine solution, a p-bromocinnamic acid solution, an inorganic powder, and a palladium bis(pinacolato)borane solution, and then carrying out a reaction to obtain the cinnamic acid derivative. The preparation method provided by the present invention is simple and easy to implement, and the raw materials are widely sourced and inexpensive.

[0040] The present invention also provides a hydromagnesite composite powder, which is prepared from raw materials with the following molar ratios: a cinnamic acid derivative, hydromagnesite, and an inorganic powder. Hydromagnesite is a composite of magnesium carbonate and magnesium hydroxide, with good thermal stability, capable of withstanding the processing temperatures of most polymer materials, effectively preventing its degradation during processing, having a wider decomposition temperature, and being able to exert effects in multiple stages during the degradation process. During the pyrolysis process, a large amount of water vapor and carbon dioxide are released, which can dilute the concentration of degradation fragments. In addition, the magnesium oxide generated during the degradation process has better thermal stability and can adhere to the surface of the combustible to block the transfer of heat flow, air flow, and mass flow.

[0041] The present invention also provides a method for preparing a hydromagnesite composite powder, which comprises the following steps: reacting a solution of a cinnamic acid derivative, a solution of hydromagnesite, and an inorganic powder to obtain the hydromagnesite composite powder. The preparation process has no complex technology and does not rely on large-scale equipment, with low energy consumption, meeting the current popular low-carbon environmental protection strategy. In addition, the cinnamic acid derivative can significantly reduce the oil absorption value of the powder, which is beneficial for reducing the consumption of additives and resins during processing and also helps to improve the interfacial bonding strength in the polymer matrix. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 TEM image of the hydromagnesite composite powder prepared in Example 1;

[0043] Figure 2 Particle size distribution diagram of the hydromagnesite composite powder prepared in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0044] The present invention provides a cinnamic acid derivative, whose structure is shown in Formula I:

[0045]

[0046] The present invention also provides a method for preparing the cinnamic acid derivative, which comprises the following steps:

[0047] Mixing a 4-bromophenyl diphenylphosphine solution, a p-bromocinnamic acid solution, an inorganic powder, and a palladium bis(pinacolato)borane solution, and then carrying out a reaction to obtain the cinnamic acid derivative.

[0048] The present invention also provides a method for preparing the 4-bromophenyl diphenylphosphine solution, which comprises the following steps: dissolving 4-bromophenyl diphenylphosphine fully in a solvent, and stirring evenly to obtain the 4-bromophenyl diphenylphosphine solution.

[0049] In the present invention, the structure of the 4-bromophenyl diphenylphosphine is as shown in Formula II:

[0050]

[0051] In the present invention, the stirring speed is preferably 300 - 1000 rpm, more preferably 500 - 800 rpm, and still more preferably 600 - 700 rpm.

[0052] The stirring time is preferably 10 - 120 min, more preferably 30 - 100 min, and still more preferably 40 - 90 min.

[0053] The present invention also provides a method for preparing the p-bromocinnamic acid solution, which comprises the following steps:

[0054] Dissolving p-bromocinnamic acid fully in a solvent, and stirring evenly to obtain the p-bromocinnamic acid solution.

[0055] In the present invention, the structure of the p-bromocinnamic acid is as shown in Formula III:

[0056]

[0057] In the present invention, the stirring speed is preferably 500 - 1200 rpm, more preferably 600 - 1100 rpm, and still more preferably 800 - 1000 rpm.

[0058] The stirring time is preferably 10 - 120 min, more preferably 30 - 90 min, and still more preferably 30 - 60 min.

[0059] In the present invention, the solvents of the 4-bromophenyl diphenylphosphine solution and the p-bromocinnamic acid solution are independently preferably methanol, ethanol, ethyl acetate, dimethyl sulfoxide or N,N-dimethylformamide.

[0060] In the present invention, the concentration of the 4-bromophenyl diphenylphosphine solution is preferably 1 - 20 mol / L, more preferably 5 - 15 mol / L, and still more preferably 8 - 12 mol / L.

[0061] In the present invention, the concentration of the p-bromocinnamic acid solution is preferably 1 - 30 mol / L, more preferably 5 - 25 mol / L, and still more preferably 10 - 20 mol / L.

[0062] In the present invention, the molar ratio of 4-bromophenyl diphenylphosphine to p-bromocinnamic acid is preferably 1:1 to 10, more preferably 1:4 to 7, and still more preferably 1:5 to 6.

[0063] In the present invention, the inorganic powder is preferably one or more of sodium carbonate, calcium carbonate, cesium carbonate, and potassium carbonate.

[0064] In the present invention, the molar ratio of 4-bromophenyl diphenylphosphine to the inorganic powder is preferably 1:1 to 100, more preferably 1:30 to 70, and still more preferably 1:40 to 60.

[0065] In the present invention, the pinacol diborate palladium solution preferably contains pinacol diborate, a palladium source, and a solvent.

[0066] The present invention also provides a method for preparing the pinacol diborate palladium solution, comprising the following steps:

[0067] (1) Mix and stir pinacol diborate and the solvent to obtain the pinacol diborate solution;

[0068] (2) Mix the palladium source and the solvent, add the obtained palladium source solution to the above pinacol diborate solution, and mix and stir to obtain the pinacol diborate palladium solution.

[0069] In the present invention, the concentration of the pinacol diborate solution is preferably 1 to 20 mol / L, more preferably 5 to 15 mol / L, and still more preferably 8 to 12 mol / L.

[0070] The concentration of the palladium source solution is preferably 0.005 mol / L to 0.1 mol / L, more preferably 0.006 to 0.009 mol / L, still more preferably 0.007 to 0.008 mol / L, and most preferably 0.0074 to 0.0075 mol / L.

[0071] In the present invention, the mixing and stirring speed in steps (1) and (2) is independently preferably 500 to 1000 rpm, more preferably 600 to 900 rpm, and still more preferably 700 to 800 rpm; the mixing and stirring time is independently preferably 30 to 100 min, more preferably 45 to 85 min, and still more preferably 60 to 70 min.

[0072] In the present invention, the molar ratio of pinacol diborate to 4-bromophenyl diphenylphosphine is preferably 1 to 10:1, more preferably 4 to 7:1, and still more preferably 5 to 6:1.

[0073] In the present invention, the palladium source is preferably palladium acetate, palladium chloride, tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloropalladium, dichloro(bis(triphenylphosphine))palladium, dichloro(bis(benzonitrile))palladium, 1,4-bis(diphenylphosphino)butane-palladium chloride, bis(acetonitrile)dichloropalladium, bis(methyldiphenylphosphine)dichloropalladium, bis(tritert-butylphosphine)palladium or dichloro(bis(ditert-butylphenylphosphine))palladium.

[0074] In the present invention, the molar ratio of the palladium source to 4-bromophenyl diphenylphosphine is preferably 0.005 to 0.1:1, more preferably 0.006 to 0.009:1, and even more preferably 0.007 to 0.008:1.

[0075] The solvent is preferably methanol, ethanol, ethyl acetate, dimethyl sulfoxide or N,N-dimethylformamide.

[0076] In the present invention, the mixing is carried out by adding an inorganic powder after dropping a solution of 4-bromophenyl diphenylphosphine into a solution of p-bromocinnamic acid, and then dropping a palladium solution of bis(pinacolato)diboron for a mixing reaction.

[0077] In the present invention, the dropping rate of the 4-bromophenyl diphenylphosphine solution and the palladium solution of bis(pinacolato)diboron is independently preferably 1 to 10 s / drop, more preferably 3 to 7 s / drop, and even more preferably 4 to 6 s / drop.

[0078] In the present invention, the temperature of the reaction is preferably 25 to 100 °C, more preferably 50 to 75 °C, and even more preferably 55 to 70 °C; the stirring rate of the reaction is preferably 500 to 1200 rpm, more preferably 700 to 1000 rpm, and even more preferably 800 to 900 rpm; the reaction time is preferably 1 to 36 h, more preferably 10 to 26 h, and even more preferably 15 to 20 h.

[0079] In the present invention, after the reaction is completed, the mixed solution is removed of the organic solvent and subjected to extraction and purification to obtain the cinnamic acid derivative.

[0080] In the present invention, the process of extraction and purification is preferably carried out in sequence of reduced pressure distillation, extraction, concentration, purification and drying.

[0081] In the present invention, the reduced pressure distillation is preferably carried out by removing the solvent with a rotary evaporator; the extraction solution preferably contains ethyl acetate and water; the volume ratio of ethyl acetate to water is preferably 1:0.5 to 3, more preferably 1:1 to 2.5, and even more preferably 1:1.5 to 2.

[0082] In the present invention, the concentration is to remove the solvent and dry with anhydrous sodium sulfate.

[0083] In the present invention, the purification is column chromatography purification, and the reagents for column chromatography purification include ethyl acetate and methanol. The volume ratio of ethyl acetate to methanol is preferably 1-5:1, more preferably 2-4:1, and even more preferably 2.5-3.5:1.

[0084] In the present invention, the drying method is preferably drying in a vacuum oven. The drying temperature is preferably 30-60°C, more preferably 40-50°C, and even more preferably 43-47°C; the drying time is preferably 1-24 h, more preferably 5-20 h, and even more preferably 10-15 h.

[0085] The present invention also provides the application of the cinnamic acid derivative in the hydromagnesite composite powder.

[0086] The present invention also provides a hydromagnesite composite powder, which is prepared from raw materials comprising the following molar ratios:

[0087] Cinnamic acid derivative, hydromagnesite and inorganic powder;

[0088] The molar ratio of the hydromagnesite to the cinnamic acid derivative is preferably 1:0.1-20, more preferably 1:5-15, and even more preferably 1:8-12.

[0089] The inorganic powder is preferably one or more of potassium carbonate, sodium carbonate and calcium carbonate.

[0090] In the present invention, when the molar ratio of the hydromagnesite to the cinnamic acid derivative is lower than 1:0.1, the shielding effect on the hydromagnesite is poor, resulting in the still-exposed phenomenon of the hydromagnesite; when the molar ratio of the hydromagnesite to the cinnamic acid derivative is higher than 1:20, the phenomenon that multiple hydromagnesites are wrapped together may occur, the particle size is increased passively, and the ultrafine effect is greatly reduced. The dispersibility in the polymer matrix may also be affected to a greater extent.

[0091] In the present invention, the molar ratio of the inorganic powder to the cinnamic acid derivative is preferably 1-100:1, more preferably 30-70:1, and even more preferably 45-55:1.

[0092] The present invention also provides a preparation method of the hydromagnesite composite powder, which comprises the following steps:

[0093] Reacting the solution of the cinnamic acid derivative, the solution of the hydromagnesite and the inorganic powder to obtain the hydromagnesite composite powder.

[0094] The present invention also provides a preparation method of the solution of the cinnamic acid derivative, which comprises the following steps:

[0095] Adding the cinnamic acid derivative to a solvent and stirring to obtain the solution of the cinnamic acid derivative.

[0096] In the present invention, the stirring speed is preferably 100 - 1200 rpm, more preferably 400 - 800 rpm, and still more preferably 550 - 650 rpm; the stirring time is preferably 10 - 120 min, more preferably 20 - 100 min, and still more preferably 30 - 90 min.

[0097] The present invention also provides a method for preparing a solution of hydromagnesite, comprising the following steps:

[0098] Disperse hydromagnesite in a solvent, and the solution of hydromagnesite can be obtained after stirring.

[0099] In the present invention, the stirring speed is preferably 100 - 1200 rpm, more preferably 400 - 800 rpm, and still more preferably 550 - 650 rpm; the stirring time is preferably 10 - 90 min, more preferably 20 - 80 min, and still more preferably 30 - 60 min.

[0100] In the present invention, the hydromagnesite is preferably the hydromagnesite obtained by physical method; the median particle size (D 50 ) of the hydromagnesite is preferably 1.0 - 2.5 μm, more preferably 1.2 - 2.0 μm, and still more preferably 1.5 - 1.7 μm.

[0101] In the present invention, the solvent of the solution of cinnamic acid derivative is preferably one or more of ethanol, methanol and ethyl acetate.

[0102] In the present invention, the concentration of the solution of cinnamic acid derivative is preferably 1 - 40 M, more preferably 10 - 30 M, and still more preferably 15 - 25 M.

[0103] In the present invention, the solvent of the solution of hydromagnesite is preferably ethanol, methanol or water.

[0104] In the present invention, the concentration of the solution of hydromagnesite is preferably 1 - 10 M, more preferably 3 - 8 M, and still more preferably 4 - 7 M.

[0105] In the present invention, the solution of cinnamic acid derivative is dropped into the solution of hydromagnesite, and then an inorganic powder is added for reaction.

[0106] In the present invention, the dropping rate is preferably 1 - 20 s / drop, more preferably 5 - 15 s / drop, and still more preferably 8 - 12 s / drop.

[0107] In the present invention, the stirring rate of the reaction is preferably 100 - 1200 rpm, more preferably 500 - 800 rpm, and still more preferably 600 - 700 rpm; the temperature of the reaction is preferably 25 - 60 °C, more preferably 30 - 55 °C, and still more preferably 40 - 45 °C; the time of the reaction is preferably 1 - 24 h, more preferably 5 - 20 h, and still more preferably 10 - 15 h.

[0108] In the present invention, the product after the reaction is centrifuged, washed, and freeze-dried to obtain the hydromagnesite composite powder.

[0109] In the present invention, the centrifugation rate is preferably 3000 - 12000 rpm, more preferably 5000 - 10000 rpm, and still more preferably 7000 - 8000 rpm; the centrifugation time is preferably 5 - 60 min, more preferably 20 - 45 min, and still more preferably 25 - 40 min.

[0110] In the present invention, the temperature of the freeze-drying is preferably -70 to -10 °C, more preferably -60 to -30 °C, and still more preferably -50 to -40 °C; the time of the freeze-drying is preferably 1 - 24 h, more preferably 5 - 20 h, and still more preferably 10 - 15 h.

[0111] The present invention also provides the application of the hydromagnesite composite powder in energy devices.

[0112] In the present invention, the hydromagnesite powder is applied in energy device elastomers such as styrene-ethylene-butene-styrene block copolymer (SEBS), thermoplastic polyurethane (TPU), polyvinyl chloride (PVC), ethylene propylene diene monomer (EPDM), and thermoplastic elastomer (TPE).

[0113] The present invention also provides a styrene-ethylene-butene-styrene block copolymer (SEBS) matrix material, which comprises the following raw materials in parts by mass:

[0114] 10 - 30 parts of SEBS, 5 - 20 parts of PP, 5 - 40 parts of the hydromagnesite composite powder, and 2 - 15 parts of other additives.

[0115] In the present invention, the mass fraction of SEBS is preferably 12 - 28 parts, more preferably 15 - 25 parts, and still more preferably 18 - 22 parts.

[0116] In the present invention, the mass fraction of PP is preferably 8 - 17 parts, more preferably 10 - 15 parts, and still more preferably 12 - 14 parts.

[0117] In the present invention, the mass fraction of the hydromagnesite composite powder is preferably 10 to 35 parts, more preferably 15 to 30 parts, and even more preferably 20 to 25 parts.

[0118] In the present invention, the mass fraction of other additives is preferably 5 to 12 parts, more preferably 6 to 11 parts, and even more preferably 8 to 9 parts.

[0119] In the present invention, the SEBS is preferably G1651, G1654, G1650, G1660, G1657, G1701, G1641, G1642, G1643M, MD6945, RP6935, G1633, MD6944, RP6670, MD6684, D1101, D1102, KX222, MD6459, KX405, D1155, D1152, D1153 or D1192.

[0120] In the present invention, the relative density of the SEBS is preferably 0.90 to 0.96 g / cm 3 , more preferably 0.92 to 0.94 g / cm 3 , even more preferably 0.925 to 0.935 g / cm 3 ; the melting temperature is preferably 180 to 210 °C, more preferably 190 to 200 °C, and even more preferably 194 to 196 °C; the hardness is preferably 60 to 75 A, more preferably 65 to 70 A, and even more preferably 67 to 68 A.

[0121] In the present invention, the PP is preferably V30G, V2400G, X30G, F37G, HA840R, Z30G, S30G, T30G, T50G, K1008, C1008, K1215, K1514, HP500N, 1400, H32GA, PH384, T28C, F280S, HP425J, LI28F, T38F, S38F, P340, J440, EPD60R, K7002, J340, JD803, SP179, BJ300, BJ500, EPC31H, EP445L, K9920 or K7760.

[0122] In the present invention, the other additives are preferably one or more of a lubricant, an antioxidant, and a toughening agent.

[0123] In the present invention, there are no special requirements for the lubricant, and it is preferably an equal-proportion mixture of zinc stearate / oxidized polyethylene wax / mineral oil; there are no special requirements for the antioxidant, and it is preferably an equal-mass mixture of antioxidant 1010 and antioxidant 168; there are no special requirements for the toughening agent, and it is preferably an ethylene-octene copolymer.

[0124] The present invention also provides a method for preparing a styrene-ethylene-butylene-styrene block copolymer (SEBS) matrix material, comprising the following steps:

[0125] The SEBS / PP composite material is obtained by premixing SEBS, PP, hydromagnesite composite powder and other additives and then kneading them.

[0126] In the present invention, the other additives include a lubricant, an antioxidant and an ethylene-octene copolymer; the mass ratio of the lubricant, antioxidant and ethylene-octene copolymer is preferably 1-8:0.5-1:0.5-6, more preferably 2-7:0.6-0.9:2-4.5, and more preferably 4-5:0.7-0.8:2.5-4.

[0127] In the present invention, the antioxidant preferably comprises antioxidant 1010 and antioxidant 168. The mass ratio of antioxidant 1010 to antioxidant 168 is preferably 0.5-1.5:0.5-1.5, more preferably 0.7-1.3:0.7-1.3, and even more preferably 0.9-1.1:0.9-1.1.

[0128] In the present invention, the stirring speed of the premix is preferably 200-800 r / min, more preferably 300-700 r / min, more preferably 400-600 r / min; the temperature of the premix is preferably 20-60°C, more preferably 30-50°C, more preferably 35-45°C; the time of the premix is preferably 5-40 min, more preferably 10-35 min, more preferably 20-25 min.

[0129] In the present invention, the mixing temperature is preferably 170-190° C., more preferably 175-185° C., and more preferably 178-182° C.; the mixing time is preferably 2-8 min, more preferably 4-6 min, and more preferably 4.5-5.5 min.

[0130] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0131] Example 1

[0132] 1 mol of 4-bromophenyldiphenylphosphine was fully dissolved in ethyl acetate, and the mixture was stirred at a stirring rate of 600 rpm for 40 min to obtain a 4-bromophenyldiphenylphosphine solution with a concentration of 10 mol / L.

[0133] 5 mol of p-bromocinnamic acid was fully dissolved in ethyl acetate and stirred at a stirring speed of 800 rpm for 45 min to obtain a p-bromocinnamic acid solution with a concentration of 15 mol / L.

[0134] 5 mol of bis(pinacolato)diboron and N,N-dimethylformamide were stirred at a stirring speed of 800 rpm for 45 min to obtain a bis(pinacolato)diboron solution, and the solution concentration was controlled to be 5 mol / L; then 0.05 mol of bis(dibenzylideneacetone)palladium and N,N-dimethylformamide were stirred at a stirring speed of 800 rpm for 50 min to obtain a 0.05 mol / L palladium source solution; the palladium source solution was added to the bis(pinacolato)diboron solution to obtain the (dibenzylideneacetone)palladium solution of bis(pinacolato)diboron.

[0135] The 4-bromophenyl diphenylphosphine solution was dropped into the p-bromocinnamic acid solution at a rate of 3 drops / s, and 50 mol of potassium carbonate was added. Subsequently, the (dibenzylideneacetone)palladium solution of bis(pinacolato)diboron was dropped into the mixed solution at a rate of 3 drops / s. After reacting at a temperature of 77 °C and a stirring rate of 800 rpm for 24 h, the organic solvent was removed by vacuum distillation, and extraction was carried out using ethyl acetate and deionized water (volume ratio 1:1), and then anhydrous sodium sulfate was added to dry the organic layer. Purification was carried out using ethyl acetate and methanol (volume ratio 3:1), and drying was carried out at 45 °C for 12 h to obtain the cinnamic acid derivative with a yield of 85%.

[0136] After repeating the above steps, 10 mol of the cinnamic acid derivative was fully dissolved in ethanol and stirred at a stirring rate of 600 rpm for 40 min to obtain a 10 M concentration cinnamic acid derivative solution.

[0137] Take 1 mol of D 50 Hydromagnesite with a particle size of 1.8 μm was fully dissolved in ethanol and stirred at a stirring rate of 700 rpm for 30 min to obtain a 1 M concentration hydromagnesite solution.

[0138] The cinnamic acid derivative solution was dropped into the hydromagnesite solution at a rate of 6 drops / s, and then 30 mol of potassium carbonate was added. The reaction was carried out at a rotation speed of 800 rpm and a temperature of 45 °C for 12 h, and then centrifuged at a centrifugation rate of 8000 r / min for 30 min and dried at a temperature of -40 °C for 12 h to obtain the hydromagnesite composite powder.

[0139] 20 parts of SEBS, 10 parts of PP, 30 parts of the above hydromagnesite composite powder, 4 parts of lubricant (the mass ratio of zinc stearate / oxidized polyethylene wax / mineral oil is 1:1:1:1), 0.8 part of antioxidant (the mass ratio of antioxidant 1010 and 168 is 1:1), and 3 parts of ethylene-octene copolymer were premixed at a temperature of 30 °C and a stirring rate of 500 r / min for 20 min, and then kneaded by a mixer at 180 °C for 4 min. After discharging, various different test specimens were prepared by a flat vulcanizing machine for subsequent performance testing.

[0140] The hydrotalcite composite powder prepared in this example was subjected to TEM testing, and the results are as follows Figure 1 shown. From Figure 1 it can be seen that there is a film on the surface of the hydrotalcite powder, and this layer has a certain thickness and is relatively continuous on the surface, indicating that the cinnamic acid derivative is coated relatively uniformly.

[0141] The particle size of the hydrotalcite composite vermicelli prepared in this example was tested, and the results are as follows Figure 2 shown. From Figure 2 it can be seen that the particle size distribution of the hydrotalcite composite powder is relatively uniform, showing a single-peak shape and concentrating around 1.8 μm.

[0142] Example 2

[0143] 1 mol of 4-bromophenyl diphenylphosphine was fully dissolved in N,N-dimethylformamide and stirred at a stirring rate of 300 rpm for 120 min to obtain a 4-bromophenyl diphenylphosphine solution with a concentration of 10 mol / L.

[0144] 1 mol of p-bromocinnamic acid was fully dissolved in ethyl acetate and stirred at a stirring speed of 500 rpm for 120 min to obtain a p-bromocinnamic acid solution with a concentration of 1 mol / L.

[0145] 1 mol of bis(pinacolato)diboron and ethanol were stirred at a stirring speed of 500 rpm for 100 min to obtain a 1 mol / L bis(pinacolato)diboron solution; then 0.005 mol of palladium acetate and ethanol were stirred at a stirring speed of 500 rpm for 15 min to obtain a 0.005 mol / L palladium source solution; the palladium source solution was added to the above bis(pinacolato)diboron solution to obtain the palladium acetate solution of bis(pinacolato)diboron.

[0146] The 4-bromophenyl diphenylphosphine solution was dropped into the p-bromocinnamic acid solution at a rate of 1 drop / s, and 100 mol of calcium carbonate was added. Subsequently, the palladium acetate solution of bis(pinacolato)diboron was dropped into the mixed solution at a rate of 3 drops / s. After reacting for 1 h under the conditions of a temperature of 100 °C and a stirring rate of 500 rpm, the organic solvent was removed by reduced pressure distillation, and the organic layer was extracted with ethyl acetate and deionized water (volume ratio 1:0.5) and then dried with anhydrous sodium sulfate. It was purified with ethyl acetate and methanol (volume ratio 1:1) and dried at 30 °C for 24 h to obtain the cinnamic acid derivative with a yield of 79%.

[0147] Repeat the above steps. Take 1 mol of the cinnamic acid derivative and fully dissolve it in ethanol, and stir it at a stirring rate of 100 rpm for 120 min to obtain a 1 M cinnamic acid derivative solution.

[0148] Take 10 mol of D 50 1.8 μm hydromagnesite was fully dissolved in ethanol and stirred at a stirring rate of 100 rpm for 90 min to obtain a 10 M concentration hydromagnesite solution.

[0149] The cinnamic acid derivative solution was dropped into the hydromagnesite solution at a rate of 1 drop / s, then 1 mol of calcium carbonate was added, and the reaction was carried out at a rotation speed of 100 rpm and a temperature of 25 °C for 24 h. Then, it was centrifuged at a centrifugation rate of 3000 r / min for 60 min and dried at a temperature of -10 °C for 24 h to obtain the hydromagnesite composite powder.

[0150] 10 parts of SEBS, 5 parts of PP, 5 parts of hydromagnesite composite powder, 1 part of lubricant (the mass ratio of zinc stearate / oxidized polyethylene wax / white oil is 1:1:1:1), 0.5 part of antioxidant (the mass ratio of antioxidant 1010 and 168 is 1:1), and 0.5 part of ethylene-octene copolymer were premixed at a temperature of 20 °C and a stirring rate of 200 r / min for 40 min. Subsequently, it was kneaded by a mixer at 170 °C for 8 min, and after discharging, various different test specimens were prepared by a flat vulcanizing machine for subsequent performance testing.

[0151] Example 3

[0152] 2 mol of 4-bromophenyl diphenylphosphine was fully dissolved in dimethyl sulfoxide and stirred at a stirring rate of 1000 rpm for 100 min to obtain a 4-bromophenyl diphenylphosphine solution with a concentration of 20 mol / L.

[0153] 20 mol of p-bromocinnamic acid was fully dissolved in ethyl acetate and stirred at a stirring speed of 1200 rpm for 10 min to obtain a p-bromocinnamic acid solution with a concentration of 30 mol / L.

[0154] 20 mol of bis(pinacolato)diboron and methanol solution were stirred at a stirring speed of 1000 rpm for 30 min to obtain a 20 mol / L bis(pinacolato)diboron solution; then 0.1 mol of tris(dibenzylideneacetone)dipalladium and methanol solution were mixed to obtain a 0.1 mol / L palladium source solution; the palladium solution was added to the bis(pinacolato)diboron solution to obtain the tris(dibenzylideneacetone)dipalladium solution of bis(pinacolato)diboron.

[0155] The 4-bromophenyl diphenylphosphine solution was dropped into the bromocinnamic acid solution at a rate of 10 drops per second, and 200 mol of sodium carbonate was added. Subsequently, the tris(dibenzylideneacetone)dipalladium solution of bis(pinacolato)diboron was dropped into the mixed solution at a rate of 3 drops per second. After reacting for 1 h under the conditions of a temperature of 100 °C and a stirring rate of 1000 rpm, the organic solvent was removed by vacuum distillation, and the organic layer was extracted with ethyl acetate and deionized water (volume ratio 1:1) and then dried with anhydrous sodium sulfate. It was purified with ethyl acetate and methanol (volume ratio 5:1) and dried at 60 °C for 1 h to obtain the surface shielding layer of the natural product cinnamic acid derivative, with a yield of 77%.

[0156] Repeat the above steps. Dissolve 10 mol of the cinnamic acid derivative in ethanol and stir for 10 min at a stirring rate of 1200 rpm to obtain a 10 M cinnamic acid derivative solution.

[0157] Take 1 mol of D 50 Dissolve 1.8 μm of hydromagnesite in ethanol and stir for 10 min at a stirring rate of 1200 rpm to obtain a 1 M hydromagnesite solution.

[0158] Drop the cinnamic acid derivative solution into the hydromagnesite solution at a rate of 20 drops per second, add 100 mol of sodium carbonate, react for 1 h under the conditions of a rotation speed of 1200 rpm and a temperature of 60 °C, then centrifuge for 5 min under the condition of a centrifugation rate of 12000 r / min, and dry at -70 °C for 1 h to obtain the hydromagnesite composite powder.

[0159] Premix 30 parts of SEBS, 20 parts of PP, 40 parts of the hydromagnesite composite powder, 8 parts of a lubricant (mass ratio of zinc stearate / oxidized polyethylene wax / mineral oil is 1:1:1:1), 1 part of an antioxidant (mass ratio of antioxidant 1010 and 168 is 1:)and 6 parts of ethylene-octene copolymer at a temperature of 60 °C and a stirring rate of 800 rpm for 5 min, and then knead in a mixer at 190 °C for 2 min. After discharging, various different test specimens are prepared with a flat vulcanizer for subsequent performance testing.

[0160] Comparative Example 1

[0161] The steps for preparing the cinnamic acid derivative are the same as those in Example 1.

[0162] Dissolve 0.1 mol of the cinnamic acid derivative in ethanol and stir for 50 min at a stirring rate of 800 rpm to obtain a 0.1 M cinnamic acid derivative solution.

[0163] Take 10 mol of D 501.8 μm of hydromagnesite was fully dissolved in ethanol and stirred at a stirring rate of 700 rpm for 25 min to obtain a 10 M concentration hydromagnesite solution.

[0164] The cinnamic acid derivative solution was added dropwise to the hydromagnesite solution at a rate of 10 s / drop, and then 40 mol of potassium carbonate was added. The reaction was carried out at a rotation speed of 700 rpm and a temperature of 40 °C for 16 h. After centrifugation at a centrifugation rate of 8000 r / min for 35 min, it was dried at a temperature of -30 °C for 15 h to obtain the hydromagnesite composite powder.

[0165] When preparing the elastomer masterbatch material for energy devices, the formulation process was the same as in Example 1, and the hydromagnesite composite powder containing a surface shielding layer added could be replaced with the composite powder obtained in this example.

[0166] Comparative Example 2

[0167] The steps for preparing the cinnamic acid derivative were the same as in Example 1.

[0168] 10 mol of cinnamic acid derivative was fully dissolved in ethanol and stirred at a stirring rate of 500 rpm for 35 min to obtain a 10 M concentration cinnamic acid derivative solution.

[0169] Take 0.4 mol of D 50 1.8 μm of hydromagnesite was fully dissolved in ethanol and stirred at a stirring rate of 800 rpm for 15 min to obtain a 0.4 M concentration hydromagnesite solution.

[0170] The cinnamic acid derivative solution was added dropwise to the hydromagnesite solution at a rate of 8 s / drop, and then 60 mol of potassium carbonate was added. The reaction was carried out at a rotation speed of 1000 rpm and a temperature of 30 °C for 18 h. After centrifugation at a centrifugation rate of 10000 r / min for 25 min, it was dried at a temperature of -50 °C for 8 h to obtain the hydromagnesite composite powder.

[0171] When preparing the elastomer masterbatch material for energy devices, the formulation process was the same as in Step 3 of Example 1, and the hydromagnesite composite powder containing a surface shielding layer added could be replaced with the composite powder obtained in this example.

[0172] Comparative Example 3

[0173] When preparing the elastomer masterbatch material for energy devices, the only difference from the scheme of Example 1 was that the hydromagnesite composite powder was replaced with hydromagnesite prepared by a mechanical method, and the other conditions were the same.

[0174] The products prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to particle size and oil absorption value tests, and the test results are shown in Table 1:

[0175] Test method for particle size: The particle size and its distribution of the powder are measured by a laser particle size analyzer MS-3000E; Oil absorption: Test is carried out according to the standard of DB / T5211.15-2014.

[0176] Table 1 Test results of powder particle size, specific surface area and oil absorption value in Examples 1-3 and Comparative Examples 1-3

[0177]

[0178]

[0179] It can be seen from Table 1 that when the molar ratio of cinnamic acid derivative to hydromagnesite is within a reasonable range, the particle size (D 50 ) is maintained within the range of 1.6 - 2.0 μm, and the oil absorption value is maintained within the range of 30 - 36 mL / 100g; From the data obtained in Comparative Examples 1-3 of Table 1, it can be found that when the molar ratio of cinnamic acid derivative to hydromagnesite is too low, the D 50 and the oil absorption value of the powder both increase. This may be because there are still a large number of exposed hydroxyl groups on the surface of ultrafine hydromagnesite, the surface shielding effect is not good, and the overall modification effect is low; When the molar ratio of cinnamic acid derivative to hydromagnesite is too high, although both D 50 and the oil absorption value show a certain degree of decline, but the overall particle size still shows a certain degree of upward trend compared with that in Examples 1-3. This may be because too much cinnamic acid derivative wraps multiple particles together, resulting in an increase in the final particle size. At the same time, the specific surface area of the powder decreases significantly. This phenomenon is not suitable for application in the polymer matrix. When no cinnamic acid derivative is contained, that is, the original hydromagnesite, its particle size is too large due to agglomeration, even exceeding 3.0 μm, and the oil absorption value shows a significant increase. Such results are not conducive to its subsequent polymer processing and the maintenance of mechanical properties.

[0180] The powders prepared in Examples 1-3 and Comparative Examples 1-3 are respectively added to the SEBS / PP matrix to prepare corresponding tests in the elastomer masterbatch material of the energy device.

[0181] Hardness: According to the rubber test standard of GB / T 531-1999, the Shore A durometer is used for hardness test in this test item.

[0182] Maximum smoke density: Test is carried out by a smoke density tester according to the standard of GB / T8627-2007.

[0183] Limiting oxygen index: Under the test conditions required by GB8924-2005, it is the lowest oxygen concentration required for the test material to burn with flame in the O2 / N2 mixed gas stream.

[0184] UL1581 test: Conduct a combustion test on the prepared wire. The common grades are judged by this standard as VW-1 to determine whether it passes.

[0185] The above test results are shown in Table 2.

[0186] Table 2 Corresponding test results of the elastomer masterbatch materials of energy devices in Examples 1-3 and Comparative Examples 1-3

[0187] Example Hardness (A) Maximum smoke density (Dm) Limiting oxygen index (%) UL1581 (VW-1) Example 1 87.6 78.95 29.3 By Example 2 87.4 80.01 28.5 By Example 3 87.8 79.90 28.8 By Comparative example 1 88.3 90.18 24.6 Failed Comparative example 2 88.1 88.81 25.3 Failed Comparative example 3 88.4 92.62 21.4 Failed

[0188] It can be seen from Table 2 that in terms of hardness, the cinnamic acid derivative has little effect on the hardness of the final elastomer material; in terms of smoke density, adding hydromagnesite powder containing cinnamic acid derivative in the polymer matrix can obviously reduce its maximum smoke density to a certain extent. And when the content of cinnamic acid derivative is too high or too low, the maximum smoke density of the elastomer material shows an upward trend. Particularly obvious is that when directly adding hydromagnesite powder without cinnamic acid derivative, the maximum smoke density of the elastomer material increases significantly. This may be related to the dispersibility of the composite powder in the elastomer masterbatch. The presence of cinnamic acid derivative can improve the polarity of the hydromagnesite surface and its dispersibility in the elastomer substrate. Therefore, adding cinnamic acid derivative can make the ultrafine hydromagnesite powder have typical advantages in this regard; in terms of limiting oxygen index, hydromagnesite containing cinnamic acid derivative can significantly increase the final oxygen index of the elastomer masterbatch. When the cinnamic acid derivative is too high or too low or even without cinnamic acid derivative, the limiting oxygen index of the elastomer substrate will decrease. This may be because the cinnamic acid derivative and hydromagnesite cannot form an effective synergistic flame retardant effect. When there is no cinnamic acid derivative, the hydromagnesite powder has poor dispersibility and low efficiency in the substrate due to agglomeration and dispersibility reasons; in the combustion test results of energy cables, the results are also similar to the limiting oxygen index. Comparative Examples 1-3 all failed the test, indicating that the presence of cinnamic acid derivative can indeed effectively improve the combustion performance of the elastomer substrate. Inappropriate ratios or even without cinnamic acid derivative will cause the final substrate to fail the combustion test. In summary, containing cinnamic acid derivative can significantly improve the combustion and smoke suppression performance of hydromagnesite in the elastomer substrate, and can be widely used in various energy device materials with a wide range of applications.

[0189] It can be seen from the above examples that the present invention provides a cinnamic acid derivative and its preparation method and application, as well as a hydromagnesite composite powder and its preparation method and application, which include the following steps: React the solution of cinnamic acid derivative, the solution of hydromagnesite and the inorganic powder to obtain the hydromagnesite composite powder. It can be seen from the test results of the examples that the hydromagnesite composite powder D prepared by the present invention 50In the range of 1.6 - 2.0 μm and with an oil absorption value of 30 - 36 mL / 100 g, when it is applied to prepare elastomer masterbatch materials for energy devices, it can effectively reduce the maximum smoke density, reaching as low as 78.95 Dm, and at the same time improve the limiting oxygen index to 29.3%, having excellent combustion and smoke suppression performance.

[0190] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A cinnamic acid derivative, characterized in that, Its structure is as shown in Formula I: Formula I.

2. The preparation method of the cinnamic acid derivative according to claim 1, characterized in that, It includes the following steps: Mix a 4-bromophenyl diphenylphosphine solution, a p-bromocinnamic acid solution, an inorganic powder, and a palladium bis(pinacolato)borate solution and react them to obtain the cinnamic acid derivative. The inorganic powder is one or more of sodium carbonate, calcium carbonate, cesium carbonate, and potassium carbonate. The palladium bis(pinacolato)borate solution contains bis(pinacolato)borane, a palladium source, and a solvent. The palladium source is palladium acetate, palladium chloride, tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloropalladium, dichloro-bis(triphenylphosphine)palladium, dichloro-bis(benzonitrile)palladium, 1,4-bis(diphenylphosphino)butane-palladium chloride, bis(acetonitrile)dichloropalladium, bis(methyldiphenylphosphine)dichloropalladium, bis(tritert-butylphosphine)palladium, or dichloro-bis(ditert-butylphenylphosphine)palladium. The solvent is one or more of N,N-dimethylformamide, tetrahydrofuran, ethanol, ethyl acetate, dimethyl sulfoxide, methanol, and acetonitrile.

3. The preparation method according to claim 2, characterized in that, The solvents of the 4-bromophenyl diphenylphosphine solution and the p-bromocinnamic acid solution are independently methanol, ethanol, ethyl acetate, dimethyl sulfoxide, or N,N-dimethylformamide. The concentration of the 4-bromophenyl diphenylphosphine solution is 1-20 mol / L. The concentration of the p-bromocinnamic acid solution is 1-30 mol / L. The molar ratio of 4-bromophenyl diphenylphosphine to p-bromocinnamic acid is 1:1-10. The molar ratio of 4-bromophenyl diphenylphosphine to the inorganic powder is 1:1-100. The molar ratio of the bis(pinacolato)borane to 4-bromophenyl diphenylphosphine is 1-10:

1. The molar ratio of the palladium source to 4-bromophenyl diphenylphosphine is 0.005-0.1:

1.

4. The preparation method according to claim 2 or 3, characterized in that, The temperature of the reaction is 25-100 °C, the stirring rate of the reaction is 500-1200 rpm, and the reaction time is 1-36 h.

5. Use of the cinnamic acid derivative according to claim 1 in a hydromagnesite composite powder.

6. A hydromagnesite composite powder, characterized in that, Prepared from raw materials with the following molar ratios: The cinnamic acid derivative according to claim 1, hydromagnesite, and an inorganic powder; The molar ratio of the hydromagnesite to the cinnamic acid derivative according to claim 1 is 1:0.1-20. The inorganic powder is one or more of potassium carbonate, sodium carbonate, and calcium carbonate. The molar ratio of the inorganic powder to the cinnamic acid derivative according to claim 1 is 1-100:

1.

7. The preparation method of the hydromagnesite composite powder according to claim 6, wherein, It includes the following steps: React the solution of the cinnamic acid derivative according to claim 1, the solution of hydromagnesite, and the inorganic powder to obtain the hydromagnesite composite powder.

8. The preparation method according to claim 7, characterized in that, The solvent of the solution of the cinnamic acid derivative according to claim 1 is one or more of ethanol, methanol, and ethyl acetate. The concentration of the solution of the cinnamic acid derivative according to claim 1 is 1-40 M. The solvent of the solution of the hydromagnesite is ethanol, methanol, or water. The concentration of the solution of the hydromagnesite is 1-10 M.

9. The preparation method according to claim 7 or 8, characterized in that, The stirring rate of the reaction is 100-1200 rpm, the temperature of the reaction is 25-60 °C, and the reaction time is 1-24 h.

10. Use of the hydromagnesite composite powder according to claim 6 in energy devices.

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