CN115466434A - Rare earth element separant modified nano white carbon black and preparation method thereof - Google Patents

Rare earth element separant modified nano white carbon black and preparation method thereof Download PDF

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CN115466434A
CN115466434A CN202110653584.2A CN202110653584A CN115466434A CN 115466434 A CN115466434 A CN 115466434A CN 202110653584 A CN202110653584 A CN 202110653584A CN 115466434 A CN115466434 A CN 115466434A
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carbon black
white carbon
rare earth
separant
nano white
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李波
牛承祥
粱立嘉
梁滔
徐典宏
周雷
孟令坤
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Petrochina Co Ltd
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Abstract

The invention aims to provide a method for modifying the super-dispersibility of nano white carbon black filled with solution polymerized styrene butadiene rubber. Firstly, preparing a light rare earth metal-containing separant, and finally coating the separant on the surface of nano white carbon black particles to form a layer of barrier layer so as to achieve the method for separating the nano white carbon black. The separant not only solves the problem of easy agglomeration of the nano white carbon black, but also avoids the problem of agglomeration again in the blending processing process, improves the compatibility of the nano white carbon black and the solution polymerized styrene butadiene rubber, and endows the nano white carbon black with super-dispersibility in a solution polymerized styrene butadiene rubber system. The light rare earth metal double-salt-bridge unsaturated carboxylic acid compound is a novel safe environment-friendly compound without VOC emission, and has the advantages of small environmental pollution, easily obtained raw materials, simple and convenient modification process and low modification cost.

Description

Rare earth element separant modified nano white carbon black and preparation method thereof
Technical Field
The invention relates to the field of rubber filler modification, in particular to a preparation method of rare earth element separant modified nano white carbon black with super-dispersibility.
Background
The nanometer white carbon black is porous substance, and the composition can be SiO 2 ·nH 2 O represents, wherein nH 2 O exists in the form of surface hydroxyl, is white, non-toxic, amorphous and porous fine powder, has the characteristics of large internal surface area, dispersibility, light weight, high temperature resistance, non-combustion, good electrical insulation property and the like, and has stable chemical property. The white carbon black is used as an environment-friendly auxiliary agent with excellent performance and is mainly used in the fields of rubber products and the like. The nano white carbon black has small particle size, large specific surface, high surface energy and a large amount of hydroxyl on the surface, so that the nano white carbon black is extremely easy to agglomerate and is difficult to disperse uniformly in the mixing process with the rubber material, thereby not only influencing the filling modification effect, but also damaging the performance of the rubber material.
At present, from the expected effect of inorganic powder filling modified synthetic rubber, the smaller the particle size of the inorganic powder particles, the better the modification effect, but a technical problem inevitably encountered in the application process of the ultrafine inorganic powder is that the specific surface area of the ultrafine powder increases with the decrease of the particle size, the surface energy is increased, the self-aggregation capability is stronger, and the ultrafine powder is more difficult to be mixed, infiltrated and dispersed by rubber materials. Therefore, the problem of the dispersion of the ultrafine inorganic powder in the rubber has become a bottleneck in the preparation of high-performance rubber materials.
In the prior art, the nano white carbon black is modified by a coupling agent or a surfactant such as a silane coupling agent, an inorganic mineral and an oligomer, such as: CN201310356589.4 discloses a method for introducing metal soap into rubber composition. A composition comprising diene rubber and a metal soap wherein the metal ion is a metal having an oxidation state of +3 or +4 is prepared by mixing a polar solvent, a base and a carboxylate to form a solution A, adding a source of metal ions in ionic form to solution A to form a +3 or +4 carboxylic metal soap, and finally combining with the diene rubber composition. The composition can obviously enhance the physical and mechanical properties of the rubber. CN108059688A discloses a nanometer separant and a preparation method thereof. The nanometer isolating agent is a metal soap which is composed of aliphatic chains, alicyclic hydrocarbon or aromatic compounds with oxidation states of +2, +3 or +4 metallic elements and carbon atoms of 1-18 and short-chain aliphatic chains, alicyclic hydrocarbon or aromatic compounds with functional groups of 2-50 such as double bonds, amino groups, hydroxyl groups, mercapto groups, epoxy groups and the like, and the preparation method comprises the steps of firstly placing short-chain carboxylic acid with functional groups and alkali in a polar solvent to obtain a short-chain carboxylate solution A with functional groups; then putting the polymer with carboxylic acid and alkali into a polar solvent to obtain a salt solution B of the polymer with carboxylic acid; and finally, mixing the solution A and the solution B to obtain a reaction solution C, and adding a metal salt solution with an oxidation state of +2, +3 or +4 into the solution C to obtain the metal soap with functional groups and short-chain polymers, namely the nano additive. The nano additive can obviously improve the elastic modulus and the elongation at break of rubber. CN101798473A discloses a preparation method of silane modified white carbon black, which comprises the steps of adding precipitation method white carbon black and gas phase method white carbon black into a high-speed mixer according to the weight ratio of 3: 1-3: 2, slowly and uniformly adding polysulfide silane in a spraying mode, gradually heating to 100-120 ℃ to promote surface modification reaction to obtain the silane modified white carbon black. CN101817529A discloses a preparation method of modified white carbon black, which comprises the steps of introducing nitrogen into white carbon black under protectionHeating and activating for 4-5 hours at 250-300 ℃, mixing the activated white carbon black with toluene isocyanate, wherein the using amount of the toluene isocyanate is 10-20% of that of the white carbon black, adding anhydrous xylene into the mixture, wherein the mass ratio of the volume of the using amount of the anhydrous xylene to the using amount of the white carbon black is 5-8: 1, stirring and dispersing at room temperature under the protection of nitrogen, heating to 60-85 ℃, filtering, and drying to obtain the modified white carbon black. CN 1324885A discloses a method for preparing a halogen-free flame-retardant rubber material with excellent flame retardant property by using unsaturated carboxylic acid modified inorganic flame-retardant filler such as methacrylic acid (MAA) or Acrylic Acid (AA). CN101704967A discloses a preparation method of modified white carbon black, which comprises drying white carbon black at 200-240 deg.C for 4-8 hours, plasticating with 4-7 wt% abietic acid type resin acid and 12-18 wt% chlorohydrin rubber at 140-160 deg.C for 20-25 minutes, discharging, continuously extracting with tetrahydrofuran for 24 hours, and drying at 120-150 deg.C after solvent volatilization to obtain modified white carbon black. CN102558627A discloses a method for preparing white carbon black suspension, which comprises the steps of mixing white carbon black and water to obtain white carbon black-water suspension, wherein the mass ratio of the white carbon black to the water is 5-20%, carrying out surface treatment on the white carbon black in a water bath environment to organize the surface of the white carbon black-water suspension, adjusting the pH value of the white carbon black-water suspension to 9-12, and finally uniformly mixing the white carbon black-water suspension with styrene butadiene latex after the pH value is adjusted to obtain styrene butadiene rubber liquid slurry added with the white carbon black. CN107189124A discloses a preparation method of modified white carbon black, which comprises the steps of drying white carbon black for 4-8 hours at the temperature of 200-240 ℃, plastifying the white carbon black with abietic acid type resin acid and chlorohydrin rubber for 20-25 minutes at the temperature of 140-160 ℃, continuously extracting for 24 hours by tetrahydrofuran after discharging, and drying to obtain the modified white carbon black. CN106589485A discloses a method for preparing white carbon black suspension, mixing white carbon black with water to obtain white carbon black-water suspension, adjusting the temperature of the white carbon black suspension to 35-90 ℃ by a heating device, ensuring that the white carbon black suspension is in a flowing state during the period, adding a silane coupling agent into the white carbon black suspension, then adding aliphatic polyoxyethylene ether (AEO) for modification, wherein the AEO is 1-100% of the mass of the white carbon black,the silane coupling agent is 1-100% of white carbon black by mass, and is matched with high sound to modify the white carbon black for 0.5-10 hours to form white carbon black suspension with an O/W type emulsion structure. CN106832417A discloses a preparation method of an aliphatic polyoxyethylene ether modified organic white carbon black, which comprises the steps of mixing white carbon black with water to obtain a white carbon black-water suspension, wherein the mass of the white carbon black accounts for 5% -20% of the total mass of the suspension, adjusting the temperature of the white carbon black suspension to be above the melting point of the aliphatic polyoxyethylene ether through a heating device, ensuring that the white carbon black suspension is in a flowing state in the period, adding the aliphatic polyoxyethylene ether into the white carbon black suspension, fully modifying the white carbon black for 0.5-10 hours in a matching manner by high sound, ensuring that the white carbon black suspension is in a flowing state in the period, and finally dehydrating the modified white carbon black suspension to obtain dry modified white carbon black powder. Zhang Yi et al dissolve certain quality polyvinyl alcohol (PVA) in water, heat and stir at 95 deg.C for 3hr to make homogeneous solution, add high sound dispersed homogeneous White Carbon Black (WCB) aqueous solution to stir and cool to room temperature and stand still to defoam, pour mixed solution into mould and cross-link with saturated boric acid solution, prepare WCB/PVA composite hydrogel (materials guide 2016,30, 71-76). The Qiu's Fang adopts gamma-methacryloxypropyltrimethoxysilane coupling agent (MPS) to modify nano-Silica (SiO) 2 ) Then grafting polymethyl methacrylate (PMMA) through emulsion polymerization to obtain nano silicon dioxide particles (SiO) with a core-shell structure 2 MPS-PMMA) ("latex blending process" natural rubber/silica nanocomposite microstructure and performance control, 2010, master thesis at hainan university). Polybutadiene/silicon dioxide nano composite material is prepared by a single swallowwort root through an anion in-situ polymerization method, firstly, gamma- (methacryloxyphthalyloxy) propyl trimethoxy silane (MPS) is adopted to treat the surface of a nano white carbon black particle, then, modified silicon dioxide is dispersed in a butadiene and cyclohexane solvent, n-butyl lithium is added as an initiator after high-sound dispersion, polymerization reaction is carried out under the protection of nitrogen, then, a product is added into ethanol to obtain a white precipitate, and the white precipitate is filtered and dried to obtain the modified silicon dioxide nano composite material (the synthetic rubber industry, 2006,29 (6): 474).
Although the method improves the dispersibility of the nano white carbon black particles and enhances the compatibility with a rubber matrix, the method has certain limitations, some small molecular volatile matters can be generated in the modification process of the nano white carbon black particles, so that the problems of environmental pollution and human safety and health are further caused, and meanwhile, the modified nano white carbon black particles have the defects of poor stability, easy agglomeration and the like in the storage and blending processing processes, so that the application of the nano white carbon black in the field of high-end tire rubber products is influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for modifying the ultra-dispersed nano white carbon black filled with solution polymerized styrene-butadiene rubber. The method comprises the steps of firstly, under the condition of hydrothermal synthesis, utilizing light rare earth metal oxide, dicarboxylic acid and unsaturated carboxylic acid ligand to generate double-salt-bridge unsaturated carboxylic acid soap, then, taking alkyl lithium as an initiator, grafting a linear chain segment [ -PS-BR- ] n synthesized by styrene and butadiene as a reaction monomer to prepare a separant containing light rare earth elements, and finally, coating the separant on the surface of nano white carbon black particles to form a layer of barrier layer so as to achieve the method for separating the nano white carbon black. The method not only solves the problem of easy agglomeration of the nano white carbon black, but also avoids the problem of agglomeration again in the blending processing process, improves the compatibility of the nano white carbon black and the solution polymerized styrene butadiene rubber, and endows the nano white carbon black with super-dispersibility in a solution polymerized styrene butadiene rubber system.
The "parts" in the present invention mean parts by mass.
The invention relates to a preparation method for improving dispersibility of rare earth element separant modified nano white carbon black, which comprises the following specific preparation steps:
(1) The preparation of the light rare earth element separant comprises the following steps:
a, preparing the light rare earth metal disalt-bridged unsaturated carboxylic acid soap: based on 100 parts of the total mass of reactants,
firstly, 100-200 parts of deionized water and 5-10 parts of sodium hydroxide solid are added into a 3L beaker, 10-20 parts of dicarboxylic acid is added after the sodium hydroxide is completely dissolved, the temperature is raised to 80-90 ℃, and the solution is vigorously stirred for 1-2 hours until the solution is completely transparent to obtain a solution A; then taking a 3L beaker, adding 100-200 parts of deionized water and 15-20 parts of sodium hydroxide solid, adding 30-40 parts of unsaturated carboxylic acid after the sodium hydroxide is completely dissolved, heating to 80-90 ℃, and violently stirring for 1-2 hours until the solution is completely transparent to obtain a solution B; then taking a 5L beaker, adding 100-200 parts of deionized water and 10-20 parts of deionized water with molar concentration: 0.4-0.7 mol/L HCl, then 10-20 parts of light rare earth metal oxide is added, the temperature is raised to 80-90 ℃, and the mixture is stirred vigorously for 1-2 hours until the solution is completely transparent to obtain solution C; and finally, under the condition of vigorously stirring the solution C, firstly slowly pouring the solution A into the solution C at the speed of 20-30 ml/s, then slowly pouring the solution B into the solution C at the speed of 10-20 ml/s, discharging, washing and drying after a white solid product appears, and thus obtaining the white powder light rare earth metal disalt-bridge unsaturated carboxylic acid soap.
b, preparation of a separant: based on 100 parts of total mass of reactants, firstly introducing argon into a 5L stainless steel polymerization kettle with a jacket for replacement for 2-3 times, sequentially adding 100-200 parts of solvent, 40-50 parts of styrene, 0.1-0.5 part of structure regulator and initiator 1 into the polymerization kettle, heating to 50-60 ℃, and reacting for 20-40 min to form a-PS-chain segment; then adding 45-55 parts of 1, 3-butadiene and 0.1-0.5 part of structure regulator into a polymerization kettle, heating to 60-70 ℃, and reacting for 50-80 min to form a-PS-BR-chain segment; finally, 1-5 parts of light rare earth metal disalt-bridge unsaturated carboxylic acid soap is added, 0.05-0.2 part of initiator 2 is added when the temperature is raised to 80-90 ℃, the reaction is carried out for 1-2 hours, and the separant is prepared by wet coagulation and drying after the reaction is finished.
(2) Preparing the ultra-dispersed nano white carbon black: taking 100 parts by mass of nano white carbon black, adding 100 parts by mass of nano white carbon black, 1-5 parts by mass of a separant and 200-300 parts by mass of a solvent into a 5L stainless steel polymerization kettle, heating to 50-70 ℃, stirring for reaction for 1-3 hr, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black.
The separant is a light rare earth metal disalt-bridge unsaturated carboxylic acid soap-macromolecular long chain segment compound, and the structural general formula of the separant is shown as formula I:
Figure BDA0003112837290000061
wherein M is one of light rare earth metals with oxidation state of + 3: lanthanum (La), cerium (Ce), neodymium (Nd), or europium (Eu); r is an aliphatic chain containing 0 to 6 carbon atoms; r is 1 Is an aliphatic chain containing 0 to 4 carbon atoms; PS is a homopolymer block of styrene; BR is a homopolymer block of 1, 3-butadiene; n is a positive integer greater than 1; [ PS-BR-] n The number average molecular weight (Mn) of the polymer is 2000-4000.
The white carbon black is nano-scale, and the particle size is as follows: 10-100 nm.
The dicarboxylic acid is selected from one of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and suberic acid.
The unsaturated carboxylic acid is selected from one of Acrylic Acid (AA), methacrylic acid (MAA), 2-ethacrylic acid, 2-propylacrylic acid or 2-butylacrylic acid.
The light rare earth metal oxide is selected from lanthanum oxide, cerium oxide and neodymium oxide (Nd) 2 O 3 ) Or europium oxide, preferably Nd 2 O 3 。
The initiator 1 of the invention is a hydrocarbon-based monolithium compound, namely RLi, wherein R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or a composite group of the above groups, which contains 1 to 20 carbon atoms. The alkyl monolithium compound is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium and dodecyllithium, preferably n-butyllithium. The amount depends on the molecular weight of the polymer.
The initiator 2 is an oil-soluble organic peroxide, and is selected from one of tert-butyl hydroperoxide, di-tert-butyl hydroperoxide, tert-butyl peroxide, di-tert-butyl peroxide, dicumyl peroxide (DCP) or dibenzoyl peroxide (BPO), preferably dibenzoyl peroxide (BPO), and the addition amount of the oil-soluble organic peroxide is 0.05-0.2%, preferably 0.09-0.15%.
The structure regulator is selected from one of diethylene glycol dimethyl ether (2G), tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME) and triethylamine, and Tetrahydrofuran (THF) is preferred.
The solvent according to the invention may be selected from cyclohexane, carbon disulphide (CS) 2 ) One of acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, nitrobenzene, petroleum ether, tetrachloroethane, toluene, xylene and chlorobenzene, and cyclohexane is preferred.
The invention relates to a modification method for filling nano white carbon black ultra-dispersion of solution polymerized styrene butadiene rubber, which comprises the steps of firstly utilizing light rare earth metal oxide and HCl to generate salt under the hydrothermal synthesis condition, then generating unsaturated carboxylic acid soap with a light rare earth metal double-salt bridging structure with dicarboxylic acid and unsaturated carboxylic acid ligand under the alkaline condition, then grafting the unsaturated carboxylic acid soap with linear chain segment ([ -PS-BR- ] n) synthesized by styrene and butadiene as a reaction monomer by taking alkyl lithium as an initiator to prepare a light rare earth metal-containing separant, and finally coating the separant on the surface of nano white carbon black particles to form a barrier layer to separate the nano white carbon black. The separant disclosed by the invention contains light rare earth metal, polyhydroxy and polycarbonyl, and hydroxyl on the surface of the nano white carbon black realizes multi-point anchoring modification through hydrogen bond action, and high-density anchoring points are formed on the surface of the nano white carbon black particles, so that the connecting strength of the separant and the nano white carbon black particles is increased, and the phenomenon of reagglomeration caused by the separation of the separant under the conditions of high temperature and high shear in the blending processing process of the nano white carbon black particles is avoided. And the separant contains [ -PS-BR- ] n chain segment, the molecular chain structure has the characteristics of non-polarity and benzene ring structure, the molecular steric hindrance effect is large, the electrostatic adsorption and the superfine particle effect of hydroxyl on the surface of the nano white carbon black particles can be effectively shielded, a space barrier layer can be established among the nano white carbon black particles, the mutual agglomeration among the particles is hindered, and the nano white carbon black can stably exist in a single particle form (see figure 1). Meanwhile, the structure of the [ -PS-BR- ] n chain segment is completely the same as the molecular structure of the solution polymerized styrene butadiene rubber, and has good affinity with the solution polymerized styrene butadiene rubber, thereby greatly reducing the Payne effect of the nano white carbon black filler in the filled solution polymerized styrene butadiene rubber, and being beneficial to the dispersion and combination of the nano white carbon black particles in the solution polymerized styrene butadiene rubber matrix so as to realize ultra-dispersion. The light rare earth metal double-salt-bridge unsaturated carboxylic acid compound is a novel safe and environment-friendly compound without VOC emission, and has the advantages of small environmental pollution, simple and convenient modification process and low modification cost.
Drawings
FIG. 1 is an SEM electron micrograph of a sample of ultra-dispersed nano white carbon black of example 1.
Detailed Description
The present invention will be specifically described below by way of examples. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the above teachings.
All the raw materials used in the examples are of industrial polymerization grade, and are used after purification without other special requirements.
The method comprises the following steps of raw material sources:
Figure BDA0003112837290000081
Figure BDA0003112837290000091
other reagents are all commercial products
The method comprises the following steps:
analyzing a sample by an electron microscope: and (3) performing dispersion analysis on the sample before and after modification of the nano white carbon black by adopting an XL-20 scanning electron microscope produced by Philips corporation in the Netherlands. And carrying out SEM analysis on the sample under the accelerating voltage of 20kV after the sample is subjected to gold spraying treatment by a surface treatment machine.
The method for measuring the sedimentation volume comprises the following steps: weighing 10g of modified nano white carbon black, placing the modified nano white carbon black into a graduated 100mL measuring cylinder, adding a certain amount of dispersant (liquid paraffin), adding the liquid paraffin to the 100mL scale after the modified nano white carbon black is completely soaked by the liquid paraffin, fully oscillating for 5min at the oscillation frequency of 30 times/1 min to ensure that the modified nano white carbon black is uniformly dispersed in the liquid paraffin, then standing, and reading the solid volume at different time. The sedimentation volume in the same time can reflect the compatibility between the particles and the organic solvent to a certain extent, and the sedimentation volume is large, so that the carbon black is good in dispersion and easy to be compatible.
Method for measuring oil absorption: referring to the determination method of oil absorption of aluminum hydroxide for YS/T618-2007 fillers, quantitative modified nano white carbon black is put into a watch glass, diisooctyl phthalate is dropwise added according to 0.2mL each time, after each dropwise addition, the mixture is fully ground by a knife until the powder can be bonded into large groups without cracking, and the oil absorption is V of the volume of oil absorbed by each 100g of sample 0 (mL) as follows:
Figure BDA0003112837290000092
wherein upsilon is the volume of diisooctyl phthalate consumed (mL); m is the mass (g) of the sample. The oil absorption reflects the specific surface area of the modified nano white carbon black to a certain extent, and the lower the specific surface area is, the lower the oil absorption is, the better the wettability is, and vice versa.
Example 1
(1) The preparation of the light rare earth element separant comprises the following steps:
a, preparing the light rare earth metal disalt-bridged unsaturated carboxylic acid soap: firstly, adding 500g of deionized water and 25g of sodium hydroxide solid into a 3L beaker, adding 50g of oxalic acid after the sodium hydroxide is completely dissolved, heating to 80 ℃, and violently stirring for 1.0hr until the solution is completely transparent to obtain a solution A; then, adding 500g of deionized water and 75g of sodium hydroxide solid into a 3L beaker, adding 150g of MAA after the sodium hydroxide is completely dissolved, heating to 80 ℃, and violently stirring for 1.0hr until the solution is completely transparent to obtain a solution B; then, a 5L beaker was charged with 500g of deionized water and 50g of HCl (molar concentration: 0.4 mol/L)Followed by the addition of 50g La 2 O 3 Heating to 80 deg.C and stirring vigorously for 1.0hr until the solution is completely transparent to obtain solution C; and finally, under the condition of vigorously stirring the solution C, firstly slowly pouring the solution A into the solution C at the speed of 20ml/s, then slowly pouring the solution B into the solution C at the speed of 10ml/s, discharging, washing and drying after a white solid product appears, and thus obtaining the white powder light rare earth metal di-salt bridge unsaturated carboxylic acid soap.
b, preparation of a separant: firstly, introducing argon into a 5L stainless steel polymerization kettle with a jacket for replacement for 2 times, sequentially adding 1000g of cyclohexane, 400g of styrene, 1.0g of THF and 3.9mmo1 n-butyllithium into the polymerization kettle, heating to 50 ℃, and reacting for 20min to form a-PS-chain segment; then 450g of 1, 3-butadiene and 1.5g of THF are added into the polymerization kettle, the temperature is raised to 60 ℃, and the reaction is carried out for 50min to form a-PS-BR-chain segment; finally, 10g of light rare earth metal disalt-bridge unsaturated carboxylic acid soap is added, 0.9g of BPO is added when the temperature is raised to 80 ℃, the reaction is carried out for 1.0hr, and the separant (PS-BR-] n The Mn of the polymer is 2200).
(2) Preparing the ultra-dispersed nano white carbon black: 1000g of nano white carbon black (10 nm), 10g of separant and 2000g of cyclohexane are added into a 5L stainless steel polymerization kettle, the temperature is raised to 50 ℃, the mixture is stirred and reacts for 1.0hr, and then the ultra-dispersed nano white carbon black is prepared through flash evaporation, drying and grinding. Sampling and analyzing: standard test specimens were prepared and the properties tested are shown in Table 1.
Example 2
(1) The preparation of the light rare earth element separant comprises the following steps:
a, preparing the light rare earth metal disalt-bridged unsaturated carboxylic acid soap: firstly, 600g of deionized water and 30g of sodium hydroxide solid are added into a 3L beaker, 60g of oxalic acid is added after the sodium hydroxide is completely dissolved, the temperature is raised to 82 ℃, and the mixture is vigorously stirred for 1.2 hours until the solution is completely transparent to obtain a solution A; then, taking a 3L beaker, adding 600g of deionized water and 80g of sodium hydroxide solid, adding 160g of MAA after the sodium hydroxide is completely dissolved, heating to 82 ℃, and violently stirring for 1.1hr until the solution is completely transparent to obtain a solution B; then, a 5L beaker was taken and 600g of deionized water and60g of HCl (molar concentration: 0.5 mol/L), followed by the addition of 60g of Nd 2 O 3 Heating to 80 deg.C and stirring vigorously for 1.2hr until the solution is completely transparent to obtain solution C; and finally, under the condition of vigorously stirring the solution C, firstly slowly pouring the solution A into the solution C at the speed of 22ml/s, then slowly pouring the solution B into the solution C at the speed of 12ml/s, discharging, washing and drying after a white solid product appears, and thus obtaining the white powder light rare earth metal di-salt bridge unsaturated carboxylic acid soap.
b, preparation of a separant: firstly, introducing argon into a 5L stainless steel polymerization kettle with a jacket for replacement for 2 times, sequentially adding 1200g of cyclohexane, 420g of styrene, 1.5g of THF and 4.3mmo1 n-butyllithium into the polymerization kettle, heating to 52 ℃, and reacting for 25min to form a-PS-chain segment; then, 480g of 1, 3-butadiene and 2.0g of THF are added into a polymerization kettle, the temperature is raised to 62 ℃, and the reaction is carried out for 55min to form a-PS-BR-chain segment; finally adding 15g of light rare earth metal disalt-bridge unsaturated carboxylic acid soap, adding 1.1g of BPO when the temperature is raised to 80 ℃, reacting for 1.2hr, and obtaining the separant (PS-BR-] n Mn of the polymer was 2400).
(2) Preparing the ultra-dispersed nano white carbon black: 1000g of nano white carbon black (10 nm), 15g of separant and 2200g of cyclohexane are added into a 5L stainless steel polymerization kettle, the temperature is raised to 55 ℃, the mixture is stirred and reacts for 1.5 hours, and then the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 3
(1) The preparation of the light rare earth element separant comprises the following steps:
a, preparing the light rare earth metal disalt-bridged unsaturated carboxylic acid soap: firstly, 700g of deionized water and 35g of sodium hydroxide solid are added into a 3L beaker, 70g of oxalic acid is added after the sodium hydroxide is completely dissolved, the temperature is raised to 84 ℃, and the mixture is vigorously stirred for 1.5 hours until the solution is completely transparent to obtain a solution A; then taking a 3L beaker, adding 700g of deionized water and 85g of sodium hydroxide solid, adding 170g of MAA after the sodium hydroxide is completely dissolved, heating to 84 ℃, and violently stirring for 1.3 hours until the solution is completely transparent to obtain a solution B; then taking a 5L sample700g of deionized water and 70g of HCl (molar concentration: 0.5 mol/L) were added to the beaker, followed by 70g of Nd 2 O 3 Heating to 82 deg.C and stirring vigorously for 1.5hr until the solution is completely transparent to obtain solution C; and finally, under the condition of vigorously stirring the solution C, firstly slowly pouring the solution A into the solution C at the speed of 25ml/s, then slowly pouring the solution B into the solution C at the speed of 14ml/s, discharging, washing and drying after a white solid product appears, and thus obtaining the white powder light rare earth metal di-salt bridge unsaturated carboxylic acid soap.
b, preparation of a separant: firstly, introducing argon into a 5L stainless steel polymerization kettle with a jacket for replacement for 2 times, sequentially adding 1500g of cyclohexane, 440g of styrene, 2.0g of THF and 4.7mmo1 n-butyllithium into the polymerization kettle, heating to 54 ℃, and reacting for 30min to form a-PS-chain segment; then adding 500g of 1, 3-butadiene and 2.5g of THF into a polymerization kettle, heating to 64 ℃, and reacting for 60min to form a-PS-BR-chain segment; finally adding 20g of light rare earth metal disalt-bridge unsaturated carboxylic acid soap, adding 1.3g of BPO when the temperature is raised to 83 ℃, reacting for 1.5hr, and obtaining the separant (PS-BR-] n Mn of polymer 2700).
(2) Preparing the ultra-dispersed nano white carbon black: 1000g of nano white carbon black (10 nm), 20g of separant and 2400g of cyclohexane are added into a 5L stainless steel polymerization kettle, the temperature is raised to 60 ℃, the mixture is stirred and reacts for 2.0 hours, and then the ultra-dispersed nano white carbon black is prepared through flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 4
(1) The preparation of the light rare earth element separant comprises the following steps:
a, preparing the light rare earth metal disalt-bridged unsaturated carboxylic acid soap: firstly, adding 800g of deionized water and 40g of sodium hydroxide solid into a 3L beaker, adding 80g of oxalic acid after the sodium hydroxide is completely dissolved, heating to 86 ℃, and violently stirring for 1.7 hours until the solution is completely transparent to obtain a solution A; adding 800g deionized water and 90g sodium hydroxide solid into a 3L beaker, adding 180g MAA after sodium hydroxide is completely dissolved, heating to 86 deg.C, and stirring vigorously for 1.6hr until the solution is completely transparentTo solution B; then, a 5L beaker was charged with 800g of deionized water and 80g of HCl (molar concentration: 0.5 mol/L), followed by 80g of Nd 2 O 3 Heating to 84 deg.C and stirring vigorously for 1.6hr until the solution is completely transparent to obtain solution C; and finally, under the condition of vigorously stirring the solution C, firstly slowly pouring the solution A into the solution C at the speed of 27ml/s, then slowly pouring the solution B into the solution C at the speed of 16ml/s, discharging, washing and drying after a white solid product appears, and thus obtaining the white powder light rare earth metal disalt-bridge unsaturated carboxylic acid soap.
b, preparation of a separant: firstly, introducing argon to a 5L stainless steel polymerization kettle with a jacket for replacing for 2 times, sequentially adding 1700g of cyclohexane, 460g of styrene, 2.6g of THF and 5.4mmo1 n-butyl lithium into the polymerization kettle, heating to 56 ℃, and reacting for 34min to form a-PS-chain segment; then 520g of 1, 3-butadiene and 3.1g of THF are added into the polymerization kettle, the temperature is raised to 66 ℃, and the reaction is carried out for 70min, thus forming a-PS-BR-chain segment; finally adding 30g of light rare earth metal disalt-bridge unsaturated carboxylic acid soap, adding 1.5g of BPO when the temperature is raised to 85 ℃, reacting for 1.7hr, and obtaining the separant (PS-BR-] n The Mn of the polymer was 3100).
(2) Preparing the ultra-dispersed nano white carbon black: 1000g of nano white carbon black (60 nm), 30g of separant and 2600g of cyclohexane are added into a 5L stainless steel polymerization kettle, the temperature is increased to 63 ℃, the mixture is stirred and reacts for 2.2 hours, and then the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 5
(1) The preparation of the light rare earth element separant comprises the following steps:
a, preparing the light rare earth metal disalt-bridged unsaturated carboxylic acid soap: firstly, adding 900g of deionized water and 45g of sodium hydroxide solid into a 3L beaker, adding 90g of adipic acid after the sodium hydroxide is completely dissolved, heating to 88 ℃, and violently stirring for 1.9 hours until the solution is completely transparent to obtain a solution A; then adding 900g of deionized water and 95g of sodium hydroxide solid into a 3L beaker, adding 190g of AA after the sodium hydroxide is completely dissolved, heating to 88 ℃, and violently stirring1.8hr until the solution is completely transparent to obtain solution B; then, a 5L beaker was charged with 900g of deionized water and 90g of HCl (molar concentration: 0.6 mol/L), followed by 90g of Nd 2 O 3 Heating to 88 deg.C and stirring vigorously for 1.8hr until the solution is completely transparent to obtain solution C; and finally, under the condition of vigorously stirring the solution C, firstly slowly pouring the solution A into the solution C at the speed of 28ml/s, then slowly pouring the solution B into the solution C at the speed of 18ml/s, discharging, washing and drying after a white solid product appears, and thus obtaining the white powder light rare earth metal di-salt bridge unsaturated carboxylic acid soap.
b, preparation of a separant: firstly, introducing argon into a 5L stainless steel polymerization kettle with a jacket for replacement for 2 times, sequentially adding 1800g of cyclohexane, 480g of styrene, 3.0g of THF and 6.2mmo1 of n-butyllithium into the polymerization kettle, heating to 58 ℃, and reacting for 37min to form a-PS-chain segment; then 530g of 1, 3-butadiene and 3.5g of THF are added into a polymerization kettle, the temperature is raised to 68 ℃, and the reaction is carried out for 75min to form a-PS-BR-chain segment; finally adding 40g of light rare earth metal disalt-bridge unsaturated carboxylic acid soap, adding 1.7g of BPO when the temperature is raised to 87 ℃, reacting for 1.9hr, and obtaining the separant (PS-BR-] n Mn of polymer 3500).
(2) Preparing the ultra-dispersed nano white carbon black: 1000g of nano white carbon black (80 nm), 40g of separant and 2800g of cyclohexane are added into a 5L stainless steel polymerization kettle, the temperature is raised to 68 ℃, the mixture is stirred and reacts for 2.6 hours, and then the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 6
(1) The preparation of the light rare earth element separant comprises the following steps:
a, preparing the light rare earth metal disalt-bridged unsaturated carboxylic acid soap: firstly, 1000g of deionized water and 50g of sodium hydroxide solid are added into a 3L beaker, 100g of adipic acid is added after the sodium hydroxide is completely dissolved, the temperature is raised to 90 ℃, and the mixture is vigorously stirred for 2.0 hours until the solution is completely transparent to obtain a solution A; then 1000g of deionized water and 100g of sodium hydroxide solid are added into a 3L beaker, and after the sodium hydroxide is completely dissolved, the deionized water and the sodium hydroxide solid are addedHeating 200g AA to 90 deg.C, and stirring vigorously for 2.0hr until the solution is completely transparent to obtain solution B; then, a 5L beaker was charged with 1000g of deionized water and 100g of HCl (molar concentration: 0.7 mol/L), followed by 100g of Nd 2 O 3 Heating to 90 deg.C and stirring vigorously for 2.0hr until the solution is completely transparent to obtain solution C; and finally, under the condition of vigorously stirring the solution C, slowly pouring the solution A into the solution C at the speed of 30ml/s, slowly pouring the solution B into the solution C at the speed of 20ml/s, discharging, washing and drying after a white solid product appears, and thus obtaining the white powder light rare earth metal di-salt bridge unsaturated carboxylic acid soap.
b, preparation of a separant: firstly, introducing argon into a 5L stainless steel polymerization kettle with a jacket for replacement for 3 times, sequentially adding 2000g of cyclohexane, 500g of styrene, 3.8g of THF and 7.1mmo1 n-butyllithium into the polymerization kettle, heating to 60 ℃, and reacting for 40min to form a-PS-chain segment; then 550g of 1, 3-butadiene and 4.2g of THF are added into a polymerization kettle, the temperature is raised to 70 ℃, and the reaction is carried out for 80min to form a-PS-BR-chain segment; finally adding 50g of light rare earth metal disalt-bridged unsaturated carboxylic acid soap, adding 2.0g of BPO when the temperature is raised to 90 ℃, reacting for 2.0hr, and obtaining the separant ([ PS-BR-] n Mn of the polymer is 4000).
(2) Preparing the ultra-dispersed nano white carbon black: 1000g of nano white carbon black (80 nm), 50g of separant and 3000g of cyclohexane are added into a 5L stainless steel polymerization kettle, the temperature is raised to 70 ℃, the mixture is stirred and reacts for 3.0 hours, and then the ultra-dispersed nano white carbon black is prepared through flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 1
(1) The preparation of the light rare earth element separant comprises the following steps:
a, preparing the light rare earth metal disalt-bridged unsaturated carboxylic acid soap: the same as in example 1.
b, preparation of a separant: the same as in example 1.
(2) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 1 except that the amount of the release agent added during the preparation was 4g, that is: 1000g of nano white carbon black (10 nm), 4g of separant and 2000g of cyclohexane are added into a 5L stainless steel polymerization kettle, the temperature is raised to 50 ℃, the mixture is stirred and reacts for 1.0hr, and then the ultra-dispersed nano white carbon black is prepared through flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 2
(1) The preparation of the light rare earth element separant comprises the following steps:
a, preparing the light rare earth metal disalt-bridged unsaturated carboxylic acid soap: the other conditions were the same as in example 2 except that Nd was not added during the production 2 O 3 Instead, fe is added 2 O 3 Namely: firstly, 600g of deionized water and 30g of sodium hydroxide solid are added into a 3L beaker, 60g of oxalic acid is added after the sodium hydroxide is completely dissolved, the temperature is raised to 82 ℃, and the mixture is vigorously stirred for 1.2 hours until the solution is completely transparent to obtain a solution A; then, taking a 3L beaker, adding 600g of deionized water and 80g of sodium hydroxide solid, adding 160g of MAA after the sodium hydroxide is completely dissolved, heating to 82 ℃, and violently stirring for 1.1hr until the solution is completely transparent to obtain a solution B; then, a 5L beaker was charged with 600g of deionized water and 60g of HCl (molar concentration: 0.5 mol/L), followed by 60g of Fe 2 O 3 Heating to 80 deg.C and stirring vigorously for 1.2hr until the solution is completely transparent to obtain solution C; and finally, under the condition of vigorously stirring the solution C, firstly slowly pouring the solution A into the solution C at the speed of 22ml/s, then slowly pouring the solution B into the solution C at the speed of 12ml/s, discharging, washing and drying after a white solid product appears, and thus obtaining the white powder light rare earth metal di-salt bridge unsaturated carboxylic acid soap 1.
b, preparation of a separant: the other conditions were the same as in example 2 except that the light rare earth metal di-salt-bridged unsaturated carboxylic acid soap 1 was added instead of the light rare earth metal di-salt-bridged unsaturated carboxylic acid soap in the preparation process, that is: firstly, introducing argon into a 5L stainless steel polymerization kettle with a jacket for replacement for 2 times, sequentially adding 1200g of cyclohexane, 420g of styrene, 1.5g of THF and 4.3mmo1 n-butyllithium into the polymerization kettle, heating to 52 ℃, and reacting for 25min to form a-PS-chain segment; then, 480g of 1, 3-butadiene, 2 was further charged into the polymerization vessel0g of THF, heating to 62 ℃, and reacting for 55min to form a-PS-BR-chain segment; finally adding 15g of light rare earth metal disalt-bridge unsaturated carboxylic soap 1, adding 1.1g of BPO when the temperature is raised to 80 ℃, reacting for 1.2hr, and obtaining the separant 1 ([ PS-BR-] n Mn of the polymer was 2400).
(2) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 2, except that no release agent was added during the preparation, but release agent 1 was added, namely: 1000g of nano white carbon black (10 nm) and 15g of separant 1 and 2200g of cyclohexane are added into a 5L stainless steel polymerization kettle, the temperature is raised to 55 ℃, the mixture is stirred and reacts for 1.5 hours, and then the ultra-dispersed nano white carbon black is prepared through flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 3
(1) The preparation of the light rare earth element separant comprises the following steps:
a, preparing the light rare earth metal disalt-bridged unsaturated carboxylic acid soap: the same as in example 3.
b, preparation of a separant: the other conditions were the same as in example 3 except that the amount of the light rare earth metal disalt-bridged unsaturated carboxylic acid soap added in the preparation process was 8g, that is: firstly, introducing argon into a 5L stainless steel polymerization kettle with a jacket for replacement for 2 times, sequentially adding 1500g of cyclohexane, 440g of styrene, 2.0g of THF and 4.7mmo1 n-butyllithium into the polymerization kettle, heating to 54 ℃, and reacting for 30min to form a-PS-chain segment; then adding 500g of 1, 3-butadiene and 2.5g of THF into a polymerization kettle, heating to 64 ℃, and reacting for 60min to form a-PS-BR-chain segment; finally adding 8g of light rare earth metal disalt-bridge unsaturated carboxylic acid soap, adding 1.3g of BPO when the temperature is raised to 83 ℃, reacting for 1.5hr, and obtaining the separant 2 ([ PS-BR-] n Mn of polymer 2700).
(2) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 3, except that no release agent was added during the preparation, but release agent 2 was added, namely: 1000g of nano white carbon black (10 nm), 20g of separant 2 and 2400g of cyclohexane are added into a 5L stainless steel polymerization kettle, the temperature is raised to 60 ℃, the mixture is stirred and reacts for 2.0 hours, and then the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding. Sampling and analyzing: standard test specimens were prepared and the properties tested are shown in Table 1.
Comparative example 4
(1) The preparation of the light rare earth element separant comprises the following steps:
a, preparing the light rare earth metal disalt-bridged unsaturated carboxylic acid soap: the same as in example 4.
b, preparation of a separant: except that no BPO was added during the preparation, i.e.: firstly, introducing argon into a 5L stainless steel polymerization kettle with a jacket for replacement for 2 times, sequentially adding 1700g of cyclohexane, 460g of styrene, 2.6g of THF and 5.4mmo1 n-butyllithium into the polymerization kettle, heating to 56 ℃, and reacting for 34min to form a-PS-chain segment; then 520g of 1, 3-butadiene and 3.1g of THF are added into the polymerization kettle, the temperature is raised to 66 ℃, and the reaction is carried out for 70min, so as to form a-PS-BR-chain segment; finally adding 30g of light rare earth metal disalt-bridge unsaturated carboxylic acid soap, reacting for 1.7 hours when the temperature is raised to 85 ℃, and obtaining the separant 3 ([ PS-BR-] n The Mn of the polymer was 3100).
(2) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 4, except that no release agent was added during the preparation, but release agent 3 was added, namely: 1000g of nano white carbon black (60 nm), 30g of separant 3 and 2600g of cyclohexane are added into a 5L stainless steel polymerization kettle, the temperature is increased to 63 ℃, the mixture is stirred and reacts for 2.2 hours, and then the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 5
(2) The preparation of the light rare earth element separant comprises the following steps:
a, preparing the light rare earth metal disalt-bridged unsaturated carboxylic acid soap: the same as in example 5.
B, preparation of a separant: the other conditions were the same as in example 5 except that n-butyllithium was added in an amount of 2.7mmo1 during the preparation, that is: firstly, introducing argon into a 5L stainless steel polymerization kettle with a jacket for replacement for 2 times, sequentially adding 1800g of cyclohexane, 480g of styrene, 3.0g of THF and 2.5mmo1 n-butyllithium into the polymerization kettle, heating to 58 ℃, and reacting for 37min to form-a PS-segment; then 530g of 1, 3-butadiene and 3.5g of THF are added into a polymerization kettle, the temperature is raised to 68 ℃, and the reaction is carried out for 75min to form a-PS-BR-chain segment; finally, 40g of light rare earth metal disalt-bridge unsaturated carboxylic acid soap is added, 1.7g of BPO is added when the temperature is raised to 87 ℃, the reaction is carried out for 1.9hr, and the separant 4 ([ PS-BR-] n Mn of polymer 1600).
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 5, except that no release agent was added during the preparation, but release agent 4 was added, namely: 1000g of nano white carbon black (80 nm), 40g of separant 4 and 2800g of cyclohexane are added into a 5L stainless steel polymerization kettle, the temperature is raised to 68 ℃, the mixture is stirred and reacts for 2.6 hours, and then the ultra-dispersed nano white carbon black is prepared through flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 6
(1) The preparation of the light rare earth element separant comprises the following steps:
a, preparing the light rare earth metal salt bridged unsaturated carboxylic acid soap: the other conditions were the same as in example 6, except that no adipic acid was added during the preparation, but caproic acid, i.e.: firstly, 1000g of deionized water and 50g of sodium hydroxide solid are added into a 3L beaker, 100g of caproic acid is added after the sodium hydroxide is completely dissolved, the temperature is raised to 90 ℃, and the mixture is vigorously stirred for 2.0 hours until the solution is completely transparent to obtain a solution A 1 (ii) a Then adding 1000g of deionized water and 100g of sodium hydroxide solid into a 3L beaker, adding 200g of AA after the sodium hydroxide is completely dissolved, heating to 90 ℃, and violently stirring for 2.0 hours until the solution is completely transparent to obtain a solution B; then, 1000g of deionized water and 100g of HCl (molar concentration: 0.7 mol/L) were added to a 5-L beaker, followed by 100g of Nd 2 O 3 Heating to 90 deg.C and stirring vigorously for 2.0hr until the solution is completely transparent to obtain solution C; finally, the solution A is first of all mixed while the solution C is vigorously stirred 1 Slowly pouring the solution B into the solution C at a speed of 30ml/s, slowly pouring the solution B into the solution C at a speed of 20ml/s, discharging, washing and drying after a white solid product appears, and obtaining the white powder of the light rare earthMetal salt bridged unsaturated carboxylic acid soaps.
b, preparation of a separant: the other conditions were the same as in example 6 except that the light rare earth metal di-salt-bridged unsaturated carboxylic acid soap was not added in the preparation process, but the light rare earth metal salt-bridged unsaturated carboxylic acid soap was added, that is: firstly, introducing argon to a 5L stainless steel polymerization kettle with a jacket for replacing for 3 times, sequentially adding 2000g of cyclohexane, 500g of styrene, 3.8g of THF and 7.1mmo1 n-butyl lithium into the polymerization kettle, heating to 60 ℃, and reacting for 40min to form a-PS-chain segment; then 550g of 1, 3-butadiene and 4.2g of THF are added into a polymerization kettle, the temperature is raised to 70 ℃, and the reaction is carried out for 80min to form a-PS-BR-chain segment; finally adding 50g of light rare earth metal salt bridge unsaturated carboxylic acid soap, adding 2.0g of BPO when the temperature is raised to 90 ℃, reacting for 2.0hr, and obtaining the separant 5 (PS-BR-] n The Mn of the polymer was 4000).
(2) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 6, except that no release agent was added during the preparation, and release agent 5 was added, namely: 1000g of nano white carbon black (80 nm), 50g of separant 5 and 3000g of cyclohexane are added into a 5L stainless steel polymerization kettle, the temperature is raised to 70 ℃, the mixture is stirred and reacts for 3.0 hours, and then the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
TABLE 1 sedimentation volume and oil absorption rate of ultra-dispersed nano white carbon black
Figure BDA0003112837290000201
Figure BDA0003112837290000211
As can be seen from Table 1: the sedimentation volume ratio of the examples is larger than that of the comparative example at the same time, and the oil absorption is lower than that of the comparative example, which shows that the modification effect of the invention is obvious.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (16)

1. The rare earth element separant modified nano white carbon black is characterized in that the surface of the modified nano white carbon black is coated with a light rare earth element separant; the light rare earth element separant is a light rare earth metal disalt-bridge unsaturated carboxylic acid soap-macromolecular long chain segment compound, and the structural general formula of the light rare earth element separant is shown as the formula I:
Figure FDA0003112837280000011
wherein M is one of light rare earth metal ions with oxidation state of + 3: lanthanum, cerium, neodymium or europium; r is an aliphatic chain containing 0 to 6 carbon atoms; r 1 Is an aliphatic chain containing 0 to 4 carbon atoms; PS is a homopolymer block of styrene; BR is a homopolymer block of 1, 3-butadiene; n is a positive integer greater than 1; [ PS-BR-] n The number average molecular weight of the polymer is 2000-4000.
2. The rare earth element separant-modified nano white carbon black of claim 1, wherein the particle size of the modified nano white carbon black is 10-100 nm.
3. The rare earth element separant modified nano white carbon black of claim 1, wherein the preparation method of the rare earth element separant comprises the following steps:
(1) Preparing the light rare earth metal disalt-bridged unsaturated carboxylic acid soap: adding 100-200 parts of deionized water and 5-10 parts of sodium hydroxide solid into a reactor A by taking the total mass of reactants as 100 parts, adding 10-20 parts of dicarboxylic acid after the sodium hydroxide is completely dissolved, heating to 80-90 ℃, and violently stirring for 1-2 hours until the solution is completely transparent to obtain a solution A; then adding 100-200 parts of deionized water and 15-20 parts of sodium hydroxide solid into the reactor B, adding 30-40 parts of unsaturated carboxylic acid after the sodium hydroxide is completely dissolved, heating to 80-90 ℃, and violently stirring for 1-2 hours until the solution is completely transparent to obtain a solution B; adding 100-200 parts of deionized water and 10-20 parts of molar concentration into a reactor C: 0.4-0.7 mol/L HCl, then 10-20 parts of light rare earth metal oxide is added, the temperature is raised to 80-90 ℃, and the mixture is vigorously stirred for 1-2 hours until the solution is completely transparent to obtain solution C; finally, under the condition of vigorously stirring the solution C, firstly slowly pouring the solution A into the solution C at the speed of 20-30 ml/s, then slowly pouring the solution B into the solution C at the speed of 10-20 ml/s, discharging, washing and drying after a white solid product appears, and thus obtaining the light rare earth metal disalt-bridge unsaturated carboxylic acid soap;
(2) Preparing a rare earth element separant: based on 100 parts of the total mass of reactants, firstly, sequentially adding 100-200 parts of solvent, 40-50 parts of styrene, 0.1-0.5 part of structure regulator and 1 part of initiator into a polymerization kettle, heating to 50-60 ℃, and reacting for 20-40 min; then adding 45-55 parts of 1, 3-butadiene and 0.1-0.5 part of structure regulator into a polymerization kettle, heating to 60-70 ℃, and reacting for 50-80 min; finally, 1 to 5 parts of the light rare earth metal disalt-bridge unsaturated carboxylic acid soap is added, 0.05 to 0.2 part of initiator 2 is added when the temperature is raised to 80 to 90 ℃, the reaction lasts for 1 to 2 hours, and the separant is prepared by wet coagulation and drying after the reaction is finished.
4. The rare earth element separant modified nano white carbon black according to claim 3, wherein the unsaturated carboxylic acid is one selected from acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid or 2-butylacrylic acid.
5. The rare earth element separant modified nano white carbon black of claim 3, wherein the dicarboxylic acid is one selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and suberic acid.
6. The rare earth element separant modified nano white carbon according to claim 3, wherein the light rare earth metal oxide is one selected from lanthanum oxide, cerium oxide, neodymium oxide and europium oxide.
7. The rare earth element separant modified nano white carbon black of claim 6, wherein the light rare earth metal oxide is neodymium oxide.
8. The rare earth element separant modified nano white carbon black of claim 3, wherein the initiator 1 is selected from one of n-butyl lithium, sec-butyl lithium, methyl butyl lithium, phenyl butyl lithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium.
9. The rare earth element separant modified nano white carbon black of claim 8, wherein the initiator 1 is n-butyl lithium.
10. The rare earth element separant-modified nano white carbon black according to claim 3, wherein the initiator 2 is an oil-soluble organic peroxide selected from one of tert-butyl hydroperoxide, di-tert-butyl hydroperoxide, tert-butyl peroxide, di-tert-butyl peroxide, dicumyl peroxide and dibenzoyl peroxide.
11. The rare earth element separant modified nano white carbon black of claim 10, wherein the initiator 2 is dibenzoyl peroxide.
12. The rare earth element separant modified nano white carbon black of claim 11, wherein the addition amount of the initiator 2 is 0.09-0.15%.
13. The rare earth element isolating agent modified nano white carbon black of claim 3, wherein the structure regulator is selected from one of diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether and triethylamine.
14. The preparation method of the rare earth element separant modified nano white carbon black disclosed by any one of claims 3 to 13, is characterized by comprising the following steps of: taking 100 percent of nano white carbon black, 1 to 5 percent of the rare earth element separant and 200 to 300 percent of solvent by mass percent of the nano white carbon black, adding the nano white carbon black, the rare earth element separant and the solvent into a polymerization kettle, heating the mixture to 50 to 70 ℃, stirring the mixture for reaction for 1 to 3 hours, and then carrying out flash evaporation, drying and grinding on the mixture to obtain the nano white carbon black.
15. The method of claim 14, wherein the solvent is selected from one of cyclohexane, carbon disulfide, acetone, acetonitrile, dimethylformamide, dimethylsulfoxide, nitrobenzene, petroleum ether, tetrachloroethane, toluene, xylene, chlorobenzene.
16. The method of claim 15, wherein the solvent is cyclohexane.
CN202110653584.2A 2021-06-11 2021-06-11 Rare earth element separant modified nano white carbon black and preparation method thereof Pending CN115466434A (en)

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