CN111073052A - Preparation method of ultra-dispersed nano white carbon black - Google Patents

Preparation method of ultra-dispersed nano white carbon black Download PDF

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CN111073052A
CN111073052A CN201811217629.6A CN201811217629A CN111073052A CN 111073052 A CN111073052 A CN 111073052A CN 201811217629 A CN201811217629 A CN 201811217629A CN 111073052 A CN111073052 A CN 111073052A
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carbon black
white carbon
parts
butadiene rubber
mass
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徐典宏
赵燕
牛承祥
魏绪玲
马朋高
杨绮波
赵洪国
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Petrochina Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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Abstract

The invention aims to provide a preparation method of super-dispersed nano white carbon black filled with solution polymerized styrene butadiene rubber. According to the method, polyether polyol and a silane coupling agent are subjected to copolymerization reaction, the generated product, namely organic silicon/polyether polyol copolymer, is subjected to multi-point anchoring modification on the surface of nano white carbon black particles, then acid anhydride and a halogenating agent are adopted to carry out acyl halogenation on solution-polymerized styrene-butadiene rubber slurry, and finally the solution-polymerized styrene-butadiene rubber slurry is coated on the surface of the nano white carbon black particles to form a barrier layer with high connection strength so as to achieve the method for separating the nano white carbon black particles, and meanwhile, the compatibility of the nano white carbon black and solution-polymerized styrene-butadiene rubber is improved, and the super-dispersibility of the nano white carbon black in a solution-. The invention has low modification cost and little environmental pollution.

Description

Preparation method of ultra-dispersed nano white carbon black
Technical Field
The invention relates to a preparation method of nano white carbon black, in particular to a preparation method of ultra-dispersed nano white carbon black for filling rubber.
Background
The nanometer white carbon black is porous substance, and the composition can be SiO2·nH2O represents, wherein nH2O exists in the form of surface hydroxyl, is white, non-toxic, amorphous and porous fine powder, has the characteristics of large inner surface volume, dispersibility, 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 the 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 occurs in the application process of the ultrafine inorganic powder, namely, the ultrafine powder is more difficult to be mixed, soaked and dispersed by rubber materials because the specific surface area is increased, the self-polymerization capacity is stronger and the particle size is reduced. 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 coupling agents or surfactants such as silane coupling agents, toluene isocyanate, inorganic minerals and oligomers, such as: CN101798473A discloses a preparation method of silane modified white carbon black, which comprises the steps of adding precipitated white carbon black and fumed 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 manner, and 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 heating and activating white carbon black at 250-300 ℃ for 4-5 hours under the protection of nitrogen, mixing the activated white carbon black with toluene isocyanate, wherein the dosage of the toluene isocyanate is 10-20% of the dosage of the white carbon black, adding anhydrous xylene into the mixture, the mass ratio of the volume of the dosage of the anhydrous xylene to the dosage 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 halogen-free flame-retardant rubber material with excellent flame-retardant property prepared by modifying an inorganic flame-retardant filler with unsaturated carboxylic acid 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 the temperature of 200-240 ℃ for 4-8 hours, plastifying the dried white carbon black with abietic acid type resin acid accounting for 4-7% of the weight of the white carbon black and chlorohydrin rubber accounting for 12-18% of the weight of the white carbon black at the temperature of 140-160 ℃ for 20-25 minutes, continuously extracting the white carbon black for 24 hours by tetrahydrofuran after discharging, and drying the white carbon black at the temperature of 120-150 ℃ after volatilizing the solvent to obtain the modified white carbon black. CN102558627A discloses a method for preparing white carbon black suspension, which comprises the steps of mixing white carbon black with water to obtain white carbon black-water suspension, wherein the mass ratio of the white carbon black to the water is 5% -20%, then carrying out surface treatment on the white carbon black in a water bath environment to enable the surface of the white carbon black to be organic, 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 adjusted pH value with styrene butadiene latex 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 white carbon black suspension, which comprises the steps of 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 in the period, adding a silane coupling agent into the white carbon black suspension, adding aliphatic polyoxyethylene ether (AEO) for modification, wherein the AEO accounts for 1-100% of the mass of the white carbon black, the silane coupling agent accounts for 1-100% of the mass of the white carbon black, and modifying the white carbon black for 0.5-10 hours by matching with high sound to form the white carbon black suspension with an O/W type emulsion structure. CN106832417A discloses a method for preparing organic white carbon black modified by aliphatic polyoxyethylene ether, which comprises the steps of mixing white carbon black with water to obtain 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 higher than the melting point of the aliphatic polyoxyethylene ether through heating equipment, 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 with 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. CN1323687A discloses a preparation method of modified nano white carbon black, which comprises the steps of adding ethanol solution of silane coupling agent containing isocyanate group or amino group into gas phase nano white carbon black with average particle size of 1-40 nm, mixing uniformly, adding into oligomer polyol, heating to 220-240 ℃ under stirring, simultaneously vacuumizing to-0.095-0.098 Mpa, dehydrating and dealcoholizing for 2-3 hours; cooling to below 60 ℃, adding diisocyanate, and reacting for 1-2 hours at 70-80 ℃ and under the vacuum degree of-0.095-0.098 Mpa to obtain the nano white carbon black modified polyurethane prepolymer; then adding tetraethoxysilane and silane coupling agent containing isocyanate group or amino group as precursors into oligomer polyol, and taking hydrochloric acid as a catalyst to carry out hydrolysis and condensation, thereby generating the modified nano white carbon black in situ. CN106280491A discloses a preparation method of modified white carbon black, which is to add modified silicone oil into fumed silica and stir the mixture to obtain the modified fumed silica. CN201210347532.3 adopts siloxane coupling agent to process silicon dioxide through surface functionalization to prepare reactive nano silicon dioxide, and then uses in-situ emulsion polymerization to prepare nano silicon dioxide/poly conjugated diene composite emulsion with good stability.
In addition, graft polymer modification and inorganic material surface coating are adopted to modify nano white carbon black, and people like Stephania staciata dissolve a certain mass of polyvinyl alcohol (PVA) in water, heat and stir at 95 ℃ for 3hr to prepare a uniform solution, add White Carbon Black (WCB) water solution uniformly dispersed by high sound, stir uniformly, cool to room temperature, stand and defoam, pour the mixed solution into a mould, and cross-link with saturated boric acid solution to prepare WCB/PVA composite hydrogel (material guide 2016,30, 71-76). The polyacetal oligomer is prepared by condensation polymerization of paraformaldehyde and diethylene glycol by Pivotator et al, the surface of silica is activated by toluene-2, 4-diisocyanate, and then grafted with methylacryloyl (3-trimethoxy silane) propyl ester to modify the surface of the silica, and then a polystyrene layer is coated on the surface of the modified silica by soap-free polymerization (journal of macromolecules 2004,6, 835-. The Qiu 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 structure2MPS-PMMA) ("latex blending process" natural rubber/silica nanocomposite microstructure and performance control, 2010, master thesis at hainan university). Preparing polybutadiene/silicon dioxide nano composite material by using monose according to an anion in-situ polymerization method, firstly treating the surface of nano white carbon black particles by adopting Y-methyl propenephthalyloxy propyl trimethoxy silane (MPS), then dispersing the modified silicon dioxide in a butadiene and cyclohexane solvent, adding n-butyl lithium after high-sound dispersionAs an initiator, polymerization was carried out under a nitrogen atmosphere, and the product was added to ethanol to obtain a white precipitate, which was then filtered and dried to obtain a modified silica nanocomposite (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 the rubber matrix, the methods still have certain limitations and have the defects of long reaction time, high energy consumption, complex operation and the like; when the nano white carbon black is modified by using the coupling agent or the surfactant, the defects of large using amount, high production cost, poor dispersion stability, easy re-agglomeration and the like exist.
Disclosure of Invention
The invention aims to provide a preparation method of super-dispersed nano white carbon black filled with solution polymerized styrene butadiene rubber. The method comprises the steps of firstly carrying out copolymerization reaction on polyether polyol and a silane coupling agent to generate an organic silicon/polyether polyol copolymer, carrying out multi-point anchoring modification on the surface of nano white carbon black particles, then carrying out acyl halogenation treatment on solution-polymerized styrene-butadiene rubber slurry by adopting acid anhydride and a halogenating agent, and finally coating the surface of the nano white carbon black particles with the acyl-polymerized solution-polymerized styrene-butadiene rubber to form a method for separating the nano white carbon black by using an isolation layer with high connection strength and thick barrier layer. The method not only solves the problem of easy agglomeration of the nano white carbon black, but also avoids the problem of agglomeration again under the conditions of high temperature, high shear and long-term storage, 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 of super-dispersed nano white carbon black for rubber filler, which comprises the following specific preparation steps:
(1) preparation of silicone/polyether polyol copolymer: adding 100 parts by mass of a silane coupling agent and 100-200 parts by mass of a solvent into a reactor, stirring for 1-2 hr, then adding 10-40 parts by mass of polyether polyol, continuously stirring and heating until the temperature of the reactor reaches 90-120 ℃, rapidly adding 1.0-5.0 parts by mass of a catalyst under stirring, reacting for 10-15 hr, and then decompressing and distilling to obtain the organic silicon/polyether polyol copolymer.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: taking the mass of the solution-polymerized styrene-butadiene rubber cement as 100 parts, firstly adding 100 parts of solution-polymerized styrene-butadiene rubber cement and 100-300 parts of solvent into a polymerization kettle, stirring and heating, when the temperature of the polymerization kettle reaches 40-50 ℃, rapidly adding 0.05-0.2 part of catalyst under stirring, adding 3-15 parts of anhydride when the system becomes orange red, stirring and reacting for 1-4 hours, then adding 4-10 parts of halogenating agent, and dropwise adding 0.1-0.5 part of HCl-CH3And (3) reacting OH solution (the molar concentration of HCl is 0.1-0.7 mol/L) for 5-10 hr, adding 10-15 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0% to terminate the reaction, performing suction filtration and washing to obtain the haloacylation solution polymerized styrene-butadiene rubber cement (the acylation degree is 3.0-10.2%, and the bromine content is 2.0-8.7 mol%).
(3) 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, 4-15 parts by mass of organic silicon/polyether polyol copolymer and 200-400 parts by mass of solvent into a polymerization kettle, heating to 40-60 ℃, and stirring for reaction for 1-3 hours; and then adding 5-20 parts of halogen acylation solution polymerized styrene-butadiene rubber cement, stirring for reaction for 2-4 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black.
The white carbon black is nano-scale, and the particle size is as follows: 10 to 100 nm.
The silane coupling agent of the present invention may be at least one selected from the group consisting of gamma-aminopropyltriethoxysilane (KH-550), 3-glycidoxypropyltrimethoxysilane (KH-560), vinyltriethoxysilane (A-151), N- β -aminoethyl-gamma-aminopropylmethyldimethoxysilane (KH-602), gamma-methacryloxypropyltrimethoxysilane (KH-570), N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane (KH-792), vinyltrimethoxysilane (A-171), and vinyltris (β -methoxyethoxy) silane (A-172), preferably KH-550.
The polyether polyol is at least one selected from propylene glycol polyoxypropylene ether (PPG), ethylene glycol polyoxypropylene ether, propylene glycol polyoxyethylene ether, ethylene glycol polyoxyethylene ether, polytetrahydrofuran glycol (PTHF), trimethylolpropane polyoxypropylene ether and hydroxyl-terminated polytetrahydrofuran, and PPG is preferable.
The catalyst in step (1) of the present invention is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate and sodium bicarbonate, and preferably potassium hydroxide.
The solution polymerized styrene-butadiene rubber cement is prepared by the solution polymerization copolymerization of a conjugated diene compound and an aryl ethylene compound. Wherein the solid content of the solution polymerized styrene-butadiene rubber cement is 5-20 w%.
The acid anhydride is a binary acid anhydride compound, is selected from at least one of succinic anhydride, maleic anhydride and phthalic anhydride, preferably phthalic anhydride, and is added in an amount of 3-15 parts, preferably 5-11 parts.
The halogenating agent in the invention is at least one of liquid chlorine and liquid bromine, preferably liquid bromine.
The catalyst in the step (2) of the invention is selected from anhydrous aluminum trichloride (AlCl)3) Boron trifluoride (BF)3) Tin tetrachloride (SnCl)4) Zinc dichloride (ZnCl)2) Preferably AlCl3The addition amount is 0.05-0.2 part, preferably 0.08-0.13 part.
The solvent used in step (1) and step (2) of the present invention may be selected from cyclohexane, carbon disulfide (CS)2) At least one of nitrobenzene, petroleum ether, tetrachloroethane, toluene, xylene and chlorobenzene, preferably cyclohexane.
The preparation method of the ultra-dispersed nano white carbon black for the rubber filler comprises the following steps of carrying out copolymerization reaction on polyether polyol and a silane coupling agent to generate a product, namely an organic silicon/polyether polyol copolymer (see figure 1). The silicon atom, ether bond and hydroxyl in the copolymer are closely connected with the hydroxyl on the surface of the white carbon black through hydrogen bond action, so that the multi-point anchoring modification of the nano white carbon black particles is realized, and high-density anchoring points are formed on the surface of the nano white carbon black particles. The anchoring point and the polar group haloacyl of the halogenated acylation solution polymerized styrene-butadiene rubber cement generate mutual attraction between molecules, and a solution polymerized styrene-butadiene rubber cement coating layer with high connection strength is formed on the surface of the white carbon black particles. The molecular chain structure of the coating layer has the characteristic of non-polarity, the molecular chain segment is long and contains a benzene ring structure, the molecular steric hindrance effect is large, a firm steric hindrance layer can be established among the nano white carbon black particles to hinder the mutual agglomeration among the particles, and the nano white carbon black can stably exist in a single particle form (see figure 2). Meanwhile, the coating layer chain structure is similar to the molecular structure of the solution polymerized styrene butadiene rubber, has good compatibility with the solution polymerized styrene butadiene rubber, and realizes ultra-dispersion in a solution polymerized styrene butadiene rubber matrix. The invention has low modification cost and little environmental pollution.
Drawings
FIG. 1 is a structural formula of a product (organosilicon/polyether polyol copolymer) obtained after a copolymerization reaction of polyether polyol and a silane coupling agent.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the modified silica. As can be seen from the photographs: the modified white carbon black particles are stably present in a single particle form having a particle diameter of about 30 to 60 nm.
FIG. 3 is an IR spectrum of white carbon black (a) and modified white carbon black (b). Wave number at a is 1099cm-1An asymmetric secondary vibration absorption peak of Si-O-Si appears at a wave number of 804cm-1A symmetric secondary vibration absorption peak of Si-O-Si appears at a wave number of 465cm-1A bending vibration absorption peak of Si-O-Si appears. The wave number on the b is 1770-1760 cm-1A sharp absorption peak of acyl bromide groups appears, and the wave number is 1705-1710 cm-1A sharp absorption peak of carbonyl appears, and the wave number is 1050-1150 cm-1The absorption peaks of ether group and hydroxyl group tip appear, the wave number is 650-840 cm-1And a Si-O asymmetric secondary shrinkage vibration absorption peak appears, which indicates that the organic silicon/polyether glycol copolymer and the halogen acylation solution-polymerized styrene-butadiene rubber cement are attached to the surface of the nano white carbon black particles.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The "parts" described in examples and comparative examples each refer to parts by mass.
⑴ sources of raw materials:
Figure BDA0001833952530000081
other reagents are all commercial products
⑵ analytical test methods:
measurement of acylation degree: the test was carried out using an infrared spectrometer of Shimadzu, Japan, model IR-460.
And (3) determination of bromine content: the bromine content in the halogenated acylated styrene-butadiene latex is measured by adopting an alkali dissolution method and AgNO3Titration of the standard solution, calibration of its concentration with the reference substance NaCl, eosin (C)20H6O5BrNa2) For the indicator, the end point solution was titrated from light red to light purple. The bromine content is calculated as follows:
Figure BDA0001833952530000091
in the formula: C-AgNO3The concentration of the standard solution; V-AgNO3The volume consumed by the standard solution; n-mole number of acylated groups in the haloacylated styrene-butadiene latex; m-mass of dry matter in styrene-butadiene latex (g).
Infrared spectrum analysis of the sample: the functional group analysis is carried out on samples before and after the modification of the nano white carbon black by an infrared spectrometer of German Bruke spectral instrument company. Drying the sample in a vacuum oven at 100 ℃, tabletting by using potassium bromide, and collecting the sample with the wave number range of 400-4000cm-1。
Analyzing a sample by an electron microscope: and (3) carrying out dispersibility analysis on the sample before and after the 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 well dispersed and is 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 of the absolute value of each time, after each dropwise addition, the absolute value 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 absorbed by each 100g of sample0(mL) as follows:
Figure BDA0001833952530000101
wherein v 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 some extent, the lower the specific surface area is, the lower the oil absorption is, the better the wettability is, and vice versa.
Example 1
(1) Preparation of silicone/polyether polyol copolymer: adding 100 parts of KH-550 and 100 parts of cyclohexane into a reactor, stirring for 1.0hr, then adding 10 parts of PPG, continuously stirring and heating until the temperature of the reactor reaches 95 ℃, rapidly adding 1.0 part of potassium hydroxide under stirring, reacting for 11hr, and then decompressing and distilling to obtain the KH-550/PPG copolymer a.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: firstly, 100 portions of solution polymerized styrene-butadiene rubber cement SSBR2564s and 100 portions of cyclohexane are added into a polymerization kettle, stirred and heated, when the temperature of the polymerization kettle reaches 40 ℃, 0.08 portion of AlCl is rapidly added under the stirring condition35 parts of phthalic acid are added until the system turns orange-redReacting anhydride for 1hr under stirring, adding 4 parts of liquid bromine, and adding 0.1 part of HCl-CH dropwise3OH solution (HCl molar concentration: 0.1mol/L) reacts for 5hr, 10 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0% are added to stop the reaction, and the solution is filtered and washed to obtain the halogenated acylation solution polymerized styrene-butadiene rubber cement a (acylation degree: 3.9%; bromine content: 3.1 mol%).
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 4 parts of KH-550/PPG copolymer a and 200 parts of cyclohexane into a polymerization kettle, heating to 40 ℃, and stirring for reacting for 1 hr; then 5 parts of halogenated acylation solution polymerized styrene-butadiene rubber cement a is added, after stirring reaction for 2 hours, 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 2
(1) Preparation of silicone/polyether polyol copolymer: the same as in example 1.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: the same as in example 1.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 6 parts of KH-550/PPG copolymer a and 230 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hr; then adding 7 parts of halogenated acylation solution polymerized styrene-butadiene rubber cement a, stirring and reacting for 2.6 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 3
(1) Preparation of silicone/polyether polyol copolymer: the same as in example 1.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: the same as in example 1.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 7 parts of KH-550/PPG copolymer a and 270 parts of cyclohexane into a polymerization kettle, heating to 48 ℃, and stirring for reacting for 1.8 hr; then adding 9 parts of halogenated acylation solution polymerized styrene-butadiene rubber cement a, stirring and reacting for 2.9 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 4
(1) Preparation of silicone/polyether polyol copolymer: adding 100 parts of KH-550 and 150 parts of cyclohexane into a reactor, stirring for 1.5 hours, then adding 19 parts of PPG, continuously stirring and heating until the temperature of the reactor reaches 110 ℃, rapidly adding 3.0 parts of potassium hydroxide under stirring, reacting for 13 hours, and then decompressing and distilling to obtain the KH-550/PPG copolymer b.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: adding 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s and 200 parts of cyclohexane into a polymerization kettle, stirring and heating, and quickly adding 0.12 part of AlCl under stirring when the temperature of the polymerization kettle reaches 45 DEG C3Adding 10 parts of phthalic anhydride until the system turns orange red, stirring and reacting for 2hr, then adding 7 parts of liquid bromine, and dropwise adding 0.3 part of HCl-CH3OH solution (HCl molar concentration: 0.1mol/L) reacts for 8hr, 13 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0% are added to stop the reaction, and the solution is filtered and washed to prepare the halogenated acylation solution polymerized styrene-butadiene rubber cement b (acylation degree is 6.1%, bromine content is 5.2 mol%).
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 9 parts of KH-550/PPG copolymer b and 300 parts of cyclohexane into a polymerization kettle, heating to 50 ℃, and stirring for reacting for 2.0 hr; then 11 parts of halogen acylation solution polymerized styrene-butadiene rubber cement b is added, after stirring reaction for 3.0 hours, 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) Preparation of silicone/polyether polyol copolymer: the same as in example 4.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: the same as in example 4.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 10 parts of KH-550/PPG copolymer b and 320 parts of cyclohexane into a polymerization kettle, heating to 52 ℃, and stirring for reacting for 2.2 hr; then adding 13 parts of halogenated acylation solution polymerized styrene-butadiene rubber cement b, stirring and reacting for 3.3 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 6
(1) Preparation of silicone/polyether polyol copolymer: the same as in example 4.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: the same as in example 4.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 12 parts of KH-550/PPG copolymer b and 340 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reacting for 2.5 hours; then adding 15 parts of halogen acylation solution polymerized styrene-butadiene rubber cement b, stirring and reacting for 3.5 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 7
(1) Preparation of silicone/polyether polyol copolymer: adding 100 parts of A-151 and 200 parts of cyclohexane into a reactor, stirring for 2.0hr, then adding 40 parts of PTHF, continuously stirring and heating until the temperature of the reactor reaches 120 ℃, rapidly adding 5.0 parts of sodium hydroxide under stirring, reacting for 15hr, and then decompressing and distilling to obtain the A-151/PTHF copolymer.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: adding 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s and 300 parts of cyclohexane into a polymerization kettle, stirring and heating, and quickly adding 0.2 part of AlCl under stirring when the temperature of the polymerization kettle reaches 50 DEG C3Adding 15 parts of phthalic anhydride until the system turns orange red, stirring and reacting for 4hr, then adding 10 parts of liquid bromine, and dropwise adding 0.5 part of HCl-CH3OH solution (HCl molar concentration: 0.1mol/L) reacts for 10hr, 15 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0% is added to stop the reaction, and the solution is filtered and washed to prepare halogen acylation solution polymerized styrene-butadiene rubber cement c (acylation degree is 9.3%, bromine content is 6.5 mol%).
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 13 parts of A-151/PTHF copolymer and 350 parts of cyclohexane into a polymerization kettle, heating to 57 ℃, and stirring for reacting for 2.8 hours; then 17 parts of halogen acylation solution polymerized styrene-butadiene rubber cement c is added, after stirring reaction for 3.6 hours, 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 8
(1) Preparation of silicone/polyether polyol copolymer: the same as in example 7.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: the same as in example 7.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 14 parts of A-151/PTHF copolymer and 370 parts of cyclohexane into a polymerization kettle, heating to 58 ℃, and stirring for reacting for 2.9 hours; then 18 parts of halogenated acylation solution polymerized styrene-butadiene rubber cement c is added, after stirring reaction for 3.8 hours, 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 9
(1) Preparation of silicone/polyether polyol copolymer: the same as in example 7.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: the same as in example 7.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 15 parts of A-151/PTHF copolymer and 400 parts of cyclohexane into a polymerization kettle, heating to 60 ℃, and stirring for reacting for 3.0 hr; then 20 parts of halogen acylation solution polymerized styrene-butadiene rubber cement c is added, after stirring reaction for 4.0 hours, 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 1
(1) Preparation of silicone/polyether polyol copolymer: the same as in example 1.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: the same as in example 1.
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 1, except that the amount of KH-550/PPG copolymer a added during the preparation was 3.0 parts, namely: adding 100 parts of nano white carbon black (40nm), 3.0 parts of KH-550/PPG copolymer a and 200 parts of cyclohexane into a polymerization kettle, heating to 40 ℃, and stirring for reacting for 1 hr; then 5 parts of halogenated acylation solution polymerized styrene-butadiene rubber cement a is added, after stirring reaction for 2 hours, 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 2
(1) Preparation of silicone/polyether polyol copolymer: the same as in example 2.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: the same as in example 2.
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions are the same as example 2, except that the amount of the haloacylated solution polymerized styrene-butadiene rubber cement a added in the preparation process is 2.0 parts, namely: adding 100 parts of nano white carbon black (40nm), 6 parts of KH-550/PPG copolymer a and 230 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hr; then adding 2.0 parts of halogen acylation solution polymerized styrene-butadiene rubber cement a, stirring and reacting for 2.6 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 3
(1) Preparation of silicone/polyether polyol copolymer: the same as in example 3.
(2) Preparing the ultra-dispersed nano white carbon black: the other conditions are the same as example 3, except that no haloacylated solution polymerized styrene-butadiene rubber cement a is added in the preparation process, namely: adding 100 parts of nano white carbon black (40nm), 7 parts of KH-550/PPG copolymer a and 270 parts of cyclohexane into a polymerization kettle, heating to 48 ℃, stirring for reaction for 1.8hr, and performing flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 4
(1) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: the same as in example 4.
(2) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 4, except that no KH-550/PPG copolymer b was added during the preparation, i.e.: adding 100 parts of nano white carbon black (40nm) and 300 parts of cyclohexane into a polymerization kettle, heating to 50 ℃, and stirring for reacting for 2.0 hr; then 11 parts of halogen acylation solution polymerized styrene-butadiene rubber cement b is added, after stirring reaction for 3.0 hours, 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
(1) Preparation of silicone/polyether polyol copolymer: the other conditions were the same as in example 5 except that the amount of PPG added during the preparation was 2.0 parts, namely: adding 100 parts of KH-550 and 150 parts of cyclohexane into a reactor, stirring for 1.5 hours, then adding 2.0 parts of PPG, continuously stirring and heating until the temperature of the reactor reaches 110 ℃, rapidly adding 3.0 parts of potassium hydroxide under stirring, reacting for 13 hours, and then decompressing and distilling to obtain the KH-550/PPG copolymer b-1.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: the same as in example 5.
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 5, except that KH-550/PPG copolymer b was not added during the preparation, but KH-550/PPG copolymer b-1 was added, i.e.: adding 100 parts of nano white carbon black (40nm), 10 parts of KH-550/PPG copolymer b-1 and 320 parts of cyclohexane into a polymerization kettle, heating to 52 ℃, and stirring for reacting for 2.2 hr; then adding 13 parts of halogenated acylation solution polymerized styrene-butadiene rubber cement b, stirring and reacting for 3.3 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 6
(1) Preparation of silicone/polyether polyol copolymer: the other conditions were the same as in example 6, except that no PPG was added during the preparation, i.e.: adding KH-550 and cyclohexane 150 weight portions into reactor, stirring for 1.5hr, heating while stirring until the temperature reaches 110 deg.c, adding potassium hydroxide 3.0 weight portions while stirring, reacting for 13hr, and vacuum distilling to obtain KH-550/PPG copolymer b-2.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: the same as in example 6.
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 6, except that KH-550/PPG copolymer b was not added during the preparation, but KH-550/PPG copolymer b-2 was added, i.e.: adding 100 parts of nano white carbon black (40nm), 12 parts of KH-550/PPG copolymer b-2 and 340 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reacting for 2.5 hr; then adding 15 parts of halogen acylation solution polymerized styrene-butadiene rubber cement b, stirring and reacting for 3.5 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 7
(1) Preparation of silicone/polyether polyol copolymer: the same as in example 7.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: the other conditions were the same as in example 7 except that phthalic anhydride was added in an amount of 2.0 parts during the preparation, that is: adding 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s and 300 parts of cyclohexane into a polymerization kettle, stirring and heating, and quickly adding 0.2 part of AlCl under stirring when the temperature of the polymerization kettle reaches 50 DEG C3Adding 2.0 parts of phthalic anhydride until the system turns orange red, stirring for reaction for 4hr, then adding 10 parts of liquid bromine, and dropwise adding 0.5 part of HCl-CH3OH solution (HCl molar concentration: 0.1mol/L) reacts for 10hr, 15 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0% is added to stop the reaction, and the solution is filtered and washed to prepare the haloacylation solution polymerized styrene-butadiene rubber cement c-1 (acylation degree 1.2%; bromine content is 5.1 mol%).
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 7, except that the preparation process was carried out without adding the haloacylated solution-polymerized styrene-butadiene rubber cement c, but with adding the haloacylated solution-polymerized styrene-butadiene rubber cement c-1, namely: adding 100 parts of nano white carbon black (40nm), 13 parts of A-151/PTHF copolymer and 350 parts of cyclohexane into a polymerization kettle, heating to 57 ℃, and stirring for reacting for 2.8 hours; then 17 parts of halogenated acylation solution polymerized styrene-butadiene rubber cement c-1 is added, after stirring reaction for 3.6 hours, 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 8
(1) Preparation of silicone/polyether polyol copolymer: the same as in example 8.
(2) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: the other conditions were the same as in example 8, except that no liquid bromine was added during the preparation, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s and 300 parts of ring are added into a polymerization kettleHexane, stirring and heating, and when the temperature of the polymerization kettle reaches 50 ℃, 0.2 part of AlCl is rapidly added under the stirring condition3Adding 2.0 parts of phthalic anhydride when the system turns to orange red, stirring and reacting for 4 hours, then adding 15 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0 percent to terminate the reaction, filtering and washing to obtain the haloacylation solution polymerized styrene-butadiene rubber cement c-2 (the acylation degree is 5.2 percent).
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions are the same as example 8, except that no haloacylated solution polymerized styrene-butadiene rubber cement c is added in the preparation process, and haloacylated solution polymerized styrene-butadiene rubber cement c-2 is added, namely: adding 100 parts of nano white carbon black (40nm), 14 parts of A-151/PTHF copolymer and 370 parts of cyclohexane into a polymerization kettle, heating to 58 ℃, and stirring for reacting for 2.9 hours; then 18 parts of halogenated acylation solution polymerized styrene-butadiene rubber cement c-2 is added, after stirring reaction for 3.8 hours, 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 9
(1) Preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: the same as in example 9.
(2) Preparing the ultra-dispersed nano white carbon black: the other conditions were identical to those of example 9, except that the A-151/PTHF copolymer was not added during the preparation, but PTHF was added, i.e.: adding 100 parts of nano white carbon black (40nm), 15 parts of PTHF copolymer and 400 parts of cyclohexane into a polymerization kettle, heating to 60 ℃, and stirring for reacting for 3.0 hr; then 20 parts of halogen acylation solution polymerized styrene-butadiene rubber cement c is added, after stirring reaction for 4.0 hours, 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 BDA0001833952530000181
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 may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.

Claims (12)

1. The preparation method of the ultra-dispersed nano white carbon black is characterized by comprising the following preparation steps:
(1) preparation of silicone/polyether polyol copolymer: adding 100 parts by mass of silane coupling agent and 100-200 parts by mass of solvent into a reactor, stirring for 1-2 hr, then adding 10-40 parts by mass of polyether polyol, continuously stirring and heating until the temperature of the reactor reaches 90-120 ℃, rapidly adding 1.0-5.0 parts by mass of catalyst under the stirring condition, reacting for 10-15 hr, and then decompressing and distilling to obtain an organic silicon/polyether polyol copolymer;
(2) preparing halogenated acylation solution polymerized styrene-butadiene rubber cement: adding 100 parts by mass of solution-polymerized styrene-butadiene rubber cement and 100-300 parts by mass of solvent into a polymerization kettle, stirring and heating, when the temperature of the polymerization kettle reaches 40-50 ℃, rapidly adding 0.05-0.2 part by mass of catalyst under stirring, adding 3-15 parts by mass of acid anhydride until the system becomes orange red, stirring and reacting for 1-4 hours, then adding 4-10 parts by mass of halogenating agent, and dropwise adding 0.1-0.5 part by mass of HCl-CH3Reacting the OH solution for 5-10 hr, adding 10-15 parts by mass of a 5.0% sodium hydroxide aqueous solution to terminate the reaction, and performing suction filtration and washing to obtain the haloacylation solution polymerized styrene-butadiene rubber cement;
(3) preparing the ultra-dispersed nano white carbon black: adding 100 parts by mass of nano white carbon black, 4-15 parts by mass of organic silicon/polyether polyol copolymer and 200-400 parts by mass of solvent into a polymerization kettle, heating to 40-60 ℃, and stirring for reaction for 1-3 hours; and then adding 5-20 parts by mass of halogen acylation solution polymerized styrene-butadiene rubber cement, stirring for reaction for 2-4 hr, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black.
2. The method according to claim 1, wherein the nano white carbon black has a particle size of 10 to 100 nm.
3. The method according to claim 1, wherein the silane coupling agent is at least one member selected from the group consisting of gamma-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltriethoxysilane, N- β -aminoethyl-gamma-aminopropylmethyldimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltris (β -methoxyethoxy) silane.
4. The method of claim 3, wherein the silane coupling agent is gamma-aminopropyltriethoxysilane.
5. The method according to claim 1, wherein the polyether polyol is at least one member selected from the group consisting of propylene glycol polyoxypropylene ether, ethylene glycol polyoxypropylene ether, propylene glycol polyoxyethylene ether, ethylene glycol polyoxyethylene ether, polytetrahydrofuran glycol, trimethylolpropane polyoxypropylene ether, and hydroxyl terminated polytetrahydrofuran.
6. The method of claim 5, wherein the polyether polyol is propylene glycol polyoxypropylene ether.
7. The method according to claim 1, wherein the catalyst in step (1) is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, and sodium bicarbonate.
8. The method of claim 7, wherein the catalyst is potassium hydroxide.
9. The method according to claim 1, wherein the solution-polymerized styrene-butadiene rubber cement is prepared by copolymerizing a conjugated diene compound and an aryl ethylene compound through solution polymerization, and the solid content of the solution-polymerized styrene-butadiene rubber cement is 5-20 wt%.
10. The method of claim 1, wherein the acid anhydride is a dibasic acid anhydride compound selected from at least one of succinic anhydride, maleic anhydride, and phthalic anhydride.
11. The method of claim 1, wherein the halogenating agent is at least one of liquid chlorine and liquid bromine.
12. The method according to claim 1, wherein the catalyst in the step (2) is at least one selected from the group consisting of anhydrous aluminum trichloride, boron trifluoride, tin tetrachloride and zinc dichloride.
CN201811217629.6A 2018-10-18 2018-10-18 Preparation method of ultra-dispersed nano white carbon black Pending CN111073052A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104448453A (en) * 2013-09-18 2015-03-25 中国石油天然气股份有限公司 Preparation method of halogenated acylated low-smoke, flame retardant powdered butadiene styrene rubber
CN108192141A (en) * 2016-12-08 2018-06-22 中国石油天然气股份有限公司 A kind of method of modifying of gum filler carbon nanotube

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104448453A (en) * 2013-09-18 2015-03-25 中国石油天然气股份有限公司 Preparation method of halogenated acylated low-smoke, flame retardant powdered butadiene styrene rubber
CN108192141A (en) * 2016-12-08 2018-06-22 中国石油天然气股份有限公司 A kind of method of modifying of gum filler carbon nanotube

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