CN111073349A - Preparation method of high-dispersion nano white carbon black for rubber filler - Google Patents

Preparation method of high-dispersion nano white carbon black for rubber filler Download PDF

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CN111073349A
CN111073349A CN201811216564.3A CN201811216564A CN111073349A CN 111073349 A CN111073349 A CN 111073349A CN 201811216564 A CN201811216564 A CN 201811216564A CN 111073349 A CN111073349 A CN 111073349A
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carbon black
white carbon
parts
butadiene rubber
polymerized styrene
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何连成
胡海华
周雷
吴宇
赵洪国
徐典宏
宋中勤
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Petrochina Co Ltd
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Abstract

The invention aims to provide a preparation method of high-dispersion nano white carbon black for rubber fillers. According to the method, phthalic acid diester is adopted to anchor and modify the surfaces of nano white carbon black particles, then halogenating agent is adopted to halogenate solution-polymerized styrene-butadiene rubber slurry, and finally the solution-polymerized styrene-butadiene rubber slurry is coated on the surfaces of the nano white carbon black particles to form a barrier layer so as to achieve the purpose of separating the nano white carbon black. The method not only solves the problem of easy agglomeration of the nano white carbon black, but also improves the compatibility of the nano white carbon black and the solution polymerized styrene butadiene rubber and endows the nano white carbon black with high dispersibility in a solution polymerized styrene butadiene rubber system. The invention has low modification cost and little environmental pollution.

Description

Preparation method of high-dispersion nano white carbon black for rubber filler
Technical Field
The invention relates to a preparation method of high-dispersion nano white carbon black, in particular to a preparation method of high-dispersion nano white carbon black for synthetic rubber filler.
Background
The nanometer white carbon black is white, nontoxic, amorphous fine powder, and is hydrated amorphous silica or colloidal silica (Si 0)2·nH20) The composite material has the excellent performances of porosity, large internal surface area, high dispersibility, light weight, good chemical stability, high temperature resistance, non-combustion, good electrical insulation and the like. The product is mainly used as a filler of products such as rubber, plastics, synthetic resin, paint and the like, and can also be used as a lubricant and an insulating material. At present, 70% of white carbon black is used in the rubber industry all over the world, is an excellent rubber reinforcing agent, can effectively reduce rubber material lag while improving the physical and mechanical properties of rubber materials, and is difficult to replace in the preparation of energy-saving and environment-friendly 'green tire' tread rubber as a filler. Therefore, the nano white carbon black is gradually regarded as a reinforcing system to prepare the rubber composite material.
However, the nano white carbon black has small particle size, large specific surface area and high surface energy, and a large number of silicon hydroxyl groups exist on the surface, so that the nano white carbon black has the characteristics of hydrophilicity and easiness in self-polymerization, has poor compatibility with a polymer matrix, and is not easy to disperse uniformly in the mixing process of the nano white carbon black and a rubber material, thereby not only influencing the filling modification effect, but also damaging the performance of the rubber material. From the perspective of 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 in the application process of the high-fine inorganic powder, a technical problem inevitably occurs, namely, the high-fine powder is more difficult to be mixed, infiltrated and dispersed by the rubber material because of the reduction of the particle size, the specific surface area is increased, the surface energy is improved, the self-aggregation capability is stronger, and the high-fine powder is more difficult to be mixed, infiltrated and dispersed by the rubber material. Therefore, the problem of dispersion of the high-fine inorganic powder in the rubber has become a bottleneck in preparing high-performance rubber materials.
At present, in order to improve the application effect of the nano white carbon black in the rubber matrix, a modifier is usually added to modify the surface of the nano white carbon black, and the modifier is adsorbed on the surface of the white carbon black or reacts with the surface of the white carbon black, so that the agglomeration of the white carbon black in the organic matrix is reduced, the affinity of the white carbon black with the organic material is improved, and the compatibility of the nano white carbon black with the rubber is enhanced. In the prior art, the nano white carbon black is modified by a coupling agent or a surfactant such as a silane coupling agent, 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 the nano white carbon black, such as:
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 disperse homogeneous White Carbon Black (WCB) aqueous solution stir to cool to room temperature and stand and 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 polyacetal oligomer is prepared by condensation polymerization of paraformaldehyde and diethylene glycol by sweep et al, and the grafted polyacetal oligomer is used by methyl group of Taoist et al after the surface of silica is activated by toluene-2, 4-diisocyanateAcryloyl (3-trimethoxy silane) propyl ester is used for modifying the surface of silicon dioxide, and then a polystyrene layer is coated on the surface of the modified silicon dioxide through soap-free liquid polymerization (polymer academic newspaper 2004,6, 835-835). 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). Polybutadiene/silicon dioxide nano composite material is prepared by a single swallowwort root through an anion in-situ polymerization method, the surface of a nano white carbon black particle is treated by Y-methyl-acryloyloxy-propyl-trimethoxysilane (MPS), 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 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 high-dispersion nano white carbon black for rubber fillers. According to the method, phthalic acid diester is adopted to anchor and modify the surfaces of nano white carbon black particles, then halogenating agent is adopted to halogenate solution-polymerized styrene-butadiene rubber slurry, and finally the solution-polymerized styrene-butadiene rubber slurry is coated on the surfaces of the nano white carbon black particles to form a barrier layer so as to achieve the purpose of separating the nano white carbon black. The method not only solves the problem of easy agglomeration of the nano white carbon black, but also improves the compatibility of the nano white carbon black and the solution polymerized styrene butadiene rubber and endows the nano white carbon black with high dispersibility in a solution polymerized styrene butadiene rubber system.
The "parts" in the present invention mean parts by mass.
The preparation method of the high-dispersion nano white carbon black for the rubber filler comprises the following specific preparation steps:
(1) preparing halogenated solution-polymerized styrene-butadiene rubber cement: 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 45-55 ℃, quickly adding 5-20 parts of halogenating agent under stirring until the whole system becomes reddish brown, adding 0.05-1.0 part of initiator, stirring and reacting for 1-4 hr, adding 10-20 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0% to terminate the reaction, filtering and washing to obtain the halogenated solution-polymerized styrene-butadiene rubber cement (the bromine content is 2.0-13 mol%).
(2) Preparing high-dispersion nano white carbon black: taking 100 parts by mass of nano white carbon black, adding 100 parts by mass of nano white carbon black, 10-20 parts by mass of phthalic diester and 200-400 parts by mass of solvent into a polymerization kettle, heating to 40-60 ℃, and stirring for reaction for 1-3 hours; then adding 10-25 parts of halogenated solution-polymerized styrene-butadiene rubber cement, stirring and reacting for 2-4 hr, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black.
The white carbon black is nano-scale, and the particle size is as follows: 10 to 100 nm.
The phthalate diester is at least one selected from di-n-butyl phthalate (DBP), di-isononyl phthalate (DINP), di-isodecyl phthalate (DIDP), diamyl phthalate, dicyclohexyl phthalate, di-n-octyl phthalate (DNOP), diphenylmethyl phthalate, dimethyl phthalate (DMP) and diethyl phthalate (DEP), preferably DIDP.
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 halogenating agent in the invention is at least one of liquid chlorine and liquid bromine, preferably liquid bromine.
The initiator according to the present invention may be selected from at least one of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-tert-butyl peroxide, preferably dicumyl peroxide (DCP). The addition amount is 0.05-1.0 part, preferably 0.07-0.6 part.
The solvent according to the invention may be selected from cyclohexane, carbon disulphide (CS)2) At least one of nitrobenzene, petroleum ether, tetrachloroethane, toluene, xylene and chlorobenzene, preferably cyclohexane.
The preparation method of the high-dispersion nano white carbon black for the rubber filler takes ester group (CO) of diester phthalate as an anchoring group, forms anchoring points on the surface of the ester group and hydroxyl on the surface of the white carbon black through hydrogen bond action, and then carries out halogenation reaction on the solution polymerized styrene-butadiene rubber cement by using liquid bromine, so that the surface of the solution polymerized styrene-butadiene rubber cement is provided with a large amount of polar group bromine atoms. The anchoring point and the polar group bromine atom of the halogenated solution-polymerized styrene-butadiene rubber cement generate mutual attraction between molecules, and a coating layer of the solution-polymerized styrene-butadiene rubber cement is formed on the surface of the white carbon black particles. The coating layer contains a plurality of phthalic diester polar groups, so that the anchor point density is high, and the connection strength with the halogenated solution polymerized styrene-butadiene rubber cement is high. And secondly, the barrier layer chain structure has the non-polar characteristic, contains a benzene ring structure, has large molecular steric hindrance effect, and can establish a firm steric hindrance layer between the nano white carbon black particles under the mutual 'synergistic action' of the two so as to hinder the mutual agglomeration of the particles, so that the nano white carbon black can stably exist in a single particle form (see figure 1). Meanwhile, the coating layer chain structure is similar to the molecular structure of the solution polymerized styrene butadiene rubber, and has good compatibility with the solution polymerized styrene butadiene rubber. The invention has low modification cost and little environmental pollution.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of 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. 2 shows the IR spectrums of the white carbon black (a) and the 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 610-560 cm-1A sharp absorption peak of bromine radical appears, and the wave number is 1705-1710 cm-1A sharp absorption peak of carbonyl appears, and the wave number is 840-850 cm-1And a benzene ring ortho-substitution sharp absorption peak appears, which indicates that the phthalic diester and the halogen acylation solution polymerized styrene-butadiene rubber cement are attached to the surface of the nano white carbon black particle.
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:
nano white carbon black with particle size of 20-60 nm Weifang Wanli auxiliary agent Limited company
Solution polymerized styrene butadiene rubber cement SSBR2564s, 10% solids content, Mount-petrochemical company
Diisodecyl Phthalate (DIDP) Nanjing Chemicals Co., Ltd
Diisononyl phthalate (DINP), Nanjing chemical reagents Ltd
Limited chemical technology of Beijing Datu Tokuo with purity of liquid bromine more than or equal to 99%
Dicumyl peroxide (DCP) adjuvant plant in Lanzhou
Other reagents are all commercial products
⑵ analytical test methods:
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.
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 1
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).
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 BDA0001833691790000091
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) Preparing halogenated solution-polymerized styrene-butadiene rubber cement: adding 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s and 100 parts of cyclohexane into a polymerization kettle, stirring and heating, when the temperature of the polymerization kettle reaches 45 ℃, rapidly adding 5 parts of liquid bromine under stirring until the system is completely reddish brown, adding 0.07 part of DCP, stirring and reacting for 1 hour, adding 10 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0 percent to terminate the reaction, filtering and washing to obtain halogenated solution polymerized styrene-butadiene rubber cement a (the bromine content is 3.2mol percent).
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 10 parts of DIDP and 200 parts of cyclohexane into a polymerization kettle, heating to 40 ℃, and stirring for reacting for 1 hr; then adding 10 parts of halogenated solution-polymerized styrene-butadiene rubber cement a, stirring and reacting for 2 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 2
(1) Preparing halogenated solution-polymerized styrene-butadiene rubber cement: the same as in example 1.
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 11 parts of DIDP and 260 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hours; then adding 12 parts of halogenated solution-polymerized styrene-butadiene rubber cement a, stirring and reacting for 2.5 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 3
(1) Preparing halogenated solution-polymerized styrene-butadiene rubber cement: the same as in example 1.
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 12 parts of DIDP and 260 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hours; then adding 14 parts of halogenated solution-polymerized styrene-butadiene rubber cement a, stirring and reacting for 2.5 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 4
(1) Preparing halogenated solution-polymerized styrene-butadiene rubber cement: the same as in example 1.
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 13 parts of DIDP and 260 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hours; then 16 parts of halogenated solution-polymerized styrene-butadiene rubber cement a is added, after stirring reaction for 2.5 hours, the high-dispersion 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) Preparing halogenated 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, when the temperature of the polymerization kettle reaches 50 ℃, rapidly adding 13 parts of liquid bromine under stirring until the system is completely reddish brown, adding 0.5 part of DCP, stirring and reacting for 3.0h, adding 17 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0 percent to terminate the reaction, filtering, and washing to obtain halogenated solution polymerized styrene-butadiene rubber cement b (the bromine content is 8.2mol percent).
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 14 parts of DIDP and 300 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hours; then adding 18 parts of halogenated solution-polymerized styrene-butadiene rubber cement b, stirring and reacting for 3.0hr, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 6
(1) Preparing halogenated solution-polymerized styrene-butadiene rubber cement: the same as in example 5.
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 15 parts of DIDP and 320 parts of cyclohexane into a polymerization kettle, heating to 50 ℃, and stirring for reacting for 2.0 hr; then adding 19 parts of halogenated solution-polymerized styrene-butadiene rubber cement b, stirring and reacting for 3.0hr, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 7
(1) Preparing halogenated solution-polymerized styrene-butadiene rubber cement: the same as in example 5.
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 16 parts of DIDP and 320 parts of cyclohexane into a polymerization kettle, heating to 50 ℃, and stirring for reacting for 2.0 hr; then 20 parts of halogenated solution-polymerized styrene-butadiene rubber cement b is added, after stirring reaction for 3.0 hours, the high-dispersion 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) Preparing halogenated 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, when the temperature of the polymerization kettle reaches 55 ℃, rapidly adding 20 parts of liquid bromine under stirring until the system is completely reddish brown, adding 0.9 part of DCP, stirring and reacting for 4.0 hours, adding 19 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0 percent to terminate the reaction, filtering, and washing to obtain halogenated solution polymerized styrene-butadiene rubber cement c (the bromine content is 12.2mol percent).
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 18 parts of DINP and 320 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reacting for 2.5 hours; then 21 parts of halogenated solution-polymerized styrene-butadiene rubber cement c is added, after stirring reaction for 3.5 hours, the high-dispersion 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) Preparing halogenated solution-polymerized styrene-butadiene rubber cement: the same as in example 8.
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 19 parts of DINP and 400 parts of cyclohexane into a polymerization kettle, heating to 60 ℃, and stirring for reacting for 3.0 hr; then adding 23 parts of halogenated solution-polymerized styrene-butadiene rubber cement c, stirring and reacting for 4.0hr, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 10
(1) Preparing halogenated solution-polymerized styrene-butadiene rubber cement: the same as in example 8.
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 20 parts of DINP and 400 parts of cyclohexane into a polymerization kettle, heating to 60 ℃, and stirring for reacting for 3.0 hr; then adding 25 parts of halogenated solution-polymerized styrene-butadiene rubber cement c, stirring and reacting for 4.0hr, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 1
(1) Preparing halogenated solution-polymerized styrene-butadiene rubber cement: the other conditions were the same as in example 1 except that the amount of liquid bromine added during the preparation was 3.0 parts, namely: adding 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s and 100 parts of cyclohexane into a polymerization kettle, stirring and heating, when the temperature of the polymerization kettle reaches 45 ℃, rapidly adding 3.0 parts of liquid bromine under stirring until the system is completely reddish brown, adding 0.07 part of DCP, stirring and reacting for 1 hour, adding 10 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0 percent to terminate the reaction, filtering, and washing to obtain halogenated solution polymerized styrene-butadiene rubber cement a-1 (the bromine content is 1.2mol percent).
(2) Preparing high-dispersion nano white carbon black: the other conditions are the same as example 1, except that halogenated solution-polymerized styrene-butadiene rubber cement a is not added in the preparation process, and halogenated solution-polymerized styrene-butadiene rubber cement a-1 is added, namely: adding 100 parts of nano white carbon black (40nm), 10 parts of DIDP and 200 parts of cyclohexane into a polymerization kettle, heating to 40 ℃, and stirring for reacting for 1 hr; then adding 10 parts of halogenated solution-polymerized styrene-butadiene rubber cement a-1, stirring and reacting for 2 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 2
(1) Preparing halogenated solution-polymerized styrene-butadiene rubber cement: the same as in example 2.
(2) Preparing high-dispersion nano white carbon black: the other conditions are the same as example 2, except that the amount of the halogenated solution-polymerized styrene-butadiene rubber cement a added in the preparation process is 5.0 parts, namely: adding 100 parts of nano white carbon black (40nm), 11 parts of DIDP and 260 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hours; then adding 5.0 parts of halogenated solution-polymerized styrene-butadiene rubber cement a, stirring and reacting for 2.5 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 3
(1) Preparing halogenated solution-polymerized styrene-butadiene rubber cement: the other conditions were the same as in example 3 except that the amount of DCP added during the preparation was 0.04 parts, namely: adding 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s and 100 parts of cyclohexane into a polymerization kettle, stirring and heating, when the temperature of the polymerization kettle reaches 45 ℃, rapidly adding 5 parts of liquid bromine under stirring until the system is completely reddish brown, adding 0.04 part of DCP, stirring and reacting for 1 hour, adding 10 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0 percent to terminate the reaction, filtering and washing to obtain halogenated solution polymerized styrene-butadiene rubber cement a-2 (the bromine content is 1.7mol percent).
(2) Preparing high-dispersion nano white carbon black: the other conditions are the same as example 3, except that halogenated solution-polymerized styrene-butadiene rubber cement a is not added in the preparation process, and halogenated solution-polymerized styrene-butadiene rubber cement a-2 is added, namely: adding 100 parts of nano white carbon black (40nm), 6.0 parts of DIDP and 260 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hr; then adding 14 parts of halogenated solution-polymerized styrene-butadiene rubber cement a-2, stirring and reacting for 2.5 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion 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 solution-polymerized styrene-butadiene rubber cement: the same as in example 4.
(2) Preparing high-dispersion nano white carbon black: the other conditions were the same as in example 4, except that no DIDP was added during the preparation, namely: adding 100 parts of nano white carbon black (40nm) and 260 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hours; then 16 parts of halogenated solution-polymerized styrene-butadiene rubber cement a is added, after stirring reaction for 2.5 hours, the high-dispersion 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) Preparing halogenated solution-polymerized styrene-butadiene rubber cement: the other conditions were the same as in example 5 except that the amount of DCP added during the preparation was 0.02 parts, namely: adding 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s and 200 parts of cyclohexane into a polymerization kettle, stirring and heating, when the temperature of the polymerization kettle reaches 50 ℃, rapidly adding 13 parts of liquid bromine under stirring until the system is completely reddish brown, adding 0.02 part of DCP, stirring and reacting for 3.0h, adding 17 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0 percent to terminate the reaction, filtering and washing to obtain halogenated solution polymerized styrene-butadiene rubber cement b-1 (the bromine content is 0.7mol percent).
(2) Preparing high-dispersion nano white carbon black: the other conditions are the same as example 5, except that the halogenated solution-polymerized styrene-butadiene rubber cement b is not added in the preparation process, but halogenated solution-polymerized styrene-butadiene rubber cement b-1 is added, namely: adding 100 parts of nano white carbon black (40nm), 14 parts of DIDP and 300 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hours; then adding 18 parts of halogenated solution-polymerized styrene-butadiene rubber cement b-1, stirring and reacting for 3.0 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 6
Preparing high-dispersion nano white carbon black: the other conditions are the same as example 6, except that the halogenated solution-polymerized styrene-butadiene rubber cement b is not added in the preparation process, but the solution-polymerized styrene-butadiene rubber cement SSBR2564s is directly added, namely: adding 100 parts of nano white carbon black (40nm), 15 parts of DIDP and 320 parts of cyclohexane into a polymerization kettle, heating to 50 ℃, and stirring for reacting for 2.0 hr; then adding 19 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s, stirring and reacting for 3.0hr, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 7
(1) Preparing halogenated solution-polymerized styrene-butadiene rubber cement: the same as in example 7.
(2) Preparing high-dispersion nano white carbon black: the other conditions were the same as in example 7 except that the amount of the halogenated solution-polymerized styrene-butadiene rubber cement b added in the preparation process was 8.0 parts, that is: adding 100 parts of nano white carbon black (40nm), 16 parts of DIDP and 320 parts of cyclohexane into a polymerization kettle, heating to 50 ℃, and stirring for reacting for 2.0 hr; then adding 8.0 parts of halogenated solution-polymerized styrene-butadiene rubber cement b, stirring and reacting for 3.0 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 8
(1) Preparing halogenated 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 cyclohexane are added into a polymerization kettle, stirred and heated, 0.9 part of DCP is added under the stirring condition when the temperature of the polymerization kettle reaches 55 ℃, after stirring and reacting for 4.0 hours, 19 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0 percent is added to stop the reaction, and the halogenated solution polymerized styrene-butadiene rubber cement c-1 is prepared by suction filtration and washing.
(2) Preparing high-dispersion nano white carbon black: the other conditions were the same as in example 8, except that the halogenated solution-polymerized styrene-butadiene rubber cement c was not added in the preparation process, and the halogenated solution-polymerized styrene-butadiene rubber cement c-1 was added, namely: adding 100 parts of nano white carbon black (40nm), 18 parts of DINP and 320 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reacting for 2.5 hours; then 21 parts of halogenated solution-polymerized styrene-butadiene rubber cement c-1 is added, after stirring reaction for 3.5 hours, the high-dispersion 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 solution-polymerized styrene-butadiene rubber cement: the same as in example 9.
(2) Preparing high-dispersion nano white carbon black: the other conditions were the same as in example 9 except that the amount of DINP added during the preparation was 9.0 parts, that is: adding 100 parts of nano white carbon black (40nm), 9.0 parts of DINP and 400 parts of cyclohexane into a polymerization kettle, heating to 60 ℃, and stirring for reacting for 3.0 hr; then adding 23 parts of halogenated solution-polymerized styrene-butadiene rubber cement c, stirring and reacting for 4.0hr, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 10
(1) Preparing halogenated solution-polymerized styrene-butadiene rubber cement: the other conditions were the same as in example 10, except that no DCP was added during the preparation, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s and 300 parts of cyclohexane are added into a polymerization kettle, stirred and heated, when the temperature of the polymerization kettle reaches 55 ℃, 20 parts of liquid bromine is rapidly added under the stirring condition until the whole system becomes reddish brown, 19 parts of sodium hydroxide aqueous solution with the mass concentration of 5.0 percent is added to stop the reaction, and halogenated solution polymerized styrene-butadiene rubber cement c-2 (the bromine content is 0.3mol percent) is prepared by suction filtration and washing. .
(2) Preparing high-dispersion nano white carbon black: the other conditions were the same as in example 10, except that the halogenated solution-polymerized styrene-butadiene rubber cement c was not added in the preparation process, and the halogenated solution-polymerized styrene-butadiene rubber cement c-2 was added, namely: adding 100 parts of nano white carbon black (40nm), 20 parts of DINP and 400 parts of cyclohexane into a polymerization kettle, heating to 60 ℃, and stirring for reacting for 3.0 hr; then adding 25 parts of halogenated solution-polymerized styrene-butadiene rubber cement c-2, stirring and reacting for 4.0hr, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
TABLE 1 sedimentation volume and oil absorption of highly dispersed nano-white carbon black
Figure BDA0001833691790000161
Figure BDA0001833691790000171
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 (14)

1. A preparation method of high-dispersion nano white carbon black for rubber filler is characterized by comprising the following preparation steps:
(1) preparing halogenated 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 45-55 ℃, rapidly adding 5-20 parts by mass of halogenating agent under stirring until the system is completely reddish brown, adding initiator, stirring and reacting for 1-4 hours, adding 10-20 parts by mass of sodium hydroxide aqueous solution with the mass concentration of 5.0% to terminate the reaction, filtering and washing to obtain halogenated solution-polymerized styrene-butadiene rubber cement;
(2) preparing high-dispersion nano white carbon black: adding 100 parts by mass of nano white carbon black, 10-20 parts by mass of phthalic diester and 200-400 parts by mass of solvent into a polymerization kettle, heating to 40-60 ℃, and stirring for reacting for 1-3 hours; and then adding halogenated solution-polymerized styrene-butadiene rubber cement, stirring and reacting for 2-4 hr, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion 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 phthalic acid diester is at least one member selected from the group consisting of di-n-butyl phthalate, di-isononyl phthalate, di-isodecyl phthalate, di-pentyl phthalate, di-cyclohexyl phthalate, di-n-octyl phthalate, diphenylmethyl phthalate, dimethyl phthalate, and diethyl phthalate.
4. A method according to claim 3, wherein the diester phthalate is diisononyl phthalate.
5. The method according to claim 1, wherein the solution-polymerized styrene-butadiene rubber cement is prepared by 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 wt%.
6. The method of claim 1, wherein the halogenating agent is at least one of liquid chlorine and liquid bromine.
7. The method of claim 6, wherein said halogenating agent is liquid bromine.
8. The method of claim 1, wherein said initiator is selected from the group consisting of at least one of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide, and di-t-butyl peroxide.
9. The method of claim 8 wherein said initiator is dicumyl peroxide.
10. The method according to claim 8 or 9, wherein the amount of the initiator added is 0.07 to 0.6 parts by mass.
11. The method of claim 1, wherein the solvent is selected from at least one of cyclohexane, carbon disulfide, nitrobenzene, petroleum ether, tetrachloroethane, toluene, xylene, and chlorobenzene.
12. The method of claim 11, wherein the solvent is cyclohexane.
13. The method according to any one of claims 1 to 9, 11 and 12, wherein the initiator is added in an amount of 0.05 to 1.0 part by mass.
14. The method according to any one of claims 1 to 9, 11 and 12, wherein the amount of the halogenated solution-polymerized styrene-butadiene rubber cement added in the step of preparing the high-dispersion nano white carbon black is 10 to 25 parts by mass.
CN201811216564.3A 2018-10-18 2018-10-18 Preparation method of high-dispersion nano white carbon black for rubber filler Pending CN111073349A (en)

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