CN111073197A - Preparation method of high-dispersion nano white carbon black used as rubber filler - Google Patents
Preparation method of high-dispersion nano white carbon black used as rubber filler Download PDFInfo
- Publication number
- CN111073197A CN111073197A CN201811216489.0A CN201811216489A CN111073197A CN 111073197 A CN111073197 A CN 111073197A CN 201811216489 A CN201811216489 A CN 201811216489A CN 111073197 A CN111073197 A CN 111073197A
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- Prior art keywords
- carbon black
- white carbon
- parts
- nano white
- stirring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- 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 high-dispersion nano white carbon black used as rubber filler. According to the method, diester phthalate is adopted to anchor and modify the surfaces of the nano white carbon black particles, organic dibasic acid is adopted to graft polystyrene, and finally the polystyrene is coated on the surfaces of the nano white carbon black particles to form a hard shell with high connection strength and high obstruction to isolate the nano white carbon black. The method not only solves the problem that the nano white carbon black particles are agglomerated again due to long-term storage, but also endows the nano white carbon black with the dispersibility in a solution polymerized styrene butadiene rubber system. The invention has low modification cost and little environmental pollution.
Description
Technical Field
The invention relates to a preparation method of nano white carbon black, in particular to a preparation method of high-dispersity nano white carbon black used as 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 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) by emulsion polymerization to obtain nano-dioxide with a core-shell structureSilicon particles (SiO)2MPS-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 used as rubber filler. According to the method, polyether polyol is adopted to anchor and modify the surfaces of nano white carbon black particles, then unsaturated acrylate is adopted to graft polystyrene, and finally the polystyrene is coated on the surfaces of the nano white carbon black particles to form a high-barrier hard shell to isolate the nano white carbon black. The method not only solves the problem of easy agglomeration of the nano white carbon black, but also avoids the problem of agglomeration again due to 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 high 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 high-dispersion nano white carbon black used as rubber filler, which comprises the following specific preparation steps:
(1) preparation of grafted polystyrene: adding 100 parts by mass of polystyrene and 300-500 parts by mass of solvent into a reaction kettle, heating to 50-70 ℃, stirring for 5-10 hours, adding 5-20 parts by mass of unsaturated acrylate and 0.05-0.5 part by mass of initiator after the polystyrene is completely dissolved, stirring for reaction for 2-5 hours, adding 5-10 parts by mass of terminator to terminate the reaction, and performing suction filtration and washing to obtain the polystyrene graft (the grafting rate is 1.0% -7.0%).
(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, 5-15 parts by mass of polyether polyol 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 polystyrene graft, 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 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 polystyrene is a copolymer (HIPS) of styrene and polybutadiene rubber, can be powdery or granular resin, and has a Melt Flow Rate (MFR) of 0.5-20 g/10 min.
The polar monomer of the unsaturated acrylate is selected from at least one of Methyl Methacrylate (MMA), ethyl methacrylate, butyl methacrylate or tert-butyl methacrylate, and MMA is preferred.
The initiator can be at least one selected from dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-tert-butyl peroxide, and is preferably dicumyl peroxide (DCP), and the addition amount of the initiator is 0.05-0.5 part, preferably 0.1-0.3 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 chlorobenzene.
The terminating agent of the present invention may be at least one selected from diethylhydroxylamine, hydroxylamine sulfate and sodium fermet, and preferably diethylhydroxylamine.
The preparation method of the high-dispersion nano white carbon black used as the rubber filler comprises the following step of carrying out grafting reaction on HIPS by using unsaturated acrylate to ensure that the HIPS surface has a large amount of polar group ester groups. Then, the surface of the nano white carbon black particles is treated by polyether polyol, ether bonds (-R-O-R-) and hydroxyl (-OH) in the polyether polyol are used as anchoring groups, wherein the hydroxyl (-OH) and the hydroxyl on the surface of the nano white carbon black are subjected to condensation reaction to form a chemical grafting structure; meanwhile, hydroxyl on the surface of the white carbon black and oxygen atoms in ether bonds (-R-O-R-) are tightly connected with hydroxyl on the surface of the white carbon black through hydrogen bonding, and high-density polar anchor points mainly comprising ether bonds (-R-O-R-) and hydroxyl (-OH) are formed on the surface of white carbon black particles. The anchoring point and the polar group ester group of the grafted HIPS generate mutual attraction force between molecules, and a polystyrene barrier layer can be formed on the surface of the nano white carbon black particles after coating. Due to the fact that polyether polyol polar groups are multiple, anchor point density is large, connection strength is high, the blocking layers are firmly bonded, separation is difficult to occur even when the polyether polyol polar groups are stored at high temperature for a long time, secondly, the chain structure of the blocking layers has the non-polar characteristic, the blocking layers contain a benzene ring structure, molecular steric hindrance effect is large, stable steric hindrance layers can be built between the white carbon black nano-particles under the mutual 'synergistic effect' of the blocking layers and the benzene ring structure, mutual agglomeration among the particles is hindered, and the white carbon black nano-particles can stably exist in a single particle form (see attached figure 1). Meanwhile, the structure of the barrier layer chain is similar to the partial segment of the molecular structure of the solution polymerized styrene butadiene rubber, and the barrier layer chain has good compatibility with the solution polymerized styrene butadiene rubber. The invention avoids the use of a large amount of organic solvents, saves the modification cost of the white carbon black and is beneficial to environmental protection.
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 1200-1150 cm-1A sharp absorption peak of the ether group appears, and the wave number is 1705-1710 cm-1And a sharp absorption peak of the ester group appears, which indicates that the polyether polyol and the polystyrene graft containing the ester group 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
Polystyrene (HIPS), MFR2.9, Medium petrochemical Yanshan petrochemical division
Methyl Methacrylate (MMA), Guangzhou Qitai chemical Co., Ltd
Propylene glycol polyoxypropylene Ether (PPG), Haian Yongsheng chemical Co., Ltd
Polytetrahydrofuran diol (PTHF), Haian Yongsheng chemical Co., Ltd
Dicumyl peroxide (DCP), Lanzhou adjuvant plant
Other reagents are all commercial products
⑵ analytical test methods:
determination of the graft ratio: taking about 4g of sample from a three-necked bottle by using a pipette, weighing, adding 2-3 drops of hydroquinone solution, drying to constant weight, putting the sample in a Soxhlet fat extractor, extracting and extracting for 24 hours by using toluene in a water bath at 90 ℃, and drying to constant weight. The monomer grafting was calculated as follows:
in the formula: m is0-total mass of latex (g); m-sample mass (g) weighed after reaction; m ism-total mass of monomers in the reactants (g); m isSBR-mass of styrene butadiene rubber in the sample (g); m is1-mass of sample after extraction (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 method for measuring the oil absorption of aluminum hydroxide for YS/T618-2007 filler, quantitative modified nano white carbon black is put into a watch glass, diisooctyl phthalate is dropwise added according to 0.2mL of the diisooctyl phthalate, after each dropwise addition, the diisooctyl phthalate is fully ground by a knife,until the powder can be bound into large lumps without breaking, the oil absorption is in a volume V of oil absorbed per 100g of sample0(mL) as follows:
wherein upsilon is the volume of diisooctyl phthalate consumed (mL); m is the mass (g) of the sample. The oil absorption reflects the specific surface area of the modified nano white carbon black to 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 grafted polystyrene: adding 100 parts of HIPS and 300 parts of chlorobenzene into a reaction kettle, heating to 50 ℃, stirring for 5 hours, adding 5 parts of MMA and 0.1 part of DCP after the polystyrene is completely dissolved, stirring for reaction for 2 hours, adding 5 parts of diethylhydroxylamine to terminate the reaction, and performing suction filtration and washing to obtain HIPS-g-MMA (a) (the grafting rate is 1.9%).
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 5 parts of PPG and 200 parts of chlorobenzene into a polymerization kettle, heating to 40 ℃, and stirring for reacting for 1 hr; then adding 10 parts of HIPS-g-MMA (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) Preparation of grafted polystyrene: the same as in example 1.
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 6 parts of PPG and 220 parts of chlorobenzene into a polymerization kettle, heating to 43 ℃, and stirring for reacting for 1.4 hr; then adding 12 parts of HIPS-g-MMA (a), stirring and reacting for 2.3 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) Preparation of grafted polystyrene: the same as in example 1.
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 8 parts of PPG and 250 parts of chlorobenzene into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hours; then 14 parts of HIPS-g-MMA (a) are added, stirring and reacting are carried out for 2.5 hours, and flash evaporation, drying and grinding are carried out 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) Preparation of grafted polystyrene: adding 100 parts of HIPS and 350 parts of chlorobenzene into a reaction kettle, heating to 55 ℃, stirring for 7 hours, adding 9 parts of MMA and 0.2 part of DCP after polystyrene is completely dissolved, stirring for reaction for 3 hours, adding 7 parts of diethylhydroxylamine to terminate the reaction, and performing suction filtration and washing to obtain HIPS-g-MMA (b) (the grafting rate is 3.7%).
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 10 parts of PPG and 270 parts of chlorobenzene into a polymerization kettle, heating to 50 ℃, and stirring for reacting for 2.0 hr; then adding 16 parts of HIPS-g-MMA (b), stirring and reacting for 2.7 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 5
(1) Preparation of grafted polystyrene: the same as in example 4.
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 11 parts of PPG and 300 parts of chlorobenzene into a polymerization kettle, heating to 53 ℃, and stirring for reaction for 2.2 hours; then adding 18 parts of HIPS-g-MMA (b), stirring and reacting for 3.0hr, and performing 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) Preparation of grafted polystyrene: adding 100 parts of HIPS and 400 parts of chlorobenzene into a reaction kettle, heating to 65 ℃, stirring for 9 hours, adding 15 parts of MMA and 0.3 part of DCP after the polystyrene is completely dissolved, stirring for reacting for 4 hours, adding 9 parts of diethylhydroxylamine to terminate the reaction, and performing suction filtration and washing to obtain HIPS-g-MMA (c) (the grafting rate is 5.2%).
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 12 parts of PPG and 320 parts of chlorobenzene into a polymerization kettle, heating to 55 ℃, and stirring for reacting for 2.4 hours; then adding 20 parts of HIPS-g-MMA (c), stirring and reacting for 3.2 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 7
(1) Preparation of grafted polystyrene: the same as in example 6.
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 13 parts of PPG and 350 parts of chlorobenzene into a polymerization kettle, heating to 57 ℃, and stirring for reacting for 2.6 hours; then adding 22 parts of HIPS-g-MMA (c), stirring and reacting for 3.5 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 8
(1) Preparation of grafted polystyrene: adding 100 parts of HIPS and 500 parts of chlorobenzene into a reaction kettle, heating to 70 ℃, stirring for 10 hours, adding 20 parts of MMA and 0.45 part of DCP after the polystyrene is completely dissolved, stirring for reacting for 4.5 hours, adding 9 parts of diethylhydroxylamine to terminate the reaction, and performing suction filtration and washing to obtain HIPS-g-MMA (d) (the grafting rate is 6.1%).
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 14 parts of PTHF and 370 parts of chlorobenzene into a polymerization kettle, heating to 58 ℃, and stirring for reacting for 2.8 hours; then adding 23 parts of HIPS-g-MMA (d), stirring and reacting for 3.7 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 9
(1) Preparation of grafted polystyrene: the same as in example 8.
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 14.5 parts of PTHF and 390 parts of chlorobenzene into a polymerization kettle, heating to 59 ℃, and stirring for reacting for 2.8 hours; then adding 24 parts of HIPS-g-MMA (d), stirring and reacting for 3.8 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 10
(1) Preparation of grafted polystyrene: the same as in example 8.
(2) Preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 15 parts of PTHF and 400 parts of chlorobenzene into a polymerization kettle, heating to 60 ℃, and stirring for reacting for 3.0 hr; then adding 25 parts of HIPS-g-MMA (d), stirring and reacting for 4.0hr, and 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) Preparation of grafted polystyrene: the other conditions were the same as in example 1 except that the amount of MMA added during the preparation was 2.0 parts, that is: adding 100 parts of HIPS and 300 parts of chlorobenzene into a reaction kettle, heating to 50 ℃, stirring for 5 hours, adding 2.0 parts of MMA and 0.1 part of DCP after polystyrene is completely dissolved, stirring for reaction for 2 hours, adding 5 parts of diethylhydroxylamine to terminate the reaction, and performing suction filtration and washing to obtain HIPS-g-MMA (a-1) (the grafting rate is 0.5%).
(2) Preparing high-dispersion nano white carbon black: the other conditions were the same as in example 1 except that HIPS-g-MMA (a) was not added in the preparation process, but HIPS-g-MMA (a-1), that is: adding 100 parts of nano white carbon black (40nm), 5 parts of PPG and 200 parts of chlorobenzene into a polymerization kettle, heating to 40 ℃, and stirring for reacting for 1 hr; then adding 10 parts of HIPS-g-MMA (a-1), stirring and reacting for 2 hours, and 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) Preparation of grafted polystyrene: the same as in example 2.
(2) Preparing high-dispersion nano white carbon black: the other conditions were the same as in example 2 except that the amount of PPG added during the preparation was 3.0 parts, namely: adding 100 parts of nano white carbon black (40nm), 3.0 parts of PPG and 220 parts of chlorobenzene into a polymerization kettle, heating to 43 ℃, and stirring for reacting for 1.4 hr; then adding 12 parts of HIPS-g-MMA (a), stirring and reacting for 2.3 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) Preparation of grafted polystyrene: the same as in example 3.
(2) Preparing high-dispersion nano white carbon black: the other conditions were the same as in example 3 except that HIPS-g-MMA (a) was added in an amount of 5.0 parts during the preparation, that is: adding 100 parts of nano white carbon black (40nm), 8 parts of PPG and 250 parts of chlorobenzene into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hours; then adding 5.0 parts of HIPS-g-MMA (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 4
Preparing high-dispersion nano white carbon black: the other conditions were the same as in example 4, except that HIPS-g-MMA (b) was not added during the preparation, but was added directly to HIPS, that is: adding 100 parts of nano white carbon black (40nm), 10 parts of PPG and 270 parts of chlorobenzene into a polymerization kettle, heating to 50 ℃, and stirring for reacting for 2.0 hr; then adding 16 parts of HIPS, stirring and reacting for 2.7 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 5
(1) Preparation of grafted polystyrene: the same as in example 5.
(2) Preparing high-dispersion nano white carbon black: the other conditions were the same as in example 5 except that the amount of HIPS-g-MMA (b) added during the preparation was 8.0 parts, namely: adding 100 parts of nano white carbon black (40nm), 11 parts of PPG and 300 parts of chlorobenzene into a polymerization kettle, heating to 53 ℃, and stirring for reaction for 2.2 hours; then adding 8.0 parts of HIPS-g-MMA (b), stirring and reacting for 3.0hr, and 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
(1) Preparation of grafted polystyrene: the other conditions were the same as in example 6 except that the amount of MMA added during the preparation was 4.0 parts, that is: adding 100 parts of HIPS and 400 parts of chlorobenzene into a reaction kettle, heating to 65 ℃, stirring for 9 hours, adding 4.0 parts of MMA and 0.3 part of DCP after polystyrene is completely dissolved, stirring for reacting for 4 hours, adding 9 parts of diethylhydroxylamine to terminate the reaction, and performing suction filtration and washing to obtain HIPS-g-MMA (c-1) (the grafting rate is 0.9%).
(2) Preparing high-dispersion nano white carbon black: the other conditions were the same as in example 6 except that HIPS-g-MMA (c) was not added in the preparation process, but HIPS-g-MMA (c-1), that is: adding 100 parts of nano white carbon black (40nm), 12 parts of PPG and 320 parts of chlorobenzene into a polymerization kettle, heating to 55 ℃, and stirring for reacting for 2.4 hours; then adding 20 parts of HIPS-g-MMA (c-1), stirring and reacting for 3.2 hours, and 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) Preparation of grafted polystyrene: 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 PPG added during the preparation was 4.5 parts, namely: adding 100 parts of nano white carbon black (40nm), 4.5 parts of PPG and 350 parts of chlorobenzene into a polymerization kettle, heating to 57 ℃, and stirring for reacting for 2.6 hours; then adding 22 parts of HIPS-g-MMA (c), stirring and reacting for 3.5 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 8
(1) Preparation of grafted polystyrene: the other conditions were the same as in example 8 except that the amount of DCP added during the preparation was 0.04 parts, namely: adding 100 parts of HIPS and 500 parts of chlorobenzene into a reaction kettle, heating to 70 ℃, stirring for 10 hours, adding 20 parts of MMA and 0.04 part of DCP after the polystyrene is completely dissolved, stirring for reacting for 4.5 hours, adding 9 parts of diethylhydroxylamine to terminate the reaction, and performing suction filtration and washing to obtain HIPS-g-MMA (d-1) (the grafting rate is 0.7%).
(2) Preparing high-dispersion nano white carbon black: the other conditions were the same as in example 8 except that HIPS-g-MMA (d) was not added in the preparation process, but HIPS-g-MMA (d-1), that is: adding 100 parts of nano white carbon black (40nm), 14 parts of PTHF and 370 parts of chlorobenzene into a polymerization kettle, heating to 58 ℃, and stirring for reacting for 2.8 hours; then adding 23 parts of HIPS-g-MMA (d-1), stirring and reacting for 3.7 hours, and 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 9
(1) Preparation of grafted polystyrene: 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 PTHF added during the preparation was 4.0 parts, namely: adding 100 parts of nano white carbon black (40nm), 4.0 parts of PTHF and 390 parts of chlorobenzene into a polymerization kettle, heating to 59 ℃, and stirring for reacting for 2.8 hours; then adding 24 parts of HIPS-g-MMA (d), stirring and reacting for 3.8 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 10
(1) Preparation of grafted polystyrene: the other conditions were the same as in example 10, except that no DCP was added during the preparation, namely: adding 100 parts of HIPS and 500 parts of chlorobenzene into a reaction kettle, heating to 70 ℃, stirring for 10 hours, adding 20 parts of MMA after polystyrene is completely dissolved, stirring for reaction for 4.5 hours, adding 9 parts of diethylhydroxylamine to terminate the reaction, and performing suction filtration and washing to obtain HIPS-g-MMA (d-2) (the grafting rate is 0.1%).
(2) Preparing high-dispersion nano white carbon black: the other conditions were the same as in example 10 except that HIPS-g-MMA (d) was not added in the preparation process, but HIPS-g-MMA (d-2), that is: adding 100 parts of nano white carbon black (40nm), 15 parts of PTHF and 400 parts of chlorobenzene into a polymerization kettle, heating to 60 ℃, and stirring for reacting for 3.0 hr; then adding 25 parts of HIPS-g-MMA (d-2), stirring and reacting for 4.0hr, and 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
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 (11)
1. A preparation method of high-dispersion nano white carbon black used as rubber filler is characterized by comprising the following preparation steps:
(1) preparation of grafted polystyrene: adding 100 parts by mass of polystyrene and 300-500 parts by mass of solvent into a reaction kettle, heating to 50-70 ℃, stirring for 5-10 hours, adding unsaturated acrylate and 0.05-0.5 part by mass of initiator after the polystyrene is completely dissolved, stirring for reaction for 2-5 hours, adding 5-10 parts by mass of terminator to terminate the reaction, and performing suction filtration and washing to obtain a polystyrene graft;
(2) preparing high-dispersion nano white carbon black: adding 100 parts by mass of nano white carbon black, 5-15 parts by mass of polyether polyol and 200-400 parts by mass of solvent into a polymerization kettle, heating to 40-60 ℃, and stirring for reacting for 1-3 hours; then adding 10-25 parts by mass of polystyrene graft, 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 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.
4. A process according to claim 3, wherein the polyether polyol is propylene glycol polyoxypropylene ether.
5. The method of claim 1, wherein the polystyrene is a copolymer of styrene and polybutadiene rubber, is a powdered or granular resin, and has a melt flow rate of 0.5 to 20g/10 min.
6. The method of claim 1, wherein the polar monomer of the unsaturated acrylate is selected from at least one of methyl methacrylate, ethyl methacrylate, butyl methacrylate, and t-butyl methacrylate.
7. The method of claim 6, wherein the polar monomer of the unsaturated acrylate is methyl methacrylate.
8. The method according to claim 6 or 7, wherein the unsaturated acrylate is added in an amount of 5 to 20 parts by mass.
9. 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.
10. The method of claim 9 wherein said initiator is dicumyl peroxide.
11. The method according to claim 9 or 10, wherein the initiator is added in an amount of 0.1 to 0.3 part.
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